### EPA/600/P-03/002F November 2006



# An I n ven t ory of S o u rces an d En viron m en tal Releas es of Dioxin-Like Compounds in the Unite d State s for the Years 1987, 1995, and 2000

National Center for E nvironmental Assessment Office of Research and Development U.S. Environmental Protection Ag ency W a shing t on, DC 20460

### D I SC LA IM ER

Thi s docum ent has been revi ewed i n accordance wi t h U.S

. Envi ronm ent a l P r ot ect i o n Ag ency policy and approved for publication. Me ntion of trade names or commercial products
does not constitute endorsement or recommendation for use.

AB S T RACT

The purpose of this document is to presen t a comprehensive inventory and overview of
sources and environmental releases of diox in- like compounds in the United States. The major
identified sources of environmen tal releases of diox in-like co mpounds are g r ouped into six broad

c a t e g or ie s: c o mbustion sour c e s, me ta ls sme lting

, r e f i ning a nd pr oc e ss sour c e s, c h e mic a l manufacturing sources, natural s ources, and environmental rese rvoirs. Estimates of annual releases to land, air, and water are presen ted for each source categ ory and summariz e d for reference y ears 1987, 1995, and 2000. The quantitative results are ex pressed in terms of the

tox i city equivalence (TEQ) of the mix ture of poly c hlorinated dibenz o- p -di o x i n (C DD) and poly c hlorinated dibenz ofuran (CDF ) compounds present in envi ronmental releases using a procedure sanctioned by the W o rld Health Or g a niz a tion (W HO) in 1998. This TEQ procedure

t r ansl at es t h e com p l e x m i x t u re of C DDs and C D Fs charact eri s t i c of envi ronm ent a l rel eases i n t o an equivalent tox i city concen tration of 2,3,7,8-te trachorodibenz o- p -diox i n (2,3,7,8-TCDD), the

most tox i c member of this class of compounds. Using this W HO procedure, the annual releases of TEQ DF 

### -W HO 98 

### to the U.S. environment over the three reference y ears are 13,965 g in 1987, 3,444 g in 1995, and 1,422 g in 2000. This analy s is indicates that between reference y ears 1987 and 2000, there was approx imately a 90% reduction in the rel eases of diox in-like compounds to the circulating environment of the United Stat es from all known sources combined. I n 1987 and 1995, the leading source of diox in emissions to the U.S. environment was municipal waste

com bust i on; however, because of reduct i ons i n di ox i n em i ssi ons from m uni ci pal wast e combustors, it dropped to the fourth ranked s ource in 2000. B u rning of domestic refuse in backy a rd burn barrels remained fairly constant over the y ears, but in 2000, it emerg e d as the larg est source of diox in emissions to the U.S. environment.

P ref erred Ci tati on : U

. S

. EPA (En v i ron m en t a l Prot ect i o n A g en cy ). (2006) A n i n v e n t ory of s o u rces an d en v i ron m en t a l rel eas es of di ox i n

l i k e com pou n d s i n t h e U n i t e d S t at es f o r t h e y ears 1987, 1995, an d 2000. N a t i o n a l C e n t er f o r En v i ron m en t a l A s s e s s m en t , Was h i n g t on , D C ; EPA / 600/ P- 03/ 002F

. A v ai l a bl e f rom : N a t i o n a l T ech n i cal In f o rm at i o n S e rv i ce, Sp rin g f ield , VA , an d o n lin e at h ttp ://ep a .g o v /n cea.



### ii

### C O N TEN TS

L I S T O F T A B L E S

....................................................... x i i L I S T O F F I G U R E S

..................................................... x x

v L I S T O F A B B R E V I A T I O N S A N D A C R O N Y M S

................................ x x

x F O R E W O R D

......................................................... xxxiv P R E F A C E

........................................................... xxxvi A U T H O R S
, C O N T R I B U T O R S
, A N D R E V I E W E R S

........................... xxxv i i AC KNOW L E DGMENT

...................................................... x l i E X E C U T I V E S U M M A R Y

.................................................... x l i i

1. BAC KGR OUND, AP P R OAC H, AND C ONC L US I ONS

......................... 1

- 1 1.1. B A CKGROUND

................................................... 1

- 1 1.1.1. Reference Years

.............................................. 1

- 3 1.1.2. Reg ulatory Summary

.......................................... 1

- 3 1.1.3. Definition of Diox in-L ike Compound

............................. 1

- 4 1.1.4. Tox i city Equivalence F actors

.................................... 1

- 8 1.1.5. I n formation Sources

.......................................... 1

- 1 1 1.2. APPROACH

..................................................... 1

- 1 2 1.2.1. Source Classes

.............................................. 1

- 1 2 1.2.2. Quantitative Method for I nventory of Sources

...................... 1

- 2 3 1.2.3. Confidence Rating s

........................................... 1

- 2 7 1.2.3.1. Rating Scheme

....................................... 1

- 3 1 1.3. CONCL U SI ONS

.................................................. 1

- 3 7 1.3.1. Total Environmental Releases

.................................. 1

- 3 7 1.3.2. Time Trends

................................................ 1

- 4 2 1.3.3. Sources Not I ncluded in the I nventory

............................ 1

- 4 2 1.3.4. F ormation Theory

............................................ 1

- 4 3 1.3.5. Cong ener Profiles of CDD/CDF Sources

.......................... 1

- 4 4

2. MEC HANI S M S OF FOR M ATI ON OF DI OXI N-L I KE C OMP OUNDS DUR I NG C OMBUS TI ON OF OR GANI C MATER I AL S

................................. 2

- 1 2.1. MECHANI SM 1 (PASS THROUGH) : CDD/CDF CONTAMI NATI ON I N F U E L A S A S O U R C E O F C O M B U S T I O N S T A C K E M I S S I O N S

............ 2

- 3 2.2. MECHANI SM 2 (PRECURSOR): F O RMATI ON OF CDDs/CDF s F R OM P R EC UR S O R C O MP OUNDS

........................................ 2

- 4 2.3. MECHANI SM 3 ( DE N O VO S YNTHES I S ) : S YNTHES I S OF C DDs/C DFs DUR I NG C OMBUS TI ON OF OR GANI C MATER I AL S

.................. 2

- 1 2 2.4. THE ROL E OF CHL O RI NE I N THE F O RMATI ON OF CDDs/CDF s I N C O M B U S T I O N S Y S T E M S

......................................... 2

- 2 0 2.4.1. Review of L a boratory

- Scale Studies

............................. 2

- 2 1 2.4.2. Review of F ull-Scale Combustion Sy stems

........................ 2

- 2 6 2.5. POTENTI AL PREVENTI ON OF CDD/CDF F O RMATI ON I N C O M B U S T I O N S Y S T E M S

......................................... 2

- 2 8 2.6. THEORY ON THE EMI SSI ON OF PCB s

.............................. 2

- 2 9

iii

### C O N TEN TS ( c ont i nue d)

2.7. SUMMARY AND CONCL U SI ONS

.................................. 2

- 3 1 2.7.1. Mechanisms of F ormation of Diox in-L ike Compounds

............... 2

- 3 1 2.7.2. Role of Chlorine

............................................. 2

- 3 3 2.7.3. General Conclusion

........................................... 2

- 3 4

3

. C O M B U S T I O N S O U R C E S O F C D D s / C D F s : W A S T E I N C I N E R A T I O N

........... 3

- 1 3.1. MUNI CI PAL W A STE COMB USTI ON

.................................. 3

- 1 3.1.1. Description of Municipal W a ste Combustion Technolog ies

............ 3

- 2 3.1.1.1. Furnace Ty pes

........................................ 3

- 2 3.1.1.2. Air Pollution Control Devices

............................ 3

- 9 3.1.1.3. Classification Scheme

................................. 3

- 1 0 3.1.2. Characteriz ation of MW Cs in Reference Years 2000, 1995, and 1987

. . . 3-11 3.1.3. Estimation of CDD/CDF Emissions from MW Cs

................... 3

- 1 9 3.1.3.1. Estimating CDD/CDF Emissions from MW Cs in Reference Year 2000

........................................... 3

- 1 9 3.1.3.2. Estimating CDD/CDF Emissions from MW Cs in Reference Years 1995 and 1987

.................................. 3

- 2 1 3.1.4. Summary of CDD/CDF (TEQ) Emissions from MW Cs for 2000, 1995, and 1987

................................................... 3

- 2 3 3.1.5. Cong ener Profiles of Muni cipal W a ste Combustion F acilities

......... 3

- 3 1 3.1.6. Estimated CDDs/CDF s in MW C Ash

............................ 3

- 3 1 3.1.7. Recent EPA Reg ulatory Activities

............................... 3

- 4 0 3.2. HAZ ARDOUS W A STE I N CI NERATI ON

.............................. 3

- 4 1 3.2.1. Furnace Desig n s for HW I s

..................................... 3

- 4 2 3.2.2. APCDs for HW I s

............................................ 3

- 4 4 3.2.3. Estimation of CDD/CDF Emission F actors for HW I s

................ 3

- 4 5 3.2.4. Emission Estimates for HW I s

................................... 3

- 4 7 3.2.5. Recent EPA Reg ulatory Activities

............................... 3

- 5 1 3.2.6. I ndustrial B o ilers and Furnaces B u rning Haz a rdous W a ste

............ 3

- 5 1 3.2.7. Halog e n Acid Furnaces B u rning Haz a rdous W a ste

.................. 3

- 5 3 3.2.8. Solid W a ste from Haz a rdous W a ste Combustion

.................... 3

- 5 5 3.3. MEDI CAL W A STE I N CI NERATI ON

................................. 3

- 5 5 3.3.1. Desig n Ty pes of MW I s Operating in the United States

............... 3

- 5 5 3.3.2. Characteriz ation of MW I s for Reference Years 1987, 1995, and 2000

. . . 3-57 3.3.3. Estimation of CDD/CDF Emissions from MW I s

.................... 3

- 5 9 3.3.4. Summary of CDD/CDF Emissions from MW I s

..................... 3

- 6 4 3.3.5. Recent EPA Reg ulatory Activities

............................... 3

- 6 5 3.4. CREMATORI A

................................................... 3

- 6 5 3.4.1. Human Crematoria

........................................... 3

- 6 5 3.4.1.1. Emissions Data

....................................... 3

- 6 5 3.4.1.2. Activity L e vel I nformatio n.............................. 3

- 7 3 3.4.1.3. Emission Estimates

................................... 3

- 7 6 3.4.2. Animal Crematoria

........................................... 3

- 7 6

iv

### C O N TEN TS ( c ont i nue d)

3.4.2.1. Emissions Data

....................................... 3

- 7 6 3.4.2.2. Activity L e vel I nformatio n

.............................. 3

- 7 6 3.4.2.3. Emission Estimates

................................... 3

- 7 6 3.5. SEW AGE SL UDGE I N CI NERATI ON

................................. 3

- 7 7 3.5.1. Emissions Estimates from Sewag e Sludg e I n cinerators

............... 3

- 7 9 3.5.2. Solid W a ste from Sewag e Sludg e I ncinerators

...................... 3

- 8 3 3.6. TI RE COMB USTI ON

.............................................. 3

- 8 3 3.7. COMB USTI ON OF W A STEW ATER SL UDGE AT B L EACHED C H E M I C A L P U L P M I L L S

.......................................... 3

- 8 7 3.8. B I OGAS COMB USTI ON

........................................... 3

- 8 7

4. C O MBUS TI ON S OUR C E S OF C DDs/C DFs: P O W E R / ENER GY GENER A TI ON

. . . 4-1 4.1. MOTOR VEHI CL E F U EL COMB USTI ON

.............................. 4

- 1 4.1.1. Tailpipe Emission Studies

...................................... 4

- 1 4.1.2. Tunnel Emission Studies

...................................... 4

- 2 0 4.1.3. National Emission Estimates

................................... 4

- 2 8 4.1.3.1. Activity I nformation for On-Road Vehicles

................ 4

- 2 8 4.1.3.2. Activity I n formation for Off-Road Uses

................... 4

- 3 1 4.1.3.3 Emission Estimates

.................................... 4

- 3 2 4.2. W OOD COMB USTI ON

............................................ 4

- 3 8 4.2.1. F l ue Emissions from W ood Combustion (Residential)

............... 4

- 3 8 4.2.1.1. Emissions Data

....................................... 4

- 3 8 4.2.1.2. Activity L e vel I nformatio n

.............................. 4

- 4 1 4.2.1.3. Emission Estimates

................................... 4

- 4 4 4.2.2. Stack Emissions from W ood Combustion (I ndustrial)

............... 4

- 4 4 4.2.2.1. Emissions Data

....................................... 4

- 4 4 4.2.2.2. Activity L e vel I nformatio n

.............................. 4

- 5 0 4.2.2.3. Emission Estimates

................................... 4

- 5 1 4.2.3. Solid W a ste from W ood Combustion (Residential and I ndustrial)

...... 4

- 5 2 4.3. OI L COMB USTI ON

............................................... 4

- 6 0 4.3.1. I n stitutional/Comme rcial and Residen tial Oil Combustion

............ 4

- 6 1 4.3.2. Utility Sector and I ndustrial Oil Combustion

...................... 4

- 6 4 4.3.3. Used Oil Combustion

......................................... 4

- 6 7 4.4. COAL COMB USTI ON

............................................. 4

- 6 7 4.4.1. Utilities and I ndustrial B oilers

.................................. 4

- 6 8 4.4.2. Residential Coal Combustion

.................................. 4

- 7 4 4.4.3. Solid W a stes from Coal Combustion

............................. 4

- 7 7

5. C O MBUS TI ON S OUR C E S OF C DDs/C DFs: OTHER HI GH-TEMP E R A TUR E S O U R C E S

............................................................. 5

- 1 5.1. CEMENT KI L N S

.................................................. 5

- 1 5.1.1. Process Description of Portland Cement Kilns

....................... 5

- 1 5.1.2. Cement Kilns That B urn Haz a rdous W a ste

......................... 5

- 2

v

### C O N TEN TS ( c ont i nue d)

5.1.3. Air Pollution Control Devices

................................... 5

- 3 5.1.4. CDD/CDF Emissions Data

...................................... 5

- 4 5.1.4.1. Emissions Data for 1989 throug h 1996

..................... 5

- 4 5.1.4.2. Emissions Data for 1999 and 2000

......................... 5

- 7 5.1.4.3. Emission F actor Estimates for Cement Kilns B urning Haz a rdous W a s t e

............................................... 5

- 7 5.1.4.4. Emission F actor Estimates for Cement Kilns B urning Nonhaz a rdous W a ste

................................... 5

- 9 5.1.4.5. Confidence Rating s of Emission F actor Estimates

........... 5

- 1 0 5.1.5. Activity L e vel I nformatio n

..................................... 5

- 1 0 5.1.6. National CDD/CDF Emission Estimates

.......................... 5

- 1 4 5.1.6.1. Estimates for Refere nce Years 1987 and 1995

............... 5

- 1 4 5.1.6.2. Estimates for Reference Year 2000

....................... 5

- 1 5 5.1.7. EPA Reg ulatory Activities

..................................... 5

- 1 6 5.1.8. Solid W a ste from Cement Manuf acturing : Cement Kiln Dust

......... 5

- 1 6 5.2. L I GHTW EI GHT AGGREGATE KI L N S

............................... 5

- 2 1 5.3. ASPHAL T MI XI NG PL ANTS

....................................... 5

- 2 2 5.4. PETROL EUM REF I NI NG CATAL Y ST REGENERATI ON

................ 5

- 2 4 5.5. CI GARETTE SMOKI NG

........................................... 5

- 2 8 5.6. PYROL Y SI S OF B R OMI NATED F L AME RETARDANTS

............... 5

- 3 9 5.7. CARB ON REACTI VATI ON F U RNACES

............................. 5

- 3 9 5.8. KRAF T B L ACK L I QUOR RECOVERY B O I L ERS

...................... 5

- 4 2 5.9. OTHER I D ENTI F I ED SOURCES

.................................... 5

- 4 6

6. C O MBUS TI ON S OUR C ES OF C DDs/C DFs: MI NI MAL L Y C ONTR O L L ED AND UNC ONTR OL L E D C OMBUS TI ON S OUR C E S

.......................... 6

- 1 6.1. COMB USTI ON OF L ANDF I L L GAS

.................................. 6

- 1 6.1.1. Emissions Data

............................................... 6

- 1 6.1.2. Activity L e vel I nformation

...................................... 6

- 1 6.1.2.1. Activity L e vels for 1987 and 1995

......................... 6

- 3 6.1.2.2. Activity L e vel for 2000

................................. 6

- 4 6.1.3. Emission Estimates

........................................... 6

- 4 6.2. ACCI DENTAL F I RES

.............................................. 6

- 5 6.2.1. Soot and Ash Studies

.......................................... 6

- 5 6.2.2. F ume and Smoke Studies

....................................... 6

- 7 6.2.3. Data Evaluation

............................................... 6

- 8 6.2.3.1. Structural F i res

........................................ 6

- 8 6.2.3.1.1. Emissions data

................................ 6

- 8 6.2.3.1.2. Activity level information

....................... 6

- 9 6.2.3.1.3. Emission estimates

............................ 6

- 9 6.2.3.2. Vehicle F i res

......................................... 6

- 1 0 6.3. L ANDF I L L F I RES

................................................. 6

- 1 1 6.3.1. Emissions Data

.............................................. 6

- 1 1

vi

### C O N TEN TS ( c ont i nue d)

6.3.2. Activity L e vel I nforma tion and Emission Estimates

................. 6

- 1 2 6.4. F O REST AND B R USH F I RES

....................................... 6

- 1 2 6.4.1. Emissions Data

.............................................. 6

- 1 2 6.4.2. Activity L e vel I nformation

..................................... 6

- 1 8 6.4.2.1. Approach for Reference Year 2000 (Office of Air Quality P l a n n i n g a n d S t a n d a r d s [ O A Q P S ] )

....................... 6

- 1 8 6.4.2.2. Approach for Reference Years 1987 and 199 5

............... 6

- 1 8 6.4.3. Emission Estimates

........................................... 6

- 1 9 6.5. B A CKYARD B A RREL B U RNI N G

................................... 6

- 2 0 6.5.1. Emissions Data

.............................................. 6

- 2 0 6.5.2. Activity L e vel I nformation

..................................... 6

- 2 1 6.5.2.1. Summary of B a rrel B u rn Survey s

......................... 6

- 2 3 6.5.2.2. Estimates of Activity L e vel

............................. 6

- 2 4 6.5.2.3. Alternative Approach to Estimating Activity L e vel

........... 6

- 2 5 6.5.3. Emission Estimates

........................................... 6

- 2 6 6.5.4. Composition of Ash from B a rrel B urning

......................... 6

- 2 6 6.6. RESI DENTI A L YARD W A STE B U RNI N G

............................ 6

- 2 6 6.6.1. Emissions Data

.............................................. 6

- 2 6 6.6.2. Activity L e vel I nformation

..................................... 6

- 2 8 6.6.3. Emission Estimates

........................................... 6

- 2 9 6.7. L AND-CL EARI NG DEB R I S B U RNI N G

.............................. 6

- 3 0 6.7.1. Emissions Data

.............................................. 6

- 3 0 6.7.2. Activity L e vel I nformation

..................................... 6

- 3 0 6.7.2.1. Residential Construction

............................... 6

- 3 0 6.7.2.2. Nonresidential Construction

............................. 6

- 3 0 6.7.2.3. Roadway Construction

................................. 6

- 3 1 6.7.2.4. F u el L o ading F actors

.................................. 6

- 3 1 6.7.3. Emission Estimates

........................................... 6

- 3 2 6.8. UNCONTROL L ED COMB USTI ON OF POL Y CHL O RI NATED B I P H E N Y L S

..................................................... 6

- 3 2 6.9. VOL CANOES

.................................................... 6

- 3 3 6.10. F I REW O RKS

.................................................... 6

- 3 4 6.11. OPEN B U RNI NG AND OPEN DETONATI ON OF ENERGETI C M A T E R I A L S

..................................................... 6

- 3 6

7

. M E T A L S M E L T I N G A N D R E F I N I N G S O U R C E S O F C D D s / C D F s

.............. 7

- 1 7

. 1

. P R I M A R Y N O N F E R R O U S M E T A L S M E L T I N G / R E F I N I N G

............... 7

- 1 7

. 1

. 1

. P r i m a r y C o p p e r S m e l t i n g a n d R e f i n i n g

.......................... 7

- 1 7

. 1

. 2

. P r i m a r y M a g n e s i u m S m e l t i n g a n d R e f i n i n g

....................... 7

- 4 7

. 1

. 3

. P r i m a r y N i c k e l S m e l t i n g a n d R e f i n i n g

........................... 7

- 6 7

. 1

. 4

. P r i m a r y A l u m i n u m S m e l t i n g a n d R e f i n i n g

........................ 7

- 6 7

. 1

. 5

. P r i m a r y T i t a n i u m S m e l t i n g a n d R e f i n i n g

......................... 7

- 7 7

. 2

. S E C O N D A R Y N O N F E R R O U S M E T A L S M E L T I N G

.................... 7

- 8

vii

### C O N TEN TS ( c ont i nue d)

7

. 2

. 1

. S e c o n d a r y A l u m i n u m S m e l t e r s

................................ 7

- 8 7

. 2

. 2

. S e c o n d a r y C o p p e r S m e l t e r s

................................. 7

- 1 4 7

. 2

. 2

. 1 . E m i s s i o n s D a t a

................................... 7

- 1 5 7

. 2

. 2

. 2 . A c t i v i t y L e v e l I n f o r m a t i o n

............................ 7

- 2 0 7

. 2

. 2

. 3 . E m i s s i o n E s t i m a t e s

................................ 7

- 2 0 7

. 2

. 3

. S e c o n d a r y L e a d S m e l t e r s

................................... 7

- 2 2 7

. 3

. P R I M A R Y F E R R O U S M E T A L S M E L T I N G / R E F I N I N G

................. 7

- 2 7 7

. 3

. 1

. S i n t e r P r o d u c t i o n

........................................ 7

- 2 7 7

. 3

. 2

. C o k e P r o d u c t i o n

......................................... 7

- 3 2 7

. 4

. S E C O N D A R Y F E R R O U S M E T A L S M E L T I N G / R E F I N I N G

.............. 7

- 3 3 7

. 5

. F E R R O U S F O U N D R I E S

........................................ 7

- 3 6 7

. 6

. S C R A P E L E C T R I C W I R E R E C O V E R Y

............................. 7

- 4 0 7

. 7

. D R U M A N D B A R R E L R E C L A

M

A T I O N F U R N A C E S

................... 7

- 4 5 7.8. S O LID W A S T E FR OM PR IMA R Y / S E COND A R Y IR ON/ S TEEL M I L L S / F O U N D R I E S

........................................... 7

- 4 8

8. C H EMI C AL MANUFAC TUR I NG AND P R OC ES S I NG S OUR C E S

............... 8

- 1 8.1. B L EACHED CHEMI C AL W OOD PUL P AND PAPER MI L L S

.............. 8

- 1 8.1.1. Estimates of National Emissions in 1987 and 1995

................... 8

- 8 8.1.2. Estimates of Nati onal Emissions in 2000

........................... 8

- 8 8.2. MANUF ACTURE OF CHL O RI NE, CHL O RI NE DERI VATI V ES, AND METAL C H L O R I D E S

...................................................... 8

- 9 8.2.1. Manufacture of Chlorine

........................................ 8

- 9 8.2.2. Manufacture of Chlorine De rivatives and Metal Chlorides

............ 8

- 1 2 8.3. MANUF ACTURE OF HAL OGENATED ORGANI C CHEMI C AL S

......... 8

- 1 4 8.3.1. Chlorophenols

............................................... 8

- 1 5 8.3.1.1. Reg ulatory Actions for Chlorophenols

..................... 8

- 1 6 8.3.2. Chlorobenz enes

.............................................. 8

- 2 4 8.3.2.1. Reg u latory Actions for Chlorobenz enes

.................... 8

- 2 6 8.3.3. Chlorobipheny ls

............................................. 8

- 2 7 8.3.4. Ethy lene Dichloride/Viny l Chlo ride Monomer/Poly viny l Chloride M a n u f a c t u r i n g

.............................................. 8

- 3 0 8.3.4.1. W a ter Releases

....................................... 8

- 3 3 8.3.4.2. L a nd Releases

........................................ 8

- 3 6 8.3.4.3. Air Releases

......................................... 8

- 3 6 8.3.4.4. Transfers to Secure L a ndfills

............................ 8

- 3 8 8.3.4.5. Products

............................................ 8

- 4 1 8.3.5. Other Aliphatic Chlorine Compounds

............................ 8

- 4 4 8.3.6. Dy es, Pig m ents, and Printing I nks

............................... 8

- 4 5 8.3.6.1. Diox az ine Dy es and Pig m ents

........................... 8

- 4 5 8.3.6.2. Phthalocy a nine Dy es and Printing I nks

.................... 8

- 4 8 8.3.7. TSCA Diox in/F uran Test Rule

.................................. 8

- 5 0 8.3.8. Halog e nated Pestic ides and F I F R A Pes ticides Data Call-I n

............ 8

- 5 2

viii

### C O N TEN TS ( c ont i nue d)

8.4. OTHER CHEMI C AL MANUF ACTURI NG AND PROCESSI NG S O U R C E S

....................................................... 8

- 7 3 8.4.1. Municipal W a stewater Treatment Plants

.......................... 8

- 7 3 8.4.1.1. Sources

............................................. 8

- 7 3 8.4.1.2. Releases to W a ter

..................................... 8

- 7 7 8.4.1.2.1 Emissions data

.............................. 8

- 7 7 8.4.1.2.2 Activity level information

..................... 8

- 7 8 8.4.1.2.3 Emission Estimates

.......................... 8

- 8 1 8.4.1.3. Sewag e Sludg e L a nd Disposal

........................... 8

- 8 1 8.4.1.3.1 Emissions data

.............................. 8

- 8 1 8.4.1.3.2 Activity level information

.................... 8

- 8 8 8.4.1.3.3 Emission estimates

.......................... 8

- 8 9 8.4.2. Drinking W a ter Treatment Plants

............................... 8

- 9 1 8.4.3. Soaps and Deterg ents

......................................... 8

- 9 3 8.4.4. Tex tile Manufacturing and Dry Cleaning

......................... 8

- 9 4

9

. I N D I C A T I O N S O F P O S S I B L E N A T U R A L S O U R C E S O F C D D s / C D F s

............. 9

- 1 9.1. B I OL OGI CAL SOURCES OF CDDs/CDF s

............................... 9

- 1 9.1.1. B i otransformation of Chlorophenols

............................... 9

- 1 9.1.2. B i otransformation of Hig her CDDs/CDF s

.......................... 9

- 4 9.1.3. Diox in-L ike Compounds in Animal Manure

......................... 9

- 6 9.2. PHOTOTRANSF O RMATI ON OF CHL O ROPHENOL S

.................... 9

- 8 9.2.1. Photoly s is of Hig her CDDs/CDF s

................................ 9

- 1 0 9.2.2. Photoly sis in W a ter

........................................... 9

- 1 1 9.2.3. Photoly sis on Soil

............................................ 9

- 1 1 9.2.4. Photoly sis on Veg e tation

....................................... 9

- 1 2 9.2.5. Photoly sis in Air

............................................. 9

- 1 3 9.3. CDDs/CDF s I N B A L L CL AY

......................................... 9

- 1 4 9.3.1. I nitial Discovery of CDD/CD F Contamination of B a ll Clay

............ 9

- 1 4 9.3.2. Characteristics of Mississippi Embay m ent B a ll Clay s

................ 9

- 1 5 9.3.3. L e vels of Diox in-L ike Compounds in B a ll Clay

.................... 9

- 1 5 9.3.4. Evidence for B a ll Clay as a Natural Source

........................ 9

- 1 6 9.3.5. Environmental Releases of Di ox in-L ike Compounds from the Mining

a n d P r o c e s s i n g o f B a l l C l a y

.................................... 9

- 1 9

10. SOURCES OF DI OXI N-L I KE POL Y CHL O RI NATED B I PHENYL S (PCB s)

........ 1 0

- 1 10.1. GENERAL F I NDI NGS OF THE EMI SSI ONS I NVENTORY

................ 1 0

- 1 10.2. REL E ASES OF COMMERCI AL PCB s

................................. 1 0

- 4 10.2.1. Approved PCB Dispos al/Destruction Methods

.................... 1 0

- 1 1 10.2.1.1. Approved I n cinerators/Hig h-Efficiency B o ilers

............ 1 0

- 1 4 10.2.1.2. Approved Chemical W a ste L a ndfills

..................... 1 0

- 1 4 10.2.1.3. Other Approved Disposal Methods

...................... 1 0

- 1 5 10.2.2. Emission Estimates

.......................................... 1 0

- 1 5

ix

### C O N TEN TS ( c ont i nue d)

10.2.3. Accidental Releases of Still-in-Service PCB s

..................... 1 0

- 1 5 10.2.3.1. L eaks and Spills

..................................... 1 0

- 1 6 10.2.3.2. Accidental F i res

..................................... 1 0

- 1 8 10.2.4. Municipal W a stewater Treatment

............................... 1 0

- 1 9 10.3. CHEMI C AL MANUF ACTURI NG AND PROCESSI NG SOURCES

......... 1 0

- 2 6 10.4. COMB USTI ON SOURCES

.......................................... 1 0

- 2 6 10.4.1. Municipal W a ste Combustors

.................................. 1 0

- 2 6 10.4.2. I ndustrial W ood Combustion

.................................. 1 0

- 2 7 10.4.3. Medical W a ste I n cineration

................................... 1 0

- 2 9 10.4.4. Tire Combustion

............................................ 1 0

- 3 0 10.4.5. Cig a rette Smoking

.......................................... 1 0

- 3 1 10.4.6. Sewag e Sludg e I ncineration

................................... 1 0

- 3 1 10.4.7. B acky a rd B a rrel B u rning

..................................... 1 0

- 3 4 10.4.8. Petroleum Refining Cataly st Reg e neration

........................ 1 0

- 3 4 10.5. NATURAL SOURCES

............................................. 1 0

- 3 6 10.5.1. B i otransformation of Other PCB s

............................... 1 0

- 3 6 10.5.2. Photochemical Transf ormation of Other PCB s

.................... 1 0

- 3 9 10.6. PAST USE OF COMMERCI AL PCB s

................................. 1 0

- 4 1

11. RESERVOI R SOURCES OF CDDs/CDF s AND DI OXI N-L I KE PCB s

.............. 1 1

- 1 11.1. POTENTI AL RESERVOI RS

.......................................... 1 1

- 1 11.2. CHARACTERI Z ATI ON OF RESERVOI R SOURCES

..................... 1 1

- 3 11.2.1. Soil

....................................................... 1 1

- 3 11.2.1.1. Potential Mass of Diox in-L ike Compounds Present

......... 1 1

- 3 11.2.1.2. Mechanisms Responsible for Releases from S u rface S o ils

.... 1 1

- 9 11.2.1.3. Estimated Annual Releas es from Soil to W a ter

............ 1 1

- 1 2 11.2.1.4. Estimated Annual Releases from Soil to Air

.............. 1 1

- 1 4 11.2.2. W a ter

..................................................... 1 1

- 1 7 11.2.2.1. Potential Mass of Diox in-L ike Compounds Present

........ 1 1

- 1 7 11.2.2.2. Mechanisms Responsible for Supply to and Releases f r o m W a t e r

........................................ 1 1

- 1 7 11.2.3. Sediment

.................................................. 1 1

- 2 0 11.2.3.1. Potential Mass of Diox in-L ike Compounds Present

........ 1 1

- 2 0 11.2.3.2. Mechanisms Responsible for Supply to and Releases f r o m S e d i m e n t

..................................... 1 1

- 2 0 11.2.3.3. Releases from Sediment to W a ter

...................... 1 1

- 2 1 11.2.4. B i ota

..................................................... 1 1

- 2 2 11.2.4.1. Potential Mass of Diox in-L ike Compounds Present

........ 1 1

- 2 2 11.2.4.2. Mechanisms Responsible for Supply to and Releases f r o m B i o t a

........................................ 1 1

- 2 2 11.2.4.3. Approaches for Measuring and Estimating Releases f r o m B i o t a

........................................ 1 1

- 2 4 11.3. SUMMARY AND CONCL U SI ONS

................................... 1 1

- 2 6

x

### C O N TEN TS ( c ont i nue d)

11.3.1. Reservoir Sources

........................................... 1 1

- 2 6 11.3.2. I m plications for Human Ex posure

.............................. 1 1

- 2 7

R E F E R E N C E S

............................................................. R

- 1

xi

### LIST OF TA BLES

Table 1-1. Nomenclature for diox in-like compounds

.............................. 1

- 2

Table 1-2. Municipal waste combustors a



### ....................................... 1

- 4

Table 1-3. Haz a rdous waste incinerators and cement kilns and lig htweig ht ag g r eg ate kilns burning haz a rdous waste

........................................... 1

- 5

Table 1-4. Cement kilns not burning haz a rdous waste

............................. 1

- 5

Table 1-5. Secondary aluminum smelters

....................................... 1

- 6

T a b l e 1

- 6

. M e d i c a l w a s t e i n c i n e r a t o r s

.......................................... 1

- 6

Ta ble 1- 7. Pulp a nd pa pe r mills

............................................... 1

- 6

Table 1-8. The TEF scheme for I

- TEQ DF 

### ....................................... 1

- 9

Table 1-9. The TEF scheme for diox in-like PCB s , as determined by the W orld Health Org a niz a tion in 1994

.............................................. 1

- 9

Table 1-10. The TEF scheme for TEQ DF P 

### -W HO 98 

### ................................ 1

- 1 0

Table 1-11. Known and suspect ed sources of CDDs/CDF s

......................... 1

- 1 4

Table 1-12. I nventory of contemporary releas es (g /y r) of diox in-like compounds from known sources in the United States for reference y ears 2000, 1995, and 1987 and preliminary release estimates for 2000

............................... 1

- 1 7

Table 1-13. Products containing CDDs/CDF s (g TEQ DF 

### -W HO 98 

### / y r )

.................. 1

- 2 3

Table 1-14. I

- TEQ DF 

### e mission f a c t or s use d to de ve lop na tiona l e mission inve ntor y e stima te s of

r e l e a s e s t o a i r

................................................... 1

- 3 2

Table 1-15. TEQ DF 

### -W HO 98 

### emission factors used to deve lop national emission inventory

e stima te s of r e le a se s to a i r

......................................... 1

- 3 4

Table 1-16. Confidence rating sche me for U.S. emission estimates

................... 1

- 3 6

Table 1-17. Ranking of sources of diox in- like compounds based on environmental releases (from hig h to low) for reference y ears 2000, 1995, and 1987

.............. 1

- 3 8

Table 2-1. Concentration of CDDs/CDF s on municipal incinerator fly ash at vary ing
t e m p e r a t u r e s

..................................................... 2

- 7

xi i

### LIST OF TA BLES ( c ont inue d )

Table 2-2. CDDs/CDF s formed from the ther moly tic reaction of 690 mg benz ene + F e Cl 3 

### s i l i c a c o m p l e x

.................................................. 2

- 1 2

Table 2-3. De novo form at i on of C DDs/ C DFs aft e r heat i n g Mg -Al si l i cat e, 4% charcoal , 7% Cl, 1% CuCl 2 

### in H 2 

### O at 300°C

..................................... 2

- 1 4

Table 3-1. I nventory of municipal waste co mbustors (MW C s) in 2000 by technolog y , air pollution control device (APCD), siz e a 

### , and annual activity level (kg / y r )

..... 3

- 1 4

Table 3-2. I nventory of municipal waste co mbustors (MW C s) in 1995 by technolog y , air pollution control device (APCD), a nd annual activity level (kg / y r )

......... 3

- 1 6

Table 3-3. I nventory of municipal waste co mbustors (MW C s) in 1987 by technolog y , air pollution control device (APCD), a nd annual activity level (kg / y r )

......... 3

- 1 8

Table 3-4. National averag e CDD/CD F cong ener concentrations for l a rg e m uni ci pal wast e com bustors (ng / dscm @ 7% O 2 

### )

.................. 3

- 2 0

Table 3-6. CDD/CDF TEQ emission factors (n g TEQ/kg wa ste ) f or

munic i pa l solid wa ste i n c i n e r a t i o n

.................................................... 3

- 2 4

Table 3-7a. Annual I

- TEQ DF 

### emissions from municipal wast e combustors (MW C s) operating in 1995

........................................................ 3

- 2 5

Table 3-7b. Annual TEQ DF 

### -W HO 98 

### emissions from municipal waste combustors (MW C s) operating in 1995

................................................ 3

- 2 7

Table 3-8a. Annual I

- TEQ DF 

### e missions to the a i r f

r o m muni ci pal wast e com bust o rs (MW C s) operating in 1987

................................................ 3

- 2 9

Table 3-8b. Annual TEQ DF 

### -W HO 98 

### e missions to the a i r f

r o m municipal waste combustors (MW C s) operating in 1987

........................................ 3

- 3 0

Table 3-9. Averag e and rang e of CDD/CDF c ong ener g r oups in fly ash from a municipal inc i ne r a tor ( : 

### g /k g )

.............................................. 3

- 3 6

Table 3-10. Comparison of the amount of TEQs g e nerated annually in municipal waste

c o m b u s t o r a s h

.................................................. 3

- 3 8

Table 3-11. Concentration of CDD/CDF cong ener g r oups (ng / kg ) in fly ash samples from

c o m b u s t i o n o f m u n i c i p a l s o l i d w a s t e i n e i g h t J a p a n e s e i n c i n e r a t o r s

......... 3

- 3 9

x iii

### LIST OF TA BLES ( c ont inue d )

Table 3-12. Concentration of CDD/CDF cong en er g r oups in fly ash samples from municipal

s o l i d w a s t e

..................................................... 3

- 3 9

Table 3-13. CDD/CDF concentrati ons in municipal solid waste ash from a newly constructed

m u n i c i p a l w a s t e c o m b u s t o r i n J a p a n

................................. 3

- 4 0

Table 3-14a. CDD/CDF emission factors for haz a rdous waste incinerato rs and boilers tested from 1993 to 1996

............................................... 3

- 4 8

Table 3-14b. CDD/CDF emission factors for haz a r dous waste incinerators and boilers tested in 2000

.......................................................... 3

- 4 9

Table 3-15. CDD/CDF emission factors fo r halog e n acid furnaces tested in 2000

....... 3

- 5 4

Table 3-16. Estimated breakdown of facilities by air pollution control device (APCD)

. . . 3-60

Table 3-17. Summary of annua l operating hours for each medical waste incinerator (MW I )
t yp e

........................................................... 3

- 6 1

Table 3-18. TEQ emissions from medical wa ste incinerators (MW I s) for reference
y ear 1987

...................................................... 3

- 6 2

Table 3-19. TEQ emissions from medical wa ste incinerators (MW I s) for reference
y ear 1995

...................................................... 3

- 6 2

Table 3-20. TEQ emissions from medical wa ste incinerators (MW I s) for reference
y ear 2000

...................................................... 3

- 6 3

Table 3-21. Cong ener-specific profile fo r Camellia Memorial L a wn crematorium

....... 3

- 7 0

Table 3-22. Cong ener-specific profile for the W oodlawn Cemetery crematorium

........ 3

- 7 1

Table 3-23. Operational data for the W oodlawn Cemetery crematorium, scrubber inlet

. . . 3-73

Table 3-24. Cong ener-specific profile for th e Camellia Memorial L a wn crematorium and the W oodlawn Cemetery crematorium

............................... 3

- 7 4

Table 3-25. Cong ener-specific pr ofile for the University of Georg i a Veterinary School

. . . 3-77

Table 3-26. CDD/CDF emission factor s for sewag e sludg e incinerators

............... 3

- 8 2

Table 3-27. CDD/CDF air emission f actors for a tire combustion facility

.............. 3

- 8 4

xi v

### LIST OF TA BLES ( c ont inue d )

Table 3-28. CDD/CDF emission factors for combustion of bleached-kraft mill sludg e in wood residue boilers

............................................. 3

- 8 8

Table 3-5. National CDD/CDF TEQ em i ssi ons (g / y r) for l a rg e and small municipal waste combustors (MW C s) operating in 2000

.............................. 3

- 9 0

Table 4-1. Description and results of vehicle emission te sting studie s f o r

CDDs

a n d C D F s

....................................................... 4

- 3

T a b l e 4

- 2

. C D D / C D F c o n g e n e r e m i s s i o n f a c t o r s ( p g / L ) f o r

d i e s e l

- f u e l e d a u t o m o b i l e s

.... 4

- 5

T a b l e 4

- 3

. C D D / C D F c o n g e n e r e m i s s i o n f a c t o r s ( p g / L ) f o r

d i e s e l

- f u e l e d t r u c k s

........ 4

- 7

Tabl e 4-4. C DD/ C DF cong ener em i ssi on fact ors (pg / L ) for l eaded g a sol i n e-fuel ed

a u t o m o b i l e s

..................................................... 4

- 9

Table 4-5. CDD/CDF cong ener emission f act ors (pg / L ) for unl eaded g a sol i n e-fuel ed automobiles without cataly tic converters

.............................. 4

- 1 1

Table 4-6. CDD/CDF cong ener emission f act ors (pg / L ) for unl eaded g a sol i n e-fuel ed automobiles with cataly tic converters

................................ 4

- 1 3

Table 4-7. Total diox in emission concen trations from heavy

- duty diesel eng i nes i n G e r m a n y

..................................................... 4

- 2 1

Table 4-8. L e vels of 2,3,7,8-chlorine-subs tituted cong eners and total CDDs/CDF s in vehicle ex haust particles (pg / g ) for g a soline eng i nes and suspended
p a r t i c u l a t e m a t t e r ( S P M )

.......................................... 4

- 2 2

Table 4-9. L e vels of 2,3,7,8-chlorine-subs tituted cong eners and total CDDs/CDF s in

v e h i c l e e x h a u s t p a r t i c l e s ( p g / g ) f o r

d i e s e l e n g i n e s

...................... 4

- 2 3

Table 4-10. CDD/CDF concentrations (pg / m 3 

### ) from European tunnel air studies

........ 4

- 2 4

Table 4-11. B a ltimore Harbor tunnel study : estimated emissi on factors (pg / km) for heavy

- d u t y d i e s e l t r u c k s

................................................ 4

- 2 6

Table 4-12. Averag e CDD/CDF concentrati on in flue g a s while burning wood and

c r o p s

.......................................................... 4

- 4 0

Table 4-13. CDD/CDF concentrations (pg TEQ /kg wood) in emissions from residential wood stoves in Canada

............................................ 4

- 4 2

xv

### LIST OF TA BLES ( c ont inue d )

Table 4-14. CDD/CDF mean emission fact ors (ng / kg wood) for industrial wood

c o m b u s t o r s

..................................................... 4

- 4 5

Table 4-15. NCASI CDD/CDF TEQ con centrations and emissions for wood

r e s i d u e

- f i r e d b o i l e r s

.............................................. 4

- 5 0

Table 4-16. CDD/CDF concentrations (ng / kg ) in residential chimney soot from wood stoves and fireplaces

........................................ 4

- 5 3

Table 4-17. CDD/CDF concentrations (ng / kg ) in bottom ash from residential wood stoves and fi repl aces

................................................... 4

- 5 4

Table 4-18. CDD/CDF concentrations in chimney soot (B avaria, Germany )

............ 4

- 5 6

Table 4-19. CDD/CDF concentrations (ng / kg ) in fly ash from wood-working industry

. . . 4-57

Table 4-20. CDD/CDF concentrations (ng / kg ) in electrostatic preci pitator waste ash from wood-fired industrial boiler

........................................ 4

- 5 9

Table 4-21. Estimated CDD/CDF emission f actors for oil-fired residential furnaces

..... 4

- 6 2

Table 4-22. CDD/CDF emission factors (pg / L o il) for oil-fired utility /industrial boilers

. . 4-65

Table 4-23. CDD/CDF concentrations (pg / Nm 3 

### ) i n st ack em i ssi ons from U.S

. coal -fi red p o w e r p l a n t s

.................................................... 4

- 7 0

Table 4-24. Characteristics of U.S. coal-fired power plants tested by the U.S. Department

o f

E n e r g y

...................................................... 4

- 7 1

Table 4-25. CDD/CDF emission factors (ng / kg coal) for coal-fired utility /industrial p o w e r p l a n t s

.................................................... 4

- 7 2

Table 4-26. CDD/CDF emission factors (ng / kg coal) for residential coal combustors

.... 4

- 7 5

Table 4-27. CDD/CDF concentrations and amount s disposed of in solid wastes from coal- f i r e d utilitie s

.................................................... 4

- 7 9

Table 5-1. CDD/CDF emission factors (ng / kg clinker produced) for cement kilns burning haz a rdous waste fo r reference y ears 1987 and 1995

............... 5

- 8

Table 5-2. CDD/CDF emission factors (ng / h r) for cement kilns burning haz a rdous waste for reference y ear 2000

........................................... 5

- 1 0

xv i

### LIST OF TA BLES ( c ont inue d )

Table 5-3. CDD/CDF emission factors (ng / kg clinker produced) for cement kilns not burning haz a rdous waste for reference y ears 1987, 1995, and 2000

......... 5

- 1 2

Ta ble 5- 4. Na tiona l e mission e stima te s f o r

c e m e n t kilns f o r

r e f e r e nc e y e a r s 1987 and 1995

.................................................. 5

- 1 5

Table 5-5. National emissi on estimates for cement kilns for reference y ear 2000

....... 5

- 1 7

Table 5-6. CDD/CDF concentrations (n g / kg ) in a sh sa mple s f r o m c e me nt kiln

e l e c t r o sta tic pr e c i pita tor a nd lig htwe ig ht a g g r e g a t e ( L WA) kiln f a br ic f ilte r

. . 5

- 2 0

Table 5-7. CDD/CDF estimates in cement kiln dust (CKD) for reference y ears 1987, 1995, and 2000

.................................................. 5

- 2 1

Table 5-8. Cong ener-specifi c emission factors (ng / kg asphalt produced) derived from the
t e s t i n g o f a i r e m i s s i o n s a t t w o h o t

- m i x a s p h a l t p l a n t s i n t h e U n i t e d S t a t e s

.... 5

- 2 4

Table 5-9. CDD/CDF emi ssion factors (ng / barrel) a 

### f o r

pe tr ole u m c a t a l y tic r e f o r ming

u n i t s

.......................................................... 5

- 2 9

Table 5-10. CDD concentrations in J a panese cig a rette s, smoke, and ash

............... 5

- 3 2

Table 5-11. CDD/CDF concentrations (pg / cig ) in cig a rette smoke, normaliz ed to a per-

c i g a r e t t e b a s i s

................................................... 5

- 3 4

Table 5-12. CDD/CDF concentra tions (pg / pack) in tobacco cig a rette brands from various countries

...................................................... 5

- 3 7

Table 5-13. CDD/CDF mean emission f actors (ng / kg feed) for black liquor

r e c o v e r y b o i l e r s

................................................. 5

- 4 4

Table 5-14. CDD/CDF TEQ emission factors and emission estimates from Kraft recovery furnaces and Kraft lime kilns

....................................... 5

- 4 7

Table 5-15. CDD/CDF concentrations in candle materials and emissions

.............. 5

- 4 7

Ta ble 6- 1. CDD/CDF e mission f a c t or s f o r

a

la ndf ill f l a r e

.......................... 6

- 2

T a b l e 6

- 2 C D D / C D F m e a n e m i s s i o n f a c t o r s ( n g /k g ) f o r

f

o r e s t f i r e s

................. 6

- 1 6

T a b l e 6

- 3

. F o r e s t f i r e f u e l l o a d i n g f a c t o r s ( t o n s / a c r e )

............................. 6

- 1 9

xv i i

### LIST OF TA BLES ( c ont inue d )

Tabl e 6-4. C DD/ C DF averag e ai r em i ssi on factors (ng / kg waste burned) from barrel burning of household waste

........................................ 6

- 2 2

Table 6-5. CDD/CDF analy s is for c o mposite a sh sa mple s f r o m ba r r e l b u r n i n g ( n g /k g a s h )

.............................................. 6

- 2 7

T a b l e 6

- 6

. P C B a n a l y s i s f o r

c o m p o s i t e a s h s a m p l e s f r o m b a rr e l b u r n i n g ( n g /k g a s h )

.... 6

- 2 8

T a b l e 6

- 7

. C D D s / C D F s i n d u s t f a l l a n d a s h e s f r o m v o l c a n o e s

...................... 6

- 3 4

Table 6-8. Residue of HpCDD/HpCDF and OC DD/OC DF (ng / kg ) in paper cartridg e s and charg e s of select py rotechnic products

............................ 6

- 3 5

Table 7-1. CDD/CDF emissi on concentrations (pg TEQ/m 3 

### @ 11% ox y g en) for primary copper smelters

.................................................. 7

- 2

Table 7-2. CDD/CDF emissions data from primary and secondary copper and secondary l e a d s m e l t e r s

..................................................... 7

- 3

Table 7-3. CDD/CDF emission factors (ng / kg scrap feed) for secondary aluminum smelters for 2000

................................................ 7

- 1 1

Table 7-4. CDD/CDF emission factors (ng / kg scrap feed) for secondary aluminum smelters for 1995 and 1987

........................................ 7

- 1 2

Table 7-5. CDD/CDF mean e mission factors (ng / kg scrap feed) for secondary copper

s m e l t e r s

....................................................... 7

- 1 7

Table 7-6. CDD/CDF emission factors (ng / kg lead produced) for secondary l e a d s m e l t e r s

.................................................... 7

- 2 5

Table 7-7. Estimated annua l TEQ emissions (g TEQ)

............................ 7

- 2 7

T a b l e 7

- 8

. C D D / C D F e m i s s i o n f a c t o r s ( n g / k g s i n t e r ) f o r

s i n t e r i n g p l a n t s

............. 7

- 3 0

T a b l e 7

- 9

. O p e r a t i n g p a r a m e t e r s f o r

U

. S

. i r o n o r e s i n t e r i n g p l a n t s

.................. 7

- 3 2

Table 7-10. CDD/CDF emission estimates for Ca nadian coke oven f acilities, blast furnace facilities, and el ectric arc furnaces

................................... 7

- 3 4

Table 7-11. CDD/CDF emission concentrati ons and rates for Canadian electric arc furnaces

....................................................... 7

- 3 7

x v iii

### LIST OF TA BLES ( c ont inue d )

Table 7-12. CDD/CDF emission fact ors for a U.S. ferrous foundry

................... 7

- 3 9

Table 7-13. Cong ener-specific profile for ferrous foundries

......................... 7

- 4 0

Table 7-14. CDD/CDF emission factor s for a scrap wire incinerator

.................. 7

- 4 2

Table 7-15. CDD/CDF concentrations in fly ash and ash/soil at me tal recovery sites

..... 7

- 4 4

Table 7-16. CDD/CDF emission factors fo r a drum and barrel reclamation facility

...... 7

- 4 6

Table 8-1. CDD/CDF concentrations in pulp and paper mill bleached pulp, wastewater sludg e, and wastewater effluent (circa 1988)

............................ 8

- 2

Table 8-2. CDD/CDF concentrations in pulp and paper mill bleached pulp, wastewater sludg e, and wastewater effluent (mid-1990s)

........................... 8

- 5

Table 8-3. Summary of bleached chemical pulp and paper mill discharg es (g /y r) of 2,3,7,8-TCDD and 2,3,7,8-TCDF

.................................... 8

- 7

Table 8-4. CDD/CDF TEQ concentrations and emissions for the paper and pulp industry by

s o u r c e

......................................................... 8

- 1 0

Table 8-5. CDD/CDF concentrations (μg / kg ) in g r aphite electrode sludg e from chlorine production

..................................................... 8

- 1 1

Table 8-6. Releases of diox in-like compounds in wastewater discharg es from chlor-alkali and mix ed chemical manufacturin g facilities to surface wate r in reference y ears 2000 and 1995

....................................................... 8

- 1 3

Table 8-7. Cong ener-specific and TEQ annual releases to air (g /y r) from chlor-alkali and mix ed chemical production facilities in 2000

.......................... 8

- 1 4

T a b l e 8

- 8

. C D D / C D F c o n c e n t r a t i o n s ( μ g /k g ) i n m e t a l c h l o r i d e s

.................... 8

- 1 5

Table 8-9. CDD/CDF concentrations (mg / kg ) in mono- throug h tetrachlorophenols

.... 8

- 1 7

Table 8-10. CDD/CDF concentrations (histori cal and current) (μg / kg ) in technical-g r ade pentachlorophenol (PCP) products

.................................. 8

- 1 8

Table 8-11. Historical C DD/CDF concentrations (μg / kg ) in pentachlorophenol-Na ( P C P

- N a )

...................................................... 8

- 2 0

xi x

### LIST OF TA BLES ( c ont inue d )

Table 8-12. Summary of specific diox in-contai ning wastes that must comply with land d i s p o s a l r e s t r i c t i o n s

.............................................. 8

- 2 1

Table 8-13. CDD/CDF concentrati ons (μg / kg ) in chlorobenz enes

.................... 8

- 2 5

Table 8-14. Concentrations of CDD/CD F cong ener g r oups in unused commercial p o l y c h l o r i n a t e d b i p h e n y l ( P C B ) m i x t u r e s ( m g /k g )

...................... 8

- 2 8

Table 8-15. 2,3,7,8-Substituted cong ener concentr ations in unused poly c hlorinated bipheny l ( P C B ) m i x t u r e s ( μ g /k g )

........................................... 8

- 2 9

Table 8-16. Reported CDD/CDF c oncentrations (μg / kg ) in wastes from poly viny l chloride ( P V C ) m a n u f a c t u r e

.............................................. 8

- 3 2

Table 8-17. Releases of diox in-like com pounds (g /y r) in wastewater discharg es from EDC/VCM/PVC a nd inte g r a t e d c h lor i ne c h e mic a l ma nuf a c t ur ing f a c ilitie s to surface water in reference y ears 2000 and 1995

........................ 8

- 3 4

Table 8-18. Cong ener-specific releases to land from an EDC/ VCM/PVC integ r ated chemical

ma nuf a c t ur ing f a c ility a 

### in reference y ears 2000 and 1995

................. 8

- 3 7

Table 8-19. Cong ener-specific and TEQ releases to air (g /y r) from EDC/VCM/PVC integ r ated chemical manufacturing facilities in reference y ears 2000 and 1995

........ 8

- 3 9

Table 8-20. Cong ener-specific and TEQ transfers to secure landfills (g /y r) a 

### from EDC/VCM/PVC integ r ated che mical production facilities in 2000

......... 8

- 4 0

Table 8-21. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC

m a n u f a c t u r e r s

................................................... 8

- 4 2

Table 8-22. CDD/CDF concentrations (μg / kg ) in samples of diox az ine dy es and pig m ents ( C a n a d a )

....................................................... 8

- 4 6

Table 8-23. CDD/CDF concentrations (ng / kg ) in printing inks (Germany )

............. 8

- 4 9

Table 8-24. Chemicals requiring Tox i c Substa nces Control Act Section 4 testing under the d i o x i n / f u r a n r u l e

................................................ 8

- 5 1

Table 8-25. Cong eners and limits of quantitation (L OQs) for wh ich quantitation is required under the diox in/furan test ru le and pesticid e Data Call-I n

................ 8

- 5 2

Table 8-26. Precursor chemicals subject to reporting requirements under Tox i c Substances C o n t r o l A c t S e c t i o n 8 ( a )

.......................................... 8

- 5 3

xx

### LIST OF TA BLES ( c ont inue d )

Table 8-27. Results of analy tical testing for diox ins and furans in the chemicals tested to date under Section 4 of the diox in/furan test rule

........................... 8

- 5 4

Table 8-28. CDD/CDF concentrations (μg / kg ) in chloranil and carba z ole violet samples

a n a l y z e d p u r s u a n t t o t h e E P A d i o x i n / f u r a n t e s t r u l e

..................... 8

- 5 5

Table 8-29. Status of first pes ticide Data Call-I n: pe sticides suspected of having the potential to become contaminated with diox ins if sy nthesiz e d under conditions favoring d i o x i n f o r m a t i o n

................................................ 8

- 6 2

Table 8-30. Status of second pesticide Data Call- I n: pesticides suspected of being

c o n t a m i n a t e d w i t h d i o x i n s

......................................... 8

- 6 7

Table 8-31. Summary of analy tical data submitte d to EPA in response to pesticide Data CallI n ( s )

.......................................................... 8

- 7 1

Table 8-32. Summary of results for CDDs /CDF s in technical 2,4-D and 2,4-D ester h e r b i c i d e s

...................................................... 8

- 7 2

Table 8-33. CDD/CDF concentrations (μg / kg ) in samples of 2,4-D and pesticide formulations containing 2,4-D

................................................ 8

- 7 4

Table 8-34. Mean CDD/CDF concentrations a nd rang e of detection limits (DL s ) (pg / L ) in

e f

f l u e n t s f r o m n i n e U

. S

. p u b l i c l y o w n e d t r e a t m e n t w o r k s ( P O T W s )

........ 8

- 7 9

Table 8-35. Effluent concentrations (pg / L ) of CDDs/CDF s from pub licly owned treatment

w o r k s i n M i s s i s s i p p i

............................................. 8

- 8 0

Table 8-36. CDD/CDF concentrations (ng / kg ) measured in the 1998/1999 National Sewag e S l u d g e S u r v e y

.................................................. 8

- 8 2

Table 8-37. CDD/CDF concentrations (ng / kg ) measured in 99 sludg es collected from U.S. publicly owned treatment works (POTW s ) during 1994

.................. 8

- 8 4

Table 8-38. Concentrations of CDDs/CDF s (ng / kg dry matter) in sewag e sludg e from publicly

o w n e d t r e a t m e n t w o r k s i n M i s s i s s i p p i

................................ 8

- 8 5

Table 8-39. CDD/CDF median concentrati ons (ng / kg ) measured in 1999 from a publicly

owne d tr e a tme nt wor k s f a c ility in Ohio

............................... 8

- 8 6

Table 8-40. CDD/CDF mean concentrations (ng / kg ) measured in the 2001 National Sewag e S l u d g e S u r v e y

.................................................. 8

- 8 7

xxi

### LIST OF TA BLES ( c ont inue d )

Table 8-41. Quantity of sewag e sludg e disposed of and potential diox in TEQ releases from primary , secondary , and adva nced treatment publicly ow ned treatment works for reference y ear 1987

.............................................. 8

- 9 0

Table 8-42. Quantity of sewag e sludg e disposed of and potential diox in TEQ releases from primary , secondary , and adva nced treatment publicly ow ned treatment works for reference y ear 1995

.............................................. 8

- 9 1

Table 8-43. Quantity of sewag e sludg e disposed of and potential diox in TEQ releases from primary , secondary , and adva nced treatment publicly ow ned treatment works for reference y ear 2000

.............................................. 8

- 9 2

Table 8-44. B i osolids disposal practices for reference y ear 2000

..................... 8

- 9 2

Table 8-45. CDD/CDF concentrations in Sw edish liquid soap, tall oil, and tall resin

..... 8

- 9 5

Table 9-1. Estimated quantity of animal manure produced in th e United States in 2000

. . . 9-7

Table 9-2. CDD and CDF concentrations (ng / kg dr y we ig ht) in sa mple s of a n ima l ma nur e in
t h e U n i t e d K i n g d o m

............................................... 9

- 8

Table 9-3. Concentrations of CDDs (pg / g , dry we ig ht) in e i g h t ba ll c l a y sa mple s in the Unite d S t a t e s

......................................................... 9

- 1 6

Table 9-4. Comparison of the mean CDD/CDF cong ener g r oup concentrations in ball clay

w i t h t h o s e i n u r b a n a n d r u r a l s o i l s i n N o r t h A m e r i c a ( p g / g , d r y w e i g h t )

..... 9

- 1 7

Table 10-1. Confidence rating classes for 2000 for releases from all known and suspected

s o u r c e c a t e g o r i e s o f d i o x i n

- l i k e P C B s

................................ 1 0

- 2

Table 10-2. I nventory of contem porary releases of diox in-like PCB s in the Unite d Sta t e s f o r 1987, 1995, and 2000 and preliminary release es timates of diox in-like PCB s for 2000 (g TEQ p 

### -W HO 98 

### / yr )

......................................... 1 0

- 3

Table 10-3. W e ig ht percent concentrations of diox in-like PCB s in Aroclors, Clophens, and K a n e c h l o r s

..................................................... 1 0

- 7

T a b l e 1 0

- 4

. D i s p o s a l r e q u i r e m e n t s f o r

P C B s a n d P C B i t e m s

....................... 1 0

- 1 2

Tabl e 10-5. Off-si t e t r ansfers of P C Bs report e d i n t h e Tox i cs R e l ease I nvent ory (TR I ) (1988–2000)

................................................... 1 0

- 1 6

xxi i

### LIST OF TA BLES ( c ont inue d )

Table 10-6. Releases of PCB s reported i n t h e Tox i cs R e l ease I nvent ory (TR I ) (1988–2000)

................................................. 1 0

- 1 7

Table 10-7. Aroclor concentrations (ng / kg ) measured in EPA’s National Sewag e S l u d g e S u r v e y

................................................. 1 0

- 2 0

Table 10-8. Diox in-like PCB concentrations m easured i n sl udg es col l ect ed from 74 U.S

. publicly owned treatment works (POTW s ) during 1994

................. 1 0

- 2 1

Table 10-9. Diox in-like PCB concentrations in se wa g e sludg e c o lle c t e d f r o m U.S. public ly owned treatment works during 1999

................................ 1 0

- 2 2

Table 10-10. Quantity of sewag e sludg e disposed of annually in 1989 by primary , secondary , or advanced treatment public ly owned treatment work s (POTW s ) and potential d i o x i n

- l i k e P C B T E Q r e l e a s e s

..................................... 1 0

- 2 3

Table 10-11. Quantity of sewag e sludg e disposed of annually in 1995 by primary , secondary , or advanced treatment public ly owned treatment work s (POTW s ) and potential d i o x i n

- l i k e P C B T E Q r e l e a s e s

..................................... 1 0

- 2 4

Table 10-12. Quantity of sewag e sludg e disposed of annually in 2000 by primary , secondary , or advanced treatment public ly owned treatment work s (POTW s ) and potential d i o x i n

- l i k e P C B T E Q r e l e a s e s

..................................... 1 0

- 2 5

Table 10-13. PCB cong ener g r oup emission factors for industrial wood combustors a



### ..... 1 0

- 2 8

Table 10-14. PCB cong ener g r oup emission factors for medical waste incinerators ( M W I s )

...................................................... 1 0

- 2 9

Table 10-15. PCB cong ener g r oup emi ssion factors for a tire combustor a



### .............. 1 0

- 3 0

Table 10-16. Diox in-like P C B concentrations in cig a rette tobacco in brands from various countries (pg / pack)

.............................................. 1 0

- 3 2

Table 10-17. Diox in-like PCB concentrations in stack g a s collected from a U.S. sewag e sludg e i n c i n e r a t o r

.................................................... 1 0

- 3 3

Table 10-18. Diox in-like PCB emission factors from backy a rd barrel burning

.......... 1 0

- 3 5

Table 10-19. PCB cong ener g r oup emission fact ors for a petroleum cataly tic reforming

u n i t

.......................................................... 1 0

- 3 5

x x iii

### LIST OF TA BLES ( c ont inue d )

Table 10-20. Estimated tropospheric half-lives of diox in-like PC B s with respect to g a s-phase

r e a c t i o n w i t h t h e O H r a d i c a l

...................................... 1 0

- 4 0

Table 10-21. Estimated PCB loads in the g l obal environment as of 1985

.............. 1 0

- 4 2

Table 10-22. Estimated domestic sales of aroclors and rel eases of PCB s , 1957–1974 (metric
t o n s )

......................................................... 1 0

- 4 3

Table 10-23. Estimated U.S. usag e of PCB s by use categ ory , 1930–1975

.............. 1 0

- 4 4

Table 10-24. Estimated direct releases of Aroclors to the U.S. environment, 1930–1974 a 

### ( m e t r i c t o n s )

................................................... 1 0

- 4 5

Table 10-25. Estimated releases of diox in- like PCB TEQs to the U.S. environment, 1930–1977

.................................................... 1 0

- 4 6

Table 11-1. Historical production, sales, a nd usag e of 2,4-dichlorophenox y

- acetic acid (2,4-D) (metric tons)

............................................. 1 1

- 4

Table 11-2. Historical production, sales, a nd usag e of 2,4,5-trichl orophen-ox y a cetic acid (2,4,5-T) (metric tons)

............................................ 1 1

- 7

Table 11-3. CDD/CDF concentrations ( : 

### g / kg ) in recent samp le of 2,4,5-trichlorophenox y acetic acid (2,4,5-T)

...................................... 1 1

- 1 0

Table 11-4. PCB 138 flux es pred icted by Harner et al. (1995)

...................... 1 1

- 1 6

T a b l e 1 1

- 5

. S u m m a r y o f f

l u x c a l c u l a t i o n s f o r

t o t a l P C B s i n G r e e n B a y

.............. 1 1

- 1 9

Ta ble 11- 6. Compa r ison of mode l- e stima te d PCB c onc e n tr a tions with obse r ve d

v a l u e s

........................................................ 1 1

- 2 2

xxi v

### L I S T OF F I G URE S

F i g ure 1-1. Chemical structur e of 2,3,7,8-TCDD and related compounds

............... 1

- 7

F i g u r e 1- 2. Estima te d CDD/CDF I

- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 1987

................................ 1

- 2 4

F i g u r e 1- 3. Estima te d CDD/CDF I

- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 1995

................................ 1

- 2 5

F i g u r e 1- 4. Estima te d CDD/CDF I

- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 2000.

................................ 1

- 2 6

F i g u re 1-5. Comparison of es timates of annual I

- TEQ emissions to air (g I

- TEQ/y r) for reference y ears 1987, 1995, and 2000.

................................ 1

- 2 7

F i g u r e 1- 6. Estima te d CDD/CDF WHO- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 1987

................................ 1

- 2 8

F i g u r e 1- 7. Estima te d CDD/CDF WHO- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 1995.

........................... 1

- 2 9

F i g u r e 1- 8. Estima te d CDD/CDF WHO- TEQ e missions to a i r f

r o m c o mbustion sour c e s in the United States for reference y ear 2000.

........................... 1

- 3 0

F i g ure 1-9. Comparison of estimates of annual W HO-TEQ emissions to air (g WHOTEQ/y r) for reference y ears 1987, 1995, and 2000.

...................... 1

- 3 1

F i g u re 1-10. Cong ener profiles (as percent distributions to the sum of CDDs and CDF s ) of anthropog enic sources of chlorinated dibenz o- p -diox i ns and chlorinated d i b e n z o f u r a n s i n t h e U n i t e d S t a t e s

.................................. 1

- 4 5

F i g ure 2-1. Ty pical mean distribution of C DD and CDF cong eners in contemporary municipal

s o l i d w a s t e

...................................................... 2

- 3

F i g u re 2-2. The de novo sy nthesis of CDDs/CDF s from hea ting carbon particulate at 300°C at

va r y ing r e te ntion time s

............................................ 2

- 1 5

F i g u r e 2

- 3

. T e m p e r a t u r e e f f

e c t s o n C D D / C D F f o r m a t i o n

.......................... 2

- 1 6

F i g u r e 3

- 1

. T y p i c a l m a s s b u r n w a t e r w a l l m u n i c i p a l s o l i d w a s t e c o m b u s t o r

............. 3

- 3

F i g u r e 3

- 2

. T y p i c a l m a s s b u r n r o t a r y k i l n c o m b u s t o r

............................... 3

- 4

F i g u re 3-3. Ty pical modular starve d-air combustor with transfer rams

................. 3

- 5

xxv

### LIST OF F I G U R ES ( c ont i nue d)

F i g u re 3-4. Ty pical modul ar ex cess-air combustor

................................ 3

- 6

F i g u r e 3

- 5

. T yp i c a l d e d i c a t e d r e f u s e

- d e r i v e d f u e l

- f i r e d s p r e a d e r s t o k e r b o i l e r

........... 3

- 7

F i g u r e 3

- 6

. F l u i d i z e d

- b e d r e f u s e

- d e r i v e d f u e l f u r n a c e

.............................. 3

- 8

F i g u re 3-7. Municipal waste co mbustor desig n classes for 1987

.................... 3

- 1 1

F i g u re 3-8. Municipal waste co mbustor desig n classes for 1995

.................... 3

- 1 2

F i g u re 3-9. Municipal waste co mbustor desig n classes for 2000

.................... 3

- 1 3

F i g u re 3-10. Cong ener and cong ener g r oup profiles for air emissions from a mass burn waterwall municipal waste combustor e quipped with a dry scrubber and fabric f ilte r

.......................................................... 3

- 3 2

F i g u re 3-11. 2,3,7,8-TCDD frequency distribution (n eg ative natural log concentration)

. . . 3-33

F i g u re 3-12. 1,2,3,7,8-PeCDD frequenc y distribution (neg ative natural log concentration)

. 3-34

F i g u re 3-13. Cong ener profile for air emissi ons from 17 haz a rdous waste incinerators tested from 1993 throug h 1996.

.......................................... 3

- 5 0

F i g u re 3-14. Cong ener and cong ener g r oup profiles for air emissions from boilers and industrial furnaces burning haz a rdous waste

.................. 3

- 5 2

F i g u re 3-15. Cong ener and cong ener g r oup pr ofiles for air emissions from medical waste incinerators without air pollution c ontrol devices (nondetects set equal
t o z e r o )

........................................................ 3

- 6 6

F i g u re 3-16. Cong ener and cong ener g r oup profiles for air emissi ons from medical waste incinerators equipped with a wet scrubber and fabric filter

................ 3

- 6 7

F i g u re 3-17. Cong ener and cong ener g r oup profiles for air emissions from the Camellia Memorial L a wn crematorium and W oodlawn Cemetery crematorium

....... 3

- 7 5

F i g u re 3-18. Cong ener profile for air emi ssions from the University of Georg i a animal

c r e m a t o r i u m

.................................................... 3

- 7 8

F i g u re 3-19. Cong ener and cong ener g r oup profiles for air emissions from

s e w a g e s l u d g e i n c i n e r a t o r s

......................................... 3

- 8 1

xxv i

### LIST OF F I G U R ES ( c ont i nue d)

F i g u re 3-20. Cong ener and cong ener g r oup profiles for air emissions from a tire

c o m b u s t o r

...................................................... 3

- 8 5

F i g u re 4-1. Cong ener and cong ener g r oup pr ofiles for air emissions from diesel-fueled

v e h i c l e s

....................................................... 4

- 1 5

F i g u re 4-2. Cong ener and cong ener g r oup profiles for air emissions from leaded
g a s

- f u e l e d v e h i c l e s

............................................... 4

- 1 6

F i g u re 4-3. Cong ener and cong ener g r oup profiles for air emissions from unleaded g a s

- f u e l e d v e h i c l e s

............................................... 4

- 1 7

F i g u re 4-4. Tunnel air concentrations

.......................................... 4

- 2 9

F i g u re 4-5a. Cong ener and cong ener g r oup profiles for air emissi ons from industrial wood

c o m b u s t o r s

..................................................... 4

- 4 6

F i g u re 4-5b. Cong ener and cong ener g r oup prof iles for air emissions from bleached Kraft mill b a r k c o m b u s t o r s

................................................. 4

- 4 7

F i g u re 4-6. Cong ener g r oup profile for ai r emissions from residential oil-fueled furnaces

....................................................... 4

- 6 3

F i g u re 4-7. Cong ener and cong ener g r oup profiles for air emissions from industrial

o i l

- f u e l e d b o i l e r s

................................................ 4

- 6 6

F i g u re 4-8. Cong ener and cong ener g r oup profiles for air emissions from industrial/utility coal-fueled combusto rs (nondetects set equal to z e ro)

...... 4

- 7 3

F i g u re 4-9. Cong ener g r oup profile for ai r emissions from residential coal-fueled

c o m b u s t o r s

..................................................... 4

- 7 7

F i g u re 5-1. Cong ener profile for air emissi ons from cement kilns burning haz a rdous waste for reference y ears 1987 and 1995 ( nondetect set equal to z e ro)

............. 5

- 9

F i g u re 5-2. Cong ener profile for air e missions from cement kilns burning haz a rdous waste for reference y ear 2000.

...................................... 5

- 1 1

F i g u re 5-3. Cong ener profile for air e missions from cement kilns burning nonhaz a rdous waste for reference y ears 1987, 1995, and 2000.

........................ 5

- 1 3

F i g u re 5-4. Cong ener and cong ener g r oup profiles for air emissions from petroleum

c a t a l y t i c r e f o r m i n g u n i t s

.......................................... 5

- 3 0

xxv i i

### LIST OF F I G U R ES ( c ont i nue d)

F i g u r e 5

- 5

. C D D p r o f i l e s f o r

J a p a n e s e c i g a r e t t e s , s m o k e , a n d a s h

................... 5

- 3 3

F i g u re 5-6. Cong ener g r oup profiles for ma instream and sidestream cig a rette smoke

.... 5

- 3 5

F i g u re 5-8 C ong ener and cong ener g r oup profiles for air emissions from Kraft black liquor recovery boile rs (nondetect set equal to z e ro )

........... 5

- 4 5

Fig u re 5-7. Cong ener g r oup profiles for cig a rette tobacco from various countries

....... 5

- 3 8

F i g u r e 6- 1. Cong e n e r pr of ile f o r

la ndf ill f l a r e a i r e missions

......................... 6

- 3

F i g u r e 6

- 2

. C o n g e n e r p r o f i l e f o r

f

o r e s t f i r e s i m u l a t i o n a p p r o a c h e m i s s i o n s

............ 6

- 1 7

F i g u re 7-1. Cong ener and cong ener g r oup profiles for air emissions from secondary

a l u m i n u m s m e l t e r s

............................................... 7

- 1 3

F i g u re 7-2a. Cong ener g r oup profile for air emissions from a secondary copper smelter

. . . 7-18

F i g u re 7-2b. Cong ener and cong ener g r oup profiles for a closed secondary copper

s m e l t e r

........................................................ 7

- 1 9

F i g u re 7-3. Cong ener and cong ener g r oup profiles for air emissions from secondary lead smelters

........................................... 7

- 2 6

F i g u r e 7

- 4

. C o n g e n e r p r o f i l e s f o r

a i r e m i s s i o n s f r o m U

. S

. i r o n o r e s i n t e r i n g p l a n t s

...... 7

- 3 1

F i g u re 7-5. Cong ener g r oup profile for ai r emissions from a scrap wire incinerator

...... 7

- 4 3

F i g u re 7-6. Cong ener g r oup profile for air emissions from a drum incinerator

.......... 7

- 4 7

F i g ure 8-1. 104 Mill Study full cong ener an aly s is results for pulp (nondetects equal
t o z e r o )

......................................................... 8

- 3

F i g ure 8-2. 104 Mill Study full cong ener analy s is results for sludg e

................... 8

- 3

F i g ure 8-3. 104 Mill Study full cong en er analy s is results for effluent

.................. 8

- 4

F i g u re 8-4. Cong ener profile for technical-g ra de PCP (developed from data in last column in T a b l e 8

- 1 0 )

..................................................... 8

- 5 7

F i g u re 8-5. Cong ener profile for 2,4-D (salts and esters) (based on mean concentrations

r e p o r t e d i n T a b l e 8

- 3 4 )

........................................... 8

- 7 3

xxv i i i

### LIST OF F I G U R ES ( c ont i nue d)

F i g u r e 8

- 6

. C o n g e n e r p r o f i l e s f o r

s e w a g e s l u d g e ( c r e a t e d f r o m d a t a i n T a b l e 8

- 3 8 )

...... 8

- 8 8

F i g u r e 1 1

- 1

. F l u x e s a m o n g e n v i r o n m e n t a l r e s e r v o i r s

.............................. 1 1

- 2

xxi x

### L I S T OF AB B R E V IAT I ONS AND ACRONYMS

AHA Ame r ic a n Hospita l Assoc i a tion
AMSA Assoc i a tion of Me tr opolita n Se we r a g e Ag e n c i e s APCD Air pollution control device
B DDs poly brominated dibenz o- p -diox i ns B D F s poly brominated dibenz ofurans
B t u B r itish the r ma l unit
Ca Cl 2 

### cal ci um chl o ri de
CARB California Air Resources B o ard
CB I C onf ide n tia l B u sine ss I n f o r m a tion
CDD poly c hlorinated dibenz o- p -di o x i n CDF poly c hlorinated dibenz ofuran
CF R C ode of F e de r a l Re g u la tions
CSF C onf ide n tia l Sta t e m e n t of F o r m ula
CKD cement kiln dust
CO carbon monox ide
CO 2 

### carbon diox ide
CuCl copper (I ) chloride
CuCl 2 

### copper (I I ) chloride
DBF d i b enz o furan
DCB z dichlorobenz ene DC I d at a cal l -i n DCP dichlorophenol
DL de te c tion limit
dscm dry standard cubic meter
DSI d r y sor b e n t inje c tion
EDC e t h y l ene di chl o ri de
EI A E ne r g y I n f o r m a tion Administr a tion
EPA U .S. Environmental Protection Ag ency EPRI Ele c t r i c Powe r Re se a r c h I n stitute
ESP e le c t r o sta tic pr e c i pita tor
F F f a br ic f ilte r FC EM fi el d chem i cal em i ssi ons m easurem ent
FeC l 3 

### ferri c (i ron) chl o ri de

xxx

### L I S T OF AB B R E V IAT I ONS AND ACRONYMS (con tin u e d )

FI FR A F ederal I n sect i c i d e, Fung i c i d e, and R odent i c i d e Act
GAC g r anul ar act i v at ed carbon
GC/ECD g a s c h r o ma tog r a phy /e le c t r on c a p tur e de te c t or GC/MS g a s c h r o ma tog r a phy /ma ss spe c t r o me tr y HC l h y d rog e n chl o ri de
HCB z hex achlorobenz ene HDD halog e nated dibenz o- p -di o x i n HDF halog e nated dibenz ofuran
HW I h az ardous waste incinerator
Hx CB hex achlorobipheny l
I U PAC I nternational Union of Pure and Applied Chemistry
KCl potassium chloride
L O Q limit of qua ntita tion
MB -W W m ass burn waterwall
MCB z monochlorobenz ene Mg Cl 2 

### ma g n e s ium c h lor i de Mg O m ag nesium ox ide
MSW m unicipal solid waste
MW I m edi cal wast e i n ci nerat o r NaCl sodium chloride
NaOCl s oldium hy pochlorite
NCASI N ational Council of the Paper I ndustry for Air and Stream I m provement NiC l 2 

### ni ckel chl o ri de
NiO n ic ke l ox ide
Nm 3 

### standard cubic meter
NMOC nonmethane org a nic compound OAQPS O ffice of Air Quality Planning and Standards
O 2 

### mole c u la r ox y g e n OH hy drox ide ion
OPP O f f i c e of Pe stic ide Pr og r a ms ORD O ffice of Research and Development
OSW O ffice of Solid W a ste
P b l ead

xxxi

### L I S T OF AB B R E V IAT I ONS AND ACRONYMS (con tin u e d )

PCA P ortland Cement Association
PCB poly c hlorinated bipheny l
PCP pentachlorophenol
PCP-Na pentachlorophenate
PeCB pentachlorobipheny l
P e C B z p ent achl o robenz ene PM pa r tic ula te ma tte r POTW publicly owned treatment works ppb pa r t s pe r billion

ppm pa r t s pe r million

ppmv p a r ts pe r million ( volume ba sis) ppt pa r t s pe r tr illion
PVC poly viny l chloride QA/QC qua lity a ssur a nc e / qua lity c ontr o l
RCRA Re sour c e Conse r va tion a nd Re c ove r y A c t
RDF r efuse-derived fuel
SI C S tandard I ndustr ial Classification
SI P S ta te I mple me n ta tion Pla n S NUR S i g n ificant New Use R u le
SO 2 

### sulfur diox ide
TCB z trichlorobenz ene TCDD 2,3,7,8-tetrachlorobidenz o- p -di o x i n TCDF 2,3,.7,8-tetrachlorobidenz ofuran
TeCB tetrachlorobipheny l
TeCP tetrachlorophenol
TEF tox i city equivalency factor TEQ tox i city equivalence TEQ/y r t ox icity equivalents per y ear TiCl 4 

### tita nium te tr a c h lor i de
TrCB trichlorobipheny l
TrCP trichlorophenol
TRI Tox ics Release I nventory
TSCA Tox i c Substances Control Act

xxxi i

### L I S T OF AB B R E V IAT I ONS AND ACRONYMS (con tin u e d )

2,4-D 2,4-dichlorophenox y acetic acid 2,4-DB 4-(2,4-dichlorophenox y ) buty r ic acid 2,4-DCP 2,4-dichlorophenol 2,4-DP 2-(2,4-dichlorophenox y ) propionic acid 2,4,5-T 2,4,5-trichlorophenox y (phenox y herbicides)
U.K. United King dom
US DA U.S

. Department of Ag riculture
VCM viny l chloride monomer
WHO W or ld He a lth Or g a niza tion
W S wet scrubber

xxxi i i

### F O RE WORD

The purpose of this document is to present an inventory of sour ces and environmental
releases of diox in-like compounds in the United Stat es. This inventory is associated with three distinct reference y ears: 1987, 1995, and 2000. The presentation of information in this manner permits the ranking of sources by mag n itude of annual release and allows for the evaluation of

e nvir onme n ta l tr e nds ove r time

. The t e rm “di o x i n-l i k e” i n cl udes cong eners of poly c hlorinated dibenz o- p -di o x i ns (C DDs), poly c hlorinated dibenz ofurans (CDF s) having chlorine atoms in the 2,3,7,8 positions on the
mole c u le , a nd c e r ta in c opla n a r

- substitute d poly c hlor ina t e d biphe ny ls ( P CB s)

. Diox in- like r e f e r s to the fact that these compounds have similar ch emical structure and phy sical-chemical properties
and invoke a common tox i c response. B ecause of their hy drophobic nature and resistance

t o wards m e t a bol i s m , t h ese chem i cal s persi s t and bi oaccum u l a t e i n fat t y t i ssues of ani m a l s and
humans. Consequently , the principal route of chronic population ex posure is throug h the dietary consumption of animal fats, fi sh, shellfish, and da iry products. Diox in-like compounds are persistent in soils and sediment s, with e nvir onme n ta l ha lf

- live s r a ng ing f r o m y e a r s to se ve r a l
decades. Understanding the sources and envir onmental releases of diox in-like compounds is fundamental to ultimately linki ng sources with population ex posures. I t is throug h such understanding that actions can be taken to reduce human ex posures. The qua ntita tive r e sults of the inve ntor y a r e e x pr e sse d in te r m s of the tox i c ity e quiva le nc e (TEQ) of the mix ture of poly c hlorinated dibenz o- p -diox i n (CDD) and poly c hlorinated
dibenz ofuran (CDF ) compounds present in envir onmental releases using a procedure sanctioned by the W orld Health Org a niz a tion (W HO) in 1998. This TEQ procedure translates the complex
mix ture of CDDs and CDF s charact eristic of environmental releases into an equivalent tox i city concentration of 2,3,7,8- tetrachlorodibenz o- p -diox i n (2,3,7,8-TCDD), the most tox i c member of this class of compounds. W ith this procedure, the quantity of the mix ture of CDDs and CDF s present as a rel ease i s g i ven t h e not at i on g r am s (g ) TEQ DF 

### -W HO 98 

### . This inventory of sources a nd environmental releases of diox in-like compounds concludes that, between 1987 and 2000, there wa s approx imately 90% reduction in the release of diox in-like compounds to the circulating environment of th e United States from all known sources combined. Annual emission estimates (TEQ DF 

### -W HO 98 

### ) of releases of CDDs/CDF s to air, water, and land from reasonably quantifiable sources are approx imately 1,422 g in reference y ear 2000; 3,444 g in reference y ear 1995; and 13,965 g in reference y ear 1987. I n 1987 and 1995, the leading sources of diox in emissions to the U.S. environment we re municipal waste com bustors. The inventory also identifies bleached chlorine pulp and paper mills as a sig nificant source of diox in to the aquatic environment in 1987 but a minor source in 1995 and 2000. The inventory concludes that

xxxi v

### the major source of diox in in 2000 was the uncont rolled burning of refuse in backy a rd burn
barrels in rural areas of the United States.
The reduction in environmental releases of diox in-like compounds from 1987 to 2000 is attributable to source-specific reg u lations, impr ovements in source technolog y , advancements in the pollution control technolog ies specific to cont rolling diox in discharg es and releases, and the voluntary actions of U.S. industries to reduce or prevent diox in releases.

Peter W . Preuss, Ph.D. Di rect or National Center for E nvironmental Assessment Office of Research and Development

xxxv

### P RE F ACE

This document, An Inventory of Sources and Environm ental Releases of Dioxin-Like Compounds in the United States for the Y e ars 1987, 1995, and 2000 , was prepared by the
Na tiona l Ce nte r f

o r

Envir onme n ta l Asse ssme n t, whic h is the he a lth r i sk a sse ssme n t pr og r a m in the Office of Research and Development. The document presents estimate s of annual releases of
diox in-like compounds specific for each y ear. I t is a detailed co mpilation and description of all
known U.S. sources and their associated activities that cause these compounds to be released into the open and circulating environm ent, i.e., to air, water, a nd land. The overall purpose of this report is to document and descri be sources in the United Stat es t h at rel ease di ox i n -l i k e compounds into the open environment, quantify annual releases to the environment from known

sour c e s in a sc ie ntif ic a nd tr a n spa r e n t ma nne r , a nd provide a reliable basis for observing trends in
envi ronm ent a l rel eases. To t h e ex t e nt pract i cal , the inventory is a comprehensive analy s is of
diox in sources.
Thi s fi nal docum ent refl ect s a consi d erat i on of al l com m e nt s recei ved on an Ex t e rnal
Review Draft dated March 2005 (EPA600/P-03/002A) provided by an ex pert panel at a peerreview workshop held S e ptember 13–15, 2005, a nd comments received during a 60-day public review and comment period (May 6–J uly 5, 2005).
Over 800 references were review ed and cited in the prepara tion of this document. The citations g e nerally refl ect publications up to and including the y ear 2003.

xxxv i

### AUT HORS , CONT RIB U T O RS , AND RE VIE W E R S

The National Center for Environmental Assessment (NCEA) was responsible for preparing this document. Major portions of this report were prepared by Versar, I n c. under EPA
Contract No. 68-W

- 99-041. David Cleverly of NCEA served as the EPA W o rk Assig n ment Manag e r, providing overall direction and coordination of the project, as well as author of several chapt e rs.

Authors

David Cleverly National Center for E nvironmental Assessment Office of Research and Development U.S. Environmental Protection Ag ency W a shing t on, DC

Greg S c hweer Office of Pollution Prevention and Tox i cs U.S. Environmental Protection Ag ency W a shing t on, DC

Ronald L e e Versar, I n c. Spring field, VA

Kelly McAloon Versar, I n c. Spring field, VA

C h arl e s P eck Versar, I n c. Spring field, VA

Marit Espevik Randall Versar, I n c. Spring field, VA

Karie Traub Riley Versar, I n c. Spring field, VA

xxxv i i

### AUT HORS , CONT RIB U T O RS , AND RE VIE W E R S (con tin u e d )

C o nt r i but or s

F r ank B e han, Office of Solid W a ste, Office of Solid W a ste and Emerg e ncy Response, U.S. Environmental Protection Ag ency , W a shing t on, DC

L a urel Driver, Office of Air Quality Planning and Standards, Office of Air and Radiation, U.S. Environmental Protection Ag ency , Research Triang le Park, NC

Marietta Echeverria, Na tional Center for Environmental A ssessm ent , Offi ce of R e search and Development, U.S. Environmental Protection Ag ency , W a shing t on, DC

J oseph F e rrario, Environmental Ch emistry L a boratory

, Office of Pe stic ide Pr og r a ms, Of f i c e of Prevention, Pesticides and Tox i c Substances, U. S. Environmental Protection Ag ency , Stennis S p ace C e nt er, MS

Roy Huntley , Office of Air Quality Planning a nd Standards, Office of Air and Radiation, U.S. Environmental Protection Ag ency , Research Triang le Park, NC

J ohn Schaum, National Ce nter for Environmental Assessm ent, Office of Research and Development, U.S. Environmental Protection Ag ency , W a shing t on, DC

W a lt Stevenson, Office of Air Quality Planning a nd Standards, Office of Air and Radiation, U.S. Environmental Protection Ag ency , Research Triang le Park, NC

Dwain W i nters, Office of Pollution Prevention a nd Tox i cs, Office of Prevention, Pesticides and Tox i c Substances, U.S. Environmen tal Protection Ag ency , W a shing t on, DC

Revi ew ers

Internal EP A Review : I n ternal EPA review occurred from May 2 throug h J une 5, 2003. The key reviewers included the follo wing individuals and offices:

Elmer Akin, EPA Reg i on 4, Atlanta, GA

Don Anderson, Office of Science and Technol og y , Office of W a ter, W a shing t on, DC

J ohn D B achmann, Office of Air Quality Planning and Standards, Resear ch Triang le Park, NC

Ang e la L

. B a ndemehr, Office of I n ternational Affairs, W a shing t on, DC

F r ank B e han, Office of Solid W a ste, W a shing t on, DC

xxxv i i i

### AUT HORS , CONT RIB U T O RS , AND RE VIE W E R S (con tin u e d )

Tom B r a v e r ma n, Of f i c e of Air Qua lity Pla nning a nd Sta nda r d s, Re se a r c h Tr ia ng le Pa r k, NC

L a ur e l Dr ive r , Of f i c e of Air Qua lity Pla nning a nd Sta nda r d s, Re se a r c h Tr ia ng le Pa r k, NC

Da le Eva r ts, Of f i c e of Air Qua lity Pla nning a nd Sta nda r d s, Re se a r c h Tr ia ng le Pa r k, NC

B r ia n Gulle tt, Na tiona l Risk Ma na g e me nt L a borat ory , R e search Triang le Park, NC

B ob Holloway , Office of Solid W a ste, W a shing t on, DC

Roy Huntle y , Of f i c e of Air Qua lity Pla nning a nd Sta nda r d s, Re se a r c h Tr ia ng le Pa r k, NC

Phil L o r a ng , Of f i c e of Air Qua lity Pla nning a nd Sta nda r d s, Re se a r c h Tr ia ng le Pa r k, NC

Ed Ohanian, Office of W a ter, W a shing t on, DC

Debbie Sisco, Office of Pestic ide Prog rams, W a shing t on, DC

Alan Rubin, Office of W a ter, W a shing t on, DC

J ohn Schaum, National Center for Envi ronmental Assessment, W a shing t on, DC

L a urie Schuda, Nati onal Center for Environmenta l Assessment, W a shing t on, DC

J oe Some r s, Of f i c e of Tr a nspor ta tion a nd Air Qua lity , Ann Ar bor , MI

W a lt Stevenson, Office of Air Quality Planning and Standards, Resear ch Triang le Park, NC

Dwain W i nters, Office of Pollution Prevention and Tox i cs, W a shing t on, DC

Donn Viviani, Office of Policy

, Ec onomics, and I nnovation, W a shing t on, DC

E x tern al P eer Revi ew : This document has underg one two ex ternal peer reviews: the first Ex ternal Review Draft (EPA/ 600/P-98/002Aa) published in April 1998 was reviewed by an ex pert panel at a public meeting held in Alex andr ia, Virg inia, on J une 3–4, 1998. The most recent Ex ternal Review Draft (EPA600/P-03/002A) pub lished in March 2005 was released for public review and comment on May 6, 2005, and was subsequently reviewed at a public meeting held in Arling t on, Virg inia, on September 13–15, 2005.

xxxi x

### AUT HORS , CONT RIB U T O RS , AND RE VIE W E R S (con tin u e d )

1. P eer review m eetin g S e p t em b er 13-15, 2005

P a nel Chair H e i d el ore F i ed l e r , Ph.D., Scientific Affai r s Offi cer , 

### United Nations Environment Prog ramme C h em i cal s, C h at el ai ne, S wi t z erl a nd

P a n el Mem b ers Judit h A

. A bbot t , Ph.D., Research Scientist, B ureau of Tox i c S ubstance Assessment, New York State Department of Health, Albany , NY

G a ry A. Am en d o la , Ph.D., President, Amendola Eng i neering

, W e stlake, OH

P a t r ic k D y ke , Pr e side n t, PD Consulting

, Ox f o r d, Unite d King dom

Ch ri stop h er C. L u tes , Ph.D., Pr inc i pa l Sc ie ntist/Assoc i a t e Vic e Pr e side n t, ARCADI S G& M, I n c., Durham, NC

Jozef M. P a cyn a , Ph.D., Ce nte r f

o r

Ec olog ic a l Ec onomic s, Nor w e g ia n I n stitute f o r

Air Re se a r c h

, Kjeller, Norway

2. P eer review m eetin g Ju n e 3–4, 1998

P a nel Chair Val eri e T h om as , Ph.D., Research Scientis t, Center for Energ y and Environmental Studies, Pr inc e t on Unive r sity

P a n el Mem b ers P a t r ic k D y ke , Pr e side n t, PD Consulting

, Ox f o r d, Unite d King dom

Raou f Morcos , Manag e r, National Office of Pollu tion Prevention, Environment Canada Quebec, C a nada

William Randall Se e k e r , Ph.D., Senior Vice President, En erg y and Environmental Research, I r vine, CA

C hun Y i Wu , Senior Eng i neer, Air Quality Divisi on, Minnesota Pollution Control Ag ency , St. Paul, MN

xl

### ACK NOWL E D G M E N T

The authors would like to acknowledg e the c ontributions of the following individuals:
Terri Konoz a of NCEA who manag e d the doc ument production activitie s and provided editing

, proofreading

, and word processing support; Patricia von B r ook of KB M Group who provided editing support; and Christine Chang of KB M Group who provided word processing support.

xl i

### E XE CUT IVE S UMMARY

This report, An Inventory of Sources and Environm ental Releases of Dioxin-Like Compounds in the United States for the Y e ars 1987, 1995, and 2000, presents estimates of annual
releases of diox in-like com pounds specific to each y ear. I t is a detailed compilation and description of all known U.S. sources and thei r associated activities that cause these compounds to be released into the open and circulating environment, i.e., to air, water, and land. The overall purpose of this report is to documen t and describe sources in the Un i t e d S t at es t h at rel ease di ox i n

like compounds into the open environment, quan tify annual releases to the environment from
known sources in a scientific a nd transparent manner, and provide a reliable basis for observing
trends in environmental releases. To the ex te nt practical, the invent ory is a comprehensive analy s is of diox in sources.
The term “diox i n-like” refers to chemi cal compounds that mimic the chemical and phy sical properties of diox in and have similar tox i c effects. These include compounds of
chlorinated dibenz o- p -diox i ns (CDDs), chlorinated dibenz ofurans (CDF s), and certain coplanar poly c hlorinated bipheny ls (PCB s). The diox in-lik e CDDs and CDF s have chlorine atoms in the 2,3,7,8 positions on the molecule. Diox in-like PCB s contain z e ro or one chlorine atom in the 2,2' ,6 or 6' positions. All tog e ther there are 7 CDDs, 10 CDF s , and 12 PCB s that are considered
to be diox in like. I t should be emphasiz e d th at releases of diox in-like compounds presented in this inventory are, for the most pa rt, for diox in-like CDDs and CDF s

. Sources of diox in-like
PCB s are g e nerally poorly characteriz ed.

Approach Only sources judg ed to have a reasonable likelihood for releases of diox in-like compounds
to the a i r , wa te r , a nd la nd of the Unite d Sta t e s a r e a ddr e sse d in this r e por t. The r e le a se e stima te s were derived in one of two way s : (1) di ox i n was m easured as an act ual rel ease from t h e source (i.e., points of release from the source were sample d and evaluated), or (2) diox in releases were
calculated on the basis of an emi ssion factor and activity level. The emission factor is the amount
of

diox in a n tic ipa t e d to be e mitte d pe r unit of a c tivity a nd is de r i ve d f r o m me a sur e m e n ts ma de a t sources having similar characteristics. The activ ity level is the amount of material processed, produced, or consumed by the source in the course of a y ear or, in the case of mobile sources, the
number of kilometers driven. I t can take several forms, such as kilog r a m s of ma te rial processed

per y ear by an industrial facility

, vehicle kilometers traveled per y ear by trucks and automobiles, and liters of wastewater discharg ed into surface water from industr ial sources. The activity level is multiplied by the emission factor to arrive at an estimate of annual diox in releases from those
sources l acki n g di rect m easur ement of diox in emissions.

x lii

### C onfi d ence i n t h e accuracy of bot h t h e em i ssi on fact or and t h e act i v i t y l e vel are rat e d as low, me dium, or hig h, ba se d on the qua lity of the da ta

. All the r e le a se e stima te s f r o m sour c e s in the inventory are assig n ed an overall confiden c e r a ting ba se d on the lowe st r a ting a ssig n e d to

e ithe r the e mission f a c t or or the a c tivity le ve l. I n som e cases, t h e dat a were not adequate to support even a low confidence rating

. These cases were treated in one of two way s

. I f the data were sufficient to make an appr ox imate, but clearly nonrepresenta tive, estimate of releases, the

e stima te s we r e la be le d a s pr e limina r y a nd we r e not inc l ude d in the na tiona l inve ntor y

. I f limite d data sug g e sted that diox in releases were possi ble from a source but were not adequate to support even rudimentary calculations of emissions, th e source was labeled as unquantifiable. This approach resul t e d i n t h e cl a ssification scheme shown below.

Categ o ry A H ig h Confidence I n cluded in the national Ca te g o r y B M e d ium Conf ide n c e qua ntita tive inve ntor y Categ o ry C L ow Confidence Ca te g o r y D P r e limina r y N ot inc l ude d in the na tiona l Categ ory E U nquantifiable qua ntita tive inve ntor y

Throug hout this document, environmental re lease estimates are presented in terms of

tox i city equivalence (TEQs). TEQ s are derived from a tox i city weig hting sy stem that converts all
mix ture components to a sing le value normaliz ed to the tox i city of 2,3,7,8-TCDD. This is done for convenience in presenting summary information and to facilitate compar isons across sources.
F or many situations, however, it is important to use the individual CDD/CDF and PCB cong ener values rather than TEQs. CDD and CDF cong ene r-speci fi c rel eases for m o st sources are g i ven i n tables in each chapter. The summary amount s of diox in-like compounds released to the environment are reported in units of g r ams (g ) TEQ, developed by the W o rld Health Org a niz a tion (W HO), and are g i ven the a bbreviated notation of TEQ DF 

### -W HO 98 

### throug hout the document. The major finding s of the inventory of sources and environmental rel eases of diox in-like compounds in the United States are:

1. I n 1987, 1995, and 2000, approx imately 13,965; 3,444; and 1,422 g TEQ, respectively

, we r e r e le a se d into the U.S. e nvir onme n t f r o m a ll sour c e s

. F i g ure ES-1 g r aphically di spl a y s t h ese rel eases.

x liii13, 965. 3

3, 44 4. 2

1, 4 22. 0 14, 0 00

12, 0 00

10, 0 00)QE 8, 0 00T(sam 6, 0 00gr

4, 0 00

2, 0 00

0 Ye ar 1987 Year 19 95 Ye ar 2000



### F i gu re E S -1. T o tal en vi ron m en tal rel eases of d i oxi n - l i k e com p ou n d s (g T E Q ) f

r om all q u an t if iab l e sou rces d u r in g 1987, 1995, an d 2000.

2. Environmental releases of diox in-lik e compounds decreased by approx imately 90% between 1987 and 2000

. As shown in F i g ure ES-1, most of the reductions (75%) occurred between 1987 and 1995. The overall re duction in releases of diox in-like compounds is attributed to the control of air emissions of these compounds from municipal waste combustors (MW C s), medi cal wast e i n ci nerat o rs, and cem ent ki l n s burning haz a rdous waste and of wastewater discharg es of the compounds into surface

wa te r s f r o m pulp a nd pa pe r mills using c h lor i ne

. The se r e duc tions we r e a c h ie ve d thr oug h a c o mbina tion of r e g u la tor y a c tivitie s, impr ove d e mission c ontr o ls, volunta r y actions on the part of industry

, and the cl osing of a number of facilities. Table ES-1 shows the reductions made by the larg est sources of diox in-like compound releases. Emission e stima te s f o r

individua l sour c e s tha t c ould be qua ntif ie d, i.e ., Ca te g o r i e s A, B
, and C, are presented in th e ma in te x t of this r e por t.

3. The leading source of diox in-like com pounds in 2000 was the backy a rd burning of refuse in barrels (498.5 g TEQ, or 35% of total releases) , as shown in Table ES-2, which presents the top 10 sources of releases for 2000, 1995, and 1987. B acky a rd barrel burning of refuse is an act i v i t y t h at occurs i n rural areas of t h e Uni t e d S t at es. I t is unr e g ula t e d on a na tiona l le ve l, but ma ny sta t e s ha ve ba nne d or limite d the pr a c tic e (New J e rsey , New York, California, Minne sota, W i sconsin, Mass achusetts, and

x liv

### Table ES- 1. R e duc t ions of r e le a se s of dioxin- like c o m p ounds t o t h e

en viron m en t in ref eren ce years 2000 an d 1987 f r om m a jor sou rces in th e Un i t ed S t ates

S o u rce ca teg o ry R elea ses to : 2000 ( g TEQ) 1987 ( g TEQ) P ercen t

r e duc t i on

Muni c i pa l w a s t e

c o m bus t i o n Ai r 83.8 8 ,905.1 > 99

M ed i cal waste
i n c i ne r a t i o n Ai r 378.0 2 ,570.0 85

C e m e n t kiln s b u r n i n g h azard o u s

w a s t e A i r 18.8 117.8 84

B l each ed ch emical

w o o d pul p a nd

p a p e r m ills S u rface

w a t e r 1 .0 356.0 > 99



### F l orida to name a few). I n 1995 and 1987 MW Cs were the leading source of releases (1,393.5 g , or 40% of total releases in 1995; 8,905.1 g , or 64% of releases in 1987). Howe ve r , due to str i c t r e g u la tor y r e quir e me nts limiting diox in e missions, MWCs we r e ranked fourth among the top 10 sources in 2000, with emissions of only 83.8 g , or 6% of total releases. Automobiles burning l eaded g a sol i n e were ranked as t h e ei g h t h leading source of diox in in 1987. The phase out of lead in g a soline eliminated this source by 2000. Cement kilns burning ha z a rdous waste dropped out of the top 10 sources in 2000, due primarily to voluntary ac tions of industry combined with national reg u l a t o ry requi rem e nt s t o reduce diox in emissions.

4. Environmental releases of diox in-like compounds in the United States occur from a wide variety of sources but are dom i n at ed by rel eases t o t h e ai r from com bust i o n

sources

. F i g u re ES-2 presents the breakdown of releases to air, water, and land for each reference y ear.

5. There are potential sources of diox in-lik e compounds that were not included in the inventory

. Sig nificant amounts of the diox in-like compounds produced annually in the Uni t e d S t at es are not consi d ered rel eases to the open and circul ating environment and, therefore, are not included in the national inventory

. Ex amples include diox in-like compounds g e nerated internal to a process but destroy e d before release and waste
str e a m s tha t a r e dispose d of in a ppr ove d a nd se c u r e la ndf ills. The r e a r e a l so pote n tia l

sour c e s f o r

whic h no inf o r m a tion e x ists to pe r mit a n y r e lia ble e stima te s of

xl v

### Table ES-2. Top 10 sources of dioxin-lik e com p ound releases and am ounts released (g TEQ) f o r ref eren ce years 2000, 1995, an d 1987

2000 1995 1987 Ra nk (1,422 g total ) (3,444 g total ) (13,965 g total )

1 B ack y a rd barrel bu rn in g of

ref u s e (air) 498.5 M u n i ci pal w a s t e

co m b u s tio n (in c in eratio n o f ref u se) (air) 1,393.5 M u n i ci pal w a s t e

co m b u s tio n (in c in eratio n o f ref u s e ) (air) 8,905.1

2 Medical w as t e/ p a th o l o g ical in cin e ratio n (air) 378.0 B ack y a rd barrel bu rn in g of ref u s e (air) 628.0 M edi cal

w a s t e/ pat h ol og i cal in cin e ratio n (air) 2,570.0

3 M u n i cipal w as t ew ater t r e a t m e nt sl ud ge ( a p p l i e d
to lan d an d in cin e rated ) (lan d an d air) 89.7 M edical

w a s t e/ pat h ol og i cal in cin e ratio n (air) 487.0 S econ d ary copper

sm eltin g (air) 983.0

4 M uni c i p a l w a st e

co m b u s tio n (in c in eratio n of

ref u s e ) (air) 83.8 S econ d ary copper

sm eltin g (air) 271.0 B ack y a rd barrel bu rn i n g of ref u s e (air) 604.0

5 C o a l- f i red u tility b o ilers (electric g e n e ratin g plan ts ) (air) 6 9

. 5 C em en t k iln s (h azardou s w a s t e bu rn in g ) (air) 156.1 B leach ed ch em ical

w ood pu l p an d
p a p e r m ills (lan d

, wa t e r ) 370.1

6 Diesel h eav y

- d u ty tru c k s (air) 65.4 Mu n i cipal w as t ew ater t r e a t m e nt sl ud ge (ap p lied to lan d an d in cin erated) (lan d an d air) 133.3 C em en t k i l n s (h azardou s w a s t e bu rn in g ) (air) 117.8

7 I n d u s trial w o o d

co m b u s tio n (air) 4 1

. 5 C o a l- f i red u tility b o ilers (electric g e n e ratin g plan ts ) (air) 60.1 M u n i ci pal

w as t ew ater t r e a t m e nt sl ud ge (ap p lied to lan d

an d in cin e rated) (lan d an d air) 85.0

8 D i e se l o ff-r o a d
equ i pm en t (in clu des ship s, fa r m e q uip m e n t, train s ) (air) 33.1 Et h y l en e d i ch lo rid e /v in y l ch l o ri de produ ct i o n (lan d, air, w a ter) 3 5

. 7 C o a l- f i red u tility boilers (electric ge ne r a t i ng p l a nt s ) (air) 50.9

9 E th y l en e d i ch lo rid e /v in y l ch l o ri de produ ct i o n (lan d, air, w ater ) 3 0

. 0 Diesel h eav y

- d u ty t r uc ks ( a i r ) 33.3 A u t om obi l e s u s i n g leaded g as o lin e (air) 37.5

10 Sin t erin g plan ts (air) 27.6 B leach ed ch em ical

w ood pu l p an d paper

m ills (lan d an d w a ter) 30.0 2 ,4­ D i ch l o roph en ox y acetic acid (2,4- D ) (lan d) 33.4



### xl v i

### Year 2000 Year 1995

1.8% 5.7%

92.4% 7.4% 2.6%

90.0%


### Year 1987

2.5% 0.9%

96.5%

Releases to Air Releases to Water Releases to Land



### F igur e ES- 2. R e le ase s of dioxin- like c o m p ounds t o air , wat e r , and land in 2000, 1995, and 1987.

envi ronm ent a l rel eases; t h erefore, t h ese pot ential sources could not be included in the inventory

. EPA has classi fi ed t h ese pot ent i a l sources as C a t e g o ry D sources. Ex am pl es i n cl ude forest and g r assl and fi res and acci dent al fi res at m uni ci pal sol i d

wa ste la ndf ills. Ta ke n tog e the r , the se sour c e s ha ve the pote n tia l to sig n if ic a n tly inc r e a se the e mission e stima te s in the pr e se n t inve ntor y

.

6. The amount of diox in-like PCB s releas ed from man-made s ources remains poorly charact eri z ed

. Only a total of 19.5, 78.5, and 51.5 g of PCB TEQ coul d be quantified for 2000, 1995, and 1987, respectively

. To date, only sewag e sludg e has been adequat e l y charact eri z ed as a source of di ox i n -l i k e P C B rel eases.

xl v i i

### 1. B ACK G R OUND, AP P R OACH, AND CONCL US IONS

1.1. BACK G R OUND This report presents a comprehensive inventor y of sources of releases of diox in-like compounds in the United States for the y ears 1987, 1995, and 2000. I t is a detailed review and description of all known sources and their associated activities th at cause these compounds to be released into the “open and circulating e nvironment,” i.e., air, water, and land.
The a im of this r e por t is to:

• D ocument and describe sources that release diox in-like compounds into the circulating environment of the United States.

• Q uantify annual releases to the environm ent of the United States from known sources in a sc ie ntif ic a nd tr a n spa r e n t ma nne r

.

• P r ovide a r e lia ble ba sis f o r

time

- t r e nds a n a l y se s suc h a s obse r ving c h a n g e s in tota l releases to the circulating environm ent from 1987 to 2000. Time-trend analy s es pr ovide a qua ntita tive indic a tion of the a c h ie ve me nts ma de ( o r la c k the r e o f ) in reducing environmental rel eases of diox in-like compounds from specific sources in
t h e Uni t e d S t at es.

This is the second diox in source inventory i ssued by the U.S. Environmental Protection Ag ency (EPA, or the Ag ency ). The first one wa s issued in draft form and covered the y ears 1987 and 1995 (U.S. EPA, 1998a). The current effort updates this earlier doc ument and adds annual
release estimates for 2000.
The intended audience and users of the diox in inventory include:

• M embers of the g e neral public who are inte rested in learning more about sources of emissions of diox in-like compounds to the U.S. environment and in obtaining peerr e vie w e d e s tima te s of r e le a s e s

.

• S t a t e and l o cal reg u l a t o ry ag enci es t h at ar e interested in obtaini ng reliable and peerreviewed information on sources and e nvironmental releases of diox in-like compounds.

• EPA Reg i onal and Prog ram Offices that ar e responsible for evaluating the need for
reg ulating and/or preventing diox in releases to the environment.

• R isk assessors in the private and public sectors who need reliable information on sources and releases of diox in-lik e compounds to improve quantitative risk assessments of diox in sources.

1-1

### • R e se a r c h e r s who a r e inte r e ste d in doc ume n te d a nd time

- spe c i f i c diox in sour c e a n d

e missions da ta to be use d in se que ntia l time

- t r e nds a n a l y se s.

• P rivate and public stakeholder g r oups that are interested in obtaining reliable and peer-reviewed information on diox in sour ces and releases and in observing time trends in environmental releases of diox in-like compounds from specific source
cat eg ori e s.

A c o mple te listing of the nome n c l a t ur e use d in this report is depicted in Table 1-1.

Table 1- 1. N o m e nc lat u r e for dioxin- like c o m p ounds

T erm/symb o l D ef in ition

CDD C hlorinated dibenz o- p

- d ioxin, halog ens substituted in any position

C D F C hlorinated dibenz ofuran, halog ens substituted in any position

PCB P oly c hlorinated bipheny l

M S y m bol for m ono (i.e., one halog en substitution)

D S y m bol for di (i.e., tw o halog en substitution)

Tr S y m bol for tri (i.e., three halog e n substitution)

T S y m bol for tetra (i.e., four halog en substitution)

P e S y m bol for penta (i.e., fiv e halog en substitution)

H x S y m bol for hexa (i.e., six halog en substitution)

H p S y m bol for hepta (i.e., sev en halog en substitution)

O S y m bol for octa (i.e., eig h t halog en substitution)
2,3,7,8 H a log e n substitutions in the 2,3,7,8 positions Cong ener Any one particular m em b er of the sam e chem ical fam ily (e.g ., there are 75
cong eners of CDDs). Cong ener g r oup Group of structurally related chem i cals that hav e the sam e deg r ee of chlorination (e.g ., there are eig h t cong ener g r oups of CDDs, m onochl orinated [MCDD] throug h octachlo rinated [O C D D ]).

I s om er Substances that belong to the sam e cong ener g r oup (e.g ., 22 isom ers constitute the cong ener g r oup of T C DDs). Specific isom er Denoted by uni que chem ical notation (e.g

., 2,4,8,9- tetrachlorodibenz ofuran is referred to as 2,4,8,9- T C DF).
S o u rce: A d apt e d f rom U

. S

. EPA (1989a).



### 1-2

### 1.1.1. Ref eren ce Years A central part of EPA’s diox in inventory is the org a niz a tion of estimates of annual
releases of diox in-like compounds into refe rence y ears 1987, 1995, and 2000. The selection and

use of thr e e r e f e r e nc e y e a r s pr ovide s a ba sis f o r

c o mpa r ing e nvir onme n ta l r e le a se s ove r time

. The y ear 1987 was selected as the initial re ference y ear because it was the earliest time
whe n it wa s f e a sible to a sse mble a r e a sona bly c o mpr e he nsive inve ntor y

. Pr ior to tha t time , ve r y little da ta e x iste d on diox in e missions f r o m sta c k s or othe r r e le a se points. The f i r st study providing the ty pe of data needed for a na tional inventory was EPA’ s National Diox in Study (U.S. EPA, 1987a). The y ear 1987 also corres ponds roug hly with the time when sig nificant
advances occurred in emissions measurement techniques and in the development of hig hr e solution ma ss spe c t r o me tr y a nd g a s c h r o ma tog r a phy , whic h a llowe d a n a l y tic a l la bor a t or ie s to detect low levels of poly c hlorinated dibenz o- p -diox i n (CDD) and poly c hlorinated dibenz ofuran (CDF ) cong eners in environmenta l samples. Soon after this time, a number of facilities beg a n
upg rades specifically intended to reduce CDD/ CDF emissions. Consequently , 1987 emissions
are represent a t i v e of l e vel s of emissions that occurred before the wide spr e a d insta lla tion of pollution control sy stems and pollution preventi on techniques specifically desig n ed to reduce
diox in releases from man-made sour ces into the air, land, and water.
EPA selected 1995 as the sec ond reference y ear because it reflects the completion time of
the f i r st se t of r e g u la tor y a c tivitie s spe c i f i c a lly ta ilor e d to r e duc e diox in r e le a se s f r o m ma jor

sources. B y 1995, EPA had proposed or prom ulg a ted reg ulations limiting CDD/CDF emissions from municipal waste combustors (MW C s), me dical waste incinerators (MW I s), haz a rdous waste incinerators, cement kilns burning haz a rdous waste, and pulp and paper mill facilities
usi n g bl eached chl o ri ne processes. The y ear 2000 was chosen as the most current date that could be addressed when this effort beg a n in 2002. Also, it corresponds to a reasonable time interval since 1995 when one
coul d ex pect t o see furt her chang e s occurri ng i n releases as a result of continuing reg u latory activities, voluntary actions on the part of industry , and facility closures.

1.1.2. Regulatory Sum m ary Tables 1-2 throug h 1-7 present a sy nopsis of EPA emission standards for the control of
diox in releases. As discussed in Section 1.3.2, these reg u lations (along with other factors)

c ontr i bute d to the r e duc tions in diox in e missions obse r ve d ove r time

.

1-3

### T a b l e 1-2. Mu n i ci p a l w a ste com b u s tors a



### Category b 

### S t ack emission limit c 

### (n g total CDD/ CDF / d s c m ) Ef f e c t i v e dat e New larg e 1 3 S eptem b er 20, 1994 d 

### J une 19, 1996 e



### E x isting larg e With electrostatic precipitators as the A P C D With dry scrubber/fabric filters as the A P C D 60 30 When SI Ps are approv ed f



### New sm all 13 J une 6, 2001 g



### E x isting sm all With electrostatic precipitators as the A P C D With dry scrubber/fabric filters as the A P C D 60 30 When SI Ps are approv ed h

a A i r em is s i on s t an dards prom u l g a ted Decem ber 19, 1995.

b L arg e = ag g r eg ate capacity 

### $ 225 t o n s / d ay ; s m al l = ag g r eg at e capaci t y <225 t o n s / d ay

.
c n g to tal CDD/CDF/d s cm = n a n o g r am to tal Cl 4 - Cl 8 C D D s pl u s C D F s per dry s t an dard cu bi c m e t e r of s t ack g a s

v o lu m e , corrected to 7% O 2 . d B e g a n co n s tru c tio n o n th is d a te.

e Modi f i ed or u p g raded on t h i s dat e

. f Wh en S IPs h a v e been approv ed by EPA (approx . 3 y r f rom t h e f i n a l ru l e or 1998).

g Fo r f acilities co n s tru c ted o n o r b e f o re th is d a te.
h Wh en S IPs h a v e been approv ed by EPA (approx . 3 y r f rom t h e f i n a l ru l e or 2003).

A P CD = A i r p o llu tio n co n t ro l d e v i ce SIP = State Im plem en tation P l an



### 1.1.3. Def i nition of Dioxin-Like Com p ound This inventory of sources and environmental releases addresses specific compounds in

t h e fol l o wi ng chem i cal cl asses: C DDs, C D Fs, and poly c hlorinated bipheny ls (PCB s). These
subset s of chem i cal s are defi ned as “di o x i n l i k e.” Di ox i n -l i k e refers t o t h e fact t h at t h ese compounds have similar chemical structures and phy sical-chemical propertie s, and they invoke a common battery of tox i c responses. B ecause of their hy drophobic nature and resistance towards

m e t a bol i s m , t h ese chem i cal s persi s t and bi oaccum u l a t e i n t h e fat t y t i ssues of ani m a l s and
humans. The CDDs include 75 individual compounds; CDF s include 135 compounds. These individual compounds are technically referred to as cong eners. Only 7 of the 75 cong eners of CDDs, or of brominated dibenz o- p -diox i ns (B DDs), are thoug ht to have diox in-like tox i city ; they

a r e the one s with c h lor i ne substitutions in—a t a minimum—the 2, 3, 7, a nd 8 positions. Only 10 of the 135 possible cong eners of CDF s are thoug ht to have diox in-like tox i city ; they also are the

one s with substitutions in the 2, 3, 7, a nd 8 positions. This sug g e sts tha t 17 individua l
CDDs/CDF s e x hibit diox in- like tox i c ity

.

1-4

### T a b l e 1-3. H a zard ou s w a ste i n ci n erators an d cem en t k i l n s an d l i g h t w e i g h t aggr e gat e kilns bur ning haz a r d ous wast e a



### S o u rce S t an d a rd s f o r n e w f a cilities b 

### S t an d a rd s f o r ex istin g f a cilities b



### Haz a rdous waste incinerators 0.11 ng I

- T EQ/dscm for dry APCD and/or waste heat boiler

sources
0.20 ng I

- T EQ/dscm for all other incinerators 0.20 ng I

- T EQ/dscm and
tem p erature control <400° F at the A P C D inlet

0.40 ng I

- T EQ/dscm when PM control dev i ce operated >400° F

Cem ent k ilns burning haz a rdous waste 0.20 ng I

- T EQ/dscm and
tem p erature control <400° F at the A P C D inlet

0.40 ng I

- T EQ/dscm when PM control dev i ce operated >400° F 0.20 ng I

- T EQ/dscm and
tem p erature control <400° F at the A P C D inlet

0.40 ng I

- T EQ/dscm when PM control dev i ce operated >400° F

Lig h tw eig h t ag g r eg ate k ilns burning haz a rdous waste 0.20 ng I

- T EQ/dscm or rapid quench below 400° F at k iln exit 0.20 ng I

- T EQ/dscm or rapid quench below 400° F at k iln exit

a A i r em is s i on s t an dards prom u l g a ted S e ptem ber 30, 1999, an d Decem ber, 2005. b n g I- T E Q/ds cm = n a n o g r am I- T E Q per dry s t an dard cu bic m e ter of s t ack g a s v o lu m e , corrected to 7% O 2 .

A P CD = A i r p o llu tio n co n t ro l d ev i ce (d ry = d r y scru b b er o r f ab r ic f ilter) P M = P a rticu l ate m a tter



### Table 1- 4. C e m e nt kilns not bur ning haz a r d ous wast e a



### E x isting cement kilns b 

### N ew cement kilns b



### 0.20 ng I

- T EQ/dscm and tem p erature control 0.20 ng I

- T EQ/dscm and tem p erature control <400° F at the APCD inlet <400° F at the APCD inlet

0.40 ng I

- T EQ/dscm when PM control dev i ce 0.40 ng I

- T EQ/dscm when PM control dev i ce operated >400° F operated >400° F

a A i r em i s s i on s t an dards prom u l g a t e d Ju n e 14, 1999.

b n g I- T E Q/ds cm = n a n o g r am I- T E Q per dry s t an dard cu bic m e ter of s t ack g a s v o lu m e , corrected to 7% O 2 .

A P CD = A i r p o llu tio n co n t ro l d e v i ce P M = P a rticu l ate m a tter



### There are 209 PCB cong eners, of which only 12 are thoug ht to have diox in-like tox i city ; those with four or more latera l chlorine atoms with one or no substitution in the ortho position. These compounds are sometimes referred to as copl anar, meaning that they can assume a flat config uration with ring s alig ned along the same plane. Th e phy si cal / c hem i cal properties of each

cong ener vary according to the deg r ee and position of chlorine substitution.

1-5

### T a b l e 1-5. S econ d a ry al u m i n u m sm el ters a



### P rocess E mission standard

Sweat furnace 0.8 ng I

- T EQ/dscm stack g a s corrected to 7% O 2 

### T h erm al chip dry er 2.50 μg I

- T EQ per m etric ton of scrap charg ed to the dry er Scrap dry er/delacquering k iln/decoating k iln 0.25 g I

- T EQ per m etric ton of scrap charg ed to the k

iln Scrap dry er/delacquering k iln/decoating k iln equipped with an afterburner 5.0 g I

- T EQ per m etric ton of scrap charg ed to the k iln

a A i r em i s s i on s t an dards prom u l g a t e d March 23, 2000.



### T a b l e 1-6. Med i c al w a ste i n ci n erators a



### Category b 

### St andard c 

### When built

Ne w Sm al l

Medium and larg e 125 ng total CDD/CDF/dscm or 2.3 ng I

- T EQ/dscm

25 ng total CDD/CDF/dscm or 0.6 ng I

- T EQ/dscm Constructed after J une 20, 1996, or existing units that

com m enced m odification after March 16, 1998.

Existing (all siz es) 125 ng total CDD/CDF/dscm or 2.3 ng I

- T EQ/dscm Constructed on or before J une 20, 1996; requires
approv al of SI Ps d

a A i r em i s s i on s t an dards prom u l g a t e d S e pt em ber 15, 1997.

b S m al l = capaci t y <100 k g / h r; m e di u m = capaci t y >100 t o 227 k g / h r; l a rg e = capaci t y >227 k g / h r.

c n g / ds cm = n a n o g r am per dry s t an dard cu bic m e ter of s t ack g a s v o lu m e , corrected to 7% O 2 . d Wh en S IPs h a v e been approv ed by EPA (approx . 5 y r f rom t h e f i n a l ru l e or 2002).



### Table 1- 7. P u lp and pape r m ills a



### P o llutant Max i mum 1-day w a stew ater discharge

T etrachlorodibenz o- p

- d ioxin < 5 parts per quadrillion

T etrachlorodibenz ofuran 31.9 picog r am s per liter

a Ef f l u e n t s t an dards prom u l g a t e d N o v e m b er 14, 1997.



### 1-6

### Ge ne r a lly spe a k ing

, this doc ume n t f o c u se s on the 17 CDDs/CDF s and a few of the coplanar PCB s that are frequently encountered in source characteriz ation or environmental

sa mple s. CDDs and CDF s are tricy c lic aromatic compounds that have similar phy sical and chemical properties. Certain PC B s (the so-called coplanar or mono-ortho coplanar cong eners)

a r e a l so str u c t ur a lly a nd c onf or ma tiona lly simila r

. The most wide ly studie d of this g e ne r a l c l a ss of compounds is 2,3,7,8-tetrachlorodibenz o- p -diox i n (TCDD). TCDD, often called simply
“diox i n,” represents the reference compound for this class of compounds. The structures of
TCDD and several relate d compounds are shown in F i g u re 1-1. Althoug h sometimes confusing

, the te r m “ d iox i n” is of te n a l so use d to r e f e r

to the c o mple x mix tur e s of TCDD a nd r e la te d compounds emitted from sources or found in the envi ronment or in biolog ical samples. I t can also be used to refer to the total TCDD “equivale nts” found in a sample. This concept of tox i city equivalence is discussed below.

Cl Cl

Cl Cl

2 , 3,7,8-T etr ac h l o rod ibe n zo-p -d i o x i n O

O Cl Cl

Cl Cl

2 , 3,7 , 8

- T e t r ac h l oro d ib enzo f u r a n O

Cl Cl

Cl Cl

2,3,4,7, 8-Pen t ac h l o r o d i b e n z o f u r a n O Cl Cl Cl

Cl Cl O

O 1 ,2,3,7,8

- P e n t a c h lo r o d ib en z o - p - d io x i n Cl

Cl Cl

Cl Cl

Cl Cl 3 , 3',4 , 4 ',5,5 '

- H exach lor o b i p h e n y l Cl Cl

Cl Cl

Cl 

### 3 , 3',4 , 4 ' , 5- P e nt achlo r obi phe ny l



### F i gure 1-1. Chem ical structure of 2,3,7,8-TCDD a nd related com p ounds.

1-7

### 1.1.4. Toxicity E quivalence F a ctors CDDs, CDF s , and PCB s are commonly found as complex mix tures when detected in environmental media and biolog i cal t i ssues or when m easured as envi ronm ent a l rel eases from speci fi c sources. Hum a ns are l i k el y t o be ex pos ed to mix tures of CDDs, CDF s , and diox in-like
PCB cong eners that vary by source and pathwa y , c o mplic a ting the a sse ssme n t of huma n he a lth
ri sk assessm ent

. I n order t o address t h i s probl em , t h e concept of a “t ox i c i t y equi val e nce” (TEQ)
has been considered and discusse d by the sc ie ntif ic c o mmunity , a nd tox i city equivalence factors ( TEF s) ha ve be e n de ve lope d a nd intr oduc e d to f a c ilita te r i sk a sse ssme n t of e x posur e to the se

c h e mic a l mix tur e s. On t h e m o st basi c l e vel

, TEFs com p are t h e pot ent i a l t o x i ci t y of each di ox i n -l i k e compound in the mix ture to the well-studied a nd well-understood tox i city of TCDD, the most

tox i c member of the g r oup. The comparison pro cedure involves assig ning individual TEF s to the 2,3,7,8-substituted CDD/CDF cong eners and diox in- like PCB s

. To accomplish this, scientists
have reviewed the tox i colog i cal databases and, with considerations of chemical structure, persi s t e nce, and resi st ance t o m e t a bol i s m , have ag reed t o ascri b e speci fi c “order of m a g n i t ude”
TEFs for each di ox i n -l i k e cong ener rel a t i v e t o TC DD, whi c h i s assi g n ed a TEF of 1. The ot her

cong eners have TEF values rang ing from 1 to 0.00001. Thus, the se TEF s a r e the r e sult of sc ie ntif ic judg ment of a panel of ex perts using all of the
available data and are selected to account for un certainties in the availa ble data and to avoid underestimating risk. I n this sense, they can be described as “public h ealth-conservative” values. To apply this TEF concept, the TEF of each cong ener present in a mix ture is multiplied by the respective mass concentration, and the products are summed to represent the 2,3,7,8-TCDD TEQ
of the mix ture (eq 1-1).

TEQ 

### – 3 i



### ! n( Congener i 

### × TEF i 

### ) 

### % ( C ongener j 

### × TEF j 

### ) 

### %

...... ( C ongener n 

### × TEF
n 

### ) (1-1)

The TEF values for CDDs and CDF s were orig inally adopted by in ternational convention (U.S. EPA, 1989a). These values were further reviewed and/ or revised, and TEF s were also developed for PCB s (Ahlborg et al., 1994; Van den B e rg et al., 1998). A problem arises in that

pa st a nd pr e se n t qua ntita tive e x posur e a nd r i sk a sse ssme n ts ma y not ha ve c l e a r ly ide n tif ie d
whic h of thr e e TEF sc he me s wa s use d to e stima te the TEQ. This doc ume nt use s a ne w unif or m TEQ nom encl at ure t h at cl earl y di st i n g u i s hes be twe e n the dif f

e r e nt TEF sc he me s a nd ide n tif ie s the cong ener g r oups included in specific TEQ cal culations. The nomenclat ure uses the following abbreviations to desig nate which TEF sc heme was used in the TEQ calculation:

1-8

### • I -TEQ refers to the international TEF scheme adopted by EPA in 1989 (U.S. EPA, 1989a). See Table 1-8.

• TEQ-W HO 94 

### refers to the 1994 W o rld Health Or g a niz a tion (W HO) ex tension of the I

- TEF scheme to include 13 diox in-like PC B s (Ahlborg et al., 1994). See Table 1-9.

• TEQ-W HO 98 

### refers to the 1998 W HO update to th e previously established TEF s for diox ins, furans, and diox in-like PCB s (V an den B e rg et al., 1998). See Table 1-10.

Table 1- 8. The TEF sc he m e for I- TEQ DF



### Di oxi n con g en er T E F F u ran con g en er T E F
2,3,7,8-TCDD 1 2,3,7,8-TCDF 0.1 1,2,3,7,8-PeCDD 0.5 1,2,3,7,8-PeCDF 0.05 1,2,3,4,7,8-Hx CDD 0.1 2,3,4,7,8-PeCDF 0.5 1,2,3,6,7,8-Hx CDD 0.1 1,2,3,4,7,8-Hx CDF 0.1 1,2,3,7,8,9-Hx CDD 0.1 1,2,3,6,7,8-Hx CDF 0.1 1,2,3,4,6,7,8-HpCDD OC DD 0.01 0.001 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 0.1 0.1 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.01 0.01 0.001

Table 1-9. The TEF schem e f or dioxi n-like P C Bs, as determ ined by the World Health Or ganization in 1994

Ch em ical stru ctu r e I UP AC n u m b e r T E F
3,3' ,4,4' -TCB 2,3,3' ,4,4' -PeCB 2,3,4,4' ,5-PeCB 2,3' ,4,4' ,5-PeCB 2' ,3,4,4' ,5-PeCB 3,3' ,4,4' ,5-PeCB 2,3,3' ,4,4' ,5-Hx CB 2,3' ,4,4' ,5,5' -Hx C B 3,3' ,4,4' ,5,5' -Hx C B 3,3' ,4,4' ,5,5' -Hx C B 2,2' ,3,3' ,4,4' ,5-HpCB 2,2' ,3,4,4' ,5,5' -HpCB 2,3,3' ,4,4' ,5,5' -HpCB PCB

- 77 PCB

- 105 PCB

- 114 PCB

- 118 PCB

- 123 PCB

- 126 PCB

- 156 PCB

- 157 PCB

- 167 PCB

- 169 PCB

- 170 PCB

- 180 PCB

- 189 0.0005 0.0001 0.0005 0.0001 0.0001 0.1 0.0005 0.0005 0.00001 0.01 0.0001 0.00001 0.0001

1-9

### Table 1-10. The TEF schem e f or TEQ DF P 

### -WH O 98



### Di oxi n con g en er T E F F u ran con g en er T E F
2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 1 1 0.1 0.1 0.1 0.01 0.0001 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.1 0.05 0.5 0.1 0.1 0.1 0.1 0.01 0.01 0.0001

Ch em ical stru ctu r e I UP AC n u m b e r T E F

3,3' ,4,4' -TCB 3,4,4' ,5-TCB 2,3,3' ,4,4' -PeCB 2,3,4,4' ,5-PeCB 2,3' ,4,4' ,5-PeCB 2' ,3,4,4' ,5-PeCB 3,3' ,4,4' ,5-PeCB 2,3,3' ,4,4' ,5-Hx CB 2,3,3' ,4,4' ,5' -Hx C B 2,3' ,4,4' ,5,5' -Hx C B 3,3' ,4,4' ,5,5' -Hx C B 2,3,3' ,4,4' ,5,5' -HpCB PCB

- 77 PCB

- 81 PCB

- 105 PCB

- 114 PCB

- 118 PCB

- 123 PCB

- 126 PCB

- 156 PCB

- 157 PCB

- 167 PCB

- 169 PCB

- 189 0.0001 0.0001 0.0001 0.0005 0.0001 0.0001 0.1 0.0005 0.0005 0.00001 0.01 0.0001

The nomenclature also uses subscripts to i ndicate which family of compounds is included in any specific TEQ calculation. Under this c onvention, a subscript D is used to desig nate
diox ins, a subscript F to desig n ate furans, and a subscri p t P t o desi g n at e P C Bs. As an ex am pl e, TEQ DF 

### -W HO 98 

### would be used to describe a mix ture for which only diox in and furan cong eners were det e rm i n ed and where t h e TEQ was cal cul a t e d usi n g t h e W HO 98 

### scheme. I f PCB s had also been determined, the nomenclature would be TEQ DF P 

### -W HO 98 

### . Note that the desig nations TEQ DF 

### WH O 98 

### and I

- TEQ DF 

### are i n t e rchang eabl e , as t h e TEFs for di ox i n s and furans are t h e sam e i n each
scheme. Note also that in this document I

- TEQ sometimes appears without the D or F subscripts.
Thi s i ndi cat es t h at t h e TEQ cal cul a t i on i n cl udes both diox ins and furans. This document emphasiz e s the W H O 98 

### TEF scheme as the preferred sche me to be used to assig n TEQs to

c o mple x e nvir onme n ta l mix tur e s.

1-10

### Throug hout this document, environmental re lease estimates are presented in terms of TEQs. This is done for convenience in pres enting summary informa tion and to facilitate comparisons across sources. F o r purposes of environmental fate m odeling , however, it is important to use the individual CDD/CDF and PCB cong ener values rather than TEQs. This is
because t h e phy si cal / c hem i cal propert i e s of i ndi vi dual C DD/ C D F cong eners vary and,

c onse que ntly , the c ong e n e r s will be ha ve dif f

e r e ntly in the e nvir onme n t. F o r e x a m ple

, the
relative mix of cong eners released from a stack cannot be assumed to re main constant during

tr a n spor t thr oug h the a tmosphe r e and deposition to various media. The ful l cong ener-speci fi c

r e le a se r a te s f o r

most sour c e s a r e g i ve n in a n e l e c t r onic da ta ba se tha t will be c o me a v a ila ble a s a

c o mpa n ion to this doc ume n t.

1.1.5. In f o rm ation S o u rces I n g e neral, the literature used to prepare this report includes documents published in 2003
or earlier. Some 2004 documents are cited, primarily in Chap ter 2, which covers formation theory , but a thoroug h literature revi ew was not ex tended past 2003.
EPA’s Tox i cs Release I nventory (TRI ) be g a n collecting data on PCB s in 1988 and on
CDDs/CDF s in 2000 (U.S. EPA, 2003c). These data were considered in this report for purposes
of

ide n tif y i ng possible sour c e s, but the y we r e not use d f o r

ma king qua ntita tive r e le a se e stima te s because of t h e fol l o wi ng consi d erat i ons:

• W ith r e spe c t to PCB s, the TRI da ta a r e r e por te d a s tota l PCB s r a the r tha n on a cong ener-specific basis. Thus, it is unknown what portion of these releases are diox in-like PCB s , and TEQs cannot be calcula ted. I n their present format, the PCB TRI da ta a r e not r e a d ily usa b le within th e structure of this diox in inventory

.

• W ith respect to CDDs/CDF s, the reportin g format under TRI is the sum quantity of the 17 tox i c CDDs/CDF s that are emitted in a g i ven y ear (i.e., the sum of the 2,3,7,8­ chlorine-substituted compounds). Neither th e releases of the individual CDD/CDF
cong eners nor the TEQs must be reported; therefore, the diox in TRI data are not readily usable within the structure of this diox in inventory

.

• The accuracy of the TRI data is unknown because they are self-reported and are not required to be based on measurements.

• The TRI reports lack specific details and de scriptions of the reporting industries. This i n form at i on i s needed for t h e di ox i n i nvent ory because t h e cal cul a t i on of sourcespecific emission factors (re presentative of industrial source categ ories) strong ly depends on closely matching facilities in terms of similarity of process, production, and pollution control.

1-11

### • T he TRI reporting format does not include information on the streng ths/weaknesses of the data, and therefore, it would be difficult to evaluate the se da ta in te r m s of the confidence rating scheme deve loped for this inventory (p resented in Section 1.2.3).

1.2. AP P R OACH Only sources judg ed to have a reasonable likelihood for releases to the circulating
environment were a ddressed in this report. F o r ex ample:

• C DDs/CDF s a nd diox in- like PCB s in a i r e missions and wastewater discharg es are included, whereas those in intermediate pr oducts or internal wastestreams are not. For ex am pl e, t h e C DDs/ C DFs i n a wast est r eam g o i n g t o an on-si t e i n ci nerat o r are not addressed in this report, but any CDDs /CDF s in the sta c k e missions f r o m the i n ci nerat o r are i n cl uded.

• C DDs/CDF s a nd diox in- like PCB s in wa ste str e a m s a pplie d to la nd in the f o r m of

“ l a nd f a r ming ” a r e inc l ude d, whe r e a s those dispose d of in pe r mitte d la ndf ills we r e

e x c l ude d. Pr ope r l y de sig n e d a nd ope r a te d la ndf ills a r e c onside r e d to a c h ie ve long

term isolation from the circul ating environment. L a nd fa rming , however, involves the application of wastes dir ectly to land, clearly allowing for releases to the ci rcul at i n g environment.

1.2.1. S o u rce Classes The major identified sources of environmenta l releases of diox in-like compounds in the United States are g r ouped in to five broad categ ories.
C o m bust ion. C DDs/ C DFs are form ed i n m o st combustion sy stems (which can include

t hose t h at i n ci nerat e wast es su ch as municipal solid waste, se wag e sludg e, medical waste, and
haz a rdous wastes); in other hi g h -temperature sources (such as cement kilns); in poorly or uncontrolled combustion sources (such as forest fires, brush fires, landfill fires, accidental fires, building fires, and open burning of wastes); and during the burning of various fuels (such as coal, wood, and petroleum products).
Metals sm elting, ref ining, and processing. CDDs/CDF s can be formed during various
ty

pes of primary and secondary metals operations, including iron ore sintering , lead smelting

, copper smelting , mag nesium a nd titanium diox ide production, st eel production, a nd scrap metal

recovery

. Chem ical m anuf acturing. CDDs/CDF s can be formed as by -products of the manufacture of chlorine-bleached wood pulp, chlorinated phenols (e .g ., pentachlorophenol [ P CP] ) , PCB s , chlorobenz enes, phenox y herbic ides (e.g ., 2,4-D and 2,4,5- T), and chlorinated aliphatic compounds (e.g ., ethy lene dichlori de, viny l chloride, poly viny l chloride).

1-12

### Natu ral sou rces an d p r ocesses. The evi d ence for t h e wi despread ex i s t e nce of nat u ral
sources of diox in is quite weak. Recent studi es sug g e st that CDDs/C DFs can form under certain environmental conditions (e.g ., composting ) fro m the a c tion of mic r oor g a nisms on chlorinated phenolic compounds. Similarly , CDDs/CDF s have been reported to form during photoly s is of hig hly chlorinated phenols. Certain clay s used in ceramics (e.g ., ball cl ay ) are believed to have
become contaminated with diox in as a re sult of natural processes, but the source of
contamination remains unknown. A lthoug h it has been sug g e sted that volcanos may be a natural source, there is no reliable evidence that volcanos produce and emit sig nificant amounts of
diox in during eruptions.
Reservoi rs. Reservoirs are environmental comp a r tme nts a nd ma te r i a l s that have the capacity to store previously formed CDDs/CDF s or diox in- like PCB s

. These compounds are thus sequestered from the open and circulating environment. Pote ntia l r e se r voir s inc l ude soils, sediments, and biota as well as some anthropog enic materials, such as PCP treated telephone poles. Diox in-like compounds in these reservoi rs have the potential for redistribution and circulation in the environment throug h the phy si cal processes of leachin g , volatiliz ation, erosion, sedimentation, and deposition. W h enever diox ins are released from their place of storag e back
into the c i r c ula ting e nvir onme n t, the r e se rvoir is considered a source of diox in.
S ources can al so be cat eg ori z ed i n t e rm s of when rel eases occur: (1) cont em porary formation sources (sources that ha ve e sse ntia lly simu ltaneous formation and release) and (2)
reservoi r sources (m at eri a l s or pl aces t h at cont ai n previ ousl y form ed C DDs/ C DFs or di ox i n -l i k e P C Bs t h at are re-rel eased t o t h e envi ronm ent )

. The cont em porary form at i on sources are discussed in Chapters 2 throug h 10 and the re servoir sources are discussed in Chapter 11. Table 1-11 provides a comprehensive list of all known or suspected sources of
C DDs/ C DFs i n t h e Uni t e d S t at es. The checkm a rks i ndi cat e how each source was cl assi fi ed i n
te r m s of the f o llowing six c a t e g or ie s:

1. Contemporary formation sources w ith reasonably well- quantified releases (see Section 1.4.2). These sources are listed in Table 1-11 and release estimates are shown in Table 1-12.

2. Contemporary formation sources without quantified release estimates . These sources are listed in Table 1-12.

3. Reservoir sources with re asonably well-quantified releases

. These sources would have been listed in Table 1-11, but none have y e t been identified.

1-13Table 1-11.Knownandsuspectedsources ofCDDs/CDFs



### 1-14Source categoryContemporary formation sourcesReservoir sourcesQuantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)Quantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)COMBUSTION SOURCESWaste incinerationMunicipal waste combustionHazardouswaste incinerationBoilers/industrial furnacesMedical waste/pathological incinerationCrematoriaSewagesludgeincinerationTire combustionPulpandpaper mill sludgeincineratorsBiogascombustionTTTTTTTTTPower/energy generationVehicle fuel combustion-leadeda-unleaded-dieselWood combustion-residential- industrialCoal combustion-residential-industrial/utilityOil combustion-residential-industrial/utilityTTTTTTTTTOther high-temperature sourcesCementkilnsburninghazardouswasteCementkilnsburningnonhazardouswasteAsphaltmixing plantsPetroleumrefining catalystregenerationCigarette combustionCarbonreactivationfurnacesKraft recoveryboilersManufacture ofball clayproductsGlassmanufacturingLime kilnsRubber manufacturingTTTTTTTTTTTTable 1-11.KnownandsuspectedCDD/CDFsources (continued)



### 1-15Source categoryContemporary formation sourcesReservoir sourcesQuantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)Quantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)Minimallycontrolled oruncontrolled combustionCombustionoflandfill gas inflaresLandfill firesAccidental fires,structuralAccidental fires,vehiclesForest, brush,and strawfiresBackyard barrel burningUncontrolledcombustionofPCBsBurningofcandlesTTTTTTTTMETAL SMELTING/REFININGFerrousmetal smelting/refiningSintering plantsCokeproductionElectric arc furnacesFerrous foundriesTTTTNonferrousmetal smelting/refiningPrimaryaluminumPrimarycopperPrimarymagnesiumPrimarynickelSecondaryaluminumSecondarycopperSecondaryleadTTTTTTTScrap electric wire recoveryTDrumand barrel reclamationTTable 1-11.KnownandsuspectedCDD/CDFsources (continued)



### 1-16Source categoryContemporary formation sourcesReservoir sourcesQuantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)Quantifiable(CategoriesA, Band C)Preliminaryestimate(CategoryD)Notquantifiable(CategoryE)CHEMICAL MANUFACTURING(releases tothe environment)Bleached chemical wood pulp and paper millsMono- through tetrachlorophenolsPentachlorophenolChlorobenzenesChlorobiphenyls (leaks/spills)Ethylenedichloride/vinylchlorideDioxazinedyesand pigments2,4-Dichlorophenoxyacetic acidMunicipal wastewater treatmentTall oil-basedliquidsoapsTTTTTTTTTTBIOLOGICALANDPHOTOCHEMICALPROCESSESTTRESERVOIR SOURCESLandAirWaterSedimentsTTTTAnthropogenic structuresPCP-treated woodTaLeaded fuel productionand the manufacture ofmotor vehicle enginesrequiringleaded fuel for highwayuse are prohibited intheUnited States.(See Chapter 4,Section4.1,for details.)Table 1-12.Inventory ofcontemporary releases (g/yr)ofdioxin-like compounds fromknownsources in theUnitedStates for reference years 2000, 1995, and1987and preliminary release estimates for 2000Source Category2000 InventoryTEQDF-WHO98I-TEQCategoryrating**a**1995 InventoryTEQDF-WHO98I-TEQCategoryrating**a**1987 InventoryTEQDF-WHO98I-TEQCategoryrating**a**2000PreliminaryindicationCategory DratingTEQDF-WHO98RELEASES TOAIRWASTE INCINERATIONMunicipalwaste combustionHazardouswaste incineration83.83.276.33.2AB1,393.55.81,101.35.7BB8,905.15.07,858.85.0BB



### 1-17Boilers/industrial furnacesHalogenacid furnacesMedicalwaste/pathologicalincineration1.80.33781.80.3357CCC0.4NA4870.4NA459CC0.8NA2,5700.8NA2,440CCCrematoria-human0.30.3C0.20.2C0.20.1C-animal<1SewagesludgeincinerationTire combustion9.60.59.40.5BC14.20.1140.1BC5.80.15.80.1BCPulpandpaper mill sludgeincineratorsbBiogascombustion<1POWER/ENERGYGENERATIONVehicle fuel combustion-leaded gasolinec-unleaded gasoline on-road- unleadedgasolineoff-road-dieselon-road (Trucks)- dieseloff-road70.465.46.70.461.7CCC1.64.7NA33.31.34.4NA31.5CCC37.53.6NA27.831.93.3NA26.3CCC-equipment-railroad226.8216.4CC127116.6CC9.45.88.85.5CC-commercial marinevessel4.34C4.84.5C3.83.6CTable 1-12.Inventory ofcontemporary releases (g/yr)ofdioxin-like compounds fromknownsources in theUnitedStates for reference years 2000, 1995, and1987and preliminary release estimates for 2000 (continued)2000Preliminary2000 Inventory1995 Inventory1987 InventoryindicationSource CategoryCategory DTEQDF-CategoryTEQDF-CategoryTEQDF-CategoryratingWHO98I-TEQrating**a**WHO98I-TEQrating**a**WHO98I-TEQrating**a**TEQDF-WHO98Wood combustion-residential11.3d11.3dC15.7d15.7dC22d22dC-industrial41.539.4C26.224.9C26.525.2CCoal combustion-utilityboilers69.570.4B60.160.9B50.951.4B-residentiale<10d-commercial/industrial>10dOil combustion



### 1-18-industrial/utility, residual oil1.71.5C10.79.3C17.815.5C-industrial/utility, distillate oil7.36.3C7.36.4C8.37.2C-institutional/commercial0.70.6C0.80.7C1.51.3Cheating,residualoil-institutional/commercial2.92.5C3.12.7C3.73.2Cheating,distillate oil-residential, distillate oil4.53.6C5.03.9C5.44.2COTHER HIGH-TEMPERATURE SOURCESCementkilnsburninghazardous18.816.6B156.1145.3C117.8109.6CwasteLightweightaggregatekilns1.9d1.8dC2.4d2.4dC3.3d3.3dCburninghazardouswasteCementkilns burning17.216.6C16.615.9C12.712.3CnonhazardouswasteAsphaltmixing plants<1dPetroleumrefiningcatalyst2.22.1C2.22.1C2.22.1CregenerationCigarette combustion0.40.4C0.80.8C11CCarbonreactivationfurnaces0.1d0.1dC0.1d0.1dC0.1d0.1dCKraftrecoveryboilers0.80.8B2.32.3B22BTable 1-12.Inventory ofcontemporary releases (g/yr)ofdioxin-like compounds fromknownsources in theUnitedStates for reference years 2000, 1995, and1987and preliminary release estimates for 2000 (continued)2000Preliminary2000 Inventory1995 Inventory1987 InventoryindicationSource CategoryCategory DTEQDF-CategoryTEQDF-CategoryTEQDF-CategoryratingWHO98I-TEQrating**a**WHO98I-TEQrating**a**WHO98I-TEQrating**a**TEQDF-WHO98MINIMALLY CONTROLLED ORUNCONTROLLED COMBUSTIONfCombustionoflandfill gas>10dLandfill fires>1,000gAccidental fires-structural>10d- vehicles>10dForestand brushfiresh>1,000Backyard barrel burningi498.5472.6C628595C604573C



### 1-19Residential yardwaste burningj<10Landclearingdebrisburning<1000METALLURGICAL PROCESSESFerrousmetal smelting/refining-sinteringplants27.624.4A2825.1B32.729.3C-cokeproduction<10d-electric arc furnaces<100-foundries>10dNonferrousmetal smelting/refining-primarycopper0.3d0.3dB<0.5d<0.5dB<0.5d<0.5dB-secondaryaluminum8.37.8C19.518.3C10.910.2C-secondarycopper0.90.9C271266C983966C-secondarylead2.52.4B1.71.6B1.31.2B- primarymagnesium4.3d4.3dA4.1d4.1dCNANADrumand barrelreclamation0.60.6C0.10.1C0.10.1CTable 1-12.Inventory ofcontemporary releases (g/yr)ofdioxin-like compounds fromknownsources in theUnitedStates for reference years 2000, 1995, and1987and preliminary release estimates for 2000 (continued)2000Source Category2000 InventoryTEQDF-WHO98I-TEQCategoryrating**a**1995 InventoryTEQDF-WHO98I-TEQCategoryrating**a**1987 InventoryTEQDF-WHO98I-TEQCategoryrating**a**PreliminaryindicationCategory DratingTEQDF-WHO98CHEMICAL MANUFACTURE/PROCESSINGSOURCESEthylenedichloride/vinylchloride/PVC5.5d5.5A11.2d11.2ANANAChor-alkali facilities1.8d1.8dA1.8d1.8dCNANATOTAL RELEASES TOAIRk1,314.51,243.6A, B, C3,239.92,857.1A, B, C13,482.612,230.7A, B, CRELEASES TOWATER



### 1-20CHEMICAL MANUFACTURE/PROCESSINGSOURCESBleached chemical wood pulpandpaper millsPOTW(municipal) wastewaterEthylenedichloride/vinylchloride/PVC1.023.1d1.023.9dAA2823.1d2823.9dAC356NA356NAA>10Chor-alkali facilitiesTOTAL RELEASES TOWATERk1.8d25.91.8d26.7AA, B, C1.8d52.91.8d53.7CA, B, CNA356NA356A,B, CRELEASES TOLANDCHEMICAL MANUFACTURING/PROCESSINGSOURCESBleached chemical wood pulpandpaper mill sludgeEthylenedichloride/vinylchloride/PVCMunicipal wastewater treatmentsludgeCommerciallymarketedsewagesludge0.11.478.21.90.11.578.21.9AAAA21.4116.1321.5156.54ABAA14.1NA76.62.614.1NA1033.5AAATable 1-12.Inventory ofcontemporary releases (g/yr)ofdioxin-like compounds fromknownsources in theUnitedStates for reference years 2000, 1995, and1987and preliminary release estimates for 2000 (continued)



### 1-212000Source Category2000 InventoryTEQDF-CategoryWHO98I-TEQrating**a**1995 InventoryTEQDF-CategoryWHO98I-TEQrating**a**1987 InventoryTEQDF-CategoryWHO98I-TEQrating**a**PreliminaryindicationCategory DratingTEQDF-WHO98NANA28.918.4A33.421.3A2,4-Dichlorophenoxyacetic acidTOTAL RELEASES TOLANDk81.681.7A, B, C151.4182.4A, B, C126.7141.9A, B, COVERALL RELEASES TOOPEN AND CIRCULATING1,422.01,352.0A, B, C3,444.23,093.2A, B, C13,965.312728.6A, B, CENVIRONMENTaThe mostreliable estimatesofenvironmental releasesare those sourcesincategoriesA,B,and C.bIncluded inestimate for wood combustion,industrial.cLeaded fuel productionand the manufacture ofmotor vehicle enginesrequiringleaded fuel for highwayuse are prohibited intheUnited States.(See Chapter 4,Section4.1for details.)dEstimate based ona TEQDF-WHO98emissionsestimate.eIncludescombustion ofbituminous/subbituminouscoal and anthracite coal.fRefers toconventional pollutantcontrol, not dioxinemissions control. Veryfewsources listedinthis inventorycontrol specificallyforCDD/CDF emissions.gCongener-specific emissionsdata were not available; the Nordic TEQ estimate wasused asa surrogate for the I-TEQDFemissionsestimate.hIncludesforestwildfiresand prescribed burningfor forestmanagement.iTermrefers tothe burningofresidential waste inbarrels.jIncludesburningofbrushand leaves.kTotal reflects onlythe total ofthe estimates madeinthis report.Categoryratings:A=Characterizationofthe source categoryjudged to beadequatefor quantitative estimationwithhigh confidenceintheemission factorandhighconfidenceinactivity level.B=Characterizationofthe source categoryjudged to beadequatefor quantitative estimationwithmediumconfidenceintheemission factorand at leastmediumconfidenceinactivity level.C=Characterizationofthe source categoryjudged to beadequatefor quantitative estimationwithlowconfidenceineither theemission factorand/or theactivity level.D =Preliminaryindicationofthe potentialmagnitude ofemissionsfrom“Unquantified” (CategoryD) sources;based on extremely limited data, judged tobeclearly nonrepresentative.D estimatesare not included inthe inventoryofsource emissions,but serve the purpose ofhighlightingsourcesinneed ofmoreadequate emissionsinformation.NA= Not available (informationis lacking).POTW=Publiclyownedtreatmentworks orsewagetreatmentplant.

### 4. Reservoir sources with pr e liminary re le ase e stimate s

. These sources are discussed in Chapter 11.

5. Reservoir sources w ithout quantified releases

. These sources are discussed in Chapter 11.

Only contemporary formation sources (num bers 1 and 2 above) are considered for
i n cl usi on i n t h e nat i onal i nvent ory

. R e servoi r sources are not consi d ered because t h ey are not

or ig ina l r e le a se s, but r a the r the r e c i r c ula tion of pa st r e le a se s. To da te , no r e lia ble e stima te s of
rel eases from t h e reservoi r sources have been m a de because i n form at i on i s ei t h er l acki n g or i s ina d e qua te to a llow f o r

e stima te s to be ma de

. This document includes discussions on produc ts that contain diox in-like compounds.
S o me of these products, such as 2,4-D, are consider ed to be sources because they are clearly used
in wa y s tha t r e sult in e nvir onme n ta l r e le a se s (e.g ., they are spray e d onto ag ricultural lands for weed control). I f a release from the product occurs , it is added to the nati onal diox in inventory

. Other products containing diox in-like compounds, such as viny l chloride products, do not appear
to have environmental releases and are not considered sources

. F or all CDD-/CDF -containing products, this document summariz e s the available information a bout contaminati on levels and, where possible, makes estimates of the total amount of CDDs/CDF s produced annually in these products. Estimates of the CDD/CDF TEQ amount s in products are summariz e d in Table 1-13.

Table 1-13. P r oducts containing CDDs/CDF s (g TEQ DF 

### -WH O 98 

### /yr )

P r oduct 2000 1995 1987

Bleached chem ical w ood pulp 0.58 40 505 Ethy lene dichloride/v iny l chloride 0.02 0.02 NA

Chloranil 1.16 64 NA Pentachlorophenol 4,395 4,800 20,000
2,4 - D ichlorophenoxy acetic acid (2,4- D ) a 

### NA 28.9 33.4

T O T A L 4,397 4,933 20,538

a On l y 2
, 4

- D i s co n s i d ered t o b e an en vi ro n m en t a l rel ease.

N A = I n f o r m a tion not a v a ila ble



### 1.2.2. Qu an titative Meth o d f o r In ven t ory of S o u rces Some sour c e ty pe s ha ve a hig h pe r c e n ta g e of f

a c ilitie s with me a sur e d CDD/CDF r e le a se s, such as municipal waste com bustion, haz a rdous waste incinera tion, and cement kilns that burn
haz a rdous waste (air emissions), and wastewater releases from chlorine-bleached pulp and paper
mills. I n addition, some source activitie s have been adequately sample d with respect to levels of

1-22

### lands and 2,4-D applied to ag ricu ltural lands. Other source categ or ies have relatively few tested
f

a c ilitie s a nd/or the a c tivity ha s not be e n c o mpr e he nsive l y e v a l ua te d f o r

diox in r e le a se s. I n the se

c a se s, EPA r e lie s on the use of e mission f a c t or s to e stima te CDD/CDF r e le a se s f r o m the unte ste d

sources. This provides a method of ex trapola tion from tested sources to national estimates of

e nvir onme n ta l r e le a se s. Ma ny of the na tiona l e mission e stima te s, the r e f or e , ha ve be e n de ve lope d using this “top-down” approach.
The f i r st ste p in this a ppr oa c h is to de r i ve from the available emissions monitoring data an emission factor (or series of emission factors) deemed to be representative of the source categ ory (or seg m ents of a sour ce categ ory that differ in, e.g

., config uration, fuel ty pe, air pollution control equipment). The emission fact or r e la te s ma ss of CDDs /CDF s or diox in-like
PCB s r e le a se d into the e nvir onme n t with some me a sur e of a c tivity ( e .g ., kilog r a m s of ma te r i a l

pr oc e sse d pe r y e a r , ve hic l e mile s tr a v e l e d pe r y e a r , lite r s of wa ste w a t e r disc ha r g e d pe r y e a r )

. I t is
de ve lope d by a v e r a g ing the e mission f a c t or s f o r

the te ste d f a c ilitie s or a c tivitie s within the particular classification of s ources. F o r ex ample, mass burn MW Cs equipped with dry scrubbers ( D Ss) c o mbine d with f a br ic f ilte r s ( F F s) will ha ve a n a v e r a g e e mission f a c t or de r i ve d f r o m the
tested facilities within this sour ce classification. This averag e e mission factor is then multiplied by the measure of activity for the nontested facilitie s in the class (e.g ., total kilog r ams of material processed by these facilities annua lly ). F i nally , emissions are summed for the tested facilities
and nontested facilities. I n g e nera l, this procedure can be repres ented by the followinge quations:

E

to ta l 

### = 

### 3 E t e s t e d, I 

### % 3 E unt e s t e d, I 

### (1-2)

E

to ta l 

### = 

### 3 E t e s t e d, I 

### % 3 (E F

i * 

### A i 

### ) unt e s t e d 

### (1-3)

where:
E to tal 

### = annual emissions from all facilities (g TEQ/y r)
E t e s t e d, I 

### = annual emissions from all tested facilities in class I (g TEQ/y r)
E unt e s t e d, I 

### = annual emissions from all unteste d facilities in class I (g TEQ/y r)
EF i 

### = me a n e mission f a c t or f

o r

te ste d f a c ilitie s in c l a ss I ( g TEQ/kg )
A i 

### = a c tivity me a sur e f o r

unte ste d f a c ilitie s in c l a ss I ( k g / y r )

F i g u res 1-2 throug h 1-4 and 1-6 throug h 1-8 depict the various source categ ories and their emission factors, activity le vels, and annual emissions fo r reference y ears 1987, 1995, and 2000, respectively

, in I

- TEQ and W HO-TEQ units. F i g u res 1-5 and 1-9 depict comparisons of the

e stima te d I

- TEQ a nd WHO- TEQ a i r e missions f o r

the se y e a r s.

1-23E m i

s si

o n

S

o u

r ce B e s t E s ti

m a te o f T o tal

A n n u al "A cti v i t y " ( t e s t

e d

/ t o t a l u n it

s ) I

- TEQ Em i s s i

o n Fa c t or ( t ho us a n d m e t r i c t

o ns

/ y r or A nn ua l I

- TE

Q E

m i

s s i

on ( n g/

k g or

n g/ L ) m i l l i o n L/ y r ) (g I

- T

E Q/

yr

)

Mu ni c i p al W as t e C o mb us t i on ( 1 9 / 11 3)

Me di c a l W as t e I n c i ne r at i on ( 8 / 500 0)

S ec ond ar y C op per S m e l t i ng ( 2 / 4)

B a c k y a rd B a rre l B u rn i n g (N A )

C e m ent K i l ns B ur n i n g H az W a s t e ( 10 / ? )

U t i l i ty / Ind us t ri a l C o a l C o mbu s ti on (1 1 / ? )

O n- r o ad Lea de d Ga s F ue l C o m bus t i on (? / ?)

Iron O r e S i n ter P l an ts ( 2 / ? )

On -r oa d D i es el Fu el C omb u s ti o n ( N A )

I n du s t r i al W o o d B u rn i ng ( 9 / ? )

R e s i de nt i al W o od B u r ni ng (7 / 250 00 000 )

O f f

- r oa d D i es el F uel C om b us t i o n ( N A )

U t i l i ty / Ind u s t ri a l R e si du al O i l C o mb us ti o n (? / ? )

S ec ond ar y A l um i nu m S m el t i n g ( 6 / 6 7)

C e m ent K i l n s N o t B u rn i n g H a z W a s t e ( 1 5 / ?)

U t i l i ty / Ind u s t ri a l D i sti l l a te O i l C o mbu s ti on (>2 / ? )

S ew a ge S l ud ge I nc i n er at i o n ( 13 / 1 99 )

H a z ar do us W as t e I n c i n er at i on (1 7 / 1 71- 2 27)

O n- r o ad U n l ead ed Gas Fu el C om b us t i o n ( ? / ? )

Ma nu f ac t ur e o f E D C / V C ( ? / ?)0.00.101.0010.00100.001000.0010000.00100000.001101001,00010,000100,0001,000,0001.0010.00100.001,000.0010,000.00100,000.001,000,000.00

Th e f i g ures i n c l ud e sources wi t h an nua l I

- T E Q em i s si o n est i m a t e s g re at er t h an 5 g I- T E Q / y r

i n
Lo w C onf i de nc e Medi um C o nf i de nc e H i gh C o nfi d e n c e Le ge n d

o n e o r bo t h of t he Re f e ren c e Y e ars 1 987 o r 1 995

. De r i va t i on o f t h e em i ssi o n f a ct ors
an d an n ua l "A c t i v i t y " e s t i m a t e s ( e

. g

. , k g of was t e i n c i ne r a t e d) ar e p r e s e nt ed i n t h e f o l l ow i n g
c h ap t e r s o f t hi s r e p or t

. T he d i f f e r e nc e i n ba r s h ad i n g i n d i cates t h e de g ree o f co nf i den c e i n t h e
e s t i m a t e

. T h e s e t of n u m b e r s f o l l o w i n g t h e source cat ego ri e s i ndi cat e s t h e num b e r of f a ci l i t i es/ s i t e s f o r w h i c h em i s si on t e st d a t a are av ai l a bl e versus t h e num b e r of f a ci l i t i es/ s i t es i n th e ca te g o r y

. A q u e s ti o n m a r k ( ? ) i n d i ca te s th a t t h e p r e c i s e n u m b e r o f f a ci l i t i e s/s i te s
cou l d not be e s t i m a t e d. 

### F i gu re 1-2. E s tim a ted CDD/CDF I-T E Q em ission s to air f r om com b u s tion

sou rces in th e Un ited S t ates f o r ref eren ce year 1987 (municipal solid waste i n ci nerat i on i s current l y referred t o as municipal waste combustion).

Some sour c e c a t e g or ie s a r e ma de up of f

a c ilitie s tha t va r y wide ly in te r m s of de sig n a n d operating conditions. F o r these sources, as ex pl ained above, an attemp t was made to create subcateg ories that g r ouped facilitie s with common features and then to develop se parate emission factors for each subcateg ory

. I m plicit in this procedure is the assu mption that facilities with similar desig n and operating c onditions should have similar C DD/CDF release potential. Fo r

m o st source cat eg ori e s, however, t h e speci fi c com b i n at i on of feat ures t h at cont ri but es m o st t o

1-24Em i s s i on S o urc e (t es te d / to ta l u n i ts )

M uni c i pal W a s t e C ombus ti on (39 / 130)

M edi c al W as t e I nc i nerati on (20 / 2400)

S ec on dary C opper S mel t i n g (2 / 3)

B a c k y a rd B a rrel B u rni ng (N A )

C em ent K i l ns B urni ng H az W as t e (10 / 34)

U t ility / Industr i a l C oal C o mbus tion ( 11 / ?)

On-road Leaded Gas Fuel C om bus ti on (? / ?)

Iron Ore S i nter P l ants (2 / 11)

On-road D i es el F uel C om bus t i on (N A )

Indus tri al W oo d B urni ng ( 9 / ?)

R es i denti al W ood B urni ng (7 / 25000000)

Off-road D i es el Fuel C om bus ti on (N A )

U t ility / Industr i a l R e sidual Oil C o mbust i on ( ? / ?)

S ec on dary A l um i num S m el ti ng (6 / 76)

C em ent K i l ns N ot B urni ng H az W as t e (15 / 178)

U t ility / Industr i a l D i stillate O il C o m bustion ( > 2 / ?)

S ew age S l udge Inc i nerat i on (13 / 2 57)

H az ardous W as t e Inc i nerati on (17 / 162)

On-road U nl eaded Gas F uel C om bus t i on (? / ?)

M anuf a c ture of E D C / V C (? / ?) B est E

st

i m ate o f To t a l

A nnua l "

A c t

i v

i t y " I

- TEQ Em i s s i on Fa c t o r ( t ho us a nd m e t r i c t ons / y r or A n nua l I

- TEQ Em i s s i on ( n g/

k g or ng/ L) m ill io n L /y

r ) (g I -T

E Q

/ y r )0.010.11101001000100001000001101001,00010,000100,0001,000,0001101001000100001000001000000

T he f i g u res i n c l ude s o u rc e s wi t h a nnu al I -T E Q em i s s i on es t i m a t e s g r eat er t ha n 5 g I- T E Q / y r i n Le gen d

on e o r bo t h o f t he R ef e re nc e Y ear s 198 7 or 19 95. D er i v at i o n of t h e em i s s i o n f ac t or s Low C onfi denc e an d a nnu al "A c t i v i t y " es t i m at es (e. g. , k g of was t e i nc i n er at ed) a re p re s e nt ed i n t h e f ol l o w i n g Medi um C onfi denc e
c hap t e rs of t hi s r epo rt

. T he di f f ere nc e i n bar s h adi n g i ndi c at es t he de g re e of c onf i de nc e i n t h e H i gh C onfi denc e

e s ti m a te

. T h e se t o f n u m b e r s fo l l o w i n g th e so u r ce ca te g o r i e s i n d i ca te s t h e n u m b e r o f f ac i l i t i es / s i t es f or whi c h e m i s s i on t es t d at a ar e avai l abl e ve rs u s t he nu m ber of f ac i l i t i es / s i t es i n t he c a t e gor y

. A qu es t i o n m ar k (? ) i ndi c at es t h at t he pr ec i s e num ber o f f ac i l i t i e s / s i t es
c oul d no t be es t i m at ed.



### F i gu re 1-3. E s tim a ted CDD/CDF I-T E Q em ission s to air f r om com b u s tion

sou rces in th e Un ited S t ates f o r ref eren ce year 1995 (municipal solid waste i n ci nerat i on i s current l y referred t o as municipal waste combustion).

CDD/CDF or diox in-like PCB releases is not well understood. Therefore, how to best
subcat eg ori z e a source cat eg ory was oft e n probl em at i c

. For each subcat eg ori z ed source cat eg ory in this document, a discussion is presented about the variability in desig n and operating conditions, what was known about how these featur es contributed to CDD/CDF or diox in-like
P C B rel eases, and t h e rat i onal e for creat i n g subcat eg ori e s.

1-25Emis s i on So ur c e ( t e st

ed

/ t

o t

a l u n it s )

Muni c i pal W as t e C om bus ti on ( 195 / 251)

Medi c al W as t e I nc i nerat i on (22 / ?)

S ec ondar y C op per S m el t i ng (1 / 2 )

B a ckya r d B a r r e l B u r n in g ( N A )

C e m ent K i l ns B urni ng H az W as t e (1 0 / ?)

U t ility / Indus tr ial C o a l C o m bust i on ( 11 / ? )

On-road Leaded Gas Fuel C o m bus ti on (0 / 0)

Iron Ore S i nt er P l ant s ( 2 / 11)

On-road D i es el F uel C om bus ti on (N A )

Indus tri al W ood B urni ng ( 9 / ?)

R e s i denti a l W oo d B urni ng (19 / 2500 0000)

Off -road D i es el Fu el C om bus t i on (N A )

U t ility / Indus tr ial R e s i dual Oil C o m bustion ( ? / ?)

S ec ondar y A l um i num S m el t i ng (6 / ? )

C e m ent K i l n s N o t B u rni ng H a z W a s t e (15 / ?)

U t ility / Indus tr ial D i s t illate Oil C o m bust i on ( > 2 / ?)

S ew age S l ud ge In c i nerat i on (14 / ?)

H a z ar dous W as t e In c i nerat i on (22 / 132)

On-road U nl eaded Gas F uel C om bus ti on (? / ?)

Manufac ture of E D C / V C (8 / 12 ) Be st E

s tim a t e o f T o t

a l An n u a l " Ac t

iv

it y " I

- TEQ E

m i

s s i on Fa c t or (th o u sa n d m e t r i c to n s / y r o r A n n u a l I

- TEQ Em i s s i on ( ng/

k g or n g/ L) milli o n

L

/ yr

) ( g I- T

E Q

/ yr

)0.010.101.0010.00100.001000.0010000.00100000.001101001,00010,000100,0001,000,0000.11101001000100001000001000000

T h e fi g u re s i n cl u d e sou r ce s wi th an nu al I-T E Q em i ssi o n esti m a tes gre a t e r th an 5 g I

- T E Q/y r i n Le ge n d

on e o r b o t h o f th e R e f e r e n c e Y e ar s 19 87 or 19 95. D e r i vat i on of t h e em i s s i o n f a c t or s Low C onf i denc e an d a n n u a l "A c t i v i t y " e s ti m a t e s ( e

. g ., k g of w a s t e i n c i n e r a t e d) ar e pr e s en te d i n t h e f o l l o w i n g Medi um C onfi d enc e
c h ap te rs o f t hi s re po r t

. T he d i f f e re nc e i n ba r s h ad i n g i nd i c at es t he de gr ee o f c o nf i d en c e i n t he H i gh C onfi denc e

e s t i m a te

. T h e set of n u m b e r s fo llo wi ng th e so ur ce ca te go r i e s in dica tes the n u m b e r o f f a c i l i t i es / s i t es f o r wh i c h em i s s i on t es t da t a ar e a v a i l a bl e v er s u s t h e nu m b er of f ac i l i t i es / s i t es in th e c a te g o r y

. A q u e s t i o n m a r k ( ? ) in d i c a te s t h a t t h e p r e c is e n u m b e r o f f a c ilit ie s / s i te s
c o ul d no t b e e s ti m a t e d

.



### F i gu re 1-4. E s tim a ted CDD/CDF I-T E Q em ission s to air f r om com b u s tion

sou rces in th e Un ited S t ates f o r ref eren ce year 2000.

The e mission f a c t or s de ve lope d f o r

the inve ntor y a r e inte nde d to be use d f o r

e stima ting

tota l e missions f o r

a

sour c e c a t e g or y r a the r tha n e missions f r o m individua l f a c ilitie s. EPA ha s

m a de uncert a i n t y det e rm i n at i ons for each of t h ese em i ssi on fact ors, based, i n part , on t h e assumption that by apply i ng them to a g r oup of facilities, the poten tial for overestimating or underestimating individual f acilities will, to some ex tent, be self-compensating

. This means that
i n usi n g t h ese em i ssi on fact ors one can pl ace si g n i f i cant l y g r eat er confi d ence i n an em i ssi on

1-26Muni ci pal W a ste C o m bus ti on
M edi cal W a st e I n c i nerati o n
S e condary C opper S m el ti ng
B a c k yard B a rrel B u rni n g
C e m e n t Kiln s Bu r n in g H a z W a s t e
Utilit y / I ndust r i a l C oal C o m b us tion
On-roa d Leaded Gas Fuel C o m b us ti on
Iron Ore S i nter P l ant s
On-road D i es el Fuel C o m bus ti on
I ndust ri a l W ood B u rni n g
R e si dent i a l W ood B u rni n g
Off-road D i es el Fuel C o m b us ti on
U t ility / Indus trial Residual Oil C o m b us tion
S e condary A l um i num S m el ti ng
Ce m e n t Kiln s No t Bu r n in g H a z W a s t e
U t ility / Indus trial Dist illate Oil C o m b us tion
S e w a ge S l udge Inc i nerati o n
H a z a rdous W a st e I n c i nerati o n
On-road U n l e aded Gas Fuel C o m b us ti on
M anufac t ure of E D C / V C

0. 1 1 10 10 0 10 00 10 000

1987 1995 2000



### F i gur e 1- 5. C o m p ar ison of e st i m a t e s of annual I- TEQ e m issions t o air (g I-TEQ/yr) f o r ref eren ce years 1987, 1995, an d 2000.

estimate for a class than in an estimate for any individual facility

. Given the limited amount of data available for deriving emission factors and the limitati ons of our understanding about facility -specific conditions that determine form ation and control of diox in-like compounds, the current state of knowledg e cannot support the deve lopment of emission factors that can be used to accurately estimate emissions on an individual facility -specific basis. The emission factors
devel oped for each of t h e cat eg ori e s di scussed i n t h i s nat i onal em i ssi ons i nvent ory are l i s t e d i n I TEQ and TEQ DF 

### -W HO 98 

### in Tables 1-14 and 1-15, respectively

.

1.2.3. Conf idence Ratings
Ea c h sour c e e mission c a l c u la tion r e quir e d e stima te s of a n e mission f a c t or a nd a n a c tivity
level. F o r each emission source, the quantity a nd quality of the available information for both

vary considerably

. Consequently , it is impor tant that emission es timates be accompanied by
some indicator of the uncertainties associated with their development. F or this reason, a ­

1-27Em is s io n S o u r c e (t est

e d

/ t o tal u n i ts)

M unic i pal W as te C om bus tion (19 / 1 05)

M edic al W as t e I n c i neration (8 / 500 0)

S ec ondary C oppe r S m elting (2 / 4 )

B a ckya r d B a r r e l B u r n in g ( N A )

C em en t K i lns B urning H az W as te (10 / ?)

U t ility / I n dust r i a l C oal C o m bustion ( 11 / ?)

O n-road Leaded G a s Fuel C om bus tion (? / ?)

Iron O r e S i nter P l ants (2 / ?)

O n -road D i es el F u e l C o m b us t i o n (N A )

Indus trial W ood B urning (9 / ? )

R es i dential W oo d B urning (7 / 25000000)

O f f-road D i es el Fuel C o m bus tion (N A )

U t ility / I n dust r i a l R e sidua l O il C o mbustion ( ? / ?)

S ec ondary A l um in um S m e l t i ng (6 / 67)

C em en t K i lns N ot B urni ng H az W a s te (15 / ?)

U t ility / I n dust r i a l D i stillate Oil C o m b u s tion ( > 2 / ?)

S ew age S l udge Inc i neration (13 / 199)

H az ardous W as t e Inc i neratio n (17 / 171-227 )

O n-road U n leaded G as Fuel C o m bus tion (? / ?)

M anufac ture of E D C / V C (? / ?) Be s t E

s t

i ma te o f Tot a l

A nnua l " A c t

i v

i t y " W

H O

- T E Q

E

m i

s s i

on Fa c t or ( t hous a nd m e t r i c

t

ons

/ y r or A n nua l W

H O- TE Q E m i

s s i on ( ng

/ k g or ng/ L) m i l l i on L/ y r ) (g WH O

- T E Q

/ y r )0.010.11101001000100001000001101001,00010,000100,0001,000,0001101001000100001000001000000

T he f i g ure s i nc l u de s o urc e s wi t h ann ual W H O- T E Q em i s s i o n e s t i m at e s gr eat er t han 5 g W H O

- T E Q/ y r i n Legen d

one or b ot h of t he Re f er enc e Y ear s 198 7 o r 1995

. D er i v at i on of t he em i s s i on f ac t ors Low C o nf i denc e and ann ual " A c t i v i t y " e s t i m at es ( e. g. , k g of was t e i nc i ner at e d) ar e p r es e nt e d i n t h e f ol l owi ng M e d i um C o n f i d en c e
c hapt er s of t hi s r epor t

. T he di f f er enc e i n bar s had i n g i ndi c at es t he de g r ee of c onf i de nc e i n t h e H i gh C onfidenc e

es t i m at e. T he s et of num b ers f ol l owi ng t he s our c e c at ego ri es i nd i c at es t he nu m ber of f ac i l i t i es / s i t es f or whi c h em i s s i on t e s t dat a are av ai l abl e v er s us t he num b er of f ac i l i t i e s / s i t es i n t he c at egor y

. A ques t i o n m a rk ( ?) i ndi c at es t hat t he pr ec i s e nu m ber of f a c i l i t i es / s i t e s
c oul d not be es t i m a t e d.



### F i gu re 1-6. E s tim a ted CDD/CDF WHO-T E Q em ission s to air f r om

com b u s tion sou rces in th e Un ited S t ates f o r ref eren c e year 1987 (municipal solid wa ste inc i ne r a tion is c u r r e ntly r e f e rred to as municipal waste combustion).

qua lita tive c onf ide n c e r a ting sc he me wa s de ve lope d a s a n inte g r a l pa r t of the e missions e stima te with the f o llowing c onside r a tions.
Em ission f actor. The unc e r ta inty in the e mission f a c t or e stima te de pe nds pr ima r ily on how we ll the te ste d f a c ilitie s r e pr e se n t the unte ste d f a c ilitie s. I n g e ne r a l, c onf ide n c e in the

e mission f a c t or inc r e a se s with inc r e a se s in the numbe r of te ste d f a c ilitie s r e la tive to the tota l
number of facilities. Variability in terms of phy sical desig n a nd operating conditions within a

1-28r E m i

s s i on S ourc e ( te s t ed

/ to ta l u n i t s )

a l W a s t e C o mbus tion (39 / 1 30)

W as te Inc i nera t io n (20 / 240 0)

a ry

C o pper S m elting (2 / 3)

r d Barrel B u rni ng (N A )

K ilns B urn ing H az W as te (10 / 3 4)

ndus trial C oal C om bus tion (11 / ?)

d Lead ed G as Fuel C om bus tion (? / ?)

e S i nter P l a n ts (2 / 11)

d D i es el Fuel C om bus tion (N A )

a l W ood B urni ng (9 / ?)

n t i al W ood B urn ing (7 / 2 5000000 )

d D i es el Fuel C ombus tion (N A )

ndus trial R e s i dual O il C o mbus tion (? / ? )

a ry A l uminum S m elting (6 / 76)

K ilns N ot B urning H az W as t e (15 / 178)

ndus trial D i s t i llate O il C o m b u s tio n (>2 / ?)

e S l udge Inc i ne ration (13 / 2 57)

o us W as te Inc i neration (17 / 162)

d U nleade d G as F u el C ombus tion (? / ?)

c ture of E D C /V C (? / ?) B e st E

s ti

m a te o f T o t

al

An n u al "Ac t i v

i t y" W

H O- TE Q E

m i

s s i on Fa c t or ( t hous a nd m e t r i c t ons / y r or A nnua l W

H O

- TE Q E m i

s s i

o n ( n g/

k g or ng/ L) m i l l i on L/ y r ) (g WH O

- T E Q

/ yr

)0.010.11101001000100001000001101001,00010,000100,0001,000,0001101001000100001000001000000

g u r es i nc l ude s our c e s wi t h annua l W H O

- T E Q e m i s s i o n es t i m a t es gre at er t han 5 g W H O

- T E Q / y r i n Legend bo t h of t h e R ef er enc e Y ears 1987 or 19 95. Der i v at i on of t h e e m i s s i o n f a c t or s Low C onfidenc e n nu al "A c t i v i t y " es t i m at es ( e. g

. , k g o f was t e i nc i ner at e d) ar e pr es ent ed i n t he f ol l owi ng Medi um C o nfidenc e
e rs of t hi s r epo rt

. T he di f f er enc e i n bar s h adi n g i n d i ca te s th e d e g r ee of c on f i d enc e i n t h e H i gh C o n f i d en c e

a t e. T he s et o f nu m bers f ol l o w i ng t he s ou r c e c a t eg ori es i ndi c at es t he num ber of

e s / s i t es f o r whi c h em i s s i on t es t d at a ar e av ai l a bl e v er s us t he num ber of f ac i l i t i es / s i t es
c at eg ory

. A que s t i on m a rk ( ?) i ndi c a t es t ha t t h e pr ec i s e num b er of f ac i l i t i es / s i t es
n ot be es t i m at ed.



### F i gu re 1-7. E s tim a ted CDD/CDF WHO-T E Q em ission s to air f r om

com b u s tion sou rces in th e Un ited S t ates f o r ref eren c e year 1995.

c l a ss or subc la ss must a l so be c onside r e d. The mor e va r i a b ility a m ong f a c ilitie s, the le ss

c onf ide n c e tha t a te st of a n y sing le f a c ility is r e pr e se n ta tive of tha t c l a ss or subc la ss. The qua lity of the supporting documentation also affects uncertainty

. W h enever possible, orig inal

eng i neering test reports were us ed. Peer-reviewed reports from th e open literature were also used for developing some emission factors. I n so me cases, however, draft reports that had underg one more limited review were also used. I n a fe w cases, unpublished references (such as personal
communication with ex perts) were used and are clearly noted in the tex t

.

1-29E m i

s si o n S o u r ce ( te ste d / to ta l u n i ts )

M un i c i pal W as t e C om bus ti on (195 / 251)

M ed i c al W as t e I nc i nerati on (22 / ?)

S ec ondary C opper S m el ti ng ( 1 / 2 )

B a ckya r d B a r r e l B u r n in g ( N A )

C em ent K i l ns B urni ng H az W as t e (20 / 22)

U t i l i t y / I ndus tri al C oal C om bus t i on (11 / ?)

On-road Leaded Gas F uel C om bus ti on (0 / 0)

Iron O r e S i nter P l ant s (4 / 11)

On-road D i es el F uel C om bus ti on (N A )

Indus t r i al W ood B u rni ng (9 / ?)

R es i denti al W ood B urni ng (19 / ?)

Off-r oad D i es el Fuel C om bus ti on (N A )

U t i l i t y / I ndus tri a l R e s i dual Oi l C o m bus ti on (? / ?)

S ec ondary A l um i num S m el ti ng (6 / ?)

C em ent K i l ns N ot B urni ng H az W as t e (15 / ?)

U t i l i t y / I ndus tri al D i s t i l l at e Oi l C om bus ti on (>2 / ?)

S ew age S l udge Inc i nerati on ( 14 / ?)

H az ardous W as t e Inc i nerati on (22 / 132 )

On-road U nl eaded Gas Fuel C om bus t i on (? / ?)

M an ufac t ur e of E D C / V C / P V C (8 / 12) B est E

st

i m a te o f Tot a l

A nnu a l " A c t

i v

i t y " W

H O- TE Q E

m i

s s i o n Fa c t or ( t hou s a n d m e t r i c t

o ns

/ y r o r A nnu a l W

H O- TEQ Em i s s i

o n (n g

/ kg

o r

n g

/ L ) milli o n

L

/ y r ) (g WH O-T E Q/

yr

)0.010.101.0010.00100.001000.0010000.00100000.001101001,00010,000100,0001,000,0000.11101001000100001000001000000

T he f i g ur es i nc l ud e s our c e s wi t h an nua l W H O

- T E Q em i s s i on e s t i m at es gr ea t e r t han 5 g W H O -T E Q / yr i n Leg end

on e or bot h o f t h e Re f er e nc e Y e ar s 1 98 7 or 1 99 5. D er i v at i on o f t h e em i s s i on f ac t or s Low C onfi denc e an d an nua l "A c t i v i t y" es t i m a t e s ( e

. g

. , k g of wa s t e i n c i n e r a t e d ) ar e p r e s ent ed i n t h e f o l l o wi ng Medi um C onf i denc e
c ha pt er s of t hi s r e por t

. T he d i f f er en c e i n bar s ha di ng i nd i c a t e s t h e deg r ee of c o nf i d enc e i n t he H i gh C onf i denc e

es t i m at e

. T he s et of n um b er s f ol l owi ng t he s o ur c e c at eg or i es i n di c at es t he n um b er o f f a c i l i t i e s / s i t es f o r whi c h e m i s s i o n t e s t d at a ar e av ai l abl e v er s us t h e nu m be r o f f ac i l i t i es / s i t e s i n t h e ca te g o r y

. A q u e st i o n m a r k ( ? ) i n d i ca te s th a t th e p r e c i s e n u m b e r o f fa ci l i ti e s/ si te s
c ou l d not be e s t i m a t e d.



### F i gu re 1-8. E s tim a ted CDD/CDF WHO-T E Q em ission s to air f r om

com b u s tion sou rces in th e Un ited S t ates f o r ref eren c e year 2000.

Activity level. The unc e r ta inty in the a c tivity le ve l e stima te wa s judg e d pr ima r ily on the
basis of the ex tent of the underly i ng data. Estimates derived from comprehensive survey s ( i nc luding most f a c ilitie s in a sour c e c a t e g or y ) we r e a ssig n e d hig h c onf ide n c e

. As the numbe r of
f

a c ilitie s in the sur v e y r e la tive to the tota l de c r e a se d, c onf ide n c e a l so de c r e a se d. The qua lity of the supporting documentation also affects uncerta inty

. P eer-reviewed reports from the open
lite r a tur e ( i nc luding g ove r n me nt a nd tr a d e a ssoc i a tion sur v e y da ta ) we r e c onside r e d to be the

1-30Muni c i p al W a s t e Comb us ti on
Medi c al W as t e I n c i nerati on
Sec on dary Cop per S m el ti ng
B a cky a r d B a rre l B u rn in g
Cement Ki l ns B ur n i ng Haz W a s t e
U t ilit y /

I n d u st r i a l C o a l C o m b u s t i o n
O n- r oad Le ade d G as F uel Com bus ti on
I r o n O r e S i nt er P l an t s
O n-r oad D i es el F uel Comb us ti on
I n dus tr i a l W ood B u r n i n g
Res i d enti al W ood B ur n i ng
O f f

- r oa d D i es el F uel Comb us ti on
U t ilit y /

I n d u s t ri a l R e sid u a l Oil C o m b u s t io n
S e c ond ar y Al u m i num Sme l ti ng
Cemen t K i l n s Not B u r n i ng Haz W a s t e
U t ilit y / I n d u s t r ia l Di st il la t e Oil C o m b u s t io n
S ewage S l udg e I n c i nerati on
Ha z a r dou s W a s t e I n c i nerati o n
O n- r o ad Unl e ade d G as F uel Comb us ti on
Ma nufac tur e o f E D C / V C

0.1 1 10 100 1 000 10 000

19 87 199 5 2 000



### F i gur e 1- 9. C o m p ar ison of e st i m a t e s of annual WHO- TEQ e m issions t o air (g WHO-TEQ/yr) f o r ref eren ce years 1987, 1995, an d 2000.

most reliable. However, as with the emission factor estimates, draft reports that had underg one more limited review were used in some cases, a nd in a few cases unpublished references such as personal communication with ex pe rt s were used. These are cl earl y not ed i n t h e t e x t

.

1.2.3.1. Rating Sc he m e The c onf ide n c e r a ting sc he me shown in Ta ble 1- 16 r e pr e se n ts the qua lita tive c r ite r i a use d to assig n a hig h, medium, or low confidence ra ting to e mission f a c t or s a nd a c tivity le ve ls f o r those sour c e c a t e g or ie s f o r

whic h e mission e stima te s c ould be r e lia bly qua ntif ie d. The ove r a ll

c onf ide n c e r a ting a ssig n e d to a n e missions e stima te wa s de te r mine d by the c onf ide n c e r a ting s assig ned to the corresponding activity level and e mission factor. I f the lowest rating assig ned to

e ithe r the a c tivity le ve l or the e mission f a c t or is “ h ig h,” the n the c a te g o r y r a ting a ssig n e d to the

e mission e stima te is hig h ( C a t e g or y A)

. I f the lowe st r a ting a ssig n e d to e ithe r the a c tivity le ve l

1-31Table 1-14.I-TEQDFemission factors used to develop national emission inventoryestimates ofreleases to air



### 1-32Source categoryI-TEQDFemission factorEmissionfactor unit200019951987WASTE INCINERATIONMunicipal waste combustionHazardouswaste incinerationBoilers/industrial furnacesHalogenacid furnacesMedicalwaste/pathologicalincinerationCrematoria-human-animalSewagesludgeincinerationTire combustionPulpandpaper mill sludgeincineratorsb2.822.121.210.803630a4100.116.650.28238.2a3.830.64598a17,0006.940.282573a3.830.641,706a17,0006.940.282ng TEQ/kg wastecombustedngTEQ/kgwaste combustedngTEQ/kgwaste combustedngTEQ/kgwaste feedng TEQ/kg wastecombustedngTEQ/bodyngTEQ/kganimalng TEQ/kg drysludgecombustedngTEQ/kgtirescombustedPOWER/ENERGYGENERATIONVehicle fuel combustion-leadedc- unleaded-dieselWood combustion-residential-industrialCoal combustion-utilityOil combustion-industrial/utilityNA1.51720.50.56–13.2d0.0790.2451.517220.56–13.2d0.0790.2451.517220.56–13.2d0.0790.2pgTEQ/kmdrivenpg TEQ/kmdrivenpgTEQ/kmdrivenngTEQ/kgwood combustedngTEQ/kgwood combustedngTEQ/kgcoal combustedngTEQ/Loil combustedOTHER HIGH-TEMPERATURE SOURCESCementkilnsburninghazardouswasteLightweightaggregatekilnsCementkilnsnot burninghazardouswastePetroleumrefiningcatalyst regenerationCigarettecombustionCarbonreactivationfurnacesKraftrecoveryboilers1.4442.060.271.520.00043–0.00291.20.0291.04–28.58e0.271.520.00043–0.00291.20.0291.04–28.58e0.271.520.00043–0.00291.20.029ng TEQ/kg clinkerproducedng TEQ/kg wastefeedngTEQ/kgclinker producedngTEQ/barrel reformer feedngTEQ/cigarettengTEQ/kgofreactivated carbonngTEQ/kgsolidscombustedTable 1-14.I-TEQDFemission factors used to develop national emission inventoryestimates ofreleases to air(continued)Source categoryI-TEQDFemission factorEmissionfactor unit200019951987MINIMALLY CONTROLLED ORUNCONTROLLED COMBUSTIONBackyard barrel burningf72.872.872.8ngTEQ/kgwaste combustedMETALLURGICAL PROCESSESFerrousmetalsmelting/refining-sinteringplantsNonferrous metalsmelting/refining-primarycopper-secondaryaluminumsmelting-secondarycopper smeltingg-secondarylead smeltersDrumand barrelreclamation0.55–4.14<0.314.90.05–8.3116.50.55–4.14<0.314.90.05–8.3116.50.55–4.14<0.314.90.05–8.3116.5ngTEQ/kgsinterngTEQ/kgcopper producedngTEQ/kgscrapfeedng TEQ/kg scrapconsumedngTEQ/kglead producedngTEQ/drumCHEMICAL MANUFACTURING/PROCESSINGSOURCESEthylenedichloride/vinylchloride0.95ang TEQ/kg EDC producedaDifferentemissionfactorswere derived for varioussubcategories withinthis industry; the value listedis a weightedaverage.bIncluded intotalfor wood combustion,industrial.cLeaded fuel productionand the manufacture ofmotor vehicle enginesrequiringleaded fuel for highwayuse are prohibited intheUnited States.(See Chapter 4,Section4.1,for details.)dEmissionfactor of0.56 ngI-TEQDF/kgused for nonsalt-ladenwood;emissionfactor of13.2 ngI-TEQDF/kgused for salt-ladenwood.eEmissionfactor of1.04 ngI-TEQDF/kgused for kilnswithair pollutioncontroldevice (APCD) inlettemperatureslessthan232°C;emissionfactor of28.58 ngI-TEQDF/kgused for kilnswithAPCDinlettemperaturesgreater than232°C.fIncludesthe burningofbrushand leafresidential yard waste.gFacility-specific emissionfactorswereused rangingfrom3.6 to 16,600 ngI-TEQDF/kg scrapconsumed.



### 1-33Table 1-15.TEQDF-WHO98emission factors used to develop nationalemission inventoryestimates ofreleasesto air



### 1-34Emission source categoryTEQDF-WHO98emission factorEmissionfactor unit200019951987WASTE INCINERATIONMunicipal waste combustionHazardouswaste incinerationBoilers/industrial furnacesHalogenacid furnacesMedicalwaste/pathologicalincinerationCrematoria -humanb-animalSewagesludgeincinerationTire combustionPulpandpaper mill sludgeincineratorsc3.102.131.210.836630a4340.126.740.28143.4a3.880.65633a17,0007.040.281644a3.880.651,811a17,0007.040.281ng TEQ/kg wastecombustedngTEQ/kgwaste combustedngTEQ/kgwaste combustedngTEQ/kgwaste feedng TEQ/kg wastecombustedngTEQ/bodyngTEQ/kganimalng TEQ/kg drysludgecombustedngTEQ/kgtirescombustedPOWER/ENERGYGENERATIONVehicle fuel combustion-leadedd- unleaded-dieselWood combustion-residential- industrialeCoal combustion-utilityOil combustion-industrial/utilityNA1.61820.5b0.6–13.20.780.23531.61822b0.6–13.20.0780.23531.61822b0.6–13.20.0780.23pgTEQ/kmdrivenpg TEQ/kmdrivenpgTEQ/kmdrivenngTEQ/kgwood combustedngTEQ/kgwood combustedngTEQ/kgcoal combustedngTEQ/Loil combustedOTHER HIGH-TEMPERATURE SOURCESCementkilnsburninghazardouswasteLightweightaggregatekilnsCementkilnsnot burninghazardouswastePetroleumrefiningcatalyst regenerationCigarettecombustionCarbonreactivationfurnacesKraftrecoveryboilers1.6351.990.261.590.00044–0.0031.2b0.0281.11–30.7f0.261.590.00044–0.0031.2b0.0281.11–30.7f0.261.590.00044–0.0031.2b0.028ng TEQ/kg clinkerproducedng TEQ/kg wastefeedngTEQ/kgclinker producedngTEQ/barrel reformer feedngTEQ/cigarettengTEQ/kgofreactivated carbonngTEQ/kgsolidscombustedTable 1-15.TEQDF-WHO98emission factors used to develop nationalemission inventoryestimates ofreleasesto air (continued)Emission source categoryTEQDF-WHO98emission factorEmissionfactor unit200019951987MINIMALLY CONTROLLED ORUNCONTROLLED COMBUSTIONBackyard barrel burningg76.8b76.8b76.8bng TEQ/kg wastecombustedMETALLURGICAL PROCESSESFerrousmetalsmelting/refining-sinteringplantsNonferrous metalsmelting/refining-primarycopperb-secondaryaluminumsmelting-secondarycopper smeltingh-secondarylead smeltersDrumand barrelreclamation0.62–4.61<0.315.20.05–8.8117.50.62–4.61<0.315.20.05–8.8117.50.62–4.61<0.315.20.05–8.8117.5ngTEQ/kgsinterngTEQ/kgcopper producedngTEQ/kgscrapfeedng TEQ/kg scrapconsumedngTEQ/kglead producedngTEQ/drumCHEMICAL MANUFACTURING/PROCESSINGSOURCESEthylenedichloride/vinylchloride0.95a,bng TEQ/kg EDC producedaDifferentemissionfactorswere derived for varioussubcategories withinthis industry; the value listedis a weightedaverage.bCongener-specific data were not available; the TEQDFemissionfactor wasused asa surrogate for the TEQDF-WHO98emissionfactor.cIncluded intotalfor wood combustion,industrial.dLeaded fuel productionand the manufacture ofmotor vehicle enginesrequiringleaded fuel for highwayuse are prohibited intheUnited States.(See Chapter 4,Section4.1,for details).eEmissionfactor of0.6 ngI-TEQDF/kgused for non-salt-ladenwood;emissionfactor of13.2 ngI-TEQDF/kgused for salt-ladenwood.fEmissionfactor of1.11 ngI-TEQDF/kgused for kilnswithair pollutioncontroldevice (APCD) inlettemperatureslessthan232°C;emissionfactor of28.58 ngI-TEQDF/kgused for kilnswithAPCDinlettemperaturesgreater than232°C.gThis termrefers tothe burningofresidential waste inbarrels.hFacility-specific emissionfactorswere used rangingfrom3.6 to 16,600 ngTEQDF-WHO98/kg scrapconsumed.



### 1-35

### Table 1-16. Conf idence rating sche m e f o r U.S. em ission estim a tes

C o n f id en ce ratin g A c tivity level estimate E m ission f a ctor estimate
Cat e gori e s/ m e di a f or w h i c h rel eases can be reasonabl y quant i f i e d

H i g h D eriv ed from com p rehensiv e

surv ey D eriv ed from com p rehensiv e surv ey

Medium B ased on estim ates of av erag e plant activ ity lev e l and num ber of plants or lim ited surv ey D e riv e d from testing at a lim ited but reasonable num ber of facilities believ ed to be representativ e of source categ ory
Low B ased on data j udg ed possibly nonrepresentativ e D e riv e d from testing at only a few

, possibly nonrepresentativ e facilities or from sim ilar source categ ories

Cat e gori e s/ m e di a f or w h i c h rel eases cannot be reasonabl y quant i f i e d

P r elim inary estim ate B ased on extrem ely lim ited data, j udg ed to be clearly nonrepresentativ e B ased on extrem ely lim ited data, j udg ed to be clearly nonrepresentativ e Not quantified N o data av ailable ( 1) Arg u m ent based on theory but no data, or (2) D ata av ailable indicating form ation but not in a form that allows dev eloping an em ission factor



### or t h e em i ssi on fact or t e rm i s “m edi u m , ” t h en t h e cat eg ory rat i n g assi g n ed t o t h e em i ssi on

e stima te is me dium ( C a t e g or y B )

. I f the lowe st r a ting a ssig n e d to e ithe r the a c tivity le ve l or the

e mission f a c t or is “ l ow,” the n the c a t e g or y r a ting a ssig n e d to the e mission e stima te is low (Categ ory C). I t is emphasiz e d that this confid ence rating scheme should not be interpreted as a

st at i s t i cal m easure, but rat h er as subj ect i v e j udg ment of the relative uncertainty among sources. For m a ny source cat eg ori e s, ei t h er em i ssi on factor informati on or activity level information was inadequate to support development of reliable quantitative release estimates for
one or more media. F o r some of these source cat eg ori e s, suffi ci ent i n form at i on was avai l a bl e t o

ma ke pr e limina r y e stima te s of e missions of CDDs/CDF s or diox in- like PCB s; howe v e r , the

c onf ide n c e in the a c tivity le ve l e stima te s or e mission f a c t or e stima te s wa s so low tha t the y c ould not be included in the sum of qua ntified emissions from sources w ith confidence rating s of A, B

,
a nd C. The se pr e limina r y e stima te s we r e g i ve n a n ove r a ll c onf ide n c e r a ting of D. The

pr e limina r y r e le a se e stima te s f o r

sour c e s with a c onf ide n c e r a ting of D a r e g i ve n in the r i g h tmost column of Table 1-12. B ecause these are order-of-mag nitude estimates, they are made for 2000 only

. As preliminary estimates of source mag n itude, they can be used to help prioritiz e

1-36

### future research and data collec tion. The actual mag n itude of e missions from these sources could be sig n ificantly lower or hig h er than these preliminary estimates. A lthoug h EPA has chosen not to include them in the more thoroug hly character iz ed emissions of the national inventory , some of these poorly characteriz ed sources have the pot ential of being major cont ributors of releases to
the environment. I t is important to presen t these estimates because th ey may help determine priorities for future data collec tion efforts. As the uncertainty around these sources is reduced,
the y will be inc l ude d in f u tur e inve ntor y c a l c u la tions.
F o r othe r sour c e s, some inf o r m a tion e x ists tha t sug g e sts tha t the y ma y r e le a se diox in- like compounds; however, the available data were judg ed to be in sufficient for developing any
qua ntita tive e missions e stima te

. The se sour c e c a t e g or ie s we r e a ssig n e d a c onf ide n c e r a ting of E
and also were not included in th e national inventory (see the “Not quantifiable” column in Table 1-11).

1.3. CONCLUSIONS
1.3.1. Total Environm ental Releases
Na tionwide e mission e stima te s of g r a m s I

- TEQ DF 

### and TEQ DF 

### -W HO 98 

### released to the open and circulating environment of the United States are presented in Table 1-12. F o r the y ear 2000, EPA draws the following conclusions:

• The total releases in the inventory (Categ ories A, B

, and C) were 1,422 g TEQ DF 

### WH O 98 

### / y r. These were dom i n at ed by rel eases t o t h e ai r (92%). Most of t h e ai r releases were from combustion sources. Tabl e 1-17 presents a ranking of sources for 2000, 1995, and 1987 based on the mag nitude of environmental release. The top three sources were backy a rd barrel burning of refuse (498.5 g

, 32% of total), MW I s (378 g
, 27%), and the incineration and la nd application of municipal wastewater treatment sludg e (89.7 g
, 5%).

• There is a sig n ificant potential for releas e of diox in-like compounds from Categ o ry D

sources. However, these sources a curren tly poorly characteriz ed. The most important Categ o ry D sources are forest fires and acci dental fires at MSW landfills. Research is recommended to confirm e missions from these sources and to provide a more
accurat e assessm ent of rel eases.

• A total of 18 contemporary formation sour ces were cl assi fi ed as C a t e g o ry E. I nformation sug g e sts these may be sources of diox in-like compounds, but it is insuf f i c i e n t to ma ke a na tiona l e stima te of r e le a se s. Additiona l r e se a r c h on the se sources is recommended in orde r to a d e qua te ly ide n tif y

the m a s a c t ua l sour c e s a nd to
pr ovide da ta f

o r

e stima ting r e le a se s.

1-37Table 1-17.Ranking ofsources ofdioxin-like compoundsbased on environmental releases (fromhigh to low)for reference years 2000, 1995, and1987



### 1-38200019951987ReleasesPercentReleasesPercentReleasesPercentSource (released to)(grams)of totalSource (released to)(grams)of totalSource (released to)(grams)of totalBackyard barrel498.535.1Municipalwaste1,393.540.5Municipalwaste8,905.163.8burningofrefuse(air)combustion(air)combustion(air)Medical378.026.6Backyard barrel628.018.2Medicalwaste/2,570.018.4waste/pathologicalburningofrefuse(air)pathological incinerationincineration(air)(air)Municipal wastewater89.76.3Medical487.014.1Secondarycopper983.07.0treatmentsludge,landwaste/pathologicalsmelters (air)applicationandincineration(air)incineration(land, air)Municipalwastecombustion(air)83.85.9Secondarycoppersmelters (air)271.07.9Backyard barrelburningofrefuse(air)604.04.3Coal fired-utility69.54.9Cementkilnsburning156.14.5Bleached chemical370.12.7boilers (air)hazardouswaste (air)wood pulpand papermills (land,water)Diesel heavy-dutytrucks (air)65.44.6Municipal wastewatertreatmentsludge,landapplicationandincineration(land andair)133.33.9Cementkilnsburninghazardouswaste (air)117.80.8Industrialwood41.52.9Coal fired-utility60.11.7Municipal wastewater85.00.6combustion(air)boilers (air)treatmentsludge,landapplicationandincineration(air, land)Dieseloff-road33.12.3Ethylene35.71.0Coal fired-utilityboilers50.90.4equipment, ships,dichloride/vinyl(air)trains, tractors (air)chloride production(land, air, water)Table 1-17.Ranking ofsources ofdioxin-like compoundsbased on environmental releases (fromhigh to low)for reference years 2000, 1995, and1987 (continued)



### 1-39200019951987Source (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalEthylenedichloride/vinylchlorideproduction(water,land, air)30.02.1Diesel heavy-dutytrucks (air)33.31.0Automobiles usingleaded gasoline (air)37.50.3Sinteringplants(air)27.61.9Bleached chemicalwood pulpand papermills (land,water)30.00.92,4-Dichlorophenoxyacetic acid (land)33.40.2Cementkilns burninghazardouswaste (air)18.81.32,4-Dichlorophenoxyacetic acid (land)28.90.8Sinteringplants(air)32.70.2Cementkilns burningnonhazardouswaste(air)17.21.2Sinteringplants(air)28.00.8Diesel heavy-dutytrucks(air)27.80.2Residential woodcombustion(air)11.30.8Industrialwoodcombustion(air)26.20.8Industrialwoodcombustion(air)26.50.2Secondaryaluminumsmelting(air)8.30.6Dieseloff-roadequipment:ships,trains, tractors (air)23.80.7Residentialwoodcombustion(air)22.00.2Industrial/utilityoilcombustion,distillateoil (air)7.30.5Secondaryaluminumsmelters (air)19.50.6Dieseloff-roadequipment:ships, trains,tractors (air)19.00.2Automobiles usingunleaded gasoline(air)7.00.5Cementkilns burningnonhazardouswaste(air)16.60.5Industrial/utilityoilcombustion,residual oil(air)17.80.1Residential heating,distillate oil (air)4.50.3Residentialwoodcombustion(air)15.70.5Cementkilnsburningnonhazardouswaste(air)12.70.1Primarymagnesiumproduction(air)4.30.3Industrial/utilityoilcombustion,residualoil (air)10.70.3Secondaryaluminumsmelting(air)10.90.1Table 1-17.Ranking ofsources ofdioxin-like compoundsbased on environmental releases (fromhigh to low)for reference years 2000, 1995, and1987 (continued)



### 1-40200019951987Source (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalChlor alkali facilities(air, water)3.60.3Industrial/utilityoilcombustion,distillateoil (air)7.30.2Industrial/utilityoilcombustion,distillate oil(air)8.30.1Hazardouswasteincineration(air)3.20.2Hazardouswasteincineration(air)5.80.2Residential heating,distillate oil (air)5.40.1Institutional/commercial heating,distillateoil (air)2.90.2Residential heating,distillate oil (air)5.00.1Hazardouswasteincineration(air)5.00.04Secondaryleadsmelting(air)2.50.2Automobiles usingunleaded gasoline(air)4.70.1Institutional/commercialheating,distillate oil(air)3.70.03Petroleumrefiningcatalyst regeneration(air)2.20.2Primarymagnesiumproduction(air)4.10.1Automobiles usingunleaded gasoline (air)3.60.03Lightweightaggregatekilns burninghazardouswaste (air)1.90.1Chlor-alkali facilities(air, water)3.60.1Lightweightaggregatekilnsburninghazardouswaste(air)3.30.02Boilers/industrialfurnaces(air)1.80.1Institutional/commercial heating,distillate oil(air)3.10.1Petroleumrefiningcatalyst regeneration(air)2.20.02Industrial/utilityoilcombustion,residualoil (air)1.70.1Lightweightaggregatekilns burninghazardouswaste (air)2.40.1Kraft recoveryboilers(air)2.00.01Bleached chemicalwood pulpand papermills (land,water)1.10.1Kraft recoveryboilers(air)2.30.1Industrial/utilityoilcombustion,residualoil(air)1.50.01Secondarycoppersmelting(air)0.90.1Petroleumrefiningcatalyst regeneration(air)2.20.1Secondaryleadsmelting(air)1.30.01Table 1-17.Ranking ofsources ofdioxin-like compoundsbased on environmental releases (fromhigh to low)for reference years 2000, 1995, and1987 (continued)



### 1-41200019951987Source (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalSource (released to)Releases(grams)Percentof totalKraft recoveryboilers(air)0.80.1Secondaryleadsmelting(air)1.70.05Cigarette combustion(air)1.00.01Institutional/commercial heating,residual oil(air)0.70.05Automobilesusingleaded gasoline (air)1.60.05Boilers/industrialfurnaces(air)0.80.01Drumand barrelreclamation(air)0.60.04Industrial/utilityoilcombustion,residualoil (air)0.80.02Primarycopper smelting(air)0.5<0.01Tire incineration(air)0.50.04Cigarette combustion(air)0.80.02Crematoria, human(air)0.2<0.01Cigarette combustion(air)0.40.03Primarycoppersmelting(air)0.50.01Carbonreactivationfurnaces(air)0.1<0.01Unleaded gasolineoff-roadequipment(air)0.40.03Boilers/industrialfurnaces(air)0.40.01Tire incineration(air)0.1<0.01Halogenacid furnaces(air)0.30.02Crematoria, human(air)0.20.01Drumand barrelreclamation(air)0.1<0.01Primarycoppersmelting(air)0.30.02Tire incineration(air)0.1<0.01Crematoria, human(air)0.30.02Carbonreactivationfurnaces(air)0.1<0.01Carbonreactivationfurnaces(air)0.10.01Drumand barrelreclamation(air)0.1<0.01Automobiles usingleaded gasoline (air)00.00TOTAL1,422.01003,444.210013,965.3100

### • R eleases from reservoir sources could sig n if icantly add to the inventory

. However, environmental reservoirs as sources of the redistribution of previously formed diox ins into the open and circulating environmen t are currently poorly understood and poorly charact eri z ed. Thi s report sug g e st s t h at urban runoff t o surface wat e r and rural soi l erosi on t o surface wat e r can be si g n i f i cant re servoi r sources. R e l eases from reservoi rs (air, sediment, water, and biota) could not be relia bly quantified, g i ven the lack of inf o r m a tion in this a r e a

.

• The amount of diox in-like PCB s releas ed from man-made s ources remains poorly characteriz ed. Only a total of 19.5, 78.5, a nd 51.5 g of PCB TEQ c ould be quantified for the y ears 2000, 1995, and 1987, respectively

. To date, only sewag e sludg e has been adequately characteriz ed in terms of the amount of diox in-like PCB s that may be rel eased from a source.

1.3.2. Tim e Trends A sig n if ic a n t r e duc tion in tota l CDD/CDF e nvironmental releases has occurred since
1987. EPA’s best estimates of rel eases of CDDs/CDF s to air, water, and land from reasonably quantifiable sources (Categ ories A, B
, and C) are approx imately 1,422 g TEQ DF 

### -W HO 98 

### in reference y ear 2000; 3,444.2 g in reference y ear 1995; and 13,965.3 g in reference y ear 1987.
F r om 1987 to 2000 there was an approx imately 90% re duction in releases to all media. Most of
the reduction in diox in releases (75%) occurred between 1987 and 1995.
I n 1987 and 1995, municipal waste combusti on was the leading source of diox in

em i ssi ons t o t h e U.S

. envi ronm ent ; however, b ecause of reduct i ons i n di ox i n em i ssi ons from
MW Cs, it dropped to the fourth ranked source in 2000. B u rning of domestic refuse in backy a rd
burn barrels remained fair ly constant over the y ears, but in 2000 it emerg e d as the larg est source
of diox in emissions.
Reductions in environmental re leases of diox in-like com pounds are attributed primarily
to reductions in air emissions from MW Cs, MW I s , and cement kilns burning haz a rdous waste, and in wastewater discharg ed into surface wa ters from pulp and paper mills using chlorine.
These reductions have occurred from a combina tion of reg u latory ac tivities (see Section 1.1.2), improved emission controls, impr oved industrial technolog ies, vol untary actions on the part of industry , and the closing of a number of anti quated facilities.

1.3.3. S o u rces Not In clu d e d in th e In ven t ory Sig nificant amounts of the diox in-like com pounds produced annually in the United States

are not consi d ered rel eases t o t h e open and ci rc ulating environment and are not included in the national inventory

. Ex amples include diox in- like compounds g e nerated internal to a process but
de str o y e d be f o r e r e le a se a nd wa ste str e a m s tha t a r e dispose d of in a ppr ove d la ndf ills.

1-42

### The only product judg ed to have the potentia l for environmental release—and therefore considered for the inventory

— was the herbicid e 2,4-D. Release estimates are provided for 1987
and 1995. Since 1995, the chemical manufacturer s of 2,4-D have been undertaking voluntary actions to sig nificantly reduce the diox in content of the product. No information is available on
the ex tent of these reductions and, therefor e, no release estimate could be made for 2000. Reg a rding other products, data are presente d on the amounts of CDDs/CDF s contained in bleached pulp, ethy lene dichloride/viny l chlori de, P C P

- treated wood, and diox az ine dy es and pig m ents. None of these products, however, was considered to have release potential; they were not included in the inventory

. A number of contemporary forma tion sources were classified as D or E and therefore were not included in the inventory

. The larg es t contemporary formation Categ o ry D sources are
forest fires and accident al fires at MSW landfills. Taken tog e ther, these sources have the
pote n tia l to sig n if ic a n tly inc r e a s e the pr e s e n t inve ntor y if pr e limina r y r e le a s e e s tima te s a r e confirmed. The possibility remains that tr uly undiscovered sources ex ist. Many of the sources that
are wel l

- accept e d t oday were di scovered onl y i n t h e past 20 y ears. For ex am pl e, C DDs/ C DFs i n stack emissions from MW Cs were not detect ed until the late 1970s; CDDs/CDF s in the
wastewater effluent from bleach ed pulp and paper mills were found unex pectedlyin the mid1980s; iron ore was not recog n iz ed as a source until the early 1990s.

1.3.4. F orm ation Theory Current theory proposes that CDDs/CDF s ar e formed within the cool-down reg i on of combustion processes, either de novo or from diox in precursors. De novo sy nthesis involves solid-phase reactions with car bon, chlorine, and ox y g en on co mbustion-g e nera ted particles promoted by copper chloride as a cataly s t. A le ss efficient but plausible formation process is the

g a s-phase formation from precursors cataly z ed by t h e presence of a t r ansi t i on m e t a l such as copper chloride. The ideal temperatures for de novo diox in formation are between 200 and
400°C. Reducing temperatures to below 200°C, especially at the air pollution control device,
will minimize diox in f o r m a tion a nd r e le a se s f r o m c o mbustion sour c e s. Chlor i ne sour c e s pr e se n t in feeds are necessary for diox in formation. Ex pe riments sug g e st that a chlorine content of 1% in
the f e e d /f ue l is the thr e shold f o r

a

dir e c t r e lationship to diox in formation from combustion sources, i.e., a chlorine content 

### $ 1% is strong ly correlated to th e amount of diox in formed, but a
chlorine content <1% is not. However, in we ll- de sig n e d, we ll- c ontr o lle d, and well-operated fullscale combustion sy stems there doe s not appear to be a direct relationship between the amount of chlorine present in the waste and the am ount of diox in emissions from the stack.

1-43

### Controversy ex ists reg a rding the role of PVC in the formation of CDDs/CDF s during municipal waste combustion. Ex perimental evidence sug g e sts th at PVC combustion g e nerates hy drog en chloride g a s (HCl) and diox in precurs ors such as chlorobenz enes and chlorophenols, both of which may contribute to diox in formation. HCl is a prog enitor of chlorine radicals that then participate in the diox in formation chemis try

. Precursors are foundation molecules to diox in
formation. I f PVC is the only source of chlorine and diox in precursors during the combustion of
MSW
, then the removal of PVC may reduce the amount of diox in formed and emitted.
Howe ve r , the c o mple x mix tur e of ma te r i a l s in MSW pr ovide s suf f i c i e n t c h lor i ne f o r de novo

sy nthesis, and diox in precursors are formed as products of the incomplete combustion of the

wa ste c onstitue n ts. The r e f or e , the e limina tion of PVC f r o m the wa ste pr ior to c o mbustion would

not ne c e ssa r ily e limina t e the f o r m a tion a nd e missions of CDDs/CDF s f r o m munic i pa l wa ste
combustion. Current information strong ly sug g e sts th at rel eases of C DDs/ C DFs t o t h e U.S

. environment occur principally from anthropog enic activities. However, sc ientific studies have
ide n tif ie d the possibility of na tur a l f o r m a tion of some CDDs/CDF s ( e .g ., in ba ll c l a y )

.

1.3.5. Con g en er P r of iles of CDD/CDF S o u rces This document presents cong ener profiles for a number of sources, as shown in F i g u re 1­
10. These profiles show the relative amounts of CDD/CDF cong eners in e nvironmental releases. These profi l e s can be useful for (1) i d ent i f y i ng source cont ri but i ons t o near-fi el d ai r

m easurem ent s of C DDs/ C DFs, (2) com p ari n g s ources, and (3) providing insig hts into the
f

o r m a tion of CDDs/CDF s in th e rel eases. There are num erous procedures for deriving a
cong ener profile, and there is no sing le ag reed-upon convention (C leverly et al., 1997; L o rber et al., 1996; Hag e nmaier et al., 1994).
F o r this report, cong ener pr ofiles were develope d pr ima r ily by c a lc ula ting the r a tio of specific 2,3,7,8-substituted CDDs/CDF s in the emissions or product to the total (Cl 4 

### - C l 8 

### )
CDDs/CDF s. W ith respect to combustion sources , the profiles were deri ved by dividing the

cong ener-speci fi c em i ssi on fact ors by t h e t o t a l (C l 4 

### - C l 8 

### ) C DD/ C DF em i ssi on fact or for each

te ste d f a c ility a nd the n a v e r a g ing the c ong e n e r pr of ile s de ve lope d f o r

a ll te ste d f a c ilitie s within

t h e com bust o r t ype. For chem i cal processes and com m e rci a l chem i cal s, C DD/ C DF profi l e s were ty pically g e nerated by dividing averag e cong ener c onc e n tr a tions ( ppt) in the c h e mic a l by the tota l
C DDs/ C DFs present

. P r ofi l e s for sel ect source cat eg ori e s are present e d i n Fi g u re 1-10.

1-444D 23

7 8 5D 12378

6D 1 2 34 7 8 6D

12 36 7 8 6D

12 3 78 9

7 D 1

2 34 67 8

8 D 12346789 12346789 4F 2378

5F

1 2 378

5F 23

47 8 6F 123478

6F 12

36 7 8 6F 123789

6F

2 346

7 8
7F

1 23 46 78

7 F 1 2 34789

8 F 123

4 6789 4D 23 7 8 5D 1 2 378 6D

1 23 47 8

6 D 12 36 78

6 D 1 23 789
7D 123

4 6 7 8

8D 1 2 346

7 89

4 F 2 3 78

5 F 1 2 37 8

5 F 2347

8

6 F 123

4 7 8

6 F 1

2 36 7 8

6 F 1 237

8 9

6 F 234

6 7 8

7 F 123

46 7 8

7 F 1 234

7 89

8F

12 34 67 8 9

4 D 2 3 7 8 5D 12

3 78 6D 12

3478

6 D 1 2 3 6 7 8 6D 123

789

7 D 123

46 7 8

8 D 1 2346

789

4 F 2

3 7 8 5F 12

3 78

5 F 2

3 4 78

6 F 1 2 347

8 6F 12

3 6 78

6 F 1 2 378

9 6F 234

678

7 F 1 2 3 4 678
7F

1 23 4 7 89

8 F 1 2 3 4 6 7 89 4D

23 7 8 5D 12

378

6 D 12

3 4 7 8 6D

1 2 3 6 7 8 6D 1 23 78 9

7 D 1 2 3 4 678

8D 12

3467

89

4 F 2 378

5F

1 23 7 8 5F 23

4 7 8

6 F 1 2 347

8

6 F 1 2 367

8 6F

1 2 3 7 89

6 F 2 3 467

8

7 F 1 2 346

7 8
7F

1234

789

8F 123

46 7 89 -

0% 2% 4% 6% 8% 10 % 12 %

0% 2% 4% 6% 8% 10% 12% 14% 16% -

0% 2% 4% 6% 8% 10 % 12 %

0% 2% 4% 6% 8% 10% 12% 14% 16% M u ni ci pal W as t e Com b ustor w i t h Hot E S P M u ni ci pal W as t e Com b ustor w i t h D S / F F

0% 1% 2% 3% 4% 5% 6% 7% 8%

0% 2% 4% 6% 8% 10% 12%

0% 1% 2% 3% 4% 5% 6% 7% 8% H a zardous W a ste In c i nerators M edical/hos pital W a ste In c i n e rators

0% 2% 4% 6% 8% 10% 12%



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p dioxins and c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s .

On the basis of inspection and comparisons of t h e averag e C DD/ C DF cong ener profi l e s across combustion and noncombustion sources, the fo llowing observations we re made (Cleverly et al., 1997) (these g e neraliz ations are derived from this data se t, and their application bey ond
the se da ta is unc e r ta in) :

• I t appears that combustion sources e mit all 2,3,7,8-substituted CDDs/CDF s, althoug h in va r y ing pe r c e n ta g e s of tota l CDDs/CDF s.

• I n combustion source emissions, 2,3,7,8-TC DD is usually 0.1 to 1% of total CDDs/CDF s. The ex ception is stack emi ssions from industrial oil-fired boilers, where the available but limited data indicate that 2,3,7,8-TCDD constitutes an
averag e of 7% of total CDD/CDF emissions.

1-454D 2 3 7 8

5 D 12

37 8

6 D 1 23 4 7 8

6 D 1 23 67 8 6D 1 23 78 9

7 D 1

2 3 4 6 78

8D 1 2 3 4 67 89

4F 237

8

5 F 1

2 3 7 8

5 F 23

4 7 8

6 F 1

2 3 4 7 8

6 F 123

6 7 8

6 F 123

78 9

6 F 234

67 8

7 F 12 3 4 6 7 8
7F 1 2 3 4 7 89

8F 12

346

7 8 9

4 D 2378

5D

12378

6 D 123

478

6 D 123678

6D 123

789

7 D 123

46 78

8 D 1234678 9

4 F 2378

5F 1237

8 5F

23478

6 F 12347

8

6 F 12367

8

6 F 12378

9 6F 234678

7F 1 2 34 67 8
7F 12

347

89

8F 1234678 9

4 D 23

78

5 D 12

3 78

6 D 12

34 78 6D 12

36 78 6D 1 23 78 9

7 D 123

4 6 78

8D 1 2 3 46 7 8 9 4F

23 78 5F

123

7 8 5F 23

4 7 8 6F 12

3 4 7 8

6 F 12

3 67 8 6F 1 237

8 9 6F 23

4 6 7 8

7 F 123

4 6 78
7F

1 2 3 47 89

8F 1 23 4 67 89 4D 2378

5D 123

78

6 D 12 3 47 8 6D 12

36 7 8 6D

12 37 8 9
7D

123

4678

8D 12346789 12346789

4 F 23 78 5F 1237

8 5F

23 478

6 F 1 2 347

8

6 F 1236

78 6F 1 237

89 6F

2 3 4678
7F

1234678

7F 1234

789

8F 1234

6789 0% 1% 1% 2% 2% 3% 3%

0% 5% 10

% 15

% 20

% 25

%

0% 1% 1% 2% 2% 3% 3% Ba c k y a r d Re f u s e Ba r r e l Bu r n i n g Ind u strial W o o d Waste C o m b u stion

0% 5% 10 % 15 % 20 % 25 %

P o rtla n d C e m e n t K iln s P o rtla n d C e m e n t K iln s B u rn in g H a za rd o u s W a ste

5%

4% 30 %

25 % 4%

20 % 3%

3%

15 % 2%

10 % 2%

1%

5% 1%

0% 0%



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p - d ioxins and c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s ( c ont inue d)

.

• I t cannot be concluded that OCDD is th e dominant cong ener for all combustiong e ne r a te d e missions of CDDs/CDF s. OCDD domina t e s tota l e missions f r o m ma ssburn MW Cs that have DSs and F F s for diox in control, industrial oil-fired boilers, industrial wood-fired boilers, unleaded g a so line combustion, diesel fuel combustion in trucks, and sewag e sl udg e incinerators. The dominant cong eners for other combustion sources are 1,2,3,4,6,7,8-HpCDF in emissions from mass-burn MW Cs equipped with hot-sided electrostatic precipitators (ESPs), haz a rdous waste incineration, and secondary aluminum sme lters and 2,4-D salts and esters; OCDF in emissions from medical waste incinerati on and industrial/utility coal-fired boilers; 2,3,4,7,8-PeCDF in cement kilns burning haz a rdous waste; and 2,3,7,8-TCDF in cement kilns not burning haz a rdous waste.

1-464D 2 378

5D

1 2378

6 D 1234

7 8

6 D 123

67 8

6 D 123

7 8 9
7D 1 2 3 4678

8D 123467 89

4F

2 37 8 5F 1237

8

5 F 2 3 47 8

6 F 123

478

6 F 1 2 3 678

6 F 1

2 3 7 89

6 F 234

67 8
7F 1 2 34 678
7F 12

3 4 78 9

8F 123467 8 9 4D 23 78 5D 1 2378

6D 1 2 34 78 6D

1 2 3678

6 D 123

7 8 9

7 D 1 2 34 67 8

8 D 123

4 6 78 9

4 F 23

7 8

5 F 123

78 5F 2 3 478

6 F 1 2 347

8 6F 12367

8 6F

1 23789

6F 2346

7 8

7 F 123

4678

7 F 12347

89

8F 1 23467

89

4 D 2

37 8

5 D 1

2 378 6D 123

4 78 6D 123

678 6D 1 23789

7 D 1 2 346

7 8

4 F 237

8 5F 1 2 3 7 8 5F 2 3 47 8 6F

1 23478

6 F 123

67 8 6F 1 2 378

9 6F 2 3 4 6 78
7F 1234

6 7 8
7F 1234

789

8D 1 23 4 67 89

8F 12

3 4 678

9

4 D 237

8

5 D 1

2 378 6D 123

4 78 6D

1 2 3 678

6 D 1

23 7 8 9

7 D 1 2 346

7 8

8 D 1

23 4 6 789

4 F 2378

5 F 1 2 3 78 5F 2 3 478

6 F 1 2 347

8 6F 12367

8 6F 1 23789

6F 2346

7 8

7 F 123

4 678

7 F 12347

8 9

8F 12

3 4 67 89 0% 5% 10% 15% 20% 25% -

0% 10 % 20 % 30 % 40 % 50 % 60 % 70 %

0% 5% 10% 15% 20% 25% C o a l

- f ir e d E l ec tr i c a l G e ne ra t i ng F a c ilit i e s O il- f i re d E l e ct ric al G e n e ra t i ng F a cilit i e s

0% 10 % 20 % 30 % 40 % 50 % 60 % 70 %

0% 5% 10% 15% 20% 25% 30% 35% 40% 45%

0% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 %

0% 5% 10% 15% 20% 25% 30% 35% 40% 45% Pe t r ol eu m Ref i n e ri es B l each ed Pul p and Pap e r M i ll s ( e f f l u e nt )

0% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 %



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p - d ioxins and c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s ( c ont inue d)

.

Evide n c e f o r

a

shif t in the c ong e n e r pa tte r n s pote n tia lly c a u se d by the a pplic a tion of different air pollution control sy stems within a combustion source ty pe can be seen in the case of mass-burn MW Cs. F o r mass-bur n MW Cs equipped with hot-sided ESPs, the most prevalent CDD/CDF cong eners are 1,2,3,4,6,7,8-Hx CDF ; OCDD; 1,2,3,4,6,7,8-HpCDD/1,2,3,4,7,8-Hx CDF ; 2,3,4,6,7,8-Hx CDF / OCDF ; 1,2,3,6,7,8­ Hx CDF

. The most pr e v a l e n t c ong e n e r s e mitte d f r o m MWCs e quippe d with DS/F F are OCDD; 1,2,3,4,6,7,8-HpCDD; 1,2,3,4,6,7,8-HpCDF ; OCDF ; and 2,3,7,8­ TCDF /1,2,3,4,7,8-Hx CDD; 2,3,4,6,7,8-Hx CDF

.

• T here i s evi d ence of m a rked di fferences in the distribution of CDD/CDF cong eners between cement kilns that burn haz a rdous waste and those that do not. W h en not burning haz a rdous waste as supplemental fu el, the dominant cong eners appear to be 2,3,7,8-TCDF ; OCDD; 1,2,3,4,6,7,8-HpCDD, and OCDF

. W hen burning haz a rdous waste, the dominant cong ener s are 2,3,7,8-PeCDF ; 2,3,7,8-TCDF ; 1,2,3,4,7,8­

1-474D 2 3 78 5D 123

7 8

6 D 1 2 3 47 8

6 D 12

36 7 8

6 D 1 2 3 78 9
7D

12 3 4 67 8

8D

12

34 678

9

4 F 2 378

5 F 12

3 7 8 5F

2 3 47 8

6 F 1 234

78

6 F 12 3 6 78

6 F 1 237

89

6 F 23 4 6 78
7F 1 2 34 6 7 8

7 F 1 234

78 9

8F

1 2 3 4 67 8 9

4 D 2 3 78 5D 123

7 8 6D 12

3 4 78 6D

1 23 6 78

6 D 1 2 3 78 9
7D 1 2 34 6 78
8D

1 2346

7 8 9 4F 2 3 78 5F 12378

5F 23478

6F

1 2 3 478 6F

1 23678

6F 1 2 37 8 9

6 F 234

6 7 8
7F 1234678

7F 1234789

8 F 1 2 3 46789

4D 2 37 8

5 D 12 3 7 8 6D

12 34 7 8 6D 1 23 67 8 6D

1 237

89
7D

1 2 3 46 78
8D

12 3 4 6 78 9 4F 23

78

5 F 12 37 8 5F

23 4 7 8

6 F 12 3 4 7 8

6 F 12

36 7 8

6 F 12

37 89

6 F 23

46 78

7 F 12 34 6 7 8

7 F 12 3 4 78 9

8 F 1

2 3 467

8 9 4 D 23

7 8 5D 1 2378

6D 1 23 478 6D 123678

6D 12

37 8 9
7D 1234

6 78
8D

1 2 34 6 78 9 4F 2378

5 F 12378

5 F 23478

6F

12347

8 6F 123

6 78 6F

1 23 789 6F 2 3 4678
7F 1 2 34678

7F

1 2 34 7 89

8 F 12

3 46789 Sec o n d ar y Al um in um S m e l te r s Sec o n d ar y Coppe r S m el te r s

14 %

12 %

10 %

8%

6%

4%

2%

0% 5%

5%

4%

4%

3%

3%

2%

2%

1%

1%

0%

Sec on d ar y L e ad Sm e l t ers I r on F o un dries

0. 0 7% 3. 000 0 %

0. 0 6% 2. 500 0 %

0. 0 5%
2. 000 0 %

0. 0 4%

1. 500 0 % 0. 0 3%

1. 000 0 % 0. 0 2%

0. 0 1% 0. 500 0 %

0. 0 0% 0. 000 0 %



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p - d ioxins and c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s ( c ont inue d)

.

x C DF ; and 1,2,3,4,6,7,8-HpCDD. W h en burning haz a rdous waste, OCDD and
OCDF a r e minor c onstitue n ts of sta c k e missions.

• The cong ener profile of 2,4-D salts and esters seems to mimic a combustion source profile in the number of cong eners repr esented and in the minimal amount of 2,3,7,8­ TCDD relative to all 2,3,7,8-s ubstituted cong eners. A major difference is the prevalence of 1,2,3,7,8-PeCDD in 2,4-D (14%), which is not seen in any other combustion or noncombustion source presented here.

1-484D 23

78 5D 1 23 78 6D

1 23 47 8

6 D 123

67 8 6D

12 37 89
7D

12 3 467

8
8D

12 3 467

89

4F

23 7 8 5F 1 2 37 8 5F

2 347

8

6 F 12

347

8

6 F 12

36 7 8

6 F 123

78 9 6F 2 3 4 678

7 F 1

2 346

7 8
7F

1 2 34 7 8 9

8 F 1 234

6 78 9

4 D 2 37 8

5 D 1

2 3 78

6 D 12 34 7 8 6D

1 236

78 6D

1 23 78 9

7 D 1 234

67 8
8D

123

4 678

9

4 F 2

3 78

5 F 1 2 3 7 8 5F 23

47 8 6F 1 2 347

8 6F

12 36 7 8 6F 12

3 7 89

6 F 23 4 67 8

7 F 12 3 46 7 8
7F

1 2 3 4 7 89

8 F 1

2 3 46 7 8 9

4 D 2

3 7 8 5D

1 23 78

6 D 1

2 34 7 8 6D

1 23 6 78

6 D 1 2 3 7 8 9
7D

1 234

67 8
8D

12

3 4 678

9

4 F 2

37 8

5 F 12

3 7 8 5F 23

47 8 6F 1 2 347

8 6F

12 3 67 8 6F 1 2 3 7 89

6 F 23 4 67 8

7 F 1

2 3 46 78
7F

1 2 34 7 8 9

8 F 1

2 34 67 8 9

4 D 237

8 5D

12

3 78

6 D 12 34 7 8 6D

1 236

78 6D

1 2 37 8 9

7 D 1 234

67 8
8D

12

3 4 678

9

4 F 2

3 78

5 F 1 2 3 7 8 5F 23

47 8 6F 1 2 347

8 6F

12 36 7 8 6F 12

3 7 89

6 F 23 4 67 8

7 F 12 3 46 78
7F

1 2 34 7 8 9

8 F 1

2 34 67 8 9 

### • T he r e a r e simila r itie s in the c ong e n e r pr of ile s of PCP, die se l tr uc k e missions, unleaded g a soline vehicle emissions, and e missions from industrial wood combustors. I n the se sour c e s, OCDD domina t e s tota l e missions, but the r e la tive r a tio of 1,2,3,4,6,7,8-HpCDD to OCDD is also quite similar.

• The cong ener profiles for diesel truck ex haust and those for ai r m easurem ent s from a tunnel study of diesel traffic are quite similar.

A u to m o bile s Bur n ing L e a d e d G a soli ne D i e s e l T r u c k E x ha us t

14 % 45%

40% 12 %

35%
10 % 30%

8% 25%

6% 20%

15% 4%

10%

2% 5%

0% 0%

0% 5% 10% 15% 20% 25% 30% 35%

0% 2% 4% 6% 8% 10% 12%

0% 5% 10% 15% 20% 25% 30% 35% A u tom o bile s Bur n ing U n Le ad e d G a s o li ne C r em at or ia

0% 2% 4% 6% 8% 10% 12%



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs

an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p -dioxins and

c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s ( c ont inue d)

.

1-494D 23 7 8

5 D 1

2 3 7 8

6 D 123478

6 D 123678

6 D 1237

89

7 D 123

4 678

8 D 1 234

67 89 4F 2 378

5F

1 2378

5F

234

78 6F 123478 6F 123

678

6F

12 3 789

6F 234

678
7F

12 3467

8
7F 1 234

78 9

8F 123

467

8 9 0% 10% 20% 30% 40% 50% 60% 70% 80%

0% 10% 20% 30% 40% 50% 60% 70% 80% 

### Fo r e s t Fi r e s



### F i gu re 1-10. Con g en er p r of iles (as p ercen t d i strib u t ion s to th e su m of CDDs

an d CDF s) of an th rop ogen i c sou rces of ch l o ri n a ted d i b e n z o- p -dioxins and

c h lor inat e d dibe nz ofur ans in t h e U n it e d St at e s ( c ont inue d)

.

1-50

### 2. ME CHANIS M S OF F O RMAT ION OF DIOXIN-L IK E COMP OUNDS DURING COMB US T I ON OF ORG ANIC MAT E R IAL S

More than a decade of combus tion research has contributed to a g e neral understanding of
the c e n tr a l mole c u la r me c h a n isms tha t f o r m CDDs/CDF s e mitte d f r o m c o mbustion sour c e s

. Current understanding of the c onditions necessary to form C DDs/CDF s were de rived primarily
from st udi es of ful l

- scal e m uni ci pal wast e co mbustors (MW C s), aug m ented with observations involving the ex perimental combustion of sy nthetic fuels and feeds in the laboratory

. However,

t h e form at i on m echani s m s el uci d at ed by t h ese st udies are g e nerally relevant to most combustion

sy ste m s in whic h or g a nic ma te r i al is burned with chlorine.
I n tensive studies have ex amined MW Cs from t h e perspect i v e of i d ent i f y i ng t h e speci fi c formation mechanism(s) that occurs within th e sy stem. This knowledg e may lead to methods that prevent the formation of CDDs/CDF s and th eir release into the environment. Althoug h much has been learned from such studies, a me thod that completely prevents CDDs/CDF s from forming during the combustion of certain org a ni c m a t e ri al s i n t h e presence of a source of
chlorine and ox y g en is still unknown. The wide va riability of org a nic mate rials incinerated and thermally processed by a wide ra ng e of combustion technolog ies th at have vary ing temperatures,

r e side nc e time s, a nd ox y g e n r e quir e me nts a dds to this c o mple x pr oble m

. Howe ve r , c e n tr a l
chemical events involved in the formation of CDDs/CDF s can be identified by evaluating

e mission te st r e sults f r o m MWCs in c o mbina tion with r e sults f r o m la bor a t or y e x pe r ime nts.
CDD/CDF emissions from combustion sources can potentially be ex plained by three principal mechanisms that should not be reg a rded as being mutually ex clusive. I n the first

m echani s m (referred t o as “pass t h roug h”), C DDs/ C DFs are present as cont am i n ant s i n t h e combusted org a nic material; they pass thr oug h the furnace and are emitted unaltered. This
mechanism is discussed in Section 2.1. I n the second mechanism (referred to as “precursor”),
CDDs/CDF s ultimately form from the therma l breakdown and molecular rearrang ement of precursor ring compounds, which are defined as ch lorinated aromatic hy dr ocarbons that have a

st ruct ural resem b l a nce t o t h e C DD/ C D F m o l ecul e s. R i ng ed precursors t h at em anat e from t h e

c o mbustion zone a r e a r e sult of the inc o mple te ox ida tion of the c onstitue n ts of the f e e d ( i .e ., products of incomplete combustion). The precurs or mechanism is discussed in Section 2.2. The
thir d me c h a n ism ( r e f e rr e d to a s “ de novo sy nthe sis” ) is simila r to the pr e c u r s or me c h a n ism a nd is
described in Section 2.3. De novo sy nthesis describes a pathwa y of C DD/ C D F form at i on from heterog e neous reactions on fly ash (particulate matter [ P M] ) involving carbon, ox y g en, hy drog en, chlorine, and a transition metal cataly s t. W ith these reactions, intermediate compounds that have

an arom at i c ri ng st ruct ure are form ed.

2-1

### Studies in this area sug g e st that ali phatic compounds, which arise as products of incomplete combustion, may play a critical role in initially forming simple ring molecules, which
la te r e volve into c o mple x a r oma tic pr e c u r s or s. CDDs/CDF s a r e the n f o r m e d f r o m the intermediate compounds. I n both the second and the third mechanism, formation occurs outside the furnace, in the so-called post-combustion z one. P a rticulate-bound carbon is sug g e sted as the

pr ima r y r e a g e n t in the de novo sy nthesis pathway

. Section 2.4 presents an overview of studies that have investig ated the role that chlorine play s in forming CDDs/CDF s. Althoug h chlorine is an essential component for the formation of
C DDs/ C DFs i n com bust i on sy st em s, t h e em pi ri cal evi d ence i ndi cat es t h at for com m e rci a l

- scal e inc i ne r a tor s , c h lor i ne le ve ls in f e e d a r e not the domina n t c ontr o lling f a c t or f

o r

r a te s of CDD/CDF

sta c k e missions. The r e a r e c o mple x itie s r e la te d to the c o mbustion pr oc e ss itse l f

, a nd some ty pe s of air pollution control equipment tend to mask an y direct association. Therefore, the chlorine
content of fuel and feeds to a combustion source is not a g ood indicator of levels of CDDs/CDF s

e mitte d f r o m the sta c k of tha t sour c e

. Section 2.6 discusses the g e neration and forma tion of coplanar poly c hlorinated bipheny ls (P C B s). The presence of copl anar P C Bs i n st ack emissions from combustors is an area in need
of further research. Evidence to date sug g e sts th a t PCB e missions a r e mostly a ttr ibuta b le to PCB

c onta mina tion in wa ste f e e d s a nd tha t e missions a r e r e la te d to the f i r s t me c h a n ism de sc r i be d
above. However, newly published re search has also indicated that it is possible that PCB s form in much the same way as described in the second and third mechanisms identified in the
formation of CDDs/CDF s within the post-combustion z one. Section 2.7 provides a closing summary of the three principal formation mechanisms and
the role of chlorine. F r om the discussions in this chapter, it should be evident that no clear
distinction ex ists between the precursor and the de novo sy nthesis mechanisms of CDD/CDF
formation. B o th formation pathway s depend on the evolution of precursors within combustion

g a ses, t h e i n t e ract i on of react i v e fl y ashes, a g e nerally ox idative environment, the presence of a

t r ansi t i on m e t a l cat al y s t , t h e presence of g a seous chlorine, and a favorable rang e of temperatures. The temperature of the combustion g a ses (i.e., flue g a ses) is perhaps the sing le most important factor in forming diox in-like compounds. Temperatures between 200 and 450°C are most
conducive to the formation of CDDs/CDF s, with max imum formation occurring at around
350°C. I f the temperature falls outside this rang e, the amount of CDDs/CDF s formed is
minimize d

.

2-2

### 2.1. MECHANISM 1 (P ASS THROUG H): CDD/CDF CONTAMINATION IN F U EL AS A S O URCE OF COMB US T I ON S T ACK E M IS S I ONS
The first mechanism involved in stack e missions of CDDs/CDF s is the incomplete
destruction of CDD/CDF contaminan ts pr e s e n t in the f u e l or f

e e d s de live r e d to the c o mbustion
cham ber. Not al l of t h ese m o l ecul e s are dest roy e d by the combustion sy stem, thus allowing
trace amounts to be emitted from the stack. Most work in this area has involved the study of incineration of municipal solid waste (MSW ), wh ere C DDs/ C DFs were anal y t i cal l y m easured i n the r a w r e f u se f e d into the inc i ne r a tor

. C DDs/CDF s are ubiquitous in the environment (air, water, and soil) and in foods a nd paper; therefore, they clearly are present in municipal waste (Tosine et al., 1983; Oz vacic, 1985; Clement et al., 1988; F e dera l Reg i ster, 1991a; Abad et al., 2002). Abad et al. (2002) provided contemporary m easurements of CDDs/CDF s in raw MSW

. Twenty -two samples were collected and anal y z ed for CDDs/CDF s over a 1-y e ar period, from September 1998 throug h September 1999. The c ong eners that dominated the total mass of
CDDs/CDF s were OCDD and 1,2,3,4,7,8,9-HpCDD. F i g u re 2-1 display s the mean CDD and
CDF cong ener distribution from this study

. Abad et al. found that the I

- TEQ concentration in the
MSW was hig h ly variable and rang ed from 1.55 to 45.16 ng I

- TEQ/kg MSW

.

350

300magr 

### 250rpe 

### 200sma 

### 150ogrci 

### 100P 

### 50

02,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCD1,2,3,6,7,8-HxCD1,2,3,7,8,9-HxCD1,2,3,4,6,7,8-HpOCDD2,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCD1,2,3,6,7,8-HxCD1,2,3,7,8,9-HxCD2,3,4,6,7,8-HxCD1,2,3,4,6,7,8-Hp1,2,3,4,7,8,9-HpOCDF

Conge ne r


### F i gu re 2-1. T y p i cal m e an d i strib u t ion of CDD an d CDF con g en ers in

con t em p o rary m u n i ci p a l sol i d w a ste.

Source: Adapted from Abad et al. (2002).

2-3

### A number of studies have provided evidence tha t most of the CDDs/CDF s pr e s e n t in
MSW are destroy e d during combustion (Abad et al., 2002; Clement et al., 1988; Commoner et al., 1984, 1985, 1987; Hay et al., 1986; Environment Canada, 1985). These studies involved a mass balance of the input versus output of C DDs/CDF s at two operational MW Cs. The mass of
CDDs/CDFs outside the incinera tor furnace was found to be much g r eater than the mass of
CDDs/CDF s in the r a w MSW f e d into the inc i ne r a tor, and the profiles of the distributions of
CDD/CDF cong eners were striking ly dif f

e r e nt. Pr ima r ily , the mor e hig h ly chlorinated cong eners

we r e de te c t e d a s c onta mina n ts in the wa ste , whe r e a s the tota l a r r a y of te tr a

- thr oug h oc ta

CDDs/CDF s could be detected in the sta c k g a se s. Mor e ove r , the r a tio of the tota l CDD

concent r at i on t o t h e t o t a l C D F concent r at i on i n t h e MS W was g r eat er t h an 1, whereas i n t ypi cal
inc i ne r a tor sta c k e missions this r a tio is le ss tha n 1 (meaning more dibenz ofurans than diox ins are

e mitte d)

. F r om suc h e v ide n c e it c a n be c onc lude d tha t CDDs/CDF s a r e be ing sy nthe size d a f te r the contaminated feed has been combusted (Abad et al., 2002). I t is also ex pected that the
condi t i ons of t h erm a l st ress i m posed by hi g h t e m p erat ures reached i n t ypi cal com bust i on woul d
dest roy and reduce t h e C DDs/ C DFs present as cont a mina n ts in the wa ste f e e d to le ve ls tha t a r e 0.0001 to 10% of the initial con centration, depending on the pe rformance of the combustion source and the level of combustion efficiency

. St ehl et al. (1973) demonstrated that the moderate temperature of 800°C enhances the decomposition of CDDs at a rate of about 99.95%, but lower

te mpe r a t ur e s r e sult in a hig h e r sur v iva l r a te

. Theoretical modeling has shown that unimo lecular destruction of CDDs/CDF s at 99.99% can occur at the following temperatures and re tention times within the combustion z one: 977°C with a retention time of 1 sec, 1,000°C at a re tention time of 0.5 sec, 1,227°C at a retention time of 4 msec, and 1,727°C at a retention time of 5 : 

### sec (Schaub and Tsang

, 1983). Thus,
CDDs/CDF s would ha ve to be in c onc e n tr a tions of pa r t s pe r million in the f e e d in the c o mbustor to be found in the parts-per-billi on or parts-per-trillion level in the stack g a s emissions (Shaub and Tsang

, 1983). However, it ca nnot be ruled out that CDDs/CDF s in the waste or fuel may contribute (up to some percentag e ) to the ove r a ll c onc e n tr a tion l eaving the stack. The only other possible ex planation for CDD/CD F emissions from hig h -tempera ture combustion of org a nic

m a t e ri al i s form at i on out si de and downst r eam of t h e furnace. The above studies point to formation mechanisms other than simple pass throug h of
noncombusted feed contamination. These formation mechanisms are discussed and reviewed in
the f o llowing se c tions.

2.2. MECHANISM 2 (P RECURSOR): F O RMATION OF CDDs/CDF s F R OM P R E CURS OR COMP OUNDS
The second mechanism involves the formati on of CDDs/CDF s from aromatic precursor compounds in the presence of a chlorine donor. This mechanism has been elucidated by

2-4

### laboratory ex periments involving the combusti on of known precursors in quartz ampules under
starved-air conditions and in ex pe r ime nts tha t inve stig a t e d th e role of combustion fly ash in promoting the formation of CDDs/CDFs from precu rsor compounds. The g e neral reaction in this formation pathway is an inte raction between an aromatic precursor compound and chlorine promoted by a transition metal cataly s t on a r eactive fly ash surface (S tanmore, 2004; Dickson and Karasek, 1987; L i ber ti and B r occo, 1982). Ex amples of well-studied precursor compounds
include chlorobenz enes, chlorophenols, phenol, and benz ene (Esposito et al., 1980). Gaseous hy drog en chloride (HCl), free chlorine (Cl 2 

### ), and chlorine radicals (Cl

A 

### ) are t h e chl o ri nat i n g

a g e n ts within the c o mbustion g a se s. CDD/CD F form at i on resul t s from heterog e neous g a s-phase reactions involving chlorinate d precursor compounds and a source of chlorine. Chlorophenol
and chlorobenz ene compounds have been measur ed in flue g a ses from MW Cs (Dickson and Karasek, 1987).

P r ecursors are carried from the furnace to the flue duct as products of incomplete
combustion. These compounds can adsorb on the su rface of combustion fly ash or entrain in the

g a s phase within the flue g a ses. Thus, th ere are t w o form at i on pat h way s from precursor compounds: heterog e neous solid-pha se reactions and homog eneous g a s-phase reactions. I n the post

- com bust i on reg i on out si de t h e furnace, het e rog e neous react i ons on t h e surface of react i v e fly ash can ensue to form CDDs/CDF s from the pr ecursor compounds. This occurs at the cooldown temperatures of 200 to 400°C. The hete rog e neous g a s-phase reactions occur from the breakdown and molecular rearrang ement of precu rsor compounds followed by condensation and chlorination at the hig h er temperatures of 500 to 800°C. B o th reaction pathway s are cataly z ed by copper chloride (CuCl 2 

### ) or another transition metal.
L a boratory ex periments involving the c ontrolled combustion of precursor compounds have caused the breakdown of the precursor reag ent and the subsequent appearance of CDDs/CDFs as products of the reaction. For ex ample, J a nsson et al. (1977) produced CDDs throug h the py roly sis of wood chips treated with tri-, tetra-, and pent achlorophenol (PCP) in a bench-scale furnace operated at 500 to 600°C. S t ehl and L a mparski (1977) combusted g r ass and paper treated with the herbic ide 2,4,5-trichlorophenox y acetic acid in a bench-scale furnace at 600 to 800°C and g e nerated ppm
v 

### levels of TCDD. Ahling a nd L i ndskog (1982) reported CDD formation during the combustion of tri- and tetrachlorophenol form ulations at temperatures of
500 to 600°C. Decreases in ox y g en during co mbustion g e nerally increased the CDD y i eld. Ahling and L i ndskog (1982) noted that addi ng copper salts to the tetrachlorophenol formulation sig n ificantly enhanced the y i eld of CDDs. This may have been an early indication of copper’s role in cataly z ing the condensation of chlorophenol to diox in. Combustion of PCP resulted in low y i elds of CDDs. However, wh en PCP was burned with an insufficient supply of

ox y g en in the presence of copper, the investig ators noted the formation of tetra- throug h

2-5

### octachlorinated cong eners. B u ser (1979) g e nerated CDDs/CDF s on the order of 0.001 to 0.08% (by weig ht) by heating tri-, te tra-, and pentachlorobenz enes at 620°C in quartz ampules in the presence of ox y g en. I t was noted that chlor ophenols formed as combustion by -products; B u ser speculated that these chlorophenol s were acting as reaction inte rmediates in the formation of
C DDs/C DFs. The second condition postulate d to reg u late the sy nthesis of CDDs/CDF s from the aromatic precursor compound is the adsorption and interaction with the reactive surface of combustion-g e nerated fly ash (PM) entrained in the combustion pl asm a and t h e presence of a transition metal cataly s t (Stanmore, 2004; Dickson et al., 1992; B r uce et al ., 1991; Cleverly et al., 1991; Gullet et al., 1990a; Commoner et al., 1987; Dickson and Karasek, 1987; Vog g et al., 1987). These are heterog e neous so lid-phase reactions that occur at temperatures below 450°C. The molecular precursor leaves the g a s phase and condenses onto the fl y ash particle. This condition, which places g r eater emphasis on hete rog e neous surface reactions and less emphasis on homog eneous g a s-phase reacti ons, was first postulated by Shaub and Tsang (1983) using
thermal-kinetic models based on the temperature of the h eat of formation, adsorption, and desorption. Shaub and Tsang modeled CDD pr oduction from chlorophenol s and concluded that solid-phase formation of CDDs/CDF s was of g r eat er i m port a nce t h an g a s- phase formation within an incineration sy stem. The te mpe r a t ur e of the c o mbustion g a se s is a c r itic a l f a c t or in the f o r m a tion of
CDDs/CDF s from aromatic precursor compounds (W eber and Hag e nmaier, 1999; F a ng mark et al., 1994; Vog g et al., 1987, 1992; Oberg et al.,1989). Vog g et al. (1987) found that formation probabl y occurs out si de of and downst r eam from t h e com bust i on z one of a furnace, i n reg i ons where the temperature of the co mbustion offg ases has cooled within a rang e of 200 to 450°C. After carefully removing org a nic conta minants from MW C fly ash, Vog g et al. (1987)
added known concentrations of isotopically labeled CDDs/CDF s to the matrix

. The MW C fly
ash was t h en heat ed for 2 hr i n a l a borat ory furn ace at vary i n g t e m p erat ures. The t r eat ed fl y ash

was ex posed to temperatures increasing in 50°C increments within a temperature rang e of 150 to
500°C. Table 2-1 summariz e s these data. B ecau se the relative concen tration of CDDs/CDFs
i n creased whi l e ex posed t o vary i n g t e m p erat ures , it was concluded that the te mpe r a t ur e of the

com bust i on g a s i s cruci a l t o prom ot i n g t h e form at i on of C DDs/ C DFs on t h e surface of fl y ash.
W ithin a temperature rang e of 200 to 450°C, the concentration of CDDs/C DF s increases to some

ma x ima ; outside this r a ng e , the c onc e n tr a tion diminishe s.

2-6

### T a b l e 2-1. Con cen tration of CDDs/CDF s on m u n i cip a l in cin erator f l y ash at varying tem p eratures

Con g en er CDD/CDF con cen tration on f l y ash (n g/g) b y tem p eratu re
200°C 250°C 300°C 350°C 400°C

CD D Tetra Penta Hex a Hepta Octa

CD F Tetra Penta Hex a Hepta Octa 15 40 65 100

90

122 129

61 48 12 26 110 217 208 147

560 367 236 195

74 188 517 1,029 1,103

483

1,379 1,256

944 689 171 220 590 550 430 200

1,185 1,010

680 428

72 50 135 110

60 15

530 687 260 112

12

S o u r ce: A d apt e d f r om V o g g et al . (1987).



### The reg i on of cooler g a s temperature is ofte n referred to as the “post-combustion reg i on.”
Thi s reg i on ex t e nds from near t h e ex i t of t h e furnace t o t h e poi nt of rel ease of t h e com bust i o n
g a ses at stack tip. The heat loss may be inhe rent in the conduction a nd transfer throug h the

c o mbustion g a s me ta l duc ting sy ste m or r e la te d to the a d sor p tion/e x c h a n g e of he a t to wa te r in
boiler tubes.
F a ng mark et al. (1994) found that CDDs /CDF s ex hibit a similar dependence at a temperature rang e of 260 to 430°C, with max imum formation occurring around 340°C. Using a pilot-scale combustor, B e hrooz and Altwicker (1996) found that the formation of CDDs/CDF s from the precursor 1,2-dichlorobenz ene rapidly o ccurred within the post-combustion reg i on in a temperature rang e of 390 to 400°C, with residen ce times of only 4 to 5 sec. On the other hand,
CDD/CDF formation from 1,2-dichlorophenol s eemed to require hig h er temperatures. Oberg et al. (1989) ex amined the role of te mperature in the formation kinetics using a full-scale haz a rdous waste incinerator (HW I ) ope rating in Sweden. The investig ators observed
tha t ma x imum CDD/CDF f o r m a tion tr a n spir e d in the boile r use d to e x tr a c t he a t f o r

c o g e ne r a tion
of

e n e r g y

. I n this study , sig n if ic a n t inc r e a s e s in tota l c onc e n tr a tion of I

- TEQ DF 

### occurred between 280 and 400°C, and concentrations declined at temperatures above 400°C. W e ber and Hag e nmaier (1999) showed that in g a s-phase r eactions, chlorophenols react in the presence of

2-7

### ox y g en at temperatures above 340°C to form C DDs/CDF s. Phenox y r adicals were formed, which
in turn caused the formation of CDDs. Poly ch lorinated dihy drox y b iphe ny ls we r e ide n tif ie d a s reaction intermediates in the g a s-phase dimeriz a tion of chlorophe nols, and these intermediates
could form CDF s

. Konduri and Altwicker ( 1994) proposed that rate-limiting fact ors were the nature and the

c onc e n tr a tions of the pr e c u r s or s, the r e a c tivity a nd a v a ila bility of the f l y

a s h sur f a c e , a nd the residence time in the post-combustion z one. Di ckson and Karasek (1987) investig ated fly ash

r e a c tivity with 13 

### C 6 

### -chlorophenol compounds. Several sa mples of fly ash from MW Cs and copper smelters and a variety of combustion fu els were heated at 300°C in quartz tubes under conditions known to cataly z e the conversion of ch lorophenols to CDDs/CDF s. The MSW fly ash included a sample from a poorly operated mass burn refractory inci nerator and a sample from a well-operated fluidiz e d-be d combustor. The MW C fly ash proved to be the most active cataly tic medium, despite simila rities among the samples with respec t to specific surface area and averag e pore diameter. The fly ash fro m the refractory MW C g e nerated about seven time s more mass of
diox in-like compounds than did the fluidiz e d-be d MW C. I n the MSW fly ashes, all CDD/CDF

cong ener g r oups were formed from labeled chlorophenols; however, only trace amounts of heptachloro- and octachlorodiox in were formed with the c opper smelter/refiner. X-ray photoelectron spectroscopy revealed the presence of chlorine ad sorbed to the surface of the
MW C fly ash but an absence of chlorine sorbed to the copper smelter fly ash. CDD cong ener g r oups have been postulated to form from the labeled PCP precursors by (1) first forming octachlorodiox in by the conde nsation of two PCP molecules, and (2) forming
other less-chlorinated diox ins throug h dechlorina tion of the more hig h ly chlorinated isomers.
These st eps seem ed t o proceed by an i n creased react i v i t y of t h e chem i s orbed precursor m o l e cul e caused by the removal of one or more hy drog en or chlorine atoms al ong the ring structure (Dickson and Karasek, 1987), an obs ervation consistent with the kinetic model of Shaub and Tsang (1983).
I n related ex periments, Dickson and Ka rasek (1987) more sp ecifically reported on forming CDDs/CDFs from condens ation reactions of chlorophe nols on the surface of MW C fly
ash heated in a bench-scale fu rnace. Their ex periment was desig n ed to mimic conditions of
MS W incineration, to identify the step-wise ch emical reactions invol ved in converting a precursor compound into diox in, and to deter mine whether MW C fly ash could promote these

r e a c tions. MWC f l y

a s h wa s obta i ne d f r o m f a c ilitie s in Ca na da a nd J a pa n. The f l y

a s h wa s

r i nse d with solve n t to r e move a n y or g a nic c onstitue n ts pr ior to initia ting the e x pe r ime nt. Twe n ty

g r am s of fl y ash were i n t r oduced i n t o a bench-scal e furnace (consi s t i n g of a si m p l e fl ow-t ube combustion apparatus) and heated at 340°C ove rnig ht to desorb any remaining org a nic compounds from the matrix

. 13 

### C 12 

### -labeled PCP and two tr ichlorophenol isotopes ( 13 

### C 12 

### -2,3,5­

2-8

### trichlorophenol and 3,4,5-tr ichlorophenol) were added to the su rface of the clean fly ash matrix and placed in the oven for 1 hr at 300°C. Pure inert nitrog en g a s (flow rate of 10 mL /min) was passed throug h the flow tube and a c onsta nt te mpe r a t ur e wa s ma inta ine d

. Te tr a

- thr oug h oc ta

- C DDs we r e f o r m e d f r o m the la be le d PCP e x pe r ime nt; mor e tha n 100

: 

### g / g of total CDDs were produced. The cong en er pattern was similar to that found in MW C
emissions. The 2,3,5-trichlorophenol ex periment primarily produ ced Hx CDDs and very small amounts of tetra- throug h octa-CDDs. The 3,4,5-trichlorophenol ex per iment mainly produced OCDD and 1,2,3,4,6,7,8-HpCDD. Dickson and Karasek (1987) proposed that CDDs on fly ash surfaces may result from chlorophenol underg oing molecular rearrang ement or isomeriz ation as a result of dechlorination, dehy drog enation, and transchlor ination before condensation o ccurs. These reactions were proposed as controlling the ty pes and amounts of C DDs that are ultimately formed. B o rn et al. (1993) conducted ex perime nts on the ox idation of chlorophenols with fly ash in a quartz tube
reactor heated to about 300°C. The MW C fly ash mediated the ox idation of chlorophenols to produce carbon diox ide (CO 2 

### ) and carbon monox ide (CO) as ma jor products and poly c hlorinated
benz enes, monobenz ofurans, and nonhalog e nated dibenz o- p -di o x i ns as t r ace speci e s. Form at i o n of these trace aromatic species occurred after residence times of only 7 to 8 sec, which was
consistent with the later ex per imental result of B e hrooz and A ltwicker (1995), which showed the pot ent i a l for rapi d form at i on from a precursor. Millig an and Altwicker (1996) fitted ex perimental flow-tube reactor data to classical cataly tic reaction models to em pirically ex plain the interacti on of 2,3,4,6-tetrachlorophenol (as a model precursor) with reactive MW C fly ash during MSW incineration. The precursor was found to be hig h ly adsorptive on the surface of fly ash, with a first-order dependence on g a sphase precursor concentration to CDD form ation. The investig ators concluded that chlorophenol’s dependence on g a s- phase concentration to form CDDs on fly ash reflects the hig h ly heterog e neous nature of the fly ash surface. Moreover, the estimated 6 × 10 18 

### a d sorp tion
si t e s per g r am of fl y ash sug g e st ed t h e presence of hig h ly e n e r g e tic site s, whic h ma y be impor ta nt in the surface-cataly z ed reactions forming CDDs. An interesting observation by Millig an and
Altwic ke r wa s tha t pr e c u r s or mole c u le s a ppe a r e d to c o mpe t e with ox y g e n mole c u le s f o r

the reactive sites; therefore, chlorophenols are ex pect ed to adsorb less readily to the fly ash surface
i n t h e presence of ox y g en. Ex perimental evidence sug g e sts that conde nsation to CDD of chlorophenol compounds
via isomeriz ation and the Smile s rearrang ement on reactive MW C fly ash surfaces is a proven pathway for the formation of diox ins fro m a precursor compound (Addink and Olie, 1995). However, no detailed mechanisms have been presented for CDD/CDF formation from other precursors such as chlorobenz enes under conditions simulating incineration.

2-9

### A condition in the sy nthesis of CDDs/CDF s from aromatic precursor compounds is that

t h e presence of a t r ansi t i on m e t a l cat al y s t prom ot es t h e chem i cal react i on on t h e surface of fl y ash. CuCl 2 

### is a strong cataly s t for promoting su rface reactions on P M to convert aromatic precursor compounds to CDDs/CDF s (Vog g et al., 1987). CuCl 2 

### promotes ring condensation reactions (of the chlorophenols) on fly ash to form CDDs/CDF s (Addink and Olie, 1995) via the Ullman reaction (B orn et al., 1993). I n the U llman reaction, copper cataly z es the formation of dipheny l ethers by the reaction of halog e nated benz enes with alka li metal phenolates (B orn et al., 1993), with copper particip ating in a nucleophilic aromatic substitution reaction. Thus, B o rn et al. proposed a similar mechanism in cataly z ing th e formation of diox in-like compounds. Using the Ullman reaction as a model, the authors pr oposed that the copper-cataly z ed condensation of two ortho-substituted chlorophenol mo lecules form chlorine-free dibenz o- p -diox i ns. Vog g et al. (1987) proposed an ox idation reacti on pathway

, g i ving rise to the formation of
C DDs/ C DFs i n t h e post -furnace reg i ons of t h e i n ci nerat o r i n t h e fol l o wi ng order: (1) HC l i s thermoly tically derived as a product of the combustion of heterog e neous fuels containing abundant chlorinated org a nic chemicals and ch lorides; (2) ox idation of HCl, with CuCl 2 

### as a cataly s t, y i elds free g a seous ch lorine via the Deacon reaction; (3) phenolic compounds (present from combustion of lig nin in the waste or other sources) entrained in th e combustion plasma are
substitute d on the r i ng str u c t ur e by c onta c t with the Cl 2 

### ; and (4) a chlorinated precursor to diox in (e.g ., chlorophenol) is further ox idiz ed (with CuCl 2 

### as a cat al y s t ) t o y i el d C DDs/ C DFs and
chlorine. Gullett et al. (1990a, b, 1991a, b, 1992) studied the formation mechanisms throug h

ex tensive combustion research at EPA and verified the observations of Vog g et al. (1987). I t was proven that CDDs/CDF s could ultimately be produced from low-temperature (i.e., 350°C) reactions between chlorine (Cl) and a phenolic precursor combining to form a chlorinated precursor, followed by ox idation of the chlorina ted precursors (cataly z ed by a copper cataly st such as C u C l 2 

### ), as shown below.

1. The initia l ste p in diox in f o r m a tion is the f o r m a tion of c h lor i ne f r o m HCl in the presence of ox y g en (the Deacon reaction), as follows (B ruce et al., 1991; Vog g et al., 1987):

Heat
2HCl + 1⁄2 O 2 

### ————> H 2 

### O + C l 2



### 2. P h enolic compounds adsorbed on the surface of fly ash are chlorinated to form the
diox in precursor, and the diox in is formed as a product of the breakdown and molecular

2-10

### rearrang ement of the precursor. The reaction is promoted by CuCl 2 

### act i n g as a cat a l y st (Vog g et al., 1987; Dickson and Karasek, 1987; Gullett et al., 1992):

(a) phenol + Cl 2 

### ————> chlorophenol (diox i n precursor)

CuCl 2 

### (b) 2-chlorophenol + 1⁄2 O 2 

### ————> diox in + Cl 2



### Eklund et al. (1986) observed the hig h -tempe rature formation of a larg e variety of
chlorinated tox i c compounds, including C DDs/CDF s, from precursors during a simple

ex periment in which phenol was ox idiz ed w ith HCl at 550°C. One millig ram of phenol was pl aced i n a quart z t ube react or wi t h an aqueous sol u t i on (10 : 

### L ) of HCl and heat ed at a temperature of 550°C for 5 min. Trichlorobe nz ene, dichlorophenol, dichlorobenz ofuran,
tetrachlorobenz ene, trichlorophe nol, and tetrachlorophenol were identified as major products
formed. Monochlorobenz ene, chlorophenol , dichlorobenz ene, tetrachloropropene, pentachloropropene, trichl orobenz ofuran, TCDF , TrCDD, TCDD, Hx CDD, Hx CDF
, pentachlorobenz ene, pentachlorobipheny l, and pentachlorodihy drox y c y l ohex a ne were observed as minor products. Trace species formed in cluded MCDF, P e CDF, P e CDD, OCDF, and OCDD. Eklund et al. (1986) hy pothesiz e d that ch lorinated org a nic compounds can be produced from phenols, acids, and any chlorine source in the hot post-combustion reg i on (just bey ond the

ex it to the furnace). The reaction was seen as very sensitive to HCl concentration. No chlorinated compounds could be detected when HCl concentrations were <10 -3 

### mol. Nestrick et al. (1987) reported that the thermoly tic reaction between benz ene (an
unsubstitute d pr e c u r s or ) a nd ir on ( III) c h l o r i d e o n a s i l i cat e surface y i el ded C DDs/ C DFs at

t e m p erat ures $ 

### 150°C. The ex perimental protocol introduced 100 to 700 mg benz ene and 13 

### C 6 

### ­ benz ene into a macroreactor sy stem consisting of a benz ene volatiliz ation chamber connected to

a g l ass t ube furnace. The i nvest i g at ors not ed t h e rel e vance of t h i s ex peri m e nt t o g e neral i z at i ons about combustion processes because benz ene is the usual combustion by -product of org a nic
fuel s. I n ert ni t r og en g a s carri ed t h e benz ene vapor t o t h e furnace area. The ex i t from t h e g l ass tubing to the furnace was plug g e d with g l ass wool, and silica g e l was introduced from the entrance end to g i ve a bed depth of 7 c m to whic h f e r r i c tr ic hlor ide ( F e C l 3 

### ) was added to form an
FeC l 3 

### /silica reag ent. The thermoly tic reaction t ook place in a temperature rang e of 150 to 400°C
at a residence time of 20 min. Althoug h di- throug h octa-CDDs/CDF s were formed by this

react i on at al l t e m p erat ures st udi ed, t h e percent y i el ds were ex t r em el y sm al l

. Tabl e 2-2

summa r i ze s the s e da ta

.

2-11

### Table 2-2. CDDs/CDF s f o rm ed f r om the therm olytic reaction of 690 m g b e n zen e + F e Cl 3 

### silic a c o m p le x

Con g en er Mass p r od u ced (n g) Nu m b er of m o l s p r od u ced P ercen t yi el d a



### DiC D D TrCDD TCDD Pe CD D Hx C D D HpC D D OC DD Tota l CDDs 4.9 54.0 130.0 220.0 170.0

98.0 20.0 696.9 0.019 0.019 0.400 0.620 0.440 0.230 0.040 1.940 4.3 e

! 

### 7 4.3 e

! 

### 6 9.0 e

! 

### 6 1.4 e

! 

### 5 9.9 e

! 

### 6 5.2 e

! 

### 6 9.0 e

! 

### 7 4.4 e

! 

### 5

DiC D F TriCDF TCDF Pe CD F Hx C D F HpC D F OC DF Tota l CDF s 990 7,800 12,000 20,000 33,000 40,000 74,000 187,000 4.2 29.0 39.0 59.0 88.0 98.0 167.0 484.2 9.5 e

! 

### 5 6.6 e

! 

### 4 8.8 e

! 

### 4 1.3 e

! 

### 3 2.0 e

! 

### 3 1.1 e

! 

### 3 3.8 e

! 

### 3 1.1 e

! 

### 2

a N u m b er of m o l s of C D D or C D F / m o l s ben zen e x 100.

FeCl 3 = f e rric ch loride

S o u r ce: N e s t ri ck et

al . (1987).



### 2.3. MECHANISM 3 ( DE NOV O S YNT HE S I S ): S YNT HE S I S OF CDDs/CDF s DURING COMB US T I ON OF ORG ANIC MAT E R IAL S
The thir d me c h a n ism pr omote s CDD/CDF f o rmation in combustion processes from the

ox idation of carbon particulate cataly z ed by a tran sition metal in the presence of chlorine. As in

t h e precursor m echani s m (m echani s m 2), sy nt hesi s i s believed to occur in reg i ons outside of the
furnace z one of t h e com bust i on process, where t h e com bust i on g a ses have cool ed t o a rang e of temperatures considered favorable to fo rmation chemistry

. A key component to de novo

sy nthesis is the production of intermediate compounds (either halog e nated or nonhalog e nated) that are precursors to CDD/CDF formation. Re search in this area has produced CDDs/CDF s directly by heating carbonaceous fly ash in the pr esence of a transition metal cataly s t without the apparent g e neration of reactive intermediates. Thus, th e specific steps involved in the de novo process have not been fully a nd succinctly delineated. However, laboratory ex pe rimentation has proven t h at MW C fl y ash i t s el f i s a react i v e subst r at e, and t h e m a t r i x can act ual l y cat al y z e t h e de

2-12

### novo formation chemistry

. Ty pically , fly ash is co mposed of an alumina-silicate construct, with
5 to 10% concentrations of s ilicon, chlorine (as inorg a nic ch lorides), sulfur, and potassium (NATO, 1988). Twenty percent of the weig ht of fly ash particles is carbon, and the particles have specific surface areas in the rang e of 200 to 400 m 2 

### /kg (NATO, 1988).
The de novo sy nthesis essentially is the ox ida tive breakdown of macromolecular carbon structures, and CDDs/CDF s are formed partially from the arom atic carbon-ox y g en functional

g r oups embedded in the carbon skeleton (Huang et al., 1999). The disting u ishing feature of the
de novo sy nthesis over the precursor sy nthesis is the ox idation of carbon in particulate at the start of the process to y i eld precursor compounds. I n mechanism 2, the precursor compound is the starting molecule of the conde nsation reactions forming CDDs /CDFs (Dickson et al., 1992). B y this distinction, however, one could arg u e that mechanism 3 is really an aug m entation of mechanism 2 because the production of CDDs/C DF s may still require the formation of a
C DD/ C D F precursor as an i n t e rm edi a t e speci es. Nevertheless, a distincti on is presented here to describe additional pa thway s sug g e sted for the thermal formation of these compounds.
To del i n eat e t h e de novo sy nthesis of CDDs/CDF s, S tieg litz et al. (1989) conducted

ex periments that involved h eating particulate carbon contai ning adsorbed mix tures of

m a g n esi u m

- al um i num (Mg

- Al ) si l i cat e i n t h e presence of C u C l 2 

### (as a cat al y s t t o t h e react i on).
The aut hors descri bed heat i n g m i x t u res of Mg -Al si l i cat e wi t h act i v at ed charcoal (4% by weig ht), chloride as potassium ch loride (7% by weig ht), and CuCl 2 

### (1% i n wat e r) i n a quart z flow tube reactor at 300°C. The retention time was varied at 15 min, 30 min, and 1, 2, and 4 hr
to obtain differences in the am ounts of CDDs/CDF s that could be formed. The results are
summariz e d in Table 2-3. I n addition to the CDDs/CDF s formed as primary products of the de

novo sy nthe sis, the inve stig a t or s obse r ve d pr e c u r s or s f o r m e d a t the va r y ing r e te ntion time s dur ing the e x pe r ime nt. I n pa r tic ula r , simila r y i e l ds of tr i- thr oug h he x a c h lor obe nze n e s , tr ithroug h heptachloronaphtha le ne s, a nd te tr a

- thr oug h heptachlorobipheny ls we r e qua ntif ie d; this was seen as hig h ly sug g e stive of the role th ese compounds may play as intermediates in the
continued formation of CDDs/CDF s. Stieg litz et al. (1989) made the following observations:

C 

### The de novo sy nthesis of CDDs/CDF s via the ox idation of carbonaceous PM occurred at a temperature of 300°C. Additionally

, the ex periment y i el ded parts-per-billion to
pa r t s- pe r

- million c onc e n tr a tions of c h lor i na te d be nze n e s , c h lor i na te d biphe ny ls, a n d

c h lor i na te d na phtha le ne s thr oug h a simila r me c h a n ism. Whe n pota ssium br omide

wa s substitute d f o r

pota ssium c h lor i de a s a sour c e of ha log e n f o r

the or g a nic compounds in the reaction, poly b rominated dibenz o- p -diox i ns and dibenz ofurans formed as reaction products.

2-13

### Table 2-3. De n o vo f o rm ation of CDDs/CDF s af ter heating Mg-Al silicate, 4% charcoal, 7% Cl, 1% CuCl 2 

### in H 2 

### O at 300°C

Con g en er Con cen tration of CDD/CDF (n g/g) b y reaction tim e (h r)

0.25 0.5 1 2 4

TCDD Pe CD D Hx C D D HpC D D OC DD Tota l CDDs 2 110 730 1,700

800 3,342 4 120 780 1,840 1,000 3,744 14 250 1,600 3,500 2,000 7,364 30 490 2,200 4,100 2,250 9,070 100 820 3,800 6,300 6,000 17,020

TCDF Pe CD F Hx C D F HpC D F OC DF Tota l CDF s 240 1,360 2,500 3,000 1,260 8,360 280 1,670 3,350 3,600 1,450 10,350 670 3,720 6,240 5,500 1,840 17,970 1,170 5,550 8,900 6,700 1,840 24,160 1,960 8,300 14,000

9,800 4,330 38,390
Cl = c h lo r i ne CuCl 2 = copper ch l o ri de M g -A l = m a gne si um -a l u m i num

Sou r ce: Stieg litz et al. (1989).



### C 

### The transition metal compound CuCl 2 

### cat al y z ed t h e de novo sy nthesis of CDDs/CDF s on the surface of particulate carbon in the presence of ox y g en, y i elding CO 2 

### and chlorinated/brominated aromatic compounds.

C 

### Particulate carbon, which is characteristic of combustion processes, may act as the source for t h e di rect form at i on of CDDs/CDF s as well as other chlorinated org a nics.

Stieg litz et al. (1991) investig ated the ro le that particulate carbon play s in the de novo
f

o r m a tion of CDDs/CDF s f r o m f l y

a s h c onta i ning a ppr e c i a b le qua ntitie s of or g a nic c h lor i ne

. The investig ators found that the fly ash contai ned 900 ng /g of bound org a nic chlorine, of which only 1% was ex tractable. Heating the fly ash at 300 to 400°C for several hours caused the carbon

to ox idiz e, leading to a reduction in the total org a nic chlorine in the matrix and a corresponding
increase in the total ex tractable org a nic chlorine (5% ex tractable total org a nic chlorine at 300°C and 25 to 30% at 400°C). F r om this, the authors concluded that the ox id ation and deg r adation of carbon in fly ash are the sources of the formation of CDDs/CDF s; therefore, they are essential in
the de novo sy nthesis of these compounds.

2-14

### Addink et al. (1991) conducte d a series of ex periments to observe the de novo sy nthesis of CDDs/CDFs in a carbon fly ash sy stem. I n th is ex periment, 4 g of carbon-free MW C fly ash were combined with 0.1 g of activated carbon a nd placed into a g l ass tube between two g l ass wool pl ug s. The g l ass t ube was t h en pl aced i n t o a furnace at speci fi c t e m p erat ures rang i n g from
200 to 400°C. This protocol was repeated for a series of retention times and temperatures. The investig ators observed that CDD/CDF forma tion was optimiz ed at 300°C and at the furnace

r e te ntion time s of 4 to 6 hr

. F i g u r e 2- 2 displa y s the r e la tionship be twe e n r e te ntion time a n d temperature in CDD/CDF production fro m the heating of carbon particulate.magrrpesmnograNa

Rete ntion time (hr )



### F i gure 2-2. The de novo syn t h e sis of CDDs/CDF s f r om h e atin g carb on particulate at 300°C at varying retention tim e s.

S o u rce: A ddi n k et

al . (1991).



### Addink et al. (1991) also investig ated the relationship between furnace temperature and CDD/CDF production from the heating of carbonace ous fly ash. Fig u re 2-3 display s this relationship. I n g e neral, the c oncentration beg a n to increase at 250°C and crested at 350°C, with a sharp decrease in concentration above 350°C. The authors also noted a relationship between

2-15magrrpesmnograNa

T e mp erat u r e ( ° C)



### F i gu re 2-3. T e m p eratu re ef f

ects on CDD/CDF f o rm ation

.

S o u rce: A ddi n k et

al . (1991).



### temperature and the CDD/CDF cong ener profile: at 300 to 350°C, th e less-chlorinated tetra- and penta-CDD/CDF cong eners increased in concen tration, whereas hex a -, hepta-, and octaCDD/CDF cong eners either remain ed the same or decreased in concentration. The cong ener profile of the orig inal MW C fly ash (not subject to de novo ex perimentation) was investig ated
with r e spe c t to c h a n g e s c a u se d by e ithe r te mpe r a t ur e or r e side nc e time in the f u r n a c e

. No sig n ificant chang e s occurred, leading the authors to propose an interesting hy pothesis for further

t e st i n g : aft e r form at i on of C DDs/ C DFs occurs on t h e surface of fl y ash, t h e cong ener profi l e

r e ma ins f i x e d a nd inse nsitive to c h a n g e s in te mpe r a t ur e or r e side nc e time , indic a ting tha t some form of equilibrium is reached in the formation kinetics.
Gullett and L e mieux (1994) used a pilot-scale combustor to study the effect of vary ing combustion g a s composition, temperature, resi dence time, quench rate, and sorbent (Ca[ OH] 2 

### ) injection on CDD/CDF formation. The fly ash loading was simulated by injecting fly ash
col l ect ed from a ful l

- scal e MW C

. S a m p l i n g and anal y s i s i ndi cat ed t h at C DDs/ C DFs form ed on

t h e i n j ect ed fl y ash at l e vel s represent a t i v e of t hose observed at ful l

- scal e MW C s

. A st at i s t i cal

2-16

### analy s is of the results showed that, althoug h the effect of combusto r operating parameters on
CDD/CDF f o r m a tion is inte r a c tive a nd ve r y c o mplic a t e d, substa ntia l r e duc tion in CDD/CDF
formation can be realiz ed with hig h -tempera tur e sor b e n t inje c tion to r e duc e HCl or Cl 2 

### concent r at i ons, cont rol ex cess ai r (whi ch al so a ffect s t h e rat i o of C DDs t o C D Fs form ed), and increase quench rate. Millig an and Altwicker (1995) found that increases in the carbon g a sification rate caused
increases in the amounts of CDDs /CDF s formed and g a ve further evidence linking the ox idation
of carbon to the formation of CDDs /CDF s. Neither the g a s-phase CO 2 

### or CO (products of
carbon ox idation) act as precursors to chlorobe nz enes or CDDs/CDFs from reactions with carbon particulate (Millig an and Altwic ker, 1995). Activated carbon, with its hig h surface area and

ex cel l e nt adsorpt i v e charact eri s t i c s, al so has t h e hi g h est g a si fi cat i on rat e of al l resi dual carbon (Addink and Olie, 1995).
Ex peri m e nt al evi d ence sug g e st s t h e fol l o wi ng fact ors for t h e de novo sy nthesis of
CDDs/CDF s from carbon: (a) carbon consisting of imp erfect and deg e nerated lay e rs of g r aphite, (b) t h e presence of ox y g en, (c) t h e presence of ch lorine, (d) caty liz ation of the reactions by CuCl 2 

### or some other transition metal, and (e) temperatures in the rang e of 200 to 350°C (Huang and
B u ekens, 1995). The ox idation of carbon in fly ash is apparently inhibited at temperatures below 200°C, thus indicating the lower temperat ure limit for the thermal inertiz ation of de novo

sy nthesis (L asag ni et al., 2000).
L a sag n i et al. (2000) determined that at a temperature of 250°C, the primary product of the g a sification of carbon in fly ash is CO 2 

### , but in a temperature rang e of 250 to 325°C, org a nic compounds are formed as products of the ox idation of the carbon. Addink and Olie (1995) raised the possibility that the molecular backbone of CDDs/CDF s may be present in carbon. I f this is the case, the g e neration of diox ins and furans from the ox idation of carbon would not require the formation of intermedia te aromatic ring structures. Mo re work is needed to confirm
the s e possibilitie s. The de novo sy nthesis of CDDs/CDF s also i nvolves the possibility that aromatic precursors are form ed wi t h i n t h e post

- com bust i on z one in the following manner: (1) fuel
molecules are broken down into sm al l e r m o l ecul a r speci es (e.g ., C 1 

### and C 2 

### mole c u le s) dur ing primary combustion, and (2) these simple molecu les recombine in the post-combustion z one to form larg er-molecular aromatic species (i.e., chlorobenz enes and chlorophenols) (Altwicker et al., 1993). Thus, small molecular products that evolve in the hot z one of the furnace as a consequence of incomplete fuel or feed material combustion may be important foundation molecules to the subsequent formation of pr ecursor compounds in the cooler, post-combustion

reg i on.

2-17

### Eklund et al. (1988) reported formation of a wide rang e of chlorinated org a nic compounds, including CDDs, CDF s , and PCB s , fro m the ox idation of methane with HCl at temperatures of 400 to 950°C in a quartz flow tube reactor. No active cataly s ts or reactive fly ashes were added to the combustion sy stem. F r om these ex perimental results, the authors hypothesiz e d that chlorocarbons, in cluding CDDs/CDF s, are formed at hig h temperatures via a

se r i e s of r e ve r s ible r e a c tions sta r ting with c h lor o me thy l r a dic a l s. The c h lor o me thy l r a dic a ls c a n be formed from the reaction of methy l radical s and HC l i n a soot i n g fl am e. Met h ane i s chlorinated by HCl in the presence of ox y g en at hig h temperatures, forming chlorinated methanes, which react with methy l radicals at hi g h er temperatures (e.g
., 800°C) to form aromatic compounds. I n an ox idative atmosphere, chlo rinated phenols are formed, but alkanes and alkenes are the primary products. The chlori nated phenols then act as precursors for the subsequent formation of CDDs/CDF s. Aliphatic compounds are common products of incomplete combustion, and they may be

c r itic a l to the f o r m a tion of simple r i ng str u c t ures in the post-combustion z one (W eber et al., 1999; Sidhu, 1999; F r oese and Hutz ing e r, 1996a , b; J a rmohamed and Mulder, 1994). The aromatic precursor compounds may be formed in a potentially rich reaction environment of aliphatic compounds, reactive fly ash particles, HCl, and ox y g en. S i dhu (1999) noted that combustion of acety l ene on carbon (a common com bustion effluent) in the presence of g a seous H C l a nd CuCl 2 

### (as a cataly s t) at 300°C led to the fo rmation of intermed iate precursors and, subsequently , CDDs/CDF s. P r opene ox idiz ed at 350 to 550°C when in contact with reactive MW C fly ash in a flow tube reactor formed a wide rang e of chlo rinated aromatic compounds when the resulting combustion g a ses were mix ed with HCl (J armohamed and Mulder, 1994). Althoug h the conversion was low (1 to 3%), the ox idation of propene on fly ash in the presence of HCl can

y i eld chlorinated benz enes and monobenz ofurans. I n corporating an ox y g en atom into the
monobenz ofuran structure then leads to th e formation of monodibenz ofuran. The HCl contributes chlorine to the aromatic ring thr oug h the Deacon reaction, and cy cliz ation on the fly ash surface can y i eld cy clohex a dieny l -substituted benz enes, which in turn can be further ox idiz ed
into CDF s

. Froese and Hutz ing e r (1996a) i nvestig ated the heterog e neous combustion reactions of the
nonchlorinated C 2 

### aliphatics. Acety l ene, as a mode l aliphatic compound, wa s allowed to react with precleaned MW C fly ash in a tube flow reactor at approx imately 600°C. Metal ox ides ( s ilic on diox ide [SiO 2 

### ]
, iron ox ide [ F e 2 

### O 3 

### ]
, and copper ox ide [ C uO] ) —rather than the metal
chl o ri des used i n ot her precursor ex peri m e nt s—we re added separat e l y as cat al y s t s

. The react ant s were put into contact with HC l vapor, which was introduced at a constant flow rate. The

2-18

### acety l ene flow was set at 1.1 mL /min and cons tantly fell to near 0.9 mL /min over 30 min.
Re g u la te d a i r f

l ow ma inta ine d home o sta tic ox ida tion c onditions.
Chlorobenz enes and chlorophenols were formed, with isomer patterns g e nerally resembling isomer patterns of chlorobenz ene and chlorophenol emissions from MW Cs. CuO was seen as cataly z ing condensation and chlo rination reactions under heterog e neous conditions
to form the chlorinated CDD/CDF precurs or compounds. Other more volatile compounds formed were short-chain alipha tic products, such as chloromethane, dichloromethane, and chloro- and dichloroacety l ene. Chlorobenz ene cong eners were not the major products formed; perchlorinated aliphatic compounds dominated as g a s-phase reaction products.
F r oese and Hutz ing e r (1997) noted that perchlorinated ali phatic compounds (e.g

., hex achloropropene, hex achloro -1,3-butadiene, and hex achloro cy clopentadiene) are important
inte r m e d ia te s in a r oma tic r i ng f o r m a tion; th ey concluded that the cataly tic reaction of C 2 

### aliphatic compounds at 600°C dram atically contributes to the formation of chlorinated and nonchlorinated aromatic compounds during com bustion. Thus, aliphatic compounds can form
CDD/CDF precursor compounds. Va riable temperature effects we re observed in the formation
of CDDs/CDF s in the same reactions. Max imal OCDD formation occurred at 400°C, and the tetra throug h hepta homolog ue g r oups were max imally formed at 600°C. F o r CDF s , production of more hig h ly chlorinated homolog ues occurred at 400°C, and the formation of TCDF s occurred
at 500°C. F r oese and Hutz ing e r (1996a) noted a 100-fold increase in TC DF formation at 500°C when compared with formation at 400°C. An ex planation for this incr ease is that the hig h er temperature max imiz ed the formation of th e CDD/CDF precursor (chlorophenol) from the aliphatic starting compound.
F r oese and Hutz ing e r (1996b) produced pol y c hlorinated benz ene and phenol compounds at a temperature rang e of 300 to 600°C, caused by the heterog e neous combustion reactions of ethy lene and ethane over fly ash in the presen ce of HCl, ox y g en, and a metal cataly s t. No
chlorobenz ene cong ener precursors were formed from ethy lene and ethane at 300°C; however, the formation rate increased with temper ature until a max imum pr oduction was achieved at
600°C. No definitive temperature dependence wa s observed for the formation of chlorophenols from the aliphatic starting compounds. However, at 500°C, 2,4,6-trichlorophenol dominated the reaction products; at 300°C, PCP was initially produced.
F r oese and Hutz ing e r (1996b) also investig at ed the effects of elemental cataly s ts on potentiating the heterog e neous combustion reactions by measuring the amount of chlorobenz ene and chlorophenol product formed from the reacti ons of ethy lene/HCl over each cataly s t at
600°C. The reaction with S i O 2 

### did not have a cataly tic e ffect. Aluminum ox ide (Al 2 

### O 3 

### ) c a ta ly tic action showed hig h intensity for the dichlorobe nz ene i s om ers and decreasi n g i n t e nsi t y for t h e hig h er-chlorinated isomers. Comparison of the amount of dichlorobenz ene product formed

2-19

### indicated that an equal quantity was produced with either Al 2 

### O 3 

### or fly ash; however, Al 2 

### O 3 

### formed four to five times more product than did the CuO cataly s t. F o r tri- to hex achlorobenz ene
cong eners, MW C fly ash reactions produced 5 to 10 times more product than did the metal

cat al y s t s

. However, t h e presence of t h e C u O cat al y s t i n t h ese react i ons produced a
chl o robenz ene cong ener pat t e rn com p arabl e t o t h at of the fly ash reactions. W ith reg a rd to chlorophenol production, Al 2 

### O 3 

### also produced a unique dichlo rophenol pattern, sug g e sting that
Al 2 

### O 3 

### has a unique cataly tic effect in th e hig h -temperature reactions of C 2 

### aliphatic compounds. Reactions with CuO produced additional products, including chlorinated methy l compounds, chlorinated C 2 

### aliphatics, and perchlorinated C 3 

### –C 5 

### alky l compounds. F r oese and
Hutz ing e r noted that these perchlorinated alky l g r oups, formed by reacting ethy lene and ethane over fly ash in the presence of the CuO cataly s t, were key intermediate compounds to the formation of first aromatic ring s in ty pical co mbustion sy stems. This emphasiz e s the importance of copper’s cataly tic effects in a combustion fly ash sy stem. Al 2 

### O 3 

### cat al y z ed react i ons produced nonchlorinated naphthalene and al ky lbipheny l compounds. F u rthermore, the org a nic chlorine in aliphatic compounds may also act as a direct source of chlorine for the formation of CDDs/CDF s in a carbon fly ash sy stem (W eber et al., 1999).
I n an earlier ex periment using a similar flow tube apparatus, F r oe se and Hutz ing e r (1994)
formed chlorinated benz enes and phenols in fly as h cat al y z ed react i ons wi t h t r i c hl oroet h y l ene at temperatures of 400 to 500°C. I n this case, metal ox ides (CuO, F e O 3 

### , and Al 2 

### O 3 

### ) were used as cataly s ts, but no HCl was added for ox y c hlorin ation of product compounds. Under combustion conditions, temperature-depende nt formation of chlorinate d aromatics occurred from the trichloroethy l ene starting compound. Reaction with fly ash at 600°C formed hex achlorobenz ene in concentrations that were about 1,000 times g r eater than those at 400 and 500°C, with similar results for chlorophenols. The authors hy pot hesiz e d that key aromatic precursors for
CDDs/CDF s are formed in the hig h er-temperature reg i on of a post-combustion z one (about 600°C) and are then carried to the cooler post-combustion reg i on (about 300°C), where the precursors form C DDs/ C DFs.

2.4. THE ROLE OF CHLORINE IN THE F O RMATION OF CDDs/CDF s IN C O M B U S TION SY STEM S The formation of CDDs/CDF s in the post-co mbustion reg i on of combustion sy stems via either the precursor or de novo sy nthe sis me c h a n isms r e quir e s the a v a ila bility of a

sour c e of chlorine (L uijk et al., 1994; Addink et al., 1995; Stanmore, 2004; W i kstrom et al., 2003 ).
Chlor i ne c onc e n tr a tion in this r e g i on is some how r e la te d to the chlorine content of combustion
fuel s and feed m a t e ri al s i n i n ci nerat i on/ com bust i on sy st em s because t h ere can be no ot her source. The ma in que stion r e g a r d ing the r o le of c h lor i ne in f o r ming CDDs/CDF s is whe t he r a

positive

2-20

### and direct correlation ex ists between the am ount of chlorine in feeds and the amount of
CDDs/CDF s f o r m e d a nd e mitte d f r o m the sta c k of a

c o mbustion sy ste m

. I f a

dir e c t r e la tionship appears to ex ist, then reductions in the chlorine content of fuels/feeds prior to combustion should result in a corresponding reduction in the c oncentrations of CDDs/CDF s formed after
combustion. I f the ox y c hlorination reactions re quire a number of steps, then the relationship
between chlorine in uncombusted fuels and C DDs/CDF s formed after combustion may not be linear, althoug h it may still be de pendent in some nonlinear asso ciation. The main question can best be addressed by ex am i n i n g bot h form at i on m echani s m s reveal ed i n l a borat ory

- scal e combustion ex periments and co rrelations between chlorine inputs with CDD/CDF outputs in

c o mme r c ia l- sc a l e c o mbustor s

.

2.4.1. Review of Laboratory-Scale Studies A wide body of ex perimental evidence has eluc idated the direct and indirect associations
between chlorine in feeds and fuels and the pote n tia l f o r m a tion of CDDs/CDF s dur ing
combustion. The de novo sy nthesis of CDDs/CDF s requires tw o basi c react i ons: (1) t h e t r ansfer of chlorine to residual carbon pa rticulate, with subsequent fo rmation of carbon-chlorine bonds,

a nd ( 2 ) the ox ida tion of this ma c r omole c u la r c o mple x to y i e l d CO 2 

### a nd vola tile a nd se mivola tile

org a nic compounds as side products (W eber et al., 1999). Transition metal compounds such as
CuCl 2 

### cat al y z e t h ese react i ons. Gaseous HC l

, C l 2 

### , and Cl
@ 

### are the most abundant sources of

c h lor i ne a v a ila ble f o r

pa r tic ipa tion in the f o r m a tion of CDDs/CDF s, a nd the y a r e initia lly f

o r m e d as a combustion by -product from the inorg a nic and org a nic chlorine contained in the fuel (W ikstrom et al., 2003; Rig o, 1998; Addink et al ., 1995; Rig o et al., 1995; Halonen et al., 1994;
L u ijk et al., 1994; Altwicker et al., 1993; W a g n er and Green, 1993; Dickson et al., 1992; B r uce et al., 1991; Gullet et al., 1990b; Comm oner et al., 1987; Vog g et al., 1987).
MSW contains approx imately 0.45 to 0.90% (w/w) chlorine (Domalski et al., 1986). The

m o st predom i n ant chl o ri ne speci es form ed from MSW combustion is g a seous HCl, which

averag es between 400 and 600 ppm in the com bustion g a s (W ikstrom et al., 2003; U.S. EPA, 1987a). Chlorine is initially released from the ch lorine in the MSW and is rapidly transformed to HCl by the abstraction of hy drog en from r eaction with hy drocarbons present in the fuel (W ikstrom et al., 2003). HCl may ox idiz e to y i eld Cl 2 

### g a s by the Deacon reaction, and the Cl 2 

### directly chlorinates a CDD/CDF precursor along the aromatic ring structure. F u rther ox idation of

t h e chl o ri nat e d precursor i n t h e presence of a

tr a n sition me ta l c a t a l y s t ( o f whic h CuCl 2 

### was found to be the most active) y i elds CDDs/CDF s (A ltwicker et al., 1993). I n creasing the y i eld of chlorine in vapor phase from HC l ox idation g e nerally increases the rate of CDD/CDF formation.
F o rmation kinetics are most favor ed at temperatures rang ing from 200 to 450°C. However HCl

2-21

### is considered a weak chlorinating ag ent because of the tenacity of the hy drog en-to-carbon bond of aromatic compounds (W ikstrom et al., 2003). Chlorine production from g a seous HCl can be reduced either by limiting initial HCl concentration or by shortening the reside nce time (B ruce et al., 1991; Gullett et al., 1990b; Commoner et al., 1987). B r uce et al. (1991) obser ved a g e neral increase in CDD/CDF formation with increases in the vapor-phase concentration of chlorine a nd verified a dependence of the
f

o r m a tion of CDDs/CDF s in the post- c o mbustion zone on the c onc e n tr a tion a nd a v a ila bility of

g a se ous c h lor i ne

. This la tte r f

i nding is in a g r e e m e n t with the r e sults of a

simple e x pe r ime nt by Eklund et al. (1986) in which unsubstituted phenol was mix ed with HCl at 550°C in a quartz
tube reactor. A wide rang e of tox i c chlo rinated hy drocarbons were formed, including
CDDs/CDF s. Eklund et al. (1988) also found a dependence of the amount s of chlorinated phenol product formed from the nonchlorinated startin g material on the increased amount of HCl
introduced into the reaction. Under the conditi ons of this ex periment, no chlorinated compounds
were form ed at an HC l c oncentration of less than 10 -3 

### mol, and max imum chlorophenol
concentration occurred at around 10 8 

### mol.
B o rn et al. (1993) also observed that increasing levels of HCl g a ve ri se to increasing rates of ox y c hlorination of precursors, with increas ing chances for the post-combustion formation of
CDDs/CDF s. However, Addink et al. (1995) observed that an HC l atmosphere and/or chlorine

pr oduc e d a ppr ox ima te ly e qua l qua ntitie s of CDDs/CDF s dur ing the de novo sy nthesis from

ox idation of particulate carbon. S u ch results sug g e st that chlorine production via the Deacon

r e a c tion in the de novo sy nthesis may not be the only ch lorination pathway

, and they may indicate that the HCl mol ecule can be a direct chlorinating ag ent. I n addition, some chlorine is

ex pect ed t o be form ed from t h e ox i d a tion of me ta l c h lorides (e.g ., CuCl 2 

### ), but Cl 2 

### form at i on from the Deacon reaction is g r eater because of th e continuous supply of HCl delivered from the combustion chamber (B ruce et al., 1991). I n this case, a first-order dependence of HCl to Cl 2 

### is
observed. However, W i kstrom et al. ( 2003) reported on the importance of chlorine species on the de

novo form at i on of C DDs/ C DFs. HC l can react wi t h ox i d i z i n g radi cal s (e.g ., hy drox y l radi cal

, or OH) to produce Cl

A



### . Cl

A 

### are hi g h l y react i v e and can repl ace hy drog en at om s wi t h chl o ri ne at om s in the H-C bond of the aromatic structure. Thus, HCl is most likely an indirect chlorinating ag ent via the formation of Cl

A



### . Ex perimentally , about 18% of the total chlorine content in fuels can be thermally
converted to Cl

A 

### in the post-combustion reg i on (P rocaccini et al., 2003). Althoug h HCl is the primary chlorine-containing product formed from the combustion of chlorine-rich fuels, it may
not be the ma jor c h lor i na ting a g e n t in the f o r m a tion of c h lor o

- o r g a n ic s in the c oole d

- down

reg i on of the combustor. The ex periments by P r ocaccini et al. (2003) indi cate that the major role

2-22

### of HCl in the formation of chloro-org anic com pounds at cooler temperatur es may be that of a
chem i cal prog eni t o r of C l

A



### . HCl reacts with the ox idiz ing radicals OH and O that are abundantly present i n com bust i on off-g ases t o reform C l

A



### . Cl

A 

### readi l y abst ract hy drog en at om s from t h e H-C bond of aromatic compounds formed as combustion by -products of org a nic fuels. B y this means, unsubstituted aromatic compounds, e.g ., benz ene, underg o ox y

- chlorination reactions with the
Cl

A 

### to form chlorobenz enes and chlorophenols. These products are well-defined precursor compounds for the sy nthesis of CDDs/CDF s. W a g n er and Green (1993) investig ated the correla tion of chlorine content in feed to stack emissions of chlorinated org a nic compounds in a pilot-scale incinerator using HCl flue g a s measurements as a surrog a te for fuel-bound org a ni c chlorine. I n addition to MSW as a fuel, variable amounts of poly v iny l ch loride (PVC) resin were added during 6 of 18 stack test runs.
The r e sulting da ta we r e r e g r e sse d to de te r mine the c o e f f i c i e n t of c o r r e la tion be twe e n HCl
measurements and total chlorobenz ene compound e mission measurements. I n nearly all of the

reg r ession analy s es performed, the relations hip between HCl emissions and emissions of chlorinated org a nic compounds was positive and we ll defined. I n addition, the investig ators found a direct dependence of HC l emission levels on the level of PVC in the waste, with

g e nerally increasing amounts of HCl formed as increasing amounts of PVC were added. F r om these ex periments, they concluded that decreas ed levels of org a nically bound chlorine in the
waste incinerated led to decreas ed levels of chlorinated org a nic compounds in stack emissions.
Kanters and L ouw (1994) investig ated a possi ble relationship between chlorine content in waste feed and chlorophenol emi ssions in a bench-scale thermal reactor. MS W incineration with a hig h er content of chlorine in the feed cau sed hig h er emissions of chlorophenols via the de novo

sy nthesis pathway

. The inves tig a t or s lowe r e d the c h lor i ne c ontent of the prototy p e MW C by replacing chlorine-containing fr act i ons wi t h cel l u l o se. They observed appreci abl e decreases i n the amounts of chlorophenol formed from combus tion, and concluded that reductions in the

c h lor i ne c onte n t of wa ste f e e d s or e limina tion of PVC pr ior to munic i pa l wa ste c o mbustion should result in a corresponding reduction in chlorophenol and CDD/CDF emissions.
I n a similar ex periment, W i kstrom et al. (1996) investig ated the influence of chlorine in
feed m a t e ri al s on t h e form at i on of CDDs/CDF s and benz enes in a laboratory

- scale fluidiz e d-bed

react or. S e ven art i f i c i a l fuel s (com posed of 34% paper, 30% wheat fl our, 14% saw dust

, 7% poly e thy l ene (PE), and 2% metals), to which va ry ing amounts of org a nic chlorine and inorg a nic
chl o ri ne (C aC l 2 

### A 

### 6H 2 

### O) were added, were combusted. The ch lorine content of these fuels varied
from 0.12 to 2%. All combustion was performed with a hig h deg r ee of combustion efficiency (99.999%) to avoid the formation of poly v iny lid ene chloride and napht halenes as products of incomplete combustion of pure PVC. W ith th e combustion conditions held constant, only the

2-23

### chlorine content of the fuel was varied. F l ue g a ses were sampled for CDDs/CDF s and
chlorobenz enes. I n these ex periments, concentrations of PCB isomers were approx imately 1,000-fold hig h er than C DDs/C DFs (ex p re ssed as concentration of I

- TEQ DF 

### ). Moreover, a correlation was
found between I

- TEQ DF 

### and PCB levels in the fl ue g a ses and the chlorine content of the fuel. A
fivefold increase in both I

- TEQ DF 

### and PCB concentrations was obs erved in the flue g a ses from combustion of fuels containing 0.5 and 1.7% tota l chlorine. F u rthermore, no differences were
observed in the amount of chlori nated product produced or when th e source of chlorine in the fuel was org a nic or inorg a nic. No correla tion was observed between tota l CDD/CDF a nd PCB
formation and total chlorine in the feed when chlo rine levels in feed we re 0.5% or lower. The hig h est amounts of CDDs/CDF s and PCB s were fo rmed from the fuel with the hig h est total chlorine content (1.7%).
Under the conditions of this ex periment, W i ks trom et al. (1996) observed that a chlorine
fuel content of 1% was a threshold for fo rmation of ex cess CDDs/CDF s and PCB s during
combustion. The authors noted that MSW in Sw eden contained about 0.7% chlorine, of which

approx imately 40% was org a nic chlorine. They concluded th at MSW was below the observed
threshold value of 1% chlorine content associat ed wi t h a g e neral i n crease i n C DD/ C D F and P C B formation in the post-combustion reg i on. They al so stated that their study did not support the hy pothe sis tha t e limina tion of only PVC f r o m wa ste pr ior to c o mbustion will c a u se a sig n if ic a n t reduction in CDD/CDF emissions if the combusti on process is well controlled (hig h combustion efficiency ). W a ng et al. (2003) verified the ex istence of a theore tical chlorine-in -fuel threshold
when t h ey dem onst r at ed de novo sy nthesis when combusting fuels with 0.8 to 1.1% chlorine. A primary by -product of PVC combustion is HCl. Paciorek et al. (1974) thermally deg r aded pure PVC resin at 400°C and produced 550 mg /g HCl vapor as a primary thermoly sis product, which was observed as being 94% of the theoretical amount, based on the percent weig ht of chlorine on the molecule. Ahling et al . (1978) concluded that HCl can act as a chlorine donor to ultimately y i eld chlorina ted aromatic hy drocarbons from the thermoly tic deg r adation of

pur e PVC a nd tha t the s e y i e l ds a r e a f

unc tion of tr a n sit time , pe r c e n t ox y g e n, a nd te mpe r a t ur e

. They observed data from 11 sepa rate ex periments c onducted with temperatures rang ing from 570 to 1,130°C. These data indicated that sig n ifi cant quantities of various isomers of dichloro-, trichloro-, tetrachloro-, and hex achlorobenz enes could be produced. Choudhry and Hutz ing e r (1983) proposed that the radical species Cl

A 

### and H

A 

### g e ne r a te d in the in cineration process may

a tta c k the c h lor i na te d be nze n e s a nd a b str a c t hy dr og e n a t oms to pr oduc e or thoc hlor ine

- substitute d chlorophenol radicals. These inte rmediate radical species then react with molecular ox y g en to

y i eld ortho-substituted chlorophenols. As a fina l step, the ortho-substituted chlorophenols act as ideal precursors to y i eld CDDs/CDF s with h eat and ox y g en. The chlorine in aliphatic

2-24

### compounds has been observed as both y i elding hig h amounts of HCl during combustion and

act i n g as a di rect chl o ri ne source for t h e de novo sy nthesis of CDDs/CDF s (W eber et al., 1999). Kim et al. (2004) determined that the co mbustion of pure PVC y i elded appreciable amounts of poly c y c lic aromatic hy drocar bons (PAHs), PCB s , chlorobenz enes, and chlorophenols. They sug g e sted that the g a s-phase production of PC B s and chlorobenz enes contributed to the g a s-phase formation of CDDs/CDF s thr oug h the pr e c u r s or me c h a n ism. Chlorophenols, however, contributed to the de novo formation. Kim et al. (2004) reported that
the de novo sy nthesis of CDDs/CDF s from chlor ophenols was approx ima tely 100 times g r eater

t h an t h ei r form at i on from P C B and chlorobenz ene precursors. Katami et al. (2002) found a clear correlation between diox in formation and the chlorine
content of mix ed plastics combusted in a laborat ory

- scale incinerator. PVC, PE, poly s ty rene (PS), poly e thy l ene terepht halate (PET), and their various mix tures were burned at temperatures

g r eater than 600°C. Averag e CO concentrations in the ex haust g a ses were varied from 2 to 880

ppm a s a g e ne r a l indic a tion of the qua lity of the f i r e in the c o mbustion c h a m be r

. Whe n i n ci nerat e d, each t y pe of pl ast i c form ed C DDs/ C DFs i n t h e ex haust g a ses. Of t h e t o t a l C DDs formed, Hx CDD and TCDD formed in the g r eatest amounts when PE was combusted. MonoCDF was the most abundant CDF formed from PE combustion. Mono-ortho coplanar PCB s were preferentially formed over nonortho-PCB s

. The combustion of PS caused TCDD to be formed in the g r eatest abundance of all possi ble CDDs, whereas TCDF was the most abundant
dibenz ofuran. Mono-ortho PCB s formed more than nonortho coplanar PCB s when PS was
combusted. The combustion of PET mostly formed MC DD and MC DF among the C DDs/C DFs
form ed.
W h en PVC was combusted with the conditions of hig h temperature and low CO (g ood combustion), a total of 53.5 ng /g of total CDD wa s formed, with the Hx CDD predominating

. I n addition, g ood combustion conditions formed a total of 771 ng /g of CDF s , with Cl 2 

### and Cl 3 

### CD F

cong eners dominating

. W h en PVC was combuste d with the conditions of low temperature and hig h CO (poor combustion), the total CDDs and CDF s formed increased sig n ificantly to 429 ng /g and 8,492 ng /g , respectively

. TrCDD and DiCD F dominated the cong ener distributions,

sug g e sting that poor combustion of PVC tends to form hig h levels of lower-chlorinated
CDDs/CDF s. The investig ators observed that maintaining g ood combustion tended to minimiz e the f o r m a tion of CDDs/CDF s f r o m the c o mbustion of chlorinated plastics. Shibata et al. (2003) reported on the form ation of CDDs/CDF s from the combustion of
P V C i n quart z am pul es. S y nt hesi s of C DDs/ C DFs proceeded de novo i n a t e m p erat ure rang e of 200 to 400°C, with the reaction cataly z ed by CuO. Max imum formation occurred at 300°C. HpC DDs and OC DD were the dominant C DDs obs erved in the flue g a ses, whereas TCDF s,

2-25

### PeCDF s , and Hx CDF s dominated the CDF s

. The r a tio of CDF s to CDDs f r o m PVC c o mbustion

was g r eater than 1, which is ty pical of MSW combustion (Shabata et al., 2003). Addink and Altwicker ( 1999) reported on the role of the inorg a nic chloride ion in the
formation of CDDs/CDF s using the labeled compound Na 37 

### Cl. The inorg a nic chloride ion forms carbon-chlorine bonds on soot par ticles during combustion. The chlorine in the soot can be directly inserted into a CDD/CDF molecule during formation, or it can ex chang e with the chloride ions in the transitional metal cataly s t, which promotes CDD/CDF formation. Thus, the inorg a nic chlorine ion participates as a chlorine donor to CDD/CDF formation.
De F r e and Ry men (1989) re ported on the formation of CDDs/CDF s from hy drocarbon combustion in a domestic g a s/oil burner in th e presence of 15 and 300 ppm concentrations of
HCl. More than 100 chlorinated org a nic compounds were detected in the flue g a ses whenever
HCl wa s inje c t e d into the sy ste m

. The inve s tig ators observed formati on of CDDs and CDF s in
all ex periments where HCl was injected in a hy dr ocarbon flame. I n this case, CDF s were alway s more abundant than CDDs. I t wa s concluded that the relationshi p between the HCl concentration
and the emitted concentration of CDDs/CDF s under fix e d combusti on conditions appeared to be

ex ponential for a wide rang e of temperatures (240 to 900°C).

2.4.2. Review of F u ll-Scale Com bustion System s The review of ex perimental da t a cl earl y i ndi cat es an associ at i on bet w een chl o ri ne cont ent of feed/fuels and the potential sy nthesis of CDDs/CDF s. Paradox i cally , the review of full-scale operating incineration pro cesses does not y i eld such unequivocal r e sults, indic a ting tha t c o mple x kinetic events make strong associ a tions dif f i c u lt in f u ll- sc a l e sy ste m s. The f o llowing is a r e vie w of studies of the association between chlorine in feeds and st ack rel eases of C DDs/ C DFs i n ful l

scal e i n ci nerat i on sy st em s. I n the stack testing of a variety of indus trial stationary combustion sources during the
National Diox in Study in 1987, EPA made a se ries of qualitative observations about the

r e la tionship be twe e n tota l c h lor i ne pr e s e n t in the f u e l/wa s te a nd the ma g n itude of e missions of
CDDs/CDF s from the stack of the tested full-s cale combustion facilities (U.S. EPA, 1987a). I n
g e ne r a l, c o mbustion units with the hig h e s t CDD e mission c onc e n tr a tions ha d g r e a t e r qua ntitie s of chlorine in the fuel; convers ely

, sites with the lowest CDD emission concentrations contained only trace quantities of chlorine in the feed. The typical chlorine content of various combustion fuels was reported by L u stenhouw er et al. (1980) as coal, 1,300 : 

### g / g ; MSW
, 2,500 : 

### g / g ; l eaded

g a soline, 300 to 1,600 : 

### g / g ; and unleaded g a soline, 1 to 6 : 

### g/ g. Thomas and Spiro (1995) also analy z ed the relationship between CDD/CDF emissions
from combustion and the chlorine content of feed materials. Thomas and Spiro (1996) plotted

averag e C DD/ C D F em i ssi on fact ors for a vari et y of com bust i on sy st em s and processes (bl ack

2-26

### liquor boilers, unleaded g a soline combustion, l eaded g a soline combustion, wire incineration, cig a rette combustion, sewag e sludg e incine ration, MW C, PCP-treated wood combustion,
haz a rdous waste incineration, a nd hospital waste incineration) ag ainst the averag e chlorine
concentration of the combusted material. The plot showed that aver ag e CDD/CDF emissions of

com bust i on source cat eg ori e s t e nded t o i n crease wi t h t h e averag e chl o ri ne cont ent of t h e

com bust e d fuel

. Thi s anal y s i s i ndi cat ed t h at combustion sources with relatively hig h combustion efficiency and adequate air pollution controls te nded to have emissions two orders of mag n itude lower than those of poorly operated sources. This sug g e sts that the mag n itude of CDD/CDF emissions is strong ly dependent on chlorine concentration in fuels in the contex t of the more poorly controlled and opera ted combustion sources, and the asso ciation becomes less apparent in
the well-controlled facilitie s operating with g ood combustion prac tices. The slope of the log

- log plot was between 1 and 2 for the poorly contro lled and operated facilities, indicating that the relationship between chlorine content and CDD/CDF emissions was more than proportional. Costner (1998) reported finding a positive corre lation between chlorine content of feed

m a t e ri al and C DD/ C D F em i ssi ons at a ful l

- scal e hospita l wa ste inc i ne r a to r. Costner concluded that emissions at this facility were dependent on chlorine input at a concentration as low as
0.031% and that there was no evidence of a threshol d in the relationship between chlorine in feed
and CDD/CDF emissions. Rig o et al. (1995) summariz e d the results of a study commissioned by the American Society of Mechanical Eng i neers (ASME, 1995). The study was a statistical evaluation of the relationship between HCl concen tration in flue g a ses and va rious combustion sy stems (MW C s, hospital waste incinerators, HW I s , biomass com bustors, laboratory combus tors, and bench-scale combustors) and stack emissions of total CDDs /CDF s. I n this study , HCl was used as a

sur r o g a te f o r

tota l c h lor i ne c onte n t in the f u e l

. The da ta a n a l y s is wa s suf f i c i e n t f o r

92 f a c ilitie s in
the da ta ba se tha t showe d both HCl a nd CDD/CDF e missions. Of the 92 f a c ilitie s, 72 did not show a statistically sig n ifi cant relationship between chlori ne input and CDD/CDF output in emissions streams, 2 showed in creasi n g C DD/ C D F concent r at i ons wi t h i n creasi n g chl o ri ne, and 8 showed decreasing CDD/CDF concentrations w ith increasing chlorine. ASME (1995) reports the following conclusion:

The f a ilur e to f i nd simulta ne ous inc r e a s e s in most cases and finding inverse relationships in a few i ndi cat es t h at any effect chl o ri ne has on C DD/ C D F

e missions is sma lle r tha n the va r i a b ility of othe r c a u sa tive f a c t or s. Wha t e v e r effect chl o ri ne has on C DD/ C D F em i ssi ons i n com m e rci a l

- scal e sy st em s i s masked by the effect of APCS (air po llution c ontr o l sy ste m s) te mpe r a t ur e , a s h chemistry

, combustion conditions, meas urement imprecision, and localiz ed flow
str a tif ic a tion.

2-27

### L i berson and B e lang er (1995) re ported the results of an analy s is of the formation and
emission of CDDs/CDF s as a function of total chlo rine in combustion feed m a t e ri al s at a rot a ry kiln HW I

. The data were g e nerated from multiple test series conducted over a 13-month period
at the HW I while operating a carbon injection sy stem specifically desig n ed to control and reduce
CDD/CDF stack emissions. The chlorine feed rates rang ed from 0 to 3,300 lb/hr, and the
CDD/CDF emission rates rang ed from 0.7 to 39 ng /d scm. The authors noted that multiple series
of CDD/CDF control sy stems were used on this HW I (a hig h -temperature secondary combustion chamber, a spray dry e r-evaporative quench that further cools the combustion g a ses, activated carbon injection to adsorb semivolatile org a nics , and a cool-side electrostatic precipitator followed by an acid g a s scrubber to collect HCl and Cl 2 

### ). F r om analy s es of the data, the authors
concluded that no correlation ex is ts between CDD/CDF emissions a nd chlorine feed in a modern
MW C using carbon injection for CDD/CDF control. More recently , W a ng et al. (2003) investig ated the association between chlorine content
of waste feeds and CDD/CDF emissions from fu ll-scale combustion sy stems. Previously

, W i kstrom et al. (1996) had discerned a chlorine content in feeds of 1% as being a threshold

concent r at i on for t h e form at i on of CDDs/CDF s, i.e., an asso c i a tion with the ma g n itude of
C DDs/ C DFs form ed occurred onl y when chl o ri ne cont ent i n t h e feed was $ 

### 1%. W a ng et al. confirmed the apparent ex istence of a chlorine threshold for emi ssions of tota l CDDs/CDF s a f te r statistically reviewing input of ch lorine in feed versus output of CDDs/CDF s in emissions at two
tested medical incinerators a nd two tested MW Cs. Additionally , the authors ex amined secondhand data from 13 other diox in sources obtained from the literature and found that the formation
of C D Fs was g r eat er t h an t h e form at i on of C DDs when t h e chl o ri ne cont ent of t h e wast e feed

ex ceeded t h e t h reshol d. However, when t h e chl o ri ne cont ent was bel o w t h e approx i m a t e 1% threshold, the formation of CDDs was g r eater th an the formation of CDF s

. The authors proposed
that chlorine content below the threshold form ed chlorinated precursors to CDDs rather than forming the dibenz ofuran molecule. Chlorine content above the threshold contributed to deterioration of combustion conditions, causing the formation of PAHs, which, in turn,
contributed to the formation of CDF s

.

2.5. P O TENTIAL P R EVENTION OF CDD/CDF F O RMATION IN COMBUSTION SY STEM S Given what is currently understood about ox y c hlorination reactions in the sy nthesis of
CDDs/CDF s, r e se a r c h e r s ha ve ide n tif ie d c e r ta in inte r v e n tions tha t c oul d be taken to reduce or impede formation in combustion sy stems. Rag hunathan and Gullett (1996) demonstrated in a pilot-scale incinerator that su lfur compounds can combine with the metal cataly s t necessary to stimulate the Deacon reaction of HCl and ox y g en to y i eld Cl 2 

### , t h ereby neut ral i z i n g t h e cat al y z i n g

2-28

### ag ent and reducing the formation of CDDs/C DF s. The Deacon reaction, which forms Cl 2 

### in the combustion plasma, is seen as occurring only in t h e presence of a cat al y s t

. Thus, t h e sul f ur diox ide (SO 2 

### ) mole c u le ( f o r m e d whe n sulf ur

in the f u e l c o mbine s with ox y g e n ) c a n inhibit the

c a t a l y tic a c tivity of the f l y

a s h by e ithe r c o mbining with a me ta l- ba se d De a c on c a t a l y s t in the f l y ash or depleting the Cl 2 

### formed. The authors observed that the principal action of sulfur in inhibiting the f o r m a tion of CDDs/CDF s in c o mbustion sy ste m s is thr oug h SO 2 

### depletion of Cl 2 

### ,

a s f o llows:

Cl 2 

### + S O 2 

### + H 2 

### O : 

### 2HCl + SO 2



### The relevance of this finding is that the co-combustion of MSW with coal (that contains sulfur) should lead to dramatic reductions in the amount of CDDs/CDF s formed and emitted, and
i t m a y ex pl ai n why

, i n t h e Uni t e d S t at es, coal combustion at power plants results in CDD/CDF

e mission r a te s mor e tha n a ma g n itude lowe r tha n those a t MWCs. Naikwadi and Karasek (1989) investig ated the addition of calcium ox ide (CaO) and

tr ie thy l a mine ( TEA) to the f l ue g a se s of a

c o mbustion sy ste m a s a n inhibitor of the c a t a l y tic activity of fly ash. They placed 500 : 

### g 13 

### C-labeled PCP (a diox in precursor) in a combustion
flow tube and allowed it to r eact with org a nic-ex tracted MW C fly ash at 300°C under an air

stream. Under these conditions , CDDs/CDF s were formed at concentrations rang ing from 1,660 to 2,200 ng /100 : 

### g 13 

### C-P C P

. The ex perimental method wa s then modified by mix ing reactive
MW C fly ash with either CaO or TEA. The re sults showed that the amount of CDDs/CDF s formed could be reduced by an order of mag n it ude from the reaction of PCP with fly ash and the
addition of TEA as an inhibitor. W h en CaO was mix ed with fly ash, the amount of CDDs/CDF s form ed decreased m o re t h an 20-fol d

.

2.6. THEORY ON THE EMISSION OF P C Bs
Air emissions of PCB s from MSW incinera tion is less well studied. Probably the
f

o r m a tion me c h a n isms tha t a pply to CDDs/CDF s would also apply to PCB s

. Mechanism 1 (pass throug h) is implicit in the Tox i c Substa nces Control Act rule, which requires 99.9999%
destruction in HW I s

. W h en this occurs, 0.0001% of the initial amount of PCB s fed into the HW I

ma y be e mitte d f r o m the sta c k. This ma y indic a t e tha t some sma ll f r a c tion of the PCB s pr e s e n t in the f u e l f e d into a n inc i ne r a tion pr oc e ss ma y r e sult in PCB e missions f r o m the sta c k of the

process. PCB s have been measured as contaminants in raw refuse prior to incineration in an MW C (Choudhry and Hutz ing e r, 1983; F e deral Reg i ster, 1991a ). Using this information, it is possible

to te st me c h a n ism 1 f o r

CDD/CDF e missions: tha t the PCB c onta mina tion pr e s e n t in the f u e l is

2-29

### _______ mainly responsible for emissions from the stac k. The mass balance of total PCB s , beg i nning
wi t h m easurem ent i n t h e raw refuse and endi ng wi t h m easurem ent at t h e st ack of a refusederived fuel (RDF ) MW C (F ederal Reg i ster, 1991a), can be used to calculate the destruction rated efficiency (DRE) of incineration of the PCB

- c onta mina t e d MSW. Using r e sults f r o m te st number 11 at the RDF facility (F ederal Reg i st er, 1991a), a computation of DRE can be made using the following equation (B runner, 1984):

W

I 

### - W O 

### DRE = × 100% W I


### where:
W I 

### = ma ss r a te of c onta mina n t f e d into the inc i ne r a tor sy ste m W O 

### = ma ss r a te of c onta mina n t e x iting the inc i ne r a tor sy ste m

I n test 11, 811 ng total PCB / g re fuse were measured in the MSW fed into the incineration

sy stem and 9.52 ng /g were measured at the inlet to the pollution control device (i.e., outside the furnace reg i on but preceding emission control). From these measuremen ts, a DRE of 98.8% can
be c a l c u la te d. The r e f or e , it a ppe a r s tha t PCB c onta mina tion in the r a w MSW f e d into this particular incinerator may ha ve accounted for the PCB emissions from the stack of the MW C.
PCB s can be thermoly tically converted into CDF s (Choudhry and Hutz ing e r, 1983;
U.S. EPA, 1984). This process occurs at temp eratures somewhat lower than those ty pically
measured inside the firebox of an MW C. L a boratory ex periments c onducted by EPA indicate that the optimum conditions for CDF formation from PCB s are near a temperature of 675°C in the presence of 8% ox y g en and a residence time of 0.8 sec (U.S. EPA, 1984). This resulted in a 3 to 4% efficiency of conversion of P C B s into CDFs. B ecause 1 to 2% of the P C B s present in
the r a w r e f u se ma y sur v ive the the r ma l str e ss impose d in the c o mbustion zone of the inc i ne r a tor (F ederal Reg i ster, 1991a), it is reasonable to pr esume that PCB s in the MSW may contribute to
the tota l ma ss of CDF e missions r e le a s e d f r o m the sta c k of the inc i ne r a tor

. Althoug h it appears that conta mination of waste feed with PCB s may be an important factor in detecting PCB s in stack emissions from combustion processes, recent research has indicated that these compounds ma y also be formed in the post-combustion reg i on, either from
de novo sy nthesis or from precursor compounds. Z h eng et al. (1999) observed the formation of
PCB s in the post-combustion reg i on from the py ro ly sis of chlorobenz enes using a laboratory

scale furnace. The investig ators observed that PCB s were optimallyformed from lesschlorinated chlorobenz enes (e.g ., 1,3- dichlorobenz ene) cataly z ed by CuCl 2 

### . I n this ex periment,

max imum PCB production occurred at a temperature of 350°C. W i kstrom et al. (1998) reported

2-30

### secondary formation of PCB s in th e post-combustion reg i on similar to the de novo sy nthesis of
CDDs/CDF s, albeit PCB s were formed in only small amounts relative to CDDs/CDF s. F a ng mark et al. (1994) postulated that form ation of PCB s and CDDs/CDF s in the postcombustion reg i on may occur throug h the same m echanisms. On the other hand, B l umenstock et al. (1998) produced results in a pilot-scale furnace that were inconsistent with the de novo
f

o r m a tion of CDDs/CDF s in the post- c o mbustion r e g i on ( i .e ., PCB s se e m e d to be optima lly formed at hig h temperatures in ox y g en-deficie nt atmospheres). Shin and Chang (1999) noted a positive c o rr e la tion be twe e n PCB c onc e n tr a tions on MSW inc i ne r a tion f l y

a s h a nd f l y

a s h
concentrations of CDDs/CDF s, sug g e sting that hi g h PCB levels in fly ash may be a contributory cause of the post-combustion formation of CDDs/CDF s (i.e., PCB s are precursors to
CDDs/CDF s). Nito et al. (1997) noted the form ation of CDDs/CDF s from the py roly sis of PCB s in a fluidiz e d-bed sy stem, indicating that PCB s in feeds may account for CDF s formed in MSW
incineration. More combustion-re lated research needs to be conducted to firmly establish
whether PCB contamination in feeds or post-co mbustion formation (or both) may ex plain the presence of PCB s in combustion flue g a ses.

2.7. SUMMARY AND CONCLUSIONS
2.7.1. Mech an ism s of F o rm ation of Dioxin-Like Com p ounds
There are t h ree pri m a ry m echani s m s for CDD/CDF emissions from combustion sources.
Mech an i s m 1 (p ass th rou g h )

. This mechanism involves CDDs/CDF s contained in the feed passing throug h the combustor intact and bein g subsequently released into the environment.
F o r most sy stems, this is not thoug ht to be a major contributor to CDD/ CDF emissions for three

reasons. F i rst, for commercial sy stems with g ood combustion controls, the temperatures and
residence times should result in th e destruction of most CDDs/C DF s in the feed. Second, mass
balance studies of a number of combustion sy stems show that mo re CDDs/CDF s can be detected
i n t h e cool -down reg i on downst r eam of t h e furnace t h an i n t h e feed. Thi r d, t h e C DD/ C D F

cong ener profile in the feed differs from th e cong ener profile in the stack emissions. Consequently , sy nthesis appears to be a more important mechanism than is pass throug h. The
concentration of CDDs/CDF s in the flue g a se s of any particular combustion sy stem will ultimately be derived as a resu lt of the balance between reacti ons leading to formation and reactions leading to dest ruction of these compounds.
Mech an i s m 2 (p recu rsor). This mechanism involves the formation of CDDs/CDF s from the thermal breakdown and molecular rea rrang ement of aromatic precursors either orig inating in the feed or forming as a product of incomplete combustion. Actual sy nthesis of
CDDs/CDF s occurs in the post-co mbustor environment. Gaseous benz ene is the most abundant aromatic compound associated w ith products of incomplete co mbustion of waste. B e nz ene

2-31

### react s wi t h C l

A 

### within the c o mbustion g a s pla s ma , c a u sing aromatic H abstraction and the subsequent formation of chlorobenz enes and ch lorophenols. Homog e neous g a s-phase formation
of CDDs/CDF s occurs from thes e precursor compounds at temper atures >500°C, cataly z e d by the presence of copper compounds. I n add ition, the CDDs/CDF s can form from g a s-phase precursors as het e rog e neous, cat al y t i c react i ons w i t h react i v e fl y ash surfaces. Thi s react i on has
been observed t o be cat al y z ed by t h e presence of a

tr a n sition me ta l sor b e d to the f l y

a s h. The most pote n t c a t a l y s t is CuCl 2 

### . Relatively low temperatures—i n the rang e of 200 to 450°C—have
been i d ent i f i e d as a necessary condi t i on for t h ese heterog e neous reactions to occur, with either lower or hig h er temperatures inhibiting th e process. B ecause these reactions involve homog eneous g a s-phase and hetero g e neous solid-phase chemistry

, the r a te of e missions is le ss dependent on reactant concentrati on than on conditions that are favorable to formation, such as

te mpe r a t ur e , r e te ntion time , sour c e a nd spe c i e s of c h lor i ne , a nd the pr e s e n c e of a

c a t a l y s t.
Mech an i s m 3 ( de novo synthesis). This mechanism involves the heterog e neous solidphase form at i on of C DDs/ C DFs i n t h e post

- co m bust i on envi ronm ent on t h e surface of fl y ash. Such heterog e neous chemistry occurs in two wa y s : (1) directly from the ox idation of carbon within the fly ash and subsequent reactions w ith org a nic and inorg a nic chlorine, and (2) the

ox idative breakdown of macromolecular carbon stru ctures (e.g ., g r aphite ) and ox y c hlorination reactions of aromatic precursor s (such as chlorobenz enes and chlorophenols) on fly ash surfaces, leading to CDD/CDF formation. I n either case, formation kinetics is most favored at temperatures in the rang e of 200 to 450°C and is promoted by the cataly tic properties of either the fly ash or the presence of a transition metal compound.

Mechani s m s 2 and 3 can occur si m u l t a ne ously , share a number of common reaction pathway s , and occur in the same phy sical environment, and they are controlled by many of the same phy sical conditions. I n well-desig n ed a nd well-operated combustion sy stems, the precursor speci es needed for m echani s m 2 are reduced; consequently de novo sy nthesis (mechanism 3) can become the dominant pathway for formation. I n sy stems with incomplete combustion, it is
dif f i c u lt to sor t out the r e la tive c ontr i bution of the s e two me c h a n isms to tota l e missions. B o th mechanisms, however, can be curtailed if st eps are taken to minimize the phy sical conditions needed to support formation (i.e., time , temperature, and reactive surface). The combustion formation chemistry of PC B s is le ss we ll studie d tha n tha t of
CDDs/CDF s, but it is reasonable to assume that t h ese sam e t h ree m echani s m s woul d appl y

. For waste incineration, PCB s can ex ist in sig n ificantly hig h er concentrations in the feed than do
CDDs/CDF s. Conse que ntly , me c h a n ism 1 ma y pla y a

mor e pr omine n t r o le in the or ig in of PCB
emissions than of CDD/CDF emissions.

2-32

### 2.7.2. Role of Chlorine
F r om the various analy s es on the role and re lationship of chlorine to CDD/CDF formation and emissions, the following observa tions and conclusions are made.

1. Althoug h chlorine is an essential co mponent in the formation of CDDs/CDF s in

com bust i on sy st em s, t h e em pi ri cal evi d ence i ndi cat es t h at , for com m e rci a l

- scal e i n ci nerat o rs, chlorine levels in feed are not the dominant controlling factor for th e amount of CDDs/CDF s rel eased i n st ack em i ssi ons. I m portant factors that can affect the r a te of CDD/CDF f o r m a tion include overall combustion efficiency , post-com bustion flue g a s temper atures and residence
time s, a nd the ty pe s a nd de sig n s of a i r pollution c ontr o l de vic e s e m ploy e d on c o mbustion

sy stems. Data from bench-, p ilot- , a nd c o mme r c ia l- sc a l e c o mbustor s indic a t e tha t CDD/CDF
form at i on can occur by t h ree pri n ci pal m echani s ms. Some of these da ta, primarilyfrom benchand pilot-scale combustors, have shown direct correlation between chl o ri ne cont ent i n fuel s and
rates of CDD/CDF formation. Ot her data, primarily from commerc ial-scale combustors, show a
weaker rel a t i onshi p bet w een t h e presence of chl o rine in feed and fuel s and rates of CDD/CDF
released from the stacks of com bustion sy stems. The conclusion that the amount of chlorine in feed is not a strong determinant of the mag n it ude of CDD/CDF stack e missions a pplie s to the overall population of comme rcial-scale combustors. F o r any individual commercial-scale

com bust o r, ci rcum st ances m a y ex i s t i n whi c h chang e s i n chl o ri ne cont ent i n feed coul d affect
CDD/CDF emissions. F o r uncontrolled combusti on, such as open burning of household waste, chlorine content of wastes may play a more si g n if ic a n t r o le in le ve ls of CDD/CDF e missions
than the one observed in commercial-scale combustors.

2. B o th org a nic and inorg a nic forms of chlorine in combustion fuels y i eld abundant

g a seous HCl in the post-combustion reg i on. I t has been shown that Cl

A 

### are t h e m o st pot ent chlorinating ag ent in the formation of chloro -org anic compounds from combustion. HCl may be

t h e dom i n ant chem i cal prog eni t o r of C l

A 

### pa r tic ipa ting in ox y c hlor in ation reactions to CDD/CDF

sy nthesis. F o rmation of Cl

A 

### from HCl occurs in the cool-down z one via the ox idation of HCl in the presence of a transition metal cataly s t (the Deacon reaction). Alt houg h the preponderance of scientific evidence sug g e sts that this is an important pathway fo r producing chlorinated compounds in emissions, it is still unclear whether HCl can also directly chlorinate aromatics or
whe t he r it must f i r s t be ox idize d to y i e l d Cl 2 

### .

3. L a boratory

- scale ex periments have ex amin ed correlations between chlorine content of
f

e e d s a nd tota l CDDs/CDF s f o r m e d in c o mbustion sy stems. These ex periments sug g e st that for feeds containing <1% chlorine, the amount of CDDs/CDF s formed is independent of the chlorine

2-33

### cont ent of t h e feed. For feeds wi t h a chl o ri ne content >1%, a direct correlation was observed.
The ex istence of an apparent threshold to the chlo rine content of waste has been verified in fullscale combustion sy stems. I t has not been dete rmined, however, whether these relationships are
relevant to poorly controlled com bustion of wastes and biomass, su ch as backy a rd barrel burning

, la ndf ill f i r e s, a nd a g r i c u ltur a l bur ning

.

4. The combustion of PVC can contribute to the f o r m a tion of CDDs/CDF s in two wa y s

. F i rst, g a seous HCl is a primary product formed fro m the combustion of PVC. W e have seen that HCl is a major contributor of Cl
@ 

### necessary for the formation of CDDs/CDF s. Thus, PVC indirectly contributes to diox in sy nthesis. Second, the combustion of PVC directly forms
benz ene, which is followed by ox y c hlorination r eact i ons t h at furt her fo rm chlorinated benz enes and chlorinated phenols; these compounds then act as precursors to CDD/CDF formation.

5. The most c r itic a l f a c t or s a ssoc i a t e d with minimizing CDD/CDF f o r m a tion in

com bust i on sy st em s are (a) achi e vi ng nearl y co mplete combustion of the feed throug h the application of g ood combustion practice (i.e., time, temperature, and turbulence), and (b) ensuring that combustion g a ses are quenched to below the temperature rang e for heterog e neous solid- pha se f o r m a tion c h e mistr y in the post- c o m bustion reg i on of the sy stem, i.e., reducing the temperature to below 200°C.

2.7.3. G e neral Conclusion Althoug h the formation chemistry of C DDs/CDF s is more complicated and less understood than the relatively simple constructs describe d in this review, the current weig ht of evidence sug g e sts that the forma tion mechanisms outlined above de scribe the principal pathway s of most CDD/CDF formation and emission from combustion sources.

2-34

### 3. COMB US T I ON S O URCE S OF CDDs/CDF s: WAS T E INCINE RAT ION

I ncineration is the destruction of solid, liqui d, or g a seous wastes throug h the application of heat within a controlled combustion sy stem. The purposes of incineration are to reduce the
volume of waste that needs land dis posal and to reduce the tox i city of the waste. I n keeping with this definition, incinerator sy stems can be cla ssified by the ty pes of wastes incinerated: municipal solid waste (MSW ) incineration (c ommonly referred to as municipal waste combustion), medical and pathol og ical waste incineration, haz a rdous waste incineration, sewag e sludg e incineration, tire incineration, and biog as flaring

. Each of these ty pes of incineration is discussed in this chapter. The purpose of this chapt e r i s t o charact eri z e and descri be wast e incineration technolog ies in the Un ited States and to derive estima tes of annual releases of CDDs
and CDF s into the atmosphere from waste in cineration facilities for reference y ears 1987, 1995,
and 2000. As discussed in Chapter 2, combustion res earch has developed three theories on the
mechanisms involved in the emission of CDDs/CDF s from combustion sy stems: (1)
CDDs/CDF s c a n be intr oduc e d into the c o mbusto r with the feed and pass throug h the sy stem unchang ed (pass throug h mechanism), (2) C DDs/CDF s can be formed during combustion (precursor m echani s m ) , and/ or (3) C DDs/ C DFs can be form ed vi a chem i cal react i ons i n t h e post

combustion portion of the sy stem ( de novo sy nthesis). Total CDD/CD F em i ssi ons are l i k el y t o be t h e net resul t of al l t h ree m echani s m s ; however, t h e rel a t i v e i m port a nce of each m e chani s m i s often uncertain.
To t h e ex t e nt pract i cal wi t h t h e avai l a bl e dat a , t h e com bust o rs i n each source cat eg ory were divided into classes accordin g to similarity of emission factor s. This classification effort attempted to reflect the emission mechanisms described above. The emission mechanisms

sug g e st that the aspects of combustor desig n and operation that could affect C DD/ C DF em i ssi ons are (a) furnace desig n, (b) composition of the wast e feed, (c) temperature in the post-combustion

reg i on of the sy stem, and (d) the ty pe of air pollution control device (APCD) used to remove

c onta mina n ts f r o m the f l ue g a se s. The r e f or e , inc i ne r a tion sy ste m s tha t a r e simila r in te r m s of
these factors should have similar CDD/CDF emi ssions. According l y , this chapter proposes
classification schemes that divide combustors into a variety of desig n classes based on these
fact ors. Desi g n cl ass, as used here, refers t o t h e com b i n at i on of furnace t y pe and accom p any i ng AP C D.

3.1. MUNICIP A L WASTE COMBUSTION As noted above, emissions can be related to seve ral factors, including furnace desig n , composition of the waste feed, temperature in the post-combustion reg i on of the sy stem, and

3-1

### ty pe of APCD used to remove contaminants from the flue g a ses. This section proposes a
classification scheme that divide s municipal waste combustors (M W C s) into a variety of desig n cl asses based on t hose fact ors. Because di fferent AP C Ds are opera t e d at di fferent t e m p erat ures, operating temperature is used to de fine some desig n classes. To account for the influence of the waste feed, the proposed classifi cation sy stem disting uishes betw een refuse-derived fuel (RDF )
and normal MSW

. This secti on beg i ns with a description of the MW C technolog y and then proposes the desig n classificati on scheme. Using this scheme, the municipal waste combustion industry is characteriz ed for the referen ce y ears 1987, 1995, and 2000. F i nally , the procedures
f

o r

e stima ting e missions a r e e x pla i ne d a nd the r e sults summa r i ze d.

3.1.1. Description of Municipal Waste Com bustion Technologies
For t h e purposes of t h i s report , m uni ci pal wast e com bust i on furnace t y pes are di vi ded into three major categ ories: mass burn, modular , and RDF

. Mass burn and RDF technolog ies dominate the larg e MW C categ ory and modular t echnolog y dominates the small MW C categ ory

. Each of t h ese furnace t y pes i s descri bed bel o w, fol l o wed by a descri pt i on of t h e AP C D s used
with the sy ste m

.

3.1.1.1. Furnace Types
M a ss bur n. Thi s furnace t y pe was so nam e d because i t burned MS W as recei ved (i .e., no preprocessing of the waste was conducted other than re moval of items too larg e to g o throug h the feed sy stem). Today

, a number of othe r furnace ty pes also burn unprocessed waste, as
descri bed bel o w. Mass burn furnaces are di st i n g u i s hed from t h e ot her t y pes because t h ey burn the waste in a sing le stationary chamber. I n a ty pical mass burn facility , MSW is placed on a

g r ate that moves throug h the combustor. Th ree subcateg ories of ma ss burn technolog ies are
described below.

• Mass burn refractory

- walled sy st em s represent an ol der cl ass of MW C s (g eneral l y built in the late 1970s to early 1980s) that were desig n ed only to reduce the volume of

wa ste dispose d of by 70 to 90%

. The se f a c ilitie s usua lly la c k boile r s to r e c ove r the combustion heat for energ y purposes. I n the mass burn refractor y

- walled desig n, the MS W i s del i v ered t o t h e com bust i on cham ber by a t r avel i n g g r at e or a ram feedi n g sy stem. Combustion air in ex cess of stoi chiometric amounts (i.e., more ox y g en is supplied than is needed for complete co mbustion) is supplied both below and above the g r ate. As of 2000, few mass burn refr actory

- walled MW Cs re main; almost all have closed or been dismantled.

• Ma ss bur n wa te r w a ll ( MB

- WW) f a c ilitie s r e pr e se n t e nha nc e d c o mbustion e f f i c i e n c y , as compared with mass burn refractory

- wa lled incinerators. Althoug h it achieves simila r volume r e duc tions, the MB

- WW inc i ne r a tor de sig n pr ovide s a mor e e f f i c i e n t de live r y of c o mbustion a i r , r e sulting in hig h e r susta i ne d te mpe r a t ur e s. F i g u r e 3- 1 is a

3-2Ai r Su p e r

- G ene r a t or Econo­ h eat er mi z e r

St a c k I n duce d D r af t Fa n

Be l t To t a l R i ddl i n g Vi b r a t i n g C onv e y or As h Se co nda r y C onv ey or Co n v e y o r D i s c har ge Fa n Qu e n c h Ta n k C om bus t i on

Gr a

t e St ea m Dr u m O v e r h ead Cr a n e

F eed Bi n Wa t e r Wa l l Se c t i o n

F o rc e d D r a ft

Fa n

Dr y i n g Gr a t e

Fee d Pi t S t eam P o llu t i o n C ont r o l De v i c e

B ur nout Gr a t e



### F i gu re 3-1. T y p i cal m a ss b u r n w a terw al l m u n i ci p a l sol i d w a ste com b u s tor.

S o u rce: U

. S

. EPA (1997a).



### schematic of a ty pical MB -W W MW C. The t e rm “wat erwal l ” refers t o a seri es of
st eel t ubes t h at run vert i cal l y al ong t h e wal l s of t h e furnace and cont ai n wat e r. Heat from combustion produces steam, which is then used t o dri v e an el ect ri cal t u rbi n e g e nerator or for other industrial needs. This transfer of energ y is called energ y recovery

. MB -W W incinerators are the do minant form of incinerator found at larg e munic i pa l wa ste c o mbustion f a c ilitie s.

• M ass burn rotary kilns use a water-cooled rota r y

c o mbustor tha t c onsists of a

r o ta ting combustion barrel config uration mounted at a 15- to 20-deg r ee ang l e of decline. The refuse is charg e d at the top of the rota ting kiln by a hy draulic ram (Donnelly , 1992). P r eheat ed com bust i on ai r i s del i v ered t o t h e kiln throug h various portals. The slow

r o ta tion of the kiln ( 10 to 20 r o ta tions/hr ) c a u se s the MSW to tumble , the r e b y

ex posing more surface area for complete bur nout of the waste. These sy stems are also equipped with boilers for energ y recovery

. F i g u re 3-2 is a sc hematic of a ty pical

r o ta r y kiln c o mbustor

.

3-3S upe r he a t e r

St e a m Dr u m

Co n v e c t i o n Se c t i o n

Ra d i a n t Se c t i o n Wa t e r Dr u m

E c on omi z e r

Br a n c h Pi p e Ri n g He a d e r

Co a x i a l Li ne

Ro t a r y Jo i n t

A f t e r bur ni ng

Gr a t e

Re s i d u e C onv e y or W i n dbox H o p per Fe e d Ch u t e F eed Th r o a t C hut e

R e si st a n c e Sh r o u d D oor Ti r e

C om bus t or

B a rre l

Ra m Fe e d i n g Ri n g Sy

s t e m H eader

W i ndb ox

S u ppor t Fram e MS W

Fl ue Ga s



### F i gu re 3-2. T y p i cal m a ss b u r n rotary k i l n com b u s tor.

S o u rce: U

. S

. EPA (1997a).



### M o dular

. This is a second g e neral ty pe of municipal waste com bustion furnace used in
the United States. As with the mass burn ty pe, modular incinerators burn waste without preprocessing

. Modular MW Cs consist of tw o vertically mounted combustion chambers (a primary and a secondary chamber). I n 1995, th e combustion capacity of modular combustors

rang ed from 4 to 270 metric tons per day

, i.e ., they are predominately small MW Cs. The two major ty pes of modular sy stems, ex cess ai r and starved air, are described below.

• The modular ex cess-air sy stem consists of a primary and a secondary combustion chamber, both of which operate with ai r le ve ls in e x c e ss of stoic h iome tr ic requirements (i.e., 100 to 250% ex cess air). F i g ure 3-3 illustrates a ty pical modular starved-air MW C.

3-4W a s t e T i pp i ng F l oor

Ra m F eed er
C h arge H o p per

As h Que nc h

Pr i m a r y A i r T r an s f er R am s Pr i m a r y C h a m b e r F i r e D oor S e c o nd ary C ham ber T o S t a ck o r W as t e H eat B o i l er

S e c o nda r y Ai r

S e c o nda r y Ga s B ur ne r

Fe e d C hut e Pr i m a r y Gas B urn er



### F i gure 3-3. Typical m odular starved- ai r com b u s tor w i th tran sf er ram s .

S o u rce: U

. S

. EPA (1997a).



### • I n the starved (or controlled) air ty pe of modular sy stem, air is supplied to the primary chamber at substoichi ometric levels. The products of incomplete combustion entrain i n t h e com bust i on g a ses t h at are form ed in the primary combustion chamber and then pass into a secondary combustion chamber. Ex cess air is added to the secondary chamber, and combustion is completed by el evat ed t e m p erat ures sust ai ned wi t h

aux iliary fuel (usually natural g a s). Th e hig h, uniform temperature of the secondary

c h a m be r , c o mbine d with the tur bule n t mix ing of the c o mbustion g a se s, r e sults in low le ve ls of pa r tic ula t e ma tte r ( P M) a nd or g a nic c onta mina n ts be ing f o r m e d a nd e mitte d. Therefore, many ex isting modular units l ack post-combustion APCDs. F i g ure 3-4 is a schematic view of a modular ex cess-air MW C.

Ref u se-d eri ved f u el (RDF ). The third major ty pe of MW C furnace technolog y is desig ned to combust RDF ; this technolog y is g e nerally used at very la rg e MW C facilities. RDF is a g e neral term that describes MSW from wh ich relatively noncombustib le items are removed,

3-5Pr o c e s s Co n t r o l Ro o m R oom F l ue Gas R e c i rc u l a t i o n (F GR ) Ma n i f o l d

S e c onda r y T e rt i a ry Ch a m b e r U nde r f i r e Ch a m b e r

Ai r

Ti p p i n g R oom H o ppe r He a t Re c o v e r

y P l en um

H oppe r Ov erf i re D oor FG R U nde rf i r e FG R

Fi r e L o ader do or Wa t e r C o ol ed RA M ( s ) I s ol at i o n Da m p e r

T

T

Re l i e f D oor

As h T r ough
an d C onv e y

or FG R Mi x i n g Z one O 2

A s h C o nv ey o r



### F i gure 3-4. Typical m odular excess-air com bustor.

S o u rce: U

. S

. EPA (1997a).



### the r e b y e nha nc ing the c o mbustibility of the wa ste

. RDF is c o mmonly pr e p a r e d by shr e dding

,

sor ting

, a nd se pa r a ting out me ta ls to c r e a t e a dense MSW fuel in a pelletiz ed form having a uniform siz e

. Three ty pes of RDF sy stems are described below.

• The dedi cat ed R DF sy st em burns R DF ex cl usively

. F i g u re 3-5 shows a ty pical dedi cat ed R DF furnace usi n g a spreader-st oker boi l e r. P e l l e t i z ed R D F i s fed i n t o t h e combustor throug h a feed chute using air-swe pt distributors; this allows a portion of the f e e d to bur n in suspe n sion a nd the r e ma inde r to bur n out a f te r f

a lling on a hori z ont al t r avel i n g g r at e. The t r avel i n g g r at e m oves from t h e rear t o t h e front of t h e furnace, and distributor setting s are adjusted so that most of the waste lands on the

r e a r two- thir ds of the g r a t e

. This a llows mor e time to c o mple te c o mbustion on the
g r ate. Underfire and overfire air are in troduced to enhance combustion, and these incinerators ty pically opera te at 80 to 100% ex cess air. W a terwall tubes, a

3-6Fo r c e d Dr a ft F a n

S t eam C o i l A i r P r e h eat er
As h R e m o v a l T r av

el i n g Gr a t e U nde r f i r e Ai r RDF D i s t r i but or

Ov e r f i re

Ai r Bo i l e r T u bes

F eed C hut e S u p erheat er

Ai r

Gas Fl o w

Ga s B ur ne r s I nduc e d D r a ft F a n Ov

e r f i r e Ai r

E c ono m i z e r St a c k

RDF

As h Q u e n c h Ch a m b e r P o ll u t io n Co n t r o l De v i c e



### F i gu re 3-5. T y p i cal d e d i cated ref u s e-d eri ved f u el -f i red sp read er stok er b o i l er.

S o u rce: U

. S

. EPA (1997a).



### superheater, and an economiz er are used to recover heat for production of steam or electricity

. The 1995 invent ory indicated that dedicat ed RDF facilities rang e from 227 to 2,720 metric tons per da y total combustion capacity

.

• C ofi r ed R DF furnaces burn ei t h er R DF or norm a l MS W al ong wi t h anot her fuel

.

The fl ui di z e d-bed R D F furnace burns t h e wast e i n a t u rbul ent and sem i s uspended bed of sand. The MSW may be fed into the inci nerator either as unprocessed waste or as a form of RDF

. The RDF may be injected into or above the bed throug h ports in the combustor wall. The sand bed is susp ended during combustion by introducing underfire air at a hig h velocity , hence the te rm “fluidiz ed.” Overfire air at 100% of stoichiometric requirements is injected above the sand suspension. W a ste-fired fluidiz e d-bed RDF furnaces ty pically operate at 30 to 100% ex cess air levels and at

3-7

### bed temperatures around 815°C. A ty pical fluidiz e d-bed RDF furnace is represented in F i g u re 3-6. The technolog y has two ba sic desig ns: a bubbling

- bed incineration unit and a circulating

- bed incineration unit. The 1995 inventory indicated that fluidiz e d-bed MW Cs have capacities rang ing from 184 to 920 metric tons per day

. These sy st em s are usual l y equi ppe d with boilers to produce steam.

F i gu re 3-6. F l u i d i zed -b ed ref u s e-d eri ved f u el f u rn ace.

S o u rce: U

. S

. EPA (1997a).



### 3-8

### 3.1.1.2. Air Pollution Control De v ic e s MW Cs are commonly equipped with one or more post-combustion APCDs to remove various pollutants such as PM, heavy metals, acid g a ses, and org a nic contaminants prior to
release from the stack (U.S. EPA, 1992a). Ty pes of APCDs include

C 

### Ele c t r o sta tic pr e c i pita tor

C 

### F a br ic f ilte r

C 

### Spray dry scrubbing sy stem

C 

### Dr y sor b e n t inje c tion

C 

### W e t scrubber

E l ectrostati c p reci p i tator (E S P ). The ESP is g e nerally used to collect and control PM that evolves during MSW combustion by introducing a strong electri cal field into the flue g a s stream; this in turn charg e s the particles entrained in th e combustion g a ses (Donnelly , 1992).
L a rg e collection plates r eceive an opposite charg e to attract a nd collect the particles. CDD/CDF formation can occur within the ESP at temperat ures in the rang e of 150°C to about 350°C. As temperatures at the inlet to the ESP increas e from 150 to 300°C, CDD/CDF concentrations have
been observed t o i n crease by approx i m a t e l y a fact or of 2 for each 30°C i n crease i n t e m p erat ure (U.S. EPA, 1994a). As the temperature incr eases bey ond 300°C, formation rates decline. Althoug h ESPs in this temperature rang e effi ciently remove most particulates and the
associ at ed C DDs/ C DFs, t h e C DD/ C DF form at i on t h at does occur can resul t i n a net i n crease i n CDD/CDF e missions. This te mpe r a t ur e

- r e la te d f o r m a tion of CDDs/CDF s within the ESP c a n be applied, for purposes of this report, to disting u ish c o ld- side d ESPs, whic h operate at or below 230°C, from hot-sided ESPs, which operate at an inlet temperature g r eater than 230°C. Most ESPs have been replaced with better-perfor ming and lower-cost fabr ic filter technolog y . F a br ic filt e r ( F F )

. F F s are also PM control devices that remove diox ins associated with

pa r tic le s a nd a n y va por s tha t a d sor b to the pa r tic le s. The f ilte r s a r e usua lly 6- to 8- inc h

- d ia me te r bag s , 30 feet long , made from w oven fiberg lass material, and arra ng ed in series. An induction fan forces the combustion g a ses throug h the tig h tly woven fabric. The porosity of the fabric

a llows the ba g s to a c t a s f ilte r me dia a nd r e ta in a br oa d r a ng e of pa r tic le size s ( down to le ss tha n 1 : 

### m in dia m e t e r )

. The F F is se nsitive to a c i d g a s; the r e f or e , it is usua lly ope r a te d in combination with spray dry e r (SD) adsorption of acid g a ses. Spr ay dr y sc r ubbing syst e m ( S D SS)

. Spray dry scrubbing , also called SD adsorption, involves the removal of both acid g a s and PM fro m the post-combustion g a ses. B y themselves,
the units pr oba bly ha ve little e f f

e c t on diox in e missions. I n a ty pic a l SDSS, hot c o mbustion

g a ses enter a scrubber reactor ve ssel. An atomiz ed hy drated lime slurry (water plus lime) is injected into the reactor at a controlled velocity (D onnelly , 1992). The slurry rapidly mix es with

3-9

### t h e com bust i on g a ses wi t h i n t h e react or. The wat e r i n t h e sl urry qui ckl y evaporat es, and t h e heat of evaporation causes the combustion g a s temper ature to rapidly decrease. The neutraliz ing

c a p a c ity of hy dr a t e d lime r e duc e s the a c i d g a s c onstitue n ts of the c o mbustion g a s ( e .g ., HCl a n d
SO 2 

### ) by g r eater than 70%. A dry product consis ting of PM and hy drat ed lime settles to the
bot t o m of t h e react or vessel

. SDSS technolog y is used in combination with ESPs or F F s. SDSSs reduce ESP inlet

t e m p erat ures t o m a ke a col d -si d ed ES P

. I n add ition to acid g a s, particul ate, and metals control,
SDSSs with F F s or ESPs achieve g r eater than 90% diox in control (U.S. EPA, 1992a), and they

t y pi cal l y achi e ve g r eat er t h an 90% S O 2 

### and HCl control. Dry sorb en t i n jecti o n (DS I ). DSI is used to reduce acid g a s emissions. As with SDSSs,
the se units by the m se lve s pr oba bly ha ve little e f f

e c t on diox in e missions. I n this sy ste m , dr y hy dr a t e d lime or soda a sh is inje c t e d dir e c tly into the c o mbustion c h a m be r or into the f l ue duc t of

t h e hot post

- com bust i on g a ses. I n ei t h er case, t h e reag ent react s wi t h and neut ral i z es t h e aci d g a s constituents (Donnelly , 1992).
Wet scru b b er (WS ). W S devices are desig n ed for acid g a s removal and are more
common to MW C facilities in Europe than in the United States. They should help reduce
emissions of diox in in both va por and particle forms. The devices consist of two-stag e scrubbers. The first stag e removes HCl, and the second stag e removes SO 2 

### (Donnelly , 1992).
Wa te r is use d to r e move HCl, a nd c a u stic or hy dr a t e d lime is a dde d to r e move SO 2 

### f r o m the combustion g a ses. Oth er typ e s of AP CDs. I n addition to the APCDs de scribed above, some less common ty

pes are also used in some MW Cs. An ex ampl e is activated carbon inj ection (CI ) technolog y

. Activated carbon is injected into the flue g a s prior to the g a s reaching S D S S s with FFs (or an ESP). Diox in (and mercury ) are absorbed onto the activated carbon, which is then captured by
the F F s or ESP. CI technolog y improves diox in control technolog ies by an additional 75% and
is c o mmonly r e f e r

r e d to a s f l ue g a s polishing

. Ma ny APCDs ha ve be e n r e tr of itte d to inc l ude CI
, including more than 120 larg e MW Cs.

3.1.1.3. Classif ic a tion Sc he m e B a sed on the array of municipal waste co mbustion technolog ies described above, a

c l a ssif i c a tion sy ste m f o r

de r i ving CDD/CDF e mission e stima te s wa s de ve lope d. Assuming tha t
f

a c ilitie s with c o mmon de sig n a nd ope r a ting c h a r a c t e r istic s ha ve a simila r pote n tia l f o r CDD/CDF emissions, the MW Cs operating in 1987 and 1995 were divided into categ ories according to the eig h t furnace ty pes and six AP CD s described above. This resulted in 17 desig n classes in 1987 and 40 desig n classes in 1995. B ecau se fewer ty pes of AP CDs were used in 1987

3-10

### than in 1995, fewer design classes are needed for estim ating em issions. The MW Cs operating in 2000 were divided into three furnace types and 12 APCDs, resulting in 36 design classes. Design classes for all three reference years are sum m arized in Figures 3-7 through 3-9.

3.1.2. Characteriz ation of MWCs in Reference Years 2000, 1995, and 1987 Table 3-1 lists, by design/APCD type, the num ber of f

acilities and activity level (kg
MSW incinerated/yr) for MW Cs in reference year 2000. Sim ilar inventories are provided for reference years 1995 and 1987 in Tables 3-2 and 3-3, respectively. This inform ation was
derived from five reports: U.S. EPA (1987b) , SAIC (1994), Taylor and Zannes (1996), Solid
W a ste Technologies (1994), and a m e m o ran dum dated March 27, 2003, from Jason Huckaby, ERG, to W a lt Stevenson, U.S. EPA. In gene ral, the inform ation was collected via telephone interviews with the plant operators.

Figure 3-7. Municipal w a ste combustor design classes for 1987.

DS/FF = Dry scrubber com bined with a fabric filter EGB = Electro gravel bed FF = Fabric filter H-ESP = Hot-sided electrostatic precipitator (tem perature at control device is >230°C) W S = W e t scrubber



### 3-11

### F i gure 3-8. Municipal w a ste co m bustor design classes f or 1995.

C

- ES P = C o l d

- s i d ed el ect ros t at i c preci pi t a t o r (t em perat u re at con t rol dev i ce i s <230° C ) DS/CI/FF = Dry scru b b e r w ith carb o n in j ectio n an d f a b r ic f ilter DS/FF = Dry scru b b e r co m b in ed w ith a f a b r ic f ilter DSI/FF = Dry so rb en t in j ectio n co u p led w ith a f a b r ic f ilter EGB = Electro g r av el bed H

- ES P = H o t

- s i ded el ect ros t at i c preci pi t a t o r (t em perat u re at con t rol dev i ce i s >230° C ) WS = We t s c ru bbe r



### Using Tables 3-1, 3-2, and 3-3, a number of comparisons can be made between the reference y ears:

• The number of facilities stay ed about the same (105 in 1987, 130 in 1995, and 104 in 2000), but the amount of MSW incinerated more than doubled from 1987 to 1995 (from 13.4 billion kg in 1987 to 29 billion kg in 1995); it remained constant from 1995 to 2000 (30.6 billion kg in 2000).

3-12M u ni c i pa l S ol i d Was t e I nc i ne r a t or D e s i g n C l a s s e s f o r 200 0

SD/F F/ CI

S D /F F/C I/SNC R

SD/ FF / S N CR

SD / E SP / C I

SD/ FF / S N CR

S D /F F/C I/SN C R

SD / F F

D S I/FF

ES P

FF Wat e r w al l

SD/ FF

DS I/ F F

S D /FF / C I/SNC R Rota r y K i l n Com b u s te r Ma ss B u r n

ES P

FF

SD / F F

WS / E S P M o dul a r , Ex c e s s ai r

DSI/ES P

DSI/F F

ES P

FF

SD /FF / C I

WS M o du l ar , S t ar v e d a i r

DS I/ F F

SD/ES P

SD /FF

S D /FF / C I/SNC R

DS I/ F F / H 2 O/ SN C R

SD/ES P /F F/C I

SD/F F /S N C R

SD/ FF / S N CR

ES P Re f u s e -De r ived F u el

b

c

a



### F i gure 3-9. Municipal w a ste co m bustor design classes f or 2000.

a A l s o equ i pped w ith f u rn ace dry s o rben t in j ection s y s t em

. b A l s o equ i pped w i t h f l u e g a s cool i n g (280–290° F )

.
c A l s o equ i pped w ith com p act h y brid particu l ate collector s y s t em

.

CI = Carb o n in j ectio n DSI = Dry so rb en t in j ectio n ESP = Electro static p r ecip itato r FF = Fab r ic f ilter H 2 O = Water s c ru bber SD = Sp r a y d r y e r SNC R = Selectiv e n o n cataly tic redu ction WS = We t s c ru bbe r



### • I n terms of number of facilities, the dominant furnace technolog y shifted from modular in 1987 (49 units and 1.1 billion kg ) to MB -W W facilities in 1995 (57 units and 16.8 billion kg ) and 2000 (140 units and 19 billion kg ).

• T he dominant APCD technolog y shifted fro m hot-sided ESPs in 1987 (46 units and 11 billion kg ) to SDs with F F s (SDs/F F s ) in 1995 (41 units and 12.8 billion kg ) and SDs/F F s with CI and selective noncataly tic reduction (88 units and 4.6 billion kg ), and SDs/F F s (27 units and 3.1 billion kg ) in 2000.

• The use of hot-sided ESPs dropped fro m 46 facilities in 1987 (11 billion kg ) to 12 facilities in 1995 (1.3 billion kg ). No hot-sided ESPs were used in 2000.

• The number of uncontrolle d facilities dropped from 38 in 1987 (0.6 billion kg ) to 10 in 1995 (0.2 billion kg ) and 6 in 2000 (0.08 billion kg ).

3-13Table 3-1.Inventory ofmunicipal waste combustors(MWCs) in 2000 by technology, air pollution controldevice (APCD), sizea, and annual activitylevel (kg/yr)



### 3-14APCDbMWCtypeMB/RCMBMB/WW/RCMB/REFMB/WWMOD/EAMOD/SAFB/RDFRDFTOTALSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelSize(N)ActivitylevelDSI/FFcS(4)2.78e+08S(2)6.27e+07S(3)1.13e+08S(3)4.7e+07S(2)9.41e+07S(14)5.95e+08DSI/ESPS(2)1.25e+08S(7)1.49e+08S(9)2.75e+08DSI/FF/H2O/SNCRL(2)4.44e+07L(2)4.44e+07ESPS(4)2.61e+08S(6)2.79e+08S(6)9.22e+07S(8)1.14e+08S(2)1.56e+08S(26)9.10e+08FFS(1)1.76e+07S(2)3.14e+07S(3)4.90e+07WSS(4)5.46e+07S(4)5.46e+07WS/ESPS(3)1.13e+08S(3)1.13e+08SDd/FF/CI/SNCRL(3)3.97e+08L(75)1.34e+10L(4)6.68e+08L(82)1.45e+10SD/ESPL(4)1.08e+09L(4)1.08e+06SD/ESP/CIL(4)3.74e+08L(4)3.74e+08SD/ESP/CI/SNCRL(15)2.79e+09L(15)2.79e+09SD/ESP/FFe/CIL(2)7.41e+08L(2)7.41e+08SD/FFL(6)1.11e+09S(2)6.27e+07S(4)1.25e+08S(3)1.32e+08L(12)1.69e+09S(9)L(18)3.20e+082.80e+09SD/FFe/SNCRL(13)2.99e+09L(8)1.57e+09L(21)4.56e+09SD/FF/CIS(2)1.25e+08S(4)6.27e+07S(6)1.88e+08L(5)9.51e+08L(5)9.51e+08UncS(2)3.14e+07S(4)5.17e+07S(6)8.31e+07TOTALL(9)S(8)1.51e+094.94e+08S(2)6.27e+07S(1)1.76e+07S(2)1.25e+08L(124)S(16)2.05e+106.24e+08S(15)4.50e+08S(31)5.10e+08S(2)9.41e+07L(34)S(2)5.97e+091.56e+08L(167)S(79)2.80e+102.60e+09

### 3-15Table 3-1.Inventory ofmunicipal waste combustors(MWCs) in 2000 by technology, air pollution controldevice (APCD), sizea, and annual activitylevel (kg/yr)(continued)aFor size, S = small; L= large.bSlash(es) indicatesdevicesused inconjunction.cAlsoequipped withfluegascooling(138 to143°C).dAlsoequipped withfurnace drysorbent injectionsystem.eAlsoequipped withcompact hybrid particulate collector system.APCD:CI = CarboninjectionDSI = Drysorbent injectionESP= Electrostatic precipitatorFF = Fabric filterH2O = Water scrubberSD = SpraydryerSNCR= Selective noncatalytic reductionUnc = UncontrolledWS=WetscrubberMWCtype:FB/RDF = Fluidized-bed refuse-derived fuelMB= MassburnMB/RC= MassburnrotarykilnMB/REF= MassburnrefractorywalledMB/WW/RC = Mass burnwaterwalled/refractorywalledMOD/EA= Modular excessairRDF=Refuse-derivedfuelTable 3-2.Inventory ofmunicipal waste combustors (MWCs) in 1995 by technology, air pollution control device(APCD), and annual activitylevel (kg/yr)



### 3-16APCDaMWCtypeMB/RCMB/REFMB/WWFB/RDFRDF/dedMOD/SAMOD/EATOTALNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelUnc91.87e+0811.41e+07102.01e+08H-ESP61.04e+0914.22e+0741.82e+0811.97e+07121.28e+09C-ESP22.00e+0811.69e+0882.81e+0941.81e+0941.25e+0838.28e+07225.20e+09DSI/H-ESP14.22e+0812.00e+0811.41e+0736.36e+08DS/FF21.14e+0922.68e+08288.57e+0911.69e+0872.51e+0911.18e+08411.28e+10DS/CI/FF31.17e+0931.17e+09DS/FF/C-ESP15.63e+0815.63e+08WS/FF12.82e+0712.82e+07WS/C-ESP16.76e+0716.76e+07DS/C-ESP14.22e+0882.31e+0941.75e+09134.48e+09DS/DSI/C-ESP17.60e+0717.60e+07DSI/CI/H-ESP12.75e+0812.75e+08DSI/C-ESP65.07e+0865.07e+08DSI/FF22.59e+0811.13e+0821.97e+0818.45e+0714.22e+0813.42e+0711.01e+0891.21e+09DSI/EGB11.13e+0811.13e+08WS22.04e+0834.90e+0756.94e+08TOTAL122.10e+0971.18e+09571.68e+1033.67e+08197.30e+09236.81e+0794.17e+081302.93e+10

### 3-17Table 3-2.Inventory ofmunicipal waste combustors (MWCs) in 1995 by technology, air pollution control device(APCD), and annual activitylevel (kg/yr)(continued)aSlash(es) indicatesdevicesused inconjunction.APCD:C-ESP= Cold-sidedelectrostatic precipitatorCI= CarboninjectionDS = DryscrubberDSI = Drysorbent injectionEGB= Electro gravel bedFF = Fabric filterH-ESP= Hot-sidedelectrostatic precipitatorSD = SpraydryerUnc = UncontrolledWS = Wet scrubberMWCtype:FB/RDF = Fluidized-bed refuse-derived fuelMB/RC= MassburnrotarykilnMB/REF = MassburnrefractorywalledMB/WW= Mass burnwaterwalledMOD/EA= Modular excessairMOD/SA= Modular starved airRDF/ded = Refuse-derived fuel/dedicatedTable 3-3.Inventory ofmunicipal waste combustors(MWCs) in 1987 by technology, air pollution controldevice(APCD), and annual activitylevel (kg/yr)



### 3-18APCDaMWCtypeMB/RCMB/REFMB/WWRDF/dedRDF/cofiredMOD/SAMOD/EATOTALNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelNActivitylevelUnc365.73e+0824.17e+07386.15e+08H-ESP33.94e+08122.00e+09195.20e+0973.01e+0932.53e+0821.17e+08461.10e+10DS/FF11.41e+0711.55e+0821.69e+08FF11.58e+0731.43e+0841.59e+08EGB16.76e+0716.76e+07WS79.01e+0823.38e+0845.30e+0711.27e+08141.42e+09TOTAL44.10e+08202.92e+09205.36e+0993.35e+0932.53e+08458.9e+0842.36e+081051.34e+10aSlashindicatesdevicesused inconjunction.APCD:DS = DryscrubberEGB= Electro gravel bedFF = Fabric filterH-ESP= Hot-sidedelectrostatic precipitatorUnc = UncontrolledWS = Wet scrubberMWCtype:MB/RC= MassburnrotarykilnMB/REF = MassburnrefractorywalledMB/WW= Mass burnwaterwalledMOD/EA= Modular excessairMOD/SA= Modular starved airRDF/cofired = Refuse-derived fuel/cofiredRDF/ded = Refuse-derived fuel/dedicated

### 3.1.3. Estim ation of CDD/CDF Em issions f r om MWCs
C o m p ared wi t h ot her C DD/ C DF source cat eg or ies, MW Cs have been more ex tensively
evaluated for CDD/CDF emissions. I n 2000, due to new reg u lations, EPA’s Office of Air Quality Planning and Standard s (OAQPS) obtained emission test reports for all larg e MW Cs.

3.1.3.1. Estim ating CDD/CDF Em issions fr om MWCs in Reference Y e ar 2000
EPA r e g u la te s diox in e missions f r o m MWCs on the ba sis of whe t he r a

f

a c ility is la r g e or small (see Section 3.1.7). L a rg e facilities are thos e with a total desig n combustion capacity > 250 tons/day ; small facilities are those with a co mbustion capacity < 250 tons/day ). Combustion

c a p a c ity is de te r mine d on the ba sis of a

sing le inc i ne r a tion unit. F a c ilitie s ma y c o mpr i se mor e than one incinerator unit. I n 2000, all larg e MW C facilities were source tested for stack
emissions of diox in, as required by EPA reg ula tions. Therefore, actual emissions from larg e facilities were used to represent facility -specific diox in emissions in 2000. More than 70% of the
small MW Cs have been tested for diox in emissions , and the available data were used to represent facility -specific diox in emissions in 2000. F or sm all MW Cs that were not source tested, diox in

e missions we r e e stima te d on the ba sis of e mission f a c t or s. Usi n g t h e t e st report s , concent r at i ons and e m i ssi ons were cal c ul at ed for each of t h e 17
named diox in/furan cong eners a nd the remainder of the cong en er g r oups (homolog ues), making up total diox in/furan emissions (for 27 c ong eners/g r oups) for each of the MW C units (Memorandum dated March 27, 2003, from J a son Huckaby , ERG, to W a lt Stevenson, U.S. EPA). The calculations were based on the i ndividual CDD/CDF cong en er/g roup concentrations
for the MW C, the flue g a s flow rate and MW C steam g e neration rate dur ing the te st, a nd the annual steam g e neration at the MW C. Table 3-4 presents the averag e CDD/CDF cong enerspecific stack g a s concentrations used to derive the emission fact ors for the nontested facilities.
Ta ble 3- 4 shows c onc e n tr a tions f o r

thr e e de te c tion limit ( D L ) a ssumptions: ( 1 ) a va lue of ze r o for concentrations below the DL , (2) a value of one-half the DL for concentrations below the DL
, and (3) a value of the DL for concentrations below the DL

. Table 3-5 shows facility -specific diox in emissions for all MW Cs operating in 2000 (because of its siz e , Table 3-5 is placed at the e nd of this chapter). Note that the facilities are divided into larg e and small MW Cs. I n total, 83.8 g TEQ DF 

### -W HO 98 

### (76.3 g I

- TEQ) were emitted
from all 104 MW Cs in 2000. Of this total amount, 13.8 g TEQ DF 

### -W HO 98 

### (12.7 g I

- TEQ) were emitted from larg e MW Cs and 69.9 g TEQ DF 

### -W HO 98 

### (63.6 g I

- TEQ) were emitted from sma ll
MW Cs. Althoug h 91% of the MSW combusted in 2000 was incinerated in larg e MW Cs, th e larg e MW Cs accounted for only 17% of total diox in emissions.

3-19

### T a b l e 3-4. Nation al average CDD/CDF con g en er con cen tration s f o r l a rge m u n i ci p a l w a ste com b u s tors (n g/ d s cm @ 7% O 2 

### )

Congener Nondetect s e t to zero a Non d e tect s e t to 1⁄2 detectio n lim it a Non d e tect s e t to detectio n lim it a

T r C D D 2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D
O C D D

O t h e r T C D D s
O t h e r PeC D D s
O t h e r H x C D D s
O t h e r H p C D D s 0 .031

0.005

0 .016

0 .016

0 .037

0 .032

0 .219

0.345

0.232

0.323

0.494

0.220 0.031

0.006

0.016

0.016

0.036

0.032

0.219

0.345

0.239

0.334

0.502

0.220 0.031

0.006

0.017

0.016

0.037

0.032

0.219

0.345

0.246

0.344

0.510

0.220

O C D F
O t h e r T C D F

O t h e r PeC D F
O t h e r H x C D F

O t h e r H p C D F T r C D F 2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F
0.090

1.081

0 .747

0 .326

0 .079 0 .037

0.072

0 .050

0 .069

0 .082

0 .059

0 .013

0 .066

0 .156

0 .024

0.092

1.083

0.758
0.329

0.079 0.037

0.072

0.051
0.069

0.083
0.059

0.013

0.066

0.157

0.024

0.094

1.085

0.770

0.332

0.079 0.037

0.073

0.052
0.069

0.083

0.060

0.014

0.067
0.159

0.024

T O T A L 4 .92 4 .97 5 .02

a Valu es in co rp o r atin g u s e o f th e d e tectio n lim it w h en th e l a borat ory report i n di cat ed “ n ot det ect ed” f o r i n di v i du al CD D / CD F c o nge ne r s

.

S o u r ce: Mem o ran d u m dat e d March 27, 2003, f r om Jas o n H u ck aby

, ER G
, t o Wal t S t ev en s o n , U

. S

. EPA

.



### 3-20

### _____________ 3.1.3.2. Estim ating CDD/CDF Em issions from MWCs in Reference Y e ars 1995 and 1987
Within the c onte x t of this r e por t, a d e qua te e missions te sting f o r

CDDs/CDF s wa s available for 11 of the 113 facilities in the 1987 inventory and 27 of th e 130 facilities in the 1995 inventory

. Nationwide CDD/CDF air emissi ons from MW Cs for reference y e ars 1987 and 1995

we r e e stima te d using the thr e e

- ste p pr oc e ss de sc r i be d be low.
Ste p 1. Estimation of e m issions from all stac k

- te ste d fac ilitie s. The EP A st ack t e st i n g method (EPA Method 23) produces a measur ement of CDDs/CDF s in units of mass
concentration of CDD/CDF (nanog rams per dry standard cubic meter [ ng / dscm] of combustion

g a s) at st andard t e m p erat ure and pressure (20°C a nd 1 atmosphere [ a tm] ) and adjusted to a
measurement of 7% ox y g en in the flue g a s (U.S . EPA, 1995a). This con centration is assumed to represent conditions at the point of r e le a se f r o m the sta c k into th e air. Equation 3-1 was used to
derive annual emi ssion estimates for each tested facility :

C × V × CF × H E TE Q 

### = (3-1) 10 9 

### ng/g

where:
E TEQ 

### = annual TEQ emissions (g /y r) C = combustion flue g a s TEQ concentration (ng / dscm) (20 o 

### C, 1 a tm; a d juste d to 7% O 2 

### )
V = volumetric flow rate of co mbustion flue g a s (dscm/hr) (20 o 

### C, 1 a tm; a d juste d to 7% O 2 

### )
CF = capacity factor; fraction of time that the MW C operates (0.85) H = total hours in a y ear (8,760 hr)

After calculating annual emissions for each te sted facility , the e missions were summed
across all tested facilities for each reference y ear. (Many of th e emission tests do not correspond

e x a c tly to the se two y e a r s. I n the se c a se s, the e quipme n t c onditions pr e se n t a t the time of the te st

we r e c o mpa r e d with those dur ing the r e f e r e nc e y e a r to de te r mine the i r a pplic a b ility .) Step 2. Estimation of emissions fr om all nonstack-tested facilities. This step involves multiply ing the emission factor and the annual ac tivity level for each MW C desig n class and then summing across classes. The activity levels for reference y e ars 1995 and 1987 are summariz e d in Tables 3-2 and 3-3, respectively

. The emission factors were de ri ved by averag i n g t h e em i ssi on factors across each tested facility in a desig n cl ass. The emission factor for each facility was

c a l c u la te d using the f o llowing e qua tion:

3-21

### _____ __________ _________ C × F
v



### ______ EF MW C 

### = (3-2) I

w



### where:
EF MWC 

### = emission factor; averag e ng TEQ/kg of waste burned
C = TEQ or CD D / CD F concentration in flue g a ses (ng TEQ/dscm) (20°C, 1 a tm; a d juste d to 7% O 2 

### )
F
v 

### = volume t r i c f l ue g a s f l ow r a te ( d sc m/hr ) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )
I
w 

### = averag e wast e i n ci nerat i on rat e (kg / hr)

Using an MB -W W MW C equipped with a cold-sided ESP as an ex ample, and g i ven:

C = 10 ng TEQ/dsc m ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )
F
v 

### = 40,000 dscm/hr (20°C, 1 atm; adjusted to 7% O 2 

### )
I
w 

### = 10,000 kg MSW / hr , the n

10 ng 40,000 dscm hr EF MB -W W 

### = × × dscm hr 10,000 kg

40 ng TEQ

= _____________ kg MSW burned

EPA was not able to obtain eng i neering test reports of CDD/CDF emissions for a number of desig n classes. I n these cases, the above procedure could not be us ed to derive emission
f

a c t or s. I n ste a d, the e mission f a c t or s of the te ste d de sig n c l a ss tha t wa s judg e d most simila r in
terms of diox in control was assu med to apply to the untested class. The following log i c was used
to make this decision:

1

. The t e st ed AP C D s for t h e furnace t y pe of t h e unt est e d cl ass were revi ewed t o see whe t he r a n y ope r a te d a t a simila r te mpe r a t ur e

.

2. I f any operated at similar te mperatures, the one with the most similar technolog y was assumed to apply

.

3-22

### 3. I f none operated at a similar temperature, then the most similar furnace ty pe with the same control device wa s assumed to apply

.

Ta ble 3- 6 lists a ll de sig n c a t e g or ie s with no te ste d f a c ilitie s a nd shows the c l a ss with

te ste d f a c ilitie s tha t wa s judg e d to be most simila r

. The e mission f a c t or s f o r

e a c h de sig n c l a ss
are t h e sam e for bot h reference y ears because t h e em i ssi on fact or i s det e rm i n ed onl y by t h e desig n and operating conditi ons and is independent of t h e y ear of t h e t e st

. Step 3. Summation of emissions from tested and untested facilities. This step involves summing e missions f r o m a ll te ste d a nd unte ste d f a c ilitie s. This pr oc e ss is shown in Ta ble s 3- 7a and 3-7b and 3-8a and 3-8b for the reference y ears 1995 and 1987, respectively

. The tables are

or g a nize d by de sig n c l a ss a nd show the e mission e stima te s f o r

the te ste d a nd unte ste d f a c ilitie s

se pa r a te ly

. The c a l c u la tion of e missions f r o m unte ste d f a c ilitie s is br oke n out to show the

act i v i t y l e vel and em i ssi on fact or for each desi g n cl ass.

3.1.4. Sum m ary of CDD/CDF (TEQ) Em issions f r om MWCs f or 2000, 1995, and 1987 The activity level estimates (i.e ., the amount of MSW that is annually combusted by the various municipal waste combus tion technolog ies) are g i ven a hig h confidence rating for 1987 (13.4 billion kg of waste), 1995 (29.3 billion kg of waste), and 2000 (30.6 b illion kg of waste).
F o r all three y ears, independent sources conducted comprehensive survey s of activity levels for virtually all facilities (U.S. EPA, 1987b; Solid W a ste Technolog ies, 1994; SAI C , 1994; Tay l or and Z a nnes, 1996; Memorandum dated March 27, 2003, from J a son Huckaby , ERG, to W a lt Stevenson, U.S. EPA). The emission factor estimates are g i ven a hig h confidence rating for 2000 and a medium confidence rating for both 1995 and 1987. A larg e number of MW C fac ilities were tested in 2000, whereas a moderate fraction of the fac ilities were tested in 1995 and 1987: 27 of 130 facilities (21%) in 1995 and 11 of 104 facilities in 1987 (10%). The tested facilitie s represented 27 and 21% of the total activity level of operating MW Cs in 1995 and 1987, respectively

. These

te sts r e pr e se n t most of the de sig n c a t e g or ie s ide n tif ie d in this r e por t. The e mission f a c t or s we r e developed from emission tests th at followed standard EPA pr otocols, used strict QA/QC procedures, and were well documen ted in eng i neering reports. B ecause all tests were conducted under normal operating cond itions, some uncertainty ex ists about the mag nitude of emissions that may have occurred during ot her conditions (e.g ., upset cond itions, start up, and shut down).
I n summa r y , this r e por t e stima te s the f o llowing diox in r e le a se s to a i r f

r o m MWCs ope r a ting in 2000, 1995 and 1987.

3-23

### T a b l e 3-6. CDD/CDF T E Q em ission f a ctors (n g T E Q/k g w a ste) f o r m u n i ci p a l sol i d w a ste i n ci n erati on

I n cinerator desig n Air po llutio n control device (APCD) a A v erage I

TEQ DF em is s i on factor A v erage TEQ DF -WHO 98 em i s s i on factor Bas i s an d rati on al e MOD/SA C

- ESP

DS/DSI/ C-E S P
D S I/ F F
F F

H

- ES P UNC

W S

WS / F F 16.2

16.2

0.025 16.2

7 9

0.025

16.2

16.2 1 7

1 7

0.024 17

85.7

0.024

1 7

17 B as ed on MOD/EA ; C

- ESP
, s i m ilar f u rn ace (m odu l a r des i g n ) an d s a m e A P C D
B as ed on MOD/EA ; C

- ESP , s i m ilar f u rn ace (m odu l a r des i g n ) an d s i m i l a r em i s s i on con t rol
Bas e d on di rect t e s t s Bas e d on MO D / EA ; C

- ES P, s i m i l a r f u rn ace (m odu l a r des i g n ) an d s i m i l a r em i s s i on con t rol
B as ed on di rect t e s t s Bas e d on MOD/S A ; DS I/F F , s a m e f u rn ace an d

m o s t s i m ilar ex pected em is s i on s B as ed on MOD/EA ; C

- ESP , s i m ilar f u rn ace (m odu l a r des i g n ) an d s i m i l a r A P C D tem p eratu r e Bas e d on MO D / EA ; C

- ES P, s i m i l a r f u rn ace (m odu l a r des i g n ) an d s i m i l a r A P C D tem p eratu r e MO D / EA C

- ES P DS/FF

D S I/ F F

DSI/H- ESP

EGB

H

- ES P Un c

W S

W S /C

- E SP 16.2 16.2

0.025

118

0 .025

118

0 .025

16.2

16.2 17 17

0.024

119

0.024

119

0.024

1 7

1 7 Bas e d on di rect t e s t s B a s e d on MOD/EA ; C

- ESP , s a m e f u rn ace an d sim ilar tem p eratu r e in A P CD; m a y
ov eres tim ate em is s i on s Bas e d on MO D / S A ; D S I/ F F
, s i m i l a r (m odu l a r des i g n ) f u rn ace an d s a m e A P C D
B a s e d on MOD/ EA ; H- ESP
, s am e f u rn ace an d sim ila r e m issio n s Bas e d on MOD/S A ; DS I/F F , s a m e f u rn ace an d

m o s t s i m ilar ex pected em is s i on s Bas e d on di rect t e s t s B a s e d on MOD/SA ; DSI/FF, s a m e f u rn ace an d

m o s t s i m ilar ex pected em is s i on s B as ed on MOD/EA ; C

- ESP , s a m e f u rn ace an d sim ilar A P CD tem p eratu r e B as ed on MOD/EA ; C

- ESP
, s am e f u rn ace an d sim ilar A P CD
FB /R DF DS/FF

DSI/EGB

DSI/FF 0 .63

0 .63

0.63 0 .72

0 .72

0.72 B as ed on MB /W W ; DS/FF s i m ilar f u rn ace an d

sa m e A P CD
B as ed on MB /W W ; DS/FF s i m ilar f u rn ace;
m ay u n d eres tim ate em is s i on s B as ed on MB /W W ; DS/FF s i m ilar f u rn ace;
m ay u n d eres tim ate em is s i on s

a Slas h in dicates dev i ces u s ed in con j u n ction

.
AP C D : MW C ty pe: C- ESP = Co ld

- s id ed electro static p r ecip itato r FB /R DF = Flu i dized- b ed ref u s e- d eriv ed f u el DS = Dry s c ru bber MB /W W = Mass b u rn w aterw alled DSI = Dry so rb en t in j ectio n MOD/EA = Modu lar ex ces s air EGB = Electro g r av el bed MO D / S A = Modu l a r s t arv e d ai r FF = Fab r ic f ilter H- ESP = Ho t- sid e d electro static p r ecip itato r Un c = Un co n t ro lled WS = Wet s c ru bber



### 3-24

### Table 3-7a. Annual I-TEQ DF 

### em i ssi on s f r om m u n i ci p a l w a ste com b u s tors (MWCs) operating in 1995

MW C typ e Air po llutio n control device (APCD) a I- TEQ DF e m issio n s f r o m tested fa cilities

( g TEQ/y r ) A v erage I- TEQ DF em is s i on factor (n g/k g ) Activity lev e l

no nt est e d fa cilities (k g/ yr) I- TEQ DF e m issio ns

from

no nt est e d fa cilities ( g TEQ/y r ) To t a l I- TEQ DF e m issio ns from al l fa cilities ( g TEQ/y r )

MB /W W C

- ESP DS/C

- E SP DS/C I/FF

DS/FF DSI/C I /H- E SP

DSI/FF DSI/H- ESP H- ESP 0 2.1 0.64 2 2.1 0.3 0 163 6.1 6.1 1.5 0.63

–

– 7.74 473 2.81e+09 1.88e+09 7.44e+08 5.98e+09 0 0 4.22e+08 1.79e+08 17.1 11.5

1.1 3.8 0.0 0.0 3.3 84.7 17.1 13.6

1.7 5.8 2.1 0.3 3.3 247.6

S u bt ot al 170.1 1 .20e+10 121.4 291.5

MB/R EF C

- ES P DS/C

- E SP

DS/FF DSI/FF WS 39.8 21.6

0 0 0 –

– 0.63 1.91 236 0 0 2.68e+08 1.13e+08 2.04e+08 0 0 0.2 0.2 48.1 39.8 21.6

0.2 0.2 48.1

S u bt ot al 61.4 5 .85e+08 48.5 109.9

MB /R C C

- ESP DS/FF DSI/C

- ESP

DSI/FF 0 0.25 0 5.3 47.0 0.65 47.0 47.0 2.00e+08 7.57e+08 5.07e+08 1.46e+08 9.4 0.5 23.8

6.9 9.4 0.8 23.8 12.2

S u bt ot al 5.6 1 .61e+09 40.6 46.2
RDF/d e d C-E S P DS/C

- E SP

DS/FF DSI/FF DSI/H- ESP H- ESP DS/FF/C- E S P 32.5 0.3 0.1 0 0 0 0 231 0.53 0.24 231 231 1,492 0.24 1.67e+09 1.14e+09 1.58e+09 4.22e+08 2.00e+08 4.22e+07 5.63e+08 385.8 0.6 0.4 97.5 46.2 63.0

0.1 418.3 0.9 0.5 97.5 46.2 63

0.1

S u bt ot al 32.9 5 .62e+09 593.5 626.4

MOD/SA C- ESP DSI/FF H- ESP Un c

WS WS/FF DS/DSI/C- E SP 0 0 8 0 0 0 0 16.2

– 79

0.025 16.2 16.2 16.2 1.25e+08 0 8.03e+07 1.87e+08 4.90e+07 2.82e+07 7.60e+07 2.0 0.0 6.3 0.0 0.8 0.5 1.2 2 0 14.3

0.005 0.8 0.5 1.2

S u bt ot al 8 5 .46e+08 10.9 18.9



### 3-25

### Table 3-7a. Annual I-TEQ DF 

### em i ssi on s f r om m u n i ci p a l w a ste com b u s tors (MWCs) operating in 1995 (continued)

MW C typ e Air po llutio n control device (APCD) a I- TEQ DF e m issio n s f r o m tested fa cilities

( g TEQ/y r ) A v erage I- TEQ DF em is s i on factor (n g/k g ) Activity lev e l

no nt est e d fa cilities (k g/ yr) I- TEQ DF e m issio ns

from

no nt est e d fa cilities ( g TEQ/y r ) To t a l I- TEQ DF e m issio ns from al l fa cilities ( g TEQ/y r )

MOD/EA C

- ES P DS/FF DSI/FF DSI/H- ESP H- ESP Un c WS/C

- E SP 0.1 0 0 0 2.3 0 0 16.2 16.2

0.025 118 b 0.025 16.2 6.25e+07 1.18e+08 1.01e+08 1.41e+07 0 1.41e+07 6.76e+07 1 1.9 0.003 1.7 0 0.0003 1.1 1.1 1.9 0.003 1.7 2.3 0.0003 1.1

S u bt ot al 2.4 3 .77e+08 5 .7 8.1

FB /RDF DS/FF DSI/EGB DSI/FF 0 0 0 0.63 0.63 0.63 1.69e+08 1.13e+08 8.45e+07 0.1 0.1 0.1 0.1 0.1 0.1

S u bt ot al 0 3 .67e+08 0 .3 0.3

T O T A L 280.4 2 .11e+10 820.9 1 ,101.3

a Slas h in dicates dev i ces u s ed in con j u n ction

. b Valu e cou l d n o t be calcu lated.

– = Em i s s i on s n o t dev e l oped

AP C D :

C- ESP = Co ld

- s id ed electro static p r ecip itato r C I = C a rbon in j ection DS = Dry s c ru bber DSI = Dry so rb en t in j ectio n EGB = Electro g r av el bed FF = Fab r ic f ilter H- ESP = Ho t- sid e d electro static p r ecip itato r Un c = Un co n t ro lled WS = Wet s c ru bber

MW C ty pe:

FB /R DF = Flu i dized- b ed ref u s e- d eriv ed f u el MB/R C = Mas s bu rn rotary k iln MB/R EF = Mas s bu rn ref r actory w a lled MB /W W = Mass b u rn w aterw alled MOD/EA = Modu lar ex ces s air MO D / S A = Modu l a r s t arv e d ai r R D F/ded = R ef u s e- d eriv ed f u el/dedicated



### 3-26

### Table 3- 7b. A nnual TEQ DF 

### -WH O 98 

### em issions f r om m unicipal w a ste

com bustors (MWCs) operating in 1995

MW C

typ e Air po llutio n control device (APCD) a TEQ DF ­ WH O 98 e m issio n s from tes t ed fa cilities ( g TEQ/y r ) A v erage TEQ DF ­ WH O 98 e m issio n

factor (n g/k g ) Activity level

no nt est e d fa cilities (k g/ yr) TEQ DF ­ WH O 98 e m issio n s

from

no nt est e d fa cilities ( g TEQ/y r ) To t a l TEQ DF ­ WH O 98 e m issio n s from al l fa cilities ( g TEQ/y r )

MB /W W C

- ESP DS/C

- E SP DS/C I/FF DS/FF DSI/C I /H- E SP DSI/FF DSI/H- ESP H- ESP 0 2.24 0.68 2.1 2.26 0.3 0 183 6.54 6.54 1.61 0.72

–

– 8.22 535.0 2.81e+09 1.88e+09 7.44e+08 5.98e+09 0.0 0.0 4.22e+08 1.79e+08 18.4 12.3

1.2 4.3 0.0 0.0 3.5 95.8 18.4 14.54

1.88 6.4 2.26 0.3 3.5 278.8

S u bt ot al 190.6 1 .20e+10 135.4 326.0

MB/R EF C

- ES P DS/C

- E SP DS/FF DSI/FF WS 43 22.5

0 0 0 –

– 0.72 2.07 254.0 0.0 0.0 2.68e+08 1.13e+08 2.04e+08 0.0 0.0 0.2 0.2 51.8 43.0 22.5

0.2 0.2 51.8

S u bt ot al 65.5 5 .85e+08 52.2 117.7

MB /R C C

- ESP DS/FF DSI/C

- ESP DSI/FF 0 0.265 0 10.5 93.1 0.68 93.1 93.1 2.00e+08 7.57e+08 5.07e+08 1.46e+08 18.6 0.5 47.2 13.6 18.6 0.8 47.2 24.1

S u bt ot al 10.8 1 .61e+09 79.9 90.7
RDF/d e d C-E S P DS/C

- E SP DS/FF DSI/FF DSI/H- ESP H- ESP DS/FF/C- E S P 35.6 0.34 0.1 0 0 0 0 253.0 0.56 0.26 253.0 253.0 1,679.0

253.0 1.67e+09 1.14e+09 1.58e+09 4.22e+08 2.00e+08 4.22e+07 5.63e+08 422.5 0.6 0.4 106.8

50.6 70.9 142.4 458.1 1.0 0.5 106.8

50.6 70.9 142.4

S u bt ot al 36 5.62e+09 794.2 830.2

MOD/SA C- ESP DSI/FF H- ESP Un c WS WS/FF DS/DSI/C- E SP 0 0.0008 8.69 0 0 0 0 17.0

– 85.7

0.024 17.0 17.0 17.0 1.25e+08 0.0 8.03e+07 1.87e+08 4.90e+07 2.82e+07 7.60e+07 2.1 0.0 6.9 0.0 0.8 0.5 1.3 2.1 0.001 15.6

0.005 0.8 0.5 1.3

S u bt ot al 8.7 5 .46e+08 11.6 20.3



### 3-27

### Table 3- 7b. A nnual TEQ DF 

### -WH O 98 

### em issions f r om m unicipal w a ste

com bustors (MWCs) opera ting in 1995 (continued)

MW C

typ e Air po llutio n control device (APCD) a TEQ DF ­ WH O 98 e m issio n s from tes t ed fa cilities ( g TEQ/y r ) A v erage TEQ DF ­ WH O 98 e m issio n

factor (n g/k g ) Activity level

no nt est e d fa cilities (k g/ yr) TEQ DF ­ WH O 98 e m issio n s

from

no nt est e d fa cilities ( g TEQ/y r ) To t a l TEQ DF ­ WH O 98 e m issio n s from al l fa cilities ( g TEQ/y r )

MOD/EA C

- ES P DS/FF DSI/FF DSI/H- ESP H- ESP Un c WS/C

- E SP 0.068 0 0 0 2.35 0 0 17.0 17.0

0.024 119.0

– 0.024 17.0 6.25e+07 1.18e+08 1.01e+08 1.41e+07 0.0 1.41e+07 6.76e+07 1.06 2.01 0.002 1.68 0.0 0.003 1.15 1.1 2.0 0.002 1.7 2.4 0.003 1.2

Su btotal 2.4 3 .77e+08 5 .9 8.3

FB /RDF DS/FF DSI/EGB DSI/FF 0 0 0 0.72 0.72 0.72 1.69e+08 1.13e+08 8.45e+07 0.114 0.076 0.057 0.1 0.1 0.1

Su btotal 0 3 .67e+08 0 .3 0.3

T O T A L 314 2.11e+10 1 ,079.5 1,393.5

a Slas h in dicates dev i ces u s ed in con j u n c tion

.

– = Em i s s i on s n o t dev e l oped

AP C D :

C- ESP = Co ld

- s id ed electro static p r ecip itato r C I = C a rbon in j ection DS = Dry s c ru bber DSI = Dry so rb en t in j ectio n EGB = Electro g r av el bed FF = Fab r ic f ilter H- ESP = Ho t- sid e d electro static p r ecip itato r Un c = Un co n t ro lled WS = Wet s c ru bber

MW C ty pe:

FB /R DF = Flu i dized- b ed ref u s e- d eriv ed f u el MB/R C = Mas s bu rn rotary k iln MB/R EF = Mas s bu rn ref r actory w a lled MB /W W = Mass b u rn w aterw alled MOD/EA = Modu lar ex ces s air MO D / S A = Modu l a r s t arv e d ai r R D F/ded = R ef u s e- d eriv ed f u el/dedicated



### 3-28

### Table 3-8a. Annual I-TEQ DF 

### em issions to the air f r om m unicipal w a ste

com bustors (MWCs) operating in 1987

MW C t y p e Air po llutio n control dev i ce (APCD) a I- TEQ DF e m issio n s from tes t ed fa cilities ( g TEQ/y r ) A v erage I- TEQ DF e m issio n factor (n g/k g ) Activity level

no nt est e d fa cilities (k g/ yr) I- TEQ DF e m issio n s

from

no nt est e d fa cilities ( g TEQ/y r ) To t a l ITEQ DF e m issio n s from al l fa cilities ( g TEQ/y r )
MB /W W DS/FF H- ESP 0.0373 433.0 – 473.0 1.55e+08 3.27e+09 0.0 1,546.7 0.0373 1,979.7
S u bt ot al 433.0 3 .43e+09 1,546.7 1,979.7
MB /REF DS/FF 0.0 0.63 1.41e+08 0.09 0.09 H- ESP 0.0 473.0 2.00e+09 946.0 946.0 WS 0.0 236.0 9.01e+08 212.6 212.6
S u bt ot al 0.0 3 .04e+09 1,158.7 1,158.7
MB /R C FF 0.0 47.0 1.58e+07 0.7 0.7 H- ESP 48.2 285.0 2.25e+08 64.1 112.3
S u bt ot al 48.2 2 .41e+08 64.8 113.0
RDF/d e d H-E S P WS 840.0 0.0 1,492.0 231.0 2.45e+09 3.38e+08 3,655.4 78.1 4,495.4 78.1
S u bt ot al 840.0 2.79e+09 3,733.5 4,573.5
R D F / cof i red H

- ES P 0.0 231.0 2.53e+08 58.4 58.4
MOD/SA FF H- ESP Un c WS 0.0 0.0643 0.0 0.0 16.2 79.0

0.025 16.2 1.43e+08 3.61e+08 5.73e+08 5.30e+07 2.3 28.5

0.01 0.86 2.3 28.6

0.01 0.86
S u bt ot al 0.0643 1.13e+09 31.7 31.8
MOD/EA EGB 0.0 0.025 6.76e+07 0.002 0.002 Un c 0.0 0.025 4.17e+07 0.001 0.001 WS 0.0 16.2 1.27e+08 2.057 2.057
Su btotal 0.0 2.36e+08 2.1 2.1
T O T A L 1,321.3 1 .11e+10 6 ,537.5 7 ,858.8

a Slas h in dicates dev i ces u s ed in con j u n c tion

.

AP C D :

DS = Dry s c ru bber EGB = Electro g r av el bed FF = Fab r ic f ilter H- ESP = Ho t- sid e d electro static p r ecip itato r Un c = Un co n t ro lled WS = Wet s c ru bber

MW C ty pe:

MB/R C = Mas s bu rn rotary k iln MB/R EF = Mas s bu rn ref r actory w a lled MB /W W = Mass b u rn w aterw alled MOD/EA = Modu lar ex ces s air MO D / S A = Modu l a r s t arv e d ai r R D F/cof i red = R e f u s e

- d eriv ed f u el/cof ired R D F/ded = R ef u s e- d eriv ed f u el/dedicated



### 3-29

### Table 3- 8b. A nnual TEQ DF 

### -WH O 98 

### em issions to the air f r om m u nicipal

w a ste com bustors (MWCs) operating in 1987

MW C t y p e A i r p o llu t i on

co ntro l dev i ce ( A P CD) a TEQ DF ­ WHO 98 e m ission s fr o m t e s t e d

f a c ilit ie s (g TEQ/ y r) A v e r age TEQ DF ­ WHO 98 e m ission

fa c t o r (ng / kg ) A c ti v i ty l e v e l

no ntes ted f a c ilit ie s ( k g/yr ) TEQ DF ­ WHO 98 e m ission s

fr o m

no ntes ted f a c ilit ie s (g TEQ/ y r) To ta l TEQ DF ­ WHO 98 e m ission s f r om all f a c ilit ie s (g TEQ/ y r)
MB/ W W D S / F F 0

. 0 3 9 – 0 0. 0 0. 039 H- ESP 485. 0 535. 0 3. 27e +09 1, 749. 5 2, 234. 5 S ubtota l 485. 0 1
, 749. 5 2
, 234. 5
MB/ RE F D S / F F 0

. 0 0

. 7 2 1. 41e +08 0. 1 0. 1 H- ESP 0

. 0 535. 0 2. 00e +09 1, 070. 0 1, 070. 0 W S 0

. 0 254. 0 9. 01e +08 228. 9 228. 9 S ubtota l 0. 0 1
, 299. 0 1
, 299. 0
MB/ RC FF 0

. 0 9 3

. 1 1. 58e +07 1. 47 1. 47 H- ESP 5 3

. 4 316. 0 2. 25e +08 71. 1 124. 5 S ubtota l 53. 4 72. 6 126. 0
RD F/ d e d H

- E S P 946. 0 1, 679. 0 2. 45e +09 4, 113. 6 5, 059. 6 W S 0

. 0 253. 0 3. 38e +08 85. 5 85. 5 S ubtota l 946. 0 4
, 199. 1 5
, 145. 1
R D F / c o f i r e d H

- E S P 0. 0 253. 0 2

. 53e +08 64. 0 64. 0
MO D / SA FF H- ESP 0

. 0 0

. 0 6 8 1 7

. 0 8 5

. 7 1. 43e +08 3. 61e +08 2. 4 30. 9 2. 4 31. 0 Un c 0

. 0 0

. 0 2 4 5. 73e +08 0. 01 0. 01 W S 0

. 0 1 7

. 0 5. 30e +07 0. 9 0. 9 S ubtota l 0. 068 34. 2 34. 3
M OD/ EA EGB 0

. 0 0

. 0 2 4 6. 76e +07 0. 0016 0. 0016 Un c 0

. 0 0

. 0 2 4 4. 17e +07 0. 001 0. 001 W S 0

. 0 1 7

. 0 1. 27e +08 2. 16 2. 16 Su b t o t al 0

. 0 2 .2 2

. 2
TO TA L 1, 484. 5 3

. 04e +09 7
, 420. 6 8
, 905. 1

a S l a s h indic a t e s de v i c e s use d in c onjunc tion.

AP C D :

D S = D r y sc r ubbe r E G B = E l ect ro g rav el b e d F F = F a br ic f ilte r H

- E S P = H ot- side d e le c tr osta tic pr e c ipita tor Un c = Un c o n t r o l l e d WS = We t sc r ubbe r

MW C t y p e : MB/ RC = Mas s b u rn ro t a ry k i l n MB/ RE F = Mas s b u rn refract o ry w al l ed MB/ W W = Mas s b u rn w at erw al l ed M O D /E A = M odula r e x c e ss a ir M O D /S A = M odula r sta r v e d a ir RD F/ co fi red = Refu s e- d eri v ed fu el / co fi red RD F/ d ed = Refu s e- d eri v ed fu el / d ed i cat ed



### 3-30

### R e ference y ear g TEQ DF 

### -W HO 98 

### g I

- TEQ C onfi d ence rat i n g 2000 83.8 76.3 A 1995 1,393.5 1,101.3 B 1987 8,905.1 7,858.8 B

As note d, a hig h c onf ide n c e r a ting ( A ) is a ssig n e d to the e stima te of diox in e missions
from MW Cs in 2000 because a larg e number of fac ilities were tested, provi ding a hig hly certain

a nd r e pr e se n ta tive e missions e stima te

. Ta ble 3- 5 displa y s the CDD/CDF TEQ e missions by e a c h
MW C facility operating in 2000. Moreover, the ac tivity level of MW Cs in 2000 is known and is

very representative of this source. A confiden c e r a ting B is a ssig n e d to the ove r a ll diox in a i r releases for y ears 1995 and 1987. Althoug h the ac tivity level for those y ears is known and is

c onside r e d ve r y r e pr e se n ta tive

, f e we r f

a c ilitie s we r e sta c k te ste d in those y e a r s r e la tive to the
total number of MW Cs in opera tion. Therefore, there was a reliance on the use of emission
factors to estimate releases in 1995 and 1987. Ho wever, estimates for these y ears are considered representative of MW Cs operating in those y ears.

3.1.5. Congener P r of iles of Municipa l Waste Com bustion F acilities
The air emissions from MW Cs contain a mix tu re of CDD and CDF cong eners. These

m i x t u res can be t r ansl at ed i n t o what are cal l e d “cong ener profi l e s,” whi c h represent t h e distribution of total CDDs and total CDF s presen t in the mix tur e

. A c ong e n e r pr of ile ma y se r v e as a sig n ature of the ty pes of CDDs/CDF s asso ciated with a particular MW C technolog y and
APCD. F i g u re 3-10 is a cong ener profile of an MB -W W MW C equipped with an SDSS and an
F F (the most common ty pe of MW C and APCD de sig n in use today )

. This cong ener profile
i ndi cat es t h at OC DD dom i n at es C DD/ C DF em i ssi ons and t h at every t o x i c C DD/ C DF cong ener is detected in the emissions. F i g ures 3- 11 and 3-12 present 2,3,7,8-TC DD frequency distribution and 1,2,3,7,8-PeCDD frequency distribu tion, respectively

. Accord ing to a memorandum dated March 27, 2003, from J a son Huckaby , ERG, to W a lt Stevenson, U.S. EPA, the distribution of these two cong eners varies little from MW C to MW C. Althoug h these two cong eners represent le ss tha n 1% of tota l diox in/f ur an emissions, they contribute a pprox imately 13 to 23% of the I

TEQ DF 

### emissions, depending on which TEF sy stem is used.

3.1.6. Estim ated CDDs/CDF s in MWC Ash
Ash f r o m MWCs is r e quir e d to be dispose d of in pe r mitte d la ndf ills f r o m whic h r e le a se s to the g e neral environment ar e controlled. F o r backg r ound purposes, however, some information is presented below about the quantitie s of CDDs/CDF s in ash from MW Cs.

3-31Ratio (congener emi ssion factor/total CDD/CDF emission factor)

0 0.02 0.04 0.06 0.08 0.1 0.12

Ratio (congener group emission factor /total CDD/CDF emission factor)

0 0.08 0.1 0.15 0.2 0.25



### F i gure 3-10. Congener and congener group prof iles f or air

e m issions fr om a m a ss bur n wat e r w all m unic ipal wast e

c o m bust o r e quippe d wit h a dr y sc r ubbe r and fabr ic filt e r .

3-32ND =0ND = 1⁄2 detection limitND = full detection limitArithmeticaverage (ng/dscm@ 7%O2)0.005450.005780.0061Arithmeticstandard deviation0.015420.015350.0153



### 3-33Figure 3-11.2,3,7,8-TCDD frequency distribution (negative natural log concentration).ND =0ND = 1⁄2 detection limitND = full detection limitArithmeticaverage (ng/dscm@ 7%O2)0.015890.01630.01669Arithmeticstandard deviation0.033750.033640.0336



### 3-34Figure 3-12.1,2,3,7,8-PeCDD frequency distribution (negative natural log concentration).

### An e stima te d 7 million me tr ic tons of tota l a sh ( bottom a sh plus f l y

a sh) we r e g e ne r a te d by
MW Cs in 1992 (telephone convers ation between J

. L oundsberry , U.S. EPA Office of Solid
W a ste, and L

. B r own, Versar, I n c., F e bruary 24, 1993). EPA indicated that 2 to 5 million metric tons of total ash were produced annually in the late 1980s from MW Cs, with fly ash comprising 5 to 15% of the total (U.S. EPA, 1991a) . EPA reported the results of analy s es of MW C ash samples for CDDs/CDF s (U.S. EPA, 1990a). Ashes from five state-of-t he-art facilities located in differe nt reg i ons of the United States were analy z ed for all 2,3,7,8-substituted CDDs/CDF s. The TEQ levels in the ash (fly ash mix ed with bottom ash) rang ed from 106 to 466 ng I

- TEQ DF 

### /kg

, with a mean value of 258 ng I

TEQ DF 

### /kg

. CDD/CDF le ve ls a r e g e ne r a lly muc h hi g her in fly ash than in bottom ash. F or

ex ample, F i edler and Hutz ing e r ( 1992) reported levels of 13,000 ng I

- TEQ DF 

### /kg in f l y

a sh.
I n another study (W ashing ton State Department of Ecol og y , 1998), CDD/CDF cong ener data were reported for ash and other solid residuals from three municipal incinerators (F ort
L e wis, B e lling ham [ m unicipal plus medical wastes ]
, and Spokane). The data were compiled and
evaluated to determine a total I

- TEQ concentration and loading

. Nondetect values were included
as either z e ro or one-half the DL or at the DL

. The r e sults we r e a s f ollows, a ssuming tha t nondetect values were at z e ro concentration:

L o c a tion Ty pe of Residual I

- TEQ ( : 

### g / kg ) I

- TEQ (mg / day ) F t . L e wis B ottom ash 0.0 0.0 F l y ash 4.98 0.76 B e lling h a m Mix e d a s h (averag e of three tests) 0.038 1.14 Spokane Mix e d ash 0.163 38.0 F l y ash 0.510 24.3 B o ttom ash 0.0001 0.02

I n Shane et al. (1990), ash from five municipa l incinerators was analy z ed for a number of

c onstitue n ts, inc l uding CDDs ( but not CDF s) a nd PCB s. F o r diox ins, thr e e of the inc i ne r a tor s were at nondetectable levels (DL of 1 : 

### g / kg ). The other two incinera tors had detectable levels of five CDD cong ener g r oups (no analy s es were reported for individua l cong eners), and the

averag es for the two units were 26, 59, 53, 25, and 12 : 

### g / kg for TC DD, P e C DD, Hx C DD, HpC DD, and OC DD, respectively

. These levels were much hig h er that those reported by EPA (U.S. EPA, 1990a).
F o r PCB s , the five sets of ashes were anal y z ed for 10 cong ener g r oups. All g r oups were de te c t e d f or

one of the inc i ne r a tor s. Howe ve r , the othe r f

our inc i ne r a tor s c onta i ne d little or no

3-35

### octa, nona, or deca cong eners. The averag e P C B concentration (all cong ener g r oups) for the five
incinerators was 216 : 

### g / kg , with a rang e of 99 to 322 : 

### g / kg

. No g e neration rates of the as hes were g i ven (Shane et al ., 1990); therefore, the measured concentrations cannot be readily converted to quantities of CDDs or PCB s

. The ashes from each of the five incinerators were disposed of in va rious way s

. F o r two of the incinerators, the ash

wa s se nt to me ta l r e c ove r y a nd a l so la ndf ille d. F o r a

thir d, the f l y

a sh wa s sold. F o r a

f

our th, the

a she s we r e la ndf ille d only

. F o r the f i f

t h, the a she s we r e use d in r o a d building a nd a l so la ndf ille d.
F o r those incinerators with more than one ash disposition, no breakdown was g i ven of how much
went to each location. Fifteen ot her incinerators were discussed in S h ane et al. (1990). Thirteen
of

the m dispose d of the i r a sh e x c l usive l y in la ndf ills, a nd the othe r two pa r tia lly dispose d of the i r

a sh in la ndf ills. Table 7 in Clement et al. (1988) presents 13 data sets for CDD/CDF cong ener g r oups for municipal incinerator ash. The averag e data for each cong ener g r oup and the rang es of each

g r oup are g i ven in Table 3-9. No data were presented for individual cong eners or for ash

qua ntitie s.

T a b l e 3-9. Average an d ran g e of CDD/CDF con g en er grou p s in f l y ash f r om

a m u n i ci p a l i n ci n erator ( : 

### g/kg)

Con g en er grou p A verage con cen trati o n C on cen trati o n ran g e
TCDD

PeCDD

Hx CDD HpCDD

OCDD 3.7

6.4

9.1

2.3

1.5 1.6–12

2–25

1.5–42

0.5–9.2

0.2–6

TOTAL CDDs 23.0 6.2–94

TCDF

PeCDF

Hx CDF HpCDF

OCDF 12.0

17.0

14.0

2.9

1.2 5.1–36

8.3–40

3.9–40

0.8–9.2

ND–2.1

TOTAL CDF s 47.1 22–110

S o u r ce: C l em en t et

al . (1988).



### 3-36

### Ash from three incinerators (one in North Amer ica, one in Europe, a nd one in J a pan) had mean CDD concentrations of 363, 588, and 2.6 : 

### g / kg , respectively (Table 3-3 in U.S. EPA, 1987a). The values rang ed from less than 0.5 to 3.537 : 

### g / kg

. F o r CDF s , the respective mean
concentrations for the first tw o incinerators were 923 and 288 : 

### g / kg

. Da ta f

o r

the thir d incinerator were not reported. The CDF rang e fo r the two incinerators was from less than 0.5 to 1,770 : 

### g / kg

. No da ta we r e g i ve n f or

individua l c ong e ne r s or f

or

qua ntitie s of a she s. I n Table 1 in L a hl et al. (1991), data are pr esented for concentrations of total CDDs and
total CDF s in the ash from an ESP from a m unicipal incinerator. Total CDDs were 140.46 : 

### g/ k g in the summe r sa mple s a nd 86 : 

### g / kg in the winter sample s. Total CDF s were 54.97 : 

### g / kg in the summer samples and 73.85 : 

### g / kg in the winter samples. No data were g i ven for individual

cong eners, nor was there information about the quantity of precipitator ash g e nerated. I t was assumed that the data were not for TEQs.
A wire reclamation incinera tor was reported to have 0.41 : 

### g / kg of CDDs and 11.6 : 

### g/ k g of CDF s in fly ash from its stack emissions (T able 3-11 in U.S. EPA, 1987a). F or the same incinerator, the furnace ash con centrations were reported as 0.58 : 

### g / kg CDDs and 0.73 : 

### g/ k g CDF s. Ag a i n, no da ta we r e g i ve n f or

individua l c ong e ne r s or f

or

qua ntitie s of the a she s. Dat a from t h e aforem ent i oned sources are co mpiled in Table 3-10 of this document for comparison purposes. Annual TEQ amounts were estimated by multiply ing the mean TEQ total ash concentration by the estimated amount of MW C ash g e nerated annually ( a ppr ox ima te ly 7
million metric tons in 1995 and 5 million metric tons in 1987). W here possible, ash quantities were broken down into fly ash or bottom ash. F l y ash was assumed to be 10% of the total ash,
and bottom ash was assumed to be 90% of the total ash.
I m ag awa and L ee (2001) analy z ed sample s collected from eig ht J a panese MSW
inc i ne r a tor s to de te r mine diox in le ve ls in the fly ash (Table 3-11). Specific cong ener data were

not avai l a bl e, so TEQ cal cul a tions could not be performed. Koby lecki et al. (2001) analy z ed the reduction of diox ins in fly ash by pelletiz ing the ash and reburning the pellets in a laboratory

- scale bubbling fluidiz e d-bed furnace. Fly ash for the test input material was collect ed from a fly ash filter vessel during 4 day s of MW C operation.
The concentrations of the diox in collected a nd composited cong eners are shown in Table 3-12. The total TEQ value derived by Koby lecki was 862 ng I

- TEQ DF 

### /kg of fly ash. Sakai et al. (2001) analy z ed the levels of diox ins and PCB s in fly ash and bottom ash from a newly constructed MW C in J a pan (Table 3-13). TEQ values derived from the data g i ve a total of 423 ng I

- TEQ DF 

### /kg for fly ash and 10.5 ng I

- TEQ DF 

### /kg f o r

bottom a sh f o r

diox ins a n d
31.6 ng I

- TEQ DF 

### /kg for fly ash and 0.85 ng I

- TEQ DF 

### / k g for bot t o m ash for P C Bs.

3-37

### Table 3-10. Com p ar ison of the am ount of TEQs ge ne r a te d annually in

m unic i pal wast e c o m bust o r ash

D a ta so u rce Type of

as h Mea n to ta l CDD/ CDF

co n cen tra t i

on (n g / kg ) Me an I

- TEQ DF 

### (n g / kg ) Annual TEQ

am ount 1995 val ue a 

### (g ITEQ DF 

### /y r) Annual TEQ

am ount 1987 val ue a 

### (g ITEQ DF 

### /y r) U.S. EPA ( 1990a ) M i x e d 12,383 258 1,806 1,290

W a sh in gton S t ate D e p a rtmen t of E c ology ( 1998)

Ft . L e w i s

B e llin gh am Spo k a ne B o t t o m Fl y
Mix e d

Mi xe d Fl y B o ttom 0 71,280

1
, 8 8 4
1,414 10,320 100 0 4,980

3 8

163 510 0.1 0 3,486

2 6 6 1,141

357 1 0 2,490

1 9 0

815 255 0.05

Sha n e e t a l . ( 1990) Fl y 175,000 – – – Cl e m e n t e t a l . ( 1988) Fl y 70,000 – – – U.S. EPA ( 1987a )

No r t h Am e r i c a

Eur o pe

Ja pa n

W i re reclamation Fl y

Fl y

Fl y

Fl y B o ttom 1,286,000

876,000

2,600

12,010

1,310 –

–

–

–

– –

–

–

–

– –

–

–

–

L a hl e t a l . ( 1991) Mi xe d 177,640 – – –

a I n c a l c u l a t i ng t h e a nnua l T E Q a m o unt s, fl y a s h a n d b o t t o m a s h w e r e c o nsi d e r e d t o b e 1 0 % a n d 9 0 % o f t h e t o t a l a s h,

res p ectiv ely

.

– = Valu e cou l d n o t be calcu lated



### Ea c h of the f i ve f a c ilitie s sa mple d by EPA ha d c o mpa n ion a sh disposa l f a c ilitie s equi pped wi t h l eachat e col l ect i on sy st em s or som e m eans of col l ect i n g l eachat e sam p l e s (U.S

. EP A, 1990a). L eachate samples were collected and analy z ed for each of these sy stems. Detectable levels were found in the l eachate at only one facility (3 ng I

- TEQ DF 

### /L ); the only detectable cong eners were HpC DDs, OC DD, and HpC D Fs.

3-38

### Table 3-11. Concentration of CDD/CDF congener groups (ng/kg) in f l y ash

sam p les f r om com bustion of m unici pal solid w a ste in eight Japanese i n ci n erators a



### C o n g en er

gr oup S t o k er in cin era to rs F l u i d i zed -b ed in cin era to rs
B C D E F I J L

TCDD

Pe CDD

HxCDD HpCDD

OCDD 5,000
20,000
45,000
70,000
125,000 200,000
340,000
440,000
340,000
110,000 80,000
200,000
250,000
230,000
160,000 75,000
105,000

90,000
37,000
15,000 6,000
10,000
12,000

8,000
7,000 10,000
28,000
41,000
40,000
25,000 10,000
37,000
100,000
200,000
187,000 5,000
10,000
30,000
40,000
50,000

TCDF

Pe CDF

HxCDF HpCDF

OCDF 25,000
50,000
65,000
75,000
40,000 210,000
410,000
400,000
230,000

20,000 330,000
320,000
300,000
200,000

40,000 50,000
45,000
22,000
10,000

1,000 13,000
14,000
21,000
17,000
10,000 18,000
32,000
34,000
33,000
13,000 50,000
125,000
210,000
225,000
150,000 70,000
120,000
200,000
270,000
120,000

a In cin e rators are des i g n a ted by letters becau s e th ey rem a in ed an on y m ou s

.

S o u r ce: Im ag aw a an d L ee (2001) (n u m bers es t i m at ed f r om F i g u r e 2 of report )

.



### Table 3-12. Concentration of CDD/CDF congener groups in f l y ash sam p les fr om m unic i pal solid wast e

Conge n e r gr oup C onc e n t r at i o n ( n g/ k g ) TEQ ( n g/ k g )

TCDD
Pe CDD HxCDD HpCDD OCDD 8,000 9 ,000 40,000 10,800

8,000 15 45 100

50

1 TCDF
Pe CDF HxCDF HpCDF OCDF 8,000 10,000

9 ,500 8 ,500 8,000 10 300 300

40

1 TOTAL 119,800 862

S o u r ce: K oby l eck i et al . (2001) (es t i m at ed f r om v a l u es i n F i g u r e 4 of “ B ef ore In ci n e rat i o n ” ).



### 3-39

### Table 3-13. CDD/CDF concentrations in m unicipal solid w a ste ash f r om a

ne wly c o nst r uc t e d m unic i pal wast e c o m bust o r in Japan

C o n g en er C o n cen tra t io n (n g / kg ) I -T E Q s (n g / kg )
Fl y as h B ot t o m as h F l y as h B ot t o m as h 2,3,7,8- TCDD 1,2,3,7,8- Pe CD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD
OCDD 19
78
9 2
210
130
1 ,300 2,800 1.6
3.1
2 .6 5.6
3.6
33.0
110.0 19.0 39.0

9.2
21.0
13.0
13.0

2.8 1 .6
1 .65
0 .26
0 .56
0 .36
0 .33
0 .11 2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF
OCDF 150
290
320
310
310

2 1
400
1 ,100

110
320 4.8
5.3 5.9
4.4 4.9
0 .36
6.7
23.0

1.6 9.3 15.0
14.5
160.0

31.0
31.0

2.1
40.0
11.0

1.1
0.32 0 .48
0 .265 2.95
0 .44
0 .49
0 .036
0 .67
0 .23
0 .016 0.0093
TOTAL 7 ,960 226.0 423.0 10.5

S o u r ce: S a k a i et al . (2001).



### 3.1.7. Recen t EP A Regu latory Activities As part of the 1990 Clean Air Act manda tes, EPA promulg a ted CDD/CDF emission

sta nda r d s f o r

a ll e x isting a nd ne w MWC units a t f a c ilitie s with a g g r e g a t e c o mbustion c a p a c itie s
g r eater than 35 metric tons per day (F ederal Re g i ster, 1995a). These sta ndards, established under Section 129 of the Clean Air Act, required facilities to use “max imum achievable control technolog y ” (MACT) at MW C units and emissi on control retrofit for larg e MW C units (units with capacities g r eater than 225 me tric tons per day ) by Decembe r 2000. I n response to a court remand, the reg u lations were s ubsequently amended to remove small MW C units (units with capacities rang ing from 35 to 225 metric tons per day ) (F ederal Reg i ster, 1995a). The speci fi c em i ssi on st andards for l a rg e MW Cs (ex pressed as ng /dscm of total
CDD/CDF
, based on standard dry g a s corrected to 7% ox y g en) are a function of the siz e , APCD config uration, and ag e of th e facility , as listed below.

3-40

### 1995 emission standards ( n g tota l CDD/CDF / dsc m ) F a c ility a g e , size , a nd APCD 60 Ex isting ; >225 metric tons/day ; ESPbased APCD 30 Ex isting ; >225 metric tons/day ; nonESP-based APCD 13 New; >225 metric tons/day

EP A reestablished emission standards fo r small MW Cs in December 2000. These

sta nda r d s c onta i n two diox in e mission limits: one f o r

sma ll MWCs a t pla n ts with a n a g g r e g a t e capacity g r eater than 250 tons/day (Class I MW Cs ) and another for small MW Cs at plants with

an ag g r eg ate capacity less than 250 tons/day (Cla ss I I MW Cs). The limits for the Class I MWCs were the same as the 1995 limits for larg e MW Cs

. The limit for the smaller Class I I MW Cs is 125 ng /dscm. These small MW Cs were on schedule to comply w ith the standards by December
2005. Small MW C emissions were estimated to be 63 g / y r I

- TEQ in 2000 and should be less than 2 g / y r in 2005, when all control retrof its are completed (F ederal Reg i ster, 2003).

3.2. HAZ ARDOUS WASTE INCINERATION
Haz a rdous waste incineration is the controlle d py roly sis and/or ox idation of potentially dang erous liquid, g a seous, and solid waste. I t is one of the technol og ies used to manag e ha za rdous wa ste unde r the Re sourc e Conse r va tion a nd Re c ove ry Ac t (RCRA) a nd the Comprehensive Environmental Response, Co mpensation, and L i ability Act (CERCL A, or Superfund).
Haz a rdous wastes are burned in a variety of situations and are covered in a number of different sections in this report.

• M uch haz a rdous waste is burne d in facilities dedicated to bur ning this ty pe of waste. Most of the se de dic a t e d f a c ilitie s a r e loc a t e d on- site a t c h e mic a l ma nuf a c t ur ing facilities and burn only the wast e associated with their on- site industrial operations. Haz a rdous waste is also burne d at dedicated facilities locat ed off-site. These facilities accept waste from multiple sources. On- and off-site haz a rdous waste burning facilities are addr essed in Sections 3.2.1 throug h 3.2.4.

• H az ardous waste is also burned in industria l boilers and furnaces that are permitted to burn the waste as supplemental fuel. Th ese facilities have si g n ificantly different furnace desig n s and operations than those of dedicated haz a rdous waste incinerators (HW I s). They are discussed in Section 3.2.6.

• H az ardous waste is also burned in halog e n acid furnace s (HAF s), in which halog e n acids (such as HCl) may be produced from halog e nated secondary materials. These facilities are discu ssed in Section 3.2.7.

3-41

### • A numbe r of c e m e n t kilns a nd lig htwe ig ht a g g r e g a t e kilns a r e a l so pe r mitte d to bur n haz a rdous waste as aux iliary fuel. Thes e are discussed separa tely in Section 5.1.

• M obile HW I s are ty pically used for site cleanup at Superfund sites. These units can be tr a n spor te d f r o m one loc a tion to a nothe r a nd ope r a te f o r

a

limite d dur a tion a t a n y g i ven location. B ecause these facilities are transitory , they are not included in this inve ntor y a t this time

.

The following sections review the ty pes of haz a rdous waste inci neration technolog ies

c o mmonly in use in the Unite d Sta t e s a nd pr e se n t the CDD/CDF e mission e stima te s f r o m a l l facilities operating in 1987, 1995, and 2000.

3.2.1. F u rnace Designs f or HWIs The four principal furnace desig n s employ ed for the combustion of haz a rdous waste in the United States are rotary kiln, liquid injecti on, fix e d-hearth, and flui diz e d-bed (Dempsey and Oppelt, 1993). The majority of commercial operations use rotary kiln incinerators. On-site (noncommercial) haz a rdous waste incineration technolog ies use an equal mix of rotary kiln and
l i qui d i n j ect i on furnaces, al ong wi t h som e fi x e d- heart h and fl ui di z e d-bed operat i ons (U.S . EP A, 1996a). These HW I technolog ies are discussed below.
Rot a r y kiln. Rotary kiln incinerators consist of a rotary kiln coupled with a hig h

temperature afterburner. B ecause rotary kilns are ex cess-air units desig n ed to combust haz a rdous waste in any phy sical form (i.e., liquid, semisoli d, or solid), they are the most common ty pe of
HW I used by com m e rci a l off-si t e operat o rs. The rot a ry ki l n i s a hori z ont al cy l i nder l i n ed wi t h refractory material. Rotation of the cy linder on a slig ht slope provides fo r g r a v ita tiona l tr a n spor t of the haz a rdous waste throug h the kiln (B uonico re, 1992a). The tumbling action of the rotating
kiln causes mix ing and ex posure of the waste to the heat of combustion, thereby enhancing
burnout.
Solid a nd se misolid wa ste s a r e loa d e d into the top of the kiln by a n a u g e r or r o ta ting

screw. F l uid and pumpable sludg es and wastes ar e ty pic a lly intr oduc e d into the kiln thr oug h a
water-cooled tube. L i quid haz a rdous waste is fed directly into the kiln throug h a burner noz z l e. Aux iliary fuel (natural g a s or oil) is burned in the kiln chamber at st artup to reach elevated temperatures. The ty pical heating value of haz a rdous waste ( 8,000 B r itish thermal units [ B tu] / kg ) is sufficient to sustain combustion w ithout aux iliary fuel (U.S. EPA, 1996a). The

c o mbustion g a se s e m a n a ting f r o m the kiln a r e pa ssed throug h a hig h -tem perature afterburner

c h a m be r to mor e c o mple te ly de str o y or g a nic polluta nts e n tr a i ne d in the f l ue g a se s. Rota r y kilns can be desig n ed to operate at temperatures as hig h as 2,580°C, but they more commonly operate at about 1,100°C.

3-42

### Liquid inj e c t ion. L i quid injection incinerators ar e desig ned to burn liquid haz a rdous

wast e. These wast es m u st be suffi ci ent l y fl ui d to pass throug h an atomiz er for injection as droplets into the combustion chamber. The in ci nerat o r consi s t s of a refract ory

- l i n ed st eel

cy linder mounted in either a horiz ontal or a ve rtical alig nment. The combustion chamber is equi pped wi t h one or m o re wast e burners. B ecause of t h e rat h er l a rg e surface area of t h e atomiz ed droplets of liquid haz a rdous waste, the droplets quickly vaporiz e. The moisture evaporat es, l eavi n g a hi g h l y com bust i b l e m i x of waste fumes and co mbustion air (U.S. EPA, 1996a). Secondary air is added to the combusti on chamber to complete the ox idation of the
f u me a nd a i r mix tur e

. F i xed-hearth. Fi x e d-heart h i n ci nerat o rs are st arve d-air or py roly tic incinerators. W a ste is ram-fed into the primary chamber and inci nerated at about 50 to 80% of stoichiometric requirements. The resulting smoke and py roly tic combustion produc ts are then passed throug h a secondary combustion chamber wh ere relatively hig h temperatur es are maintained by the
combustion of aux iliary fuel. Ox y g en is intr oduced into the secondary chamber to promote

c o mple te the r ma l ox ida tion of the or g a nic mole c u le s e n tr a i ne d in the g a se s. Othe r ty pe s of hearths include roller hearths and rotary hearths. Roller hearths use a convey o r sy stem to move

wa ste f r o m the kiln e n tr a n c e to the e x it. I n r o ta r y he a r ths, wa ste e n te r s a nd e x its thr oug h the

same g a te, and the hearth rotate s inside a circular tunnel kiln.
F l u i d i zed -b ed

. The f l uidize d- be d inc i ne r a tor is simila r in de sig n to the inc i ne r a tor s use d
in MSW incineration (see Section 3.1). I n fluidiz e d-bed HW I s , a lay e r of sand is placed on the
bottom of the combustion chamber. The bed is pr eheated by underfire aux iliary fuel at startup. The hot g a ses channel throug h th e sa nd a t r e la tive l y hig h ve loc ity , a nd the tur bule n t mix ing of combustion g a ses and combustion air causes th e sand to become suspended (B uonicore, 1992a) and take on the appearance of a fluid medium; he nce t h e t e rm “fl u i d i z ed-bed” com bust o r. The
inc i ne r a tor is ope r a te d a t te mpe r a t ur e s be low the me lting point of the be d ma te r i a l ( t y p ic a l temperatures are within a rang e of 650 to 940°C)

. A constraint on the ty pes of waste burned is

t h at t h e sol i d wast e part i c l e s m u st be capabl e of bei n g suspended wi t h i n a furnace. W h en t h e liquid or solid waste is combusted in the fluid medium, the ex othermic r eaction causes heat to be released into the upper portion of the combus tion chamber. The upper portion ty pically has much larg er volume than the lower portion, and temperatures can reach 1,000°C (B uonicore, 1992a). This hig h temperature is sufficient to combust volatiliz ed pollutants emanating from the
combustion bed.

3-43

### 3.2.2. AP CDs f o r HWIs
Most HW I s use APCDs to remove undesira ble components from the flue g a ses that evolve during the combustion of the haz a rdous waste. These unwanted pollutants include suspended ash particles (PM), aci d g a ses, metals, and org a nic po llutants. The APCD controls collect these pollutants and re duce the amount discharg ed from the incinerator stack to the atmosphere. The levels and ty pes of these combustion by produc ts are hig h ly site specific, depending on factors such as waste composition and incinerator sy stem desig n and operating parameters (e.g ., temperat ure and ex haust g a s velocity ). Th e AP C D t y pi cal l y com p ri ses a seri es of different devices that work tog e ther to clean the combustion ex haust flue g a s. Unit operations usually include ex haust g a s cooling followed by PM and acid g a s control.
Ex haust g a s cooling may be ach ieved by using a waste heat boiler or heat ex chang e r, mix ing with c ool a m bie n t a i r , or inje c ting a wa te r spr a y into the e x ha ust g a s. A va r i e t y of ty pe s of APCDs are used to remove PM and acid g a ses. Such devices include W S s (such as venturi,

pa c k e d be d, a nd ionizing sy ste m s) , ESPs, a nd F F s ( some time s use d in c o mbina tion with dr y a c i d

g a s scrubbing ). I n g e neral, the control sy stems can be g r ouped into the following three categ ories: wet, dry

, and hy brid wet/dry sy stems. The controls for acid g a ses (either dry or wet

sy st em s) cause t e m p erat ures t o be reduced be fore t h e g a ses reach t h e cont rol devi ce. Thi s impe d e s the f o r m a tion of CDDs/CDF s in the post- combustion area of the ty pical HW I

. I t is not
unusual for stack concentrations of CDDs/CDF s at a particular HW I to be in the rang e of 1 to 100 ng /dscm (Helble, 1993), which is low when co mpared with concentrations from other waste incineration sy stems. However, the rang e of tota l CDD/CDF f l ue g a s c onc e n tr a tions me a sur e d
in the sta c k e missions of HWI s dur ing tr ia l bur ns a c r oss the c l a ss of HWI f

a c ilitie s spa n s f our orders of mag n itude, rang ing from 0.1 to 1,600 ng /dscm (Helble).
The t h ree cat eg ori e s of AP C D sy st em s are descri bed bel o w:

• W et system

. A W S is used for both particulate and acid g a s control. Ty pically , a venturi scrubber and a packed-bed scrubber ar e used in a back-to- back arrang ement. I oniz i ng W S s, wet ESPs, and innovative vent uri-ty pe scrubbers ma y be used for more effi ci ent part i c ul at e cont rol

. W S s g e nerat e a wet effl ue nt liquid wastestream (scrubber blowdown). They are relatively ine fficient at fine par ticulate control when compared with dry control techniques, a nd they have equipment corrosion concerns. However, W S s provide efficient control of acid g a ses and ha ve lower operating temperatures (compared with dry sy stems), which may he lp control the emissions of vola tile me ta ls a nd or g a nic polluta nts.

• Dry system

. I n SDSSs, an F F or ESP is used fo r particulate control, frequently in combination with dry scrubbing for acid g a s control. Compared with W S s, SDSSs

a r e ine f f i c i e n t in c ontr o lling a c i d g a se s.

3-44

### • Hybr id syst e m . I n hy brid sy stems, a dry technique (ESP or F F ) is used for particulate control, followed by a wet tec hnique (W S) for acid g a s control. Hy brid
sy stems have the advantag es of both wet and dry sy stems (lower operating
te mpe r a t ur e f o r

c a p tur e of vola tile me ta ls, e f f i c i e n t c o lle c tion of f

i ne pa r tic ula t e s, effi ci ent capt u re of aci d g a ses) whi l e avoi ding many of the disadvantag es. I n some hy brid sy stems, known as “z ero discharg e sy stems,” the W S liquid is used in the dry scrubbing operation, thus minimiz ing th e amount of liquid by product waste.

F acilities that do not use any APCDs fall under a separate and unique categ o ry . These are

pr ima r ily liquid wa ste inje c tion f a c ilitie s, whic h bur n wa ste s with low a sh a nd low c h lor i ne

c onte n t; the r e f or e , the y a r e low e mitte r s of PM a nd a c i d g a se s.

3.2.3. Estim ation of CDD/CDF Em ission F actors f or HWIs
To e stima te e mission f a c t or s, EPA’ s Of f i c e of Re se a r c h a nd De ve lopme n t ( O RD)

g e nerally subdivides the combustors in each sour ce categ ory into desig n classes judg ed to have
simila r pote n tia l f o r

CDD/CDF e missions. Howe ve r , a s e x pla i ne d be low, de dic a t e d HWI s ha ve not been subdivided.
Tota l CDD/CDF e missions a r e like l y the ne t r e sult of a ll thr e e of the me c h a n isms described above (pass throug h, precursor, and de novo sy nthesis); however, the relative
i m port a nce of each m echani s m can vary am ong source cat eg ori e s. I n t h e case of HW I s , t h e t h i r d

m echani s m (post

- com bust i on form at i on) i s l i k el y t o dom i n at e, because HW I s are t y pi cal l y operated at hig h temperatures a nd with long residence times, and most have sophisticated realtime monitor i ng a nd c ontr o ls to ma na g e the c o mbustion pr oc e ss. The r e f or e , a n y CDDs/CDF s
pr e se n t in the f e e d or f

o r m e d dur ing c o mbustion a r e like l y to be de str o y e d be f o r e e x iting the
combustion chamber. Consequently , for purposes of g e nerating emission f actors, it was decided not to subdivide this class on the basis of furnace ty pe. Emissions r e sulting f r o m the post- c o mbustion f o r m a tion of CDDs/CDF s in HWI s c a n be
minimiz ed using a variety of technolog ies:

• R apid flue gas que nc hing. The use of wet and dry scr ubbing devices to remove acid g a se s usua lly r e sults in the r a pid reduction of flue g a s temper a t ur e s a t the inle t to the APCD. I f the temperature is reduced below 200°C, the low-temperature cataly tic f

o r m a tion of CDDs/CDF s is substa ntia lly r e ta r d e d

.

• Use of P M AP CDs. PM control devices can eff ectively capture condensed and adsorbed C DDs/ C DFs t h at are associ at ed wi t h t h e ent r ai ned P M (i n part i c ul ar, t hose adsorbed on unburned carbon-c ontaining particulates).

3-45

### • Use of activated carbon. Activated CI is used at some HW I s to collect (sorb) CDDs/CDF s from the flue g a s. This may be achieved using carbon beds or by injecting carbon and collecting it in a downstream PM APCD.

All of the se a ppr oa c h e s a ppe a r to be ve r y e f f

e c tive in c ontr o lling diox in e missions a t dedicated HW I s ; emissions data are insufficient to g e neraliz e about any minor differences. Consequently , for purposes of g e nerating emission factors, ORD decided not to subdivide this class on the basis of APCD ty pe. EPA’ s Of f i c e of Solid Wa ste ( O SW) c o mpile d a da ta ba se summa r i zing the r e sults of stack testing for CDDs/CDF s at a number of HW I s between 1993 and 2000 (U.S. EPA, 2002b).
The CDD/CDF emission factors for HW I s in 1995 are based on data from 17 HW I s tested between 1993 and 1996; emissions of HW I s in 2000 are based on data from 22 HW I s tested in
2000. The furnaces at the 22 HW I facilities tested in 2000 were 11 rotary kiln incinerators, 6 liquid injection incinerators, 2 rotary hearth units , 1 fluidiz e d-bed incinera tor, and 1 roller hearth.
R a t h er t h an cl assi fy i n g t h e dedi cat ed HW I desig ns to derive an emission factor, ORD
de c i de d to de r i ve the e mission f a c t or a s a n a v e r a g e a c r oss a ll te ste d f a c ilitie s. F i r st, a n a v e r a g e emission factor was calculated using eq 3-3.

C × F
v

__________ 

### EF HW I 

### = (3-3) I

w



### where:
EF HW I 

### = emission factor (averag e ng TEQ per kg of waste burned)
C = TEQ or CD D / CD F concentration in flue g a ses (ng TEQ/dscm) (20°C, 1 a tm; a d juste d to 7% O 2 

### )
F
v 

### = volume t r i c f l ue g a s f l ow r a te ( d sc m/hr ) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )
I
w 

### = averag e wast e i n ci nerat i on rat e (kg / hr)

Althoug h 22 HW I s were tested in 2000, the OSW database contained va lues for flue g a s flow rates for only 12 of these incinerators. Th erefore, only 12 HW I s could be used to develop

an em i ssi on fact or. Aft e r devel opi ng an av erag e em i ssi on fact or for each HW I
, t h e overal l

averag e cong ener-speci fi c em i ssi on fact or was deri ved usi n g eq 3-4.

EF
av gH W I n= 1–17 

### = ( E F

HW I 1 

### + EF HW I 2 

### + EF HW I 3 

### + ........ + EF HW I 17 

### ) / N (3-4)

3-46

### where:
EF
a vgH W I 

### = averag e em i ssi on fact or for t h e t e st ed HW I s (ng / kg )
N = numbe r of te ste d f a c ilitie s

Tables 3-14a and 3-14b present the averag e emission factors de veloped for specific

cong eners, total CDDs and to tal CDF s , and TEQs for the HW I s tested from 1993 to 1996 and in 2000, respectively

. The averag e cong ener emi ssion profile for the 17 HW I s tested from 1993 to 1996 are presented in F i g u re 3-13. The averag e emission factor for the 17 HW I s was 3.88 ng TEQ DF 

### -W HO 98 

### /kg (3.83 ng I

- TEQ DF 

### /kg ) of waste feed (assuming nondetect values were z e ro). The averag e emission factor for the 22 HW I s tested in 2000 was 2.13 ng TEQ DF 

### -W HO 98 

### /kg (2.12

ng I

- TEQ DF 

### /kg ) of waste feed (assuming nondetect va lues were z e ro). The emission factor developed for reference y ear 1995 was used as a surrog a te for reference y ear 1987.

3.2.4. Em ission Estim ates f or HWIs Althoug h emissions data were available for 10% of the HW I s operating in 1995 and 17%
of the HW I s operating in 2000 in the United St ates (i.e., 22 of the 132 HW I s operating in 2000
ha ve be e n te ste d )
, the e mission f a c t or e stima te s a r e a ssig n e d a me dium c onf ide n c e r a ting be c a u se of

unc e r ta intie s r e sulting f r o m the f o llowing :

• V ar iabilit y of t h e w a st e fe e d s. The phy si cal and chem i cal composition of the waste

c a n va r y f

r o m f a c ility to f a c ility a nd e v e n within a f

a c ility

. Conse que ntly , CDD/CDF emissions measured for one feed may not be representative of those of other feeds.

• Tr ial bur ns. Much of the CDD/CDF emissions da ta we r e c o lle c t e d dur ing tr ia l bur ns, whic h a r e r e quir e d a s pa r t of the RCRA pe r mitting pr oc e ss a nd a r e use d to establish the destruction rate efficiency of principal haz a rdous org a nic constituents in the waste. During trial burns, a protot y pe waste is burned that is intended to

max imiz e the difficulty in achieving g ood combustion. F or ex ample, chlorine, metals, and org a nics may be added to the waste. Th e HW I may also be operated outside normal operatin g conditions. The temperature of both the furnace and the APCD may vary by a wide marg in (hig h and l o w t e m p erat ures), and t h e wast e feed
sy ste m ma y be inc r e a se d to ma x imum de sig n loa d. Ac c o r d ing l y , it is unc e r ta in how

r e pr e se n ta tive the CDD/CDF e missions me a sur e d dur ing the tr ia l bur n will be of emissions during norma l operating conditions.

Dempsey and Oppelt (1993) es timated that up to 1.3 million me tric tons of haz a rdous
waste were combusted in HW I s during 1987. A conf idence rating of medium is assig ned to this
estimate. EPA estimated that 1.5 million metric tons of haz a r dous waste were combusted in
HW I s each y ear in the early 1990s (F ederal Re g i ster, 1996a). The activ ity level estimate for

3-47

### Table 3-14a. CDD/CDF em ission f actor s f or hazardous w a ste incinerators and boilers tested f r om 1993 to 1996

C o n g en er In cin era to r a v era g e m ea n

em issio n f a cto r (1 7 f a cilities) (n g / kg f eed ) H o t-sid ed E S P b o ilers m e a n

em issio n f a cto r (2 f a cilities) (n g / kg f eed )
Nonde t e c t s e t to 1⁄2 d e tectio n lim it N o n d e tect set to

zero N o n d e tect set to 1⁄2 d e tectio n lim it N o n d e tect set to

zero 2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.44 0.18 0.22 0.32 0.49 1.77 4.13 0.14 0.14 0.18 0.28 0.48 1.74 3.74 0.1 0.11 0.15 0.2 0.22 1.17 5.24 0.0 0.04 0.08 0.18 0.2 1.17 5.24 2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2.96 2.36 2.56 9.71 3.95 0.31 2.7 16.87

1.74 13.79 2.69 2.33 2.51 9.71 3.95 0.29 2.7 16.68

1.71 13.46 0.81 0.38 0.52 0.83 0.37 0.08 0.56 1.04 0.18 0.7 0.81 0.38 0.52 0.83 0.37 0.02 0.56 0.93 0.16 0.7
To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 4.22 4.29 3.83 3.88 0.78 0.83 0.64 0.65
To t a l CDD/ CDF 153 153 28.83 28.39

ESP = Electro static p r ecip itato r



### 3-48

### T a b l e 3-14b

. CDD/CDF em ission f a ctors f o r h a zard ou s w a ste in cin erators and boilers tested in 2000

C o n g en er/co n g en er gr oup In cin era to r a v era g e m e a n

em issio n f a cto r (1 2 f a cilities) (n g / kg f eed ) a 

### H o t-sid ed E S P b o ilers m e a n

em issio n f a cto r (1 f a cility ) (n g / kg f eed ) a


### N o n d e tect set to 1⁄2 d e tectio n lim it Nonde t e c t s e t to zero N o n d e tect set to 1⁄2 d e tectio n lim it N o n d e tect set to

zero 2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.0615 0.6141 0.2347 0.5408 0.3037 2.729 5.211 0.036 0.0907 0.1395 0.4351 0.2178 2.699 5.17 0.0346 0.0488 0.1149 0.1715 0.3361 1.406 1.554 0.0 0.0 0.0789 0.1228 0.231 1.4055 1.5541 2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.6931 0.9406 0.88 4.085 3.031 2.667 1.218 28.74

5.056 36.270 0.6399 0.8375 0.735 4.045 3.001 2.637 1.121 28.71

5.021 36.23 0.9531 0.4599 0.8836 3.611 0.69 0.038 1.3272 4.6345 0.1895 0.7841 0.9531 0.3862 0.8836 3.6108 0.561 0.0 1.3272 4.6345 0.1257 0.7841
To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 2.54 2.809 2.119 2.127 1.313 1.335 1.214

To t a l CDD/ CDF 195.70 194.10 17.24 16.66

a Valu es in co rp o r atin g u s e o f th e d e tectio n lim it w h en th e l a borat ory report i n di cat ed “ n ot det ect ed” f o r i n di v i du al CD D / CD F c o nge ne r s

.

ESP = Electro static p r ecip itato r NR = No t rep o r ted

S o u r ce: U

. S

. EPA (2002a).



### 3-49Ratio (congener emission factor/t otal CDD/CDF emission factor)
0 0.05 0.1 0.15



### F i gure 3-13. Congener prof ile f o r air em issions f r om 17 hazardous w aste incinerators tested f r om 1993 through 1996.

1995 is assig n ed a hig h confidence rating because it is based on a review by EP A of the various studies and survey s conducted in the 1990s to a ssess the quantity and type s of haz a rdous wastes being manag e d by various treatment, storag e, and disposal fac ilities. B ecause of a lack of data

reg a rding the amount of waste burned in 2000, the 1995 estimate (1.5 milli on metric tons) was also used for determining TEQ emissions for 2000. The annual TEQ emissions for refere nce y ears 1987, 1995, and 2000 were estimated using eq 3-5.

E HW I 

### = EF HW I 

### × A HW I 

### (3-5)
where:
E HW I 

### = annual emissions from all HW I s , tested and nontested (g TEQ/y r)
EF HW I 

### = mean emission factor for HW I s (ng TEQ/kg of waste burned)
A HW I 

### = annual activity level of all operating HW I s (million metric tons/y r)

3-50

### Apply i ng the averag e TEQ emission f actor for dedicated HW I s (3.88 ng TEQ DF 

### WH O 98 

### /kg waste [ 3.83 ng I

- TEQ DF 

### /kg waste] ) to these producti on estimates y i elds estimated emissions of 5 g TEQ (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) in 1987 and 5.8 g TEQ DF 

### -W HO 98 

### (5.7 g I

TEQ DF 

### ) in 1995. F o r 2000, apply i ng the averag e TEQ emission factors for dedicated HW I s (2.13

ng TEQ DF 

### -W HO 98 

### /kg waste [ 2.12 ng I

- TEQ DF 

### /kg waste] ) to a production estimate of 1.5 million metric tons y i elds estima ted emissions of 3.2 g TEQ DF 

### -W HO 98 

### (3.18 g I

- TEQ DF 

### ). Medium confidence rating is assig n ed to these estimates because the emission factor was g i ven a medium
confi d ence rat i n g

.

3.2.5. Recen t EP A Regu latory Activities
CDD/CDF emissions from HW I s are reg ulate d by EPA (F ederal Reg i ster, 1999a, 2004).
The r e g u la tions a r e spe c i f i c to the I

- TEQ c onc e n tr a tion in the c o mbustion g a se s le a v ing the
stack. Ex isting HW I s equipped with waste heat boilers and dry scr ubbers (as APCDs) cannot emit more than 0.28 ng I

- TEQ/dscm. All othe r ex isting HW I s are limited to 0.4 ng I

- TEQ/dscm
of

sta c k g a s. Re g u la tor y r e quir e me nts a r e mor e str i c t f o r

ne wly built HWI s: those e quippe d with waste heat boilers and dry scrubbers (as AP CDs) cannot emit more than 0.11 ng I

- TEQ/dscm,
and all others are limited to 0.2 ng I

- TEQ/dscm of stack g a s.

3.2.6. Industr ial Boile r s and F u r n ac e s Burning Hazardous Waste
I n 1991, EPA established rules that allow the combustion of some liquid haz a rdous waste in industrial boilers and furnaces (F ederal Reg i ster, 1991b). These facilitie s ty pically burn oil or coal for the primary purpose of g e nerating elect ricity

. L i quid haz a rdous waste can be burned only as supplemental (aux iliary ) fuel, and the rule limits use to no more than 5% of the primary
f u e l s. The se f a c ilitie s ty pic a lly use a n a t omize r to inje c t the wa ste a s dr ople t s into the
combustion chamber. They are equipped with pa rt i c ul at e and aci d g a s e mission controls and in

g e neral are sophisticated, well-controlled fac ilities that achieve g ood combustion.
The national OSW databa se cont ai ns cong ener-speci fi c emission concentrations for two boilers burning liquid haz a rdous waste as s upplemental fuel tested from 1993 to 1996. The

averag e cong ener and cong ener g r oup emission pr ofiles for the industria l boiler data set are presented in F i g u re 3-14. The database also c ontains cong ener-specifi c emission concentrations
for four boilers tested in 2000. Of the boilers te sted in 2000, sufficient data to calculate averag e TEQ emissions were available for only one boiler. The averag e cong ener and TEQ emission factors are presented in Tables 3-14a and 3-14b. The limited set of emissions data prevented subdividing this class to derive an emission f actor. The equation used to derive the emission factor is the same as eq 3-4. The TEQ emi ssion factors for the industrial boiler are 0.65 ng

3-51Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.05 0.1 0.15 0.2

Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.05 0.1 0.15 0.2 0.25



### F i gure 3-14. Congener and congener gr oup prof iles f or air em issions f r om boile r s and indust r ial fur n ac e s bur ning haz a r d ous wast e .

3-52

### TEQ DF 

### -W HO 98 

### /kg (0.64 ng I

- TEQ DF 

### /kg ) of waste feed for 1993 to 1996 and 1.212 ng TEQ DF 

### WH O 98 

### /kg (1.214 ng I

- TEQ DF 

### /kg ) of waste feed for 2000. Thes e emission factors are assig n ed a low confidence rating because they reflect testin g at only 2 of 136 haz a rdous waste boilers and furnaces operating from 1993 to 1996 and only 1 of the 114 haz a rdous waste boilers and furnaces operating in 2000. Dempsey and Oppelt (1993) es timated that approx imately 1.2 billion kg of haz a rdous
waste were combusted in industr ial boilers/furnaces in 1987. EPA estimated that in each y ear in the early 1990s approx imately 0.6 billion kg of ha z a rdous waste were co mbusted in industrial boilers/furnaces (Federal Reg i st er, 1996a). I t is possible that cement kilns and lig ht-weig ht

ag g r eg ate kilns burning haz a rdous waste were included in the estimate by Dempsey and Oppelt for 1987; the estimate for 1995 does not appear to include these hazardous waste-burning kilns. A confidence rating of low is assig n ed to the estimated activity level fo r 1987, which was larg ely based on a review of state permits (Dempsey a nd Oppelt, 1993). The activ ity level estimate for 1995 is assig n ed a medium confidence rating becau se it was based on a review by EP A of the various studies and survey s conducted in the 1990s to assess the quantity and ty pes of haz a rdous wastes being manag e d by various treatment, storag e, and disposal facilities. B ecause of a lack of data reg a rding the amount of waste burned in 2000, the 1995 estimate ( 1.5 million metric tons) was used as a surrog a te for 2000. Equation 3-5, which was used to calculate annual TEQ emissions for dedicated HW I s , was also used to calculate annua l TEQ emissions for industrial bo ilers/furnaces. Multiply ing the

averag e TEQ emission factors by the total es timated kg of liquid ha zardous waste burned in 1987, 1995, and 2000 y i elds annual emissions in g

- TEQ/y r. F r om this procedure, the emissions
from all industrial boilers/furnaces burning haz a rdous waste as supplemental fuel are estimated as 0.78 g TEQ DF 

### -W HO 98 

### (0.77 g I

- TEQ DF 

### ) in 1987, 0.39 g TEQ DF 

### -W HO 98 

### (0.38 g I

- TEQ DF 

### ) i n 1995, and 1.82 g TEQ (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) in 2000. B ecause of the low confidence

r a ting f o r

the e mission f a c t or , the ove r a ll c onf ide n c e r a ting is low f o r

the e mission e stima te s f o r al l t h ree reference y ears.

3.2.7. Halogen Acid F u rnaces Burning Hazardous Waste
Haz a rdous waste can be used in the pr oduction of halog e n acids using an HAF

. According to EPA rules, products that qualify as haz a rdous waste, as defined in 40 CF R 261.2 must be reg u lated as such, even if the products are used in th e production of halog e n acids using
an HAF (F ederal Reg i ster, 1991c).
The national OSW databa se cont ai ns cong ener-speci fi c emission concentrations for two
HAF s burning liquid haz a rdous wast e as supplemental fuel tested in 2000. Data from these two
f

a c ilitie s we r e use d to c a l c ula te a n e mission f a c t or f

or

HAF s. The a ve r a g e c ong e ne r a nd TEQ

3-53

### emission factors are presented in Table 3-15. The equation used to derive the emission factor is the same as eq 3-4. The averag e TEQ emission factor for HAF s is 0.836 ng TEQ DF 

### -W HO 98 

### /kg (0.803 ng I

- TEQ DF 

### /kg ) of waste feed for reference y ear 2000. This emission factor is assig ned a low confidence rating because it reflects testin g at only 12.5% of all HAFs operating in 2000 (2 out of 16).

Table 3-15. CDD/CDF em ission f a ctors f o r halogen acid f u rnaces tested in 2000

C o n g en er/co n g en er gr oup In cin era to r a v era g e m e a n em issio n f a cto r (1 2 f a cilities) (n g / kg f eed )
N o n d e tect set to 1⁄2 d e tectio n lim it N o n d e tect set to zero 2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.0274 0.1164 0.0979 0.1663 0.1686 0.9868 1.4944 0.0208 0.112 0.0913 0.1594 0.1293 0.9868 1.4944 2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.3821 0.583 0.5689 1.1244 0.7172 0.4412 0.2685 3.4914 1.0429 25.015 0.3821 0.583 0.5689 1.1244 0.7172 0.4412 0.2685 3.4914 1.0429 25.015
To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 0.8176 0.8519 0.8034 0.8356
To t a l CDD/ CDF 62.4773 62.4607

S o u r ce: U

. S

. EPA (2002a).



### The amount of haz a rdous waste combuste d using HAF s in 2000 was conservatively estimated to be 375,600 metr ic tons. This estimate is ba sed on data provided by OSW that described activity levels for each individual HAF in 2000. Activity data were available for 14 of
the 16 facilities. B y assuming that plants operate continuously thr oug hout the y e ar, that they are alway s running at 80% of max imum capacity , and that the activity levels represent the max imum capacity , a conservative estimate for the annua l quantity burned per HAF was derived (23,480

3-54

### kg /y r )

. This qua ntity multiplie d by the tota l unive r se of 16 f a c ilitie s y i e l ds the f i na l e stima te of 375,600 metric tons. This was assig ned a low c onfidence rating because the data was possibly nonrepresentative. Equation 3-5, which was used to calculate annual TEQ emissions from dedicated HW I s , was also used to calculate annual TEQ e missions from HAF s. Multiply ing the averag e TEQ emission factors by the total estimated kilog r am s of liquid haz a rdous waste burned in 2000 y i elds annual emissions in g I

- TEQ DF 

### . F r om this procedure, th e emissions from all industrial boilers/furnaces burning haz a rdous waste as supplemental fuel are estimated as 0.31 g TEQ DF 

### WH O 98 

### (0.3 g I

- TEQ DF 

### ). Because of t h e l o w confi d ence rat i n g for t h e em i ssi on fact or, t h e

ove r a ll c onf ide n c e r a ting is low f o r

the e mission e stima te s.

3.2.8. Solid Waste f r om Hazardous Waste Com bustion
U.S. EPA (1987a) contains limited data on ash g e nera ted from haz a rdous waste
incineration. The study indicates that the mean concentrations of CDDs and CDF s from an HW I
with an afterburner were 538 : 

### g / kg and 2,853 : 

### g / kg , respectively (Table 3-8 in U.S. EPA, 1987a). Specific data for cong eners a nd for ash quantities were not provided.

3.3. MEDICAL WASTE INCINERATION
Medical waste incineration is the controlled burning of solid wast e s g e ne r a te d pr ima r ily by hospita ls, ve te r i na r y f

a c ilitie s, a nd me dic a l r e se a r c h f a c ilitie s. EPA de f i ne s me dic a l wa ste a s

a n y solid wa ste g e ne r a te d in the tr e a tme nt, di ag nosis, or immuniz a tion of humans or animals or research pertaining thereto or in the production or testing of biolog icals (F ederal Reg i ster, 1997a). The primary purposes of medical waste incineration are to reduce the volume and mass
of

wa ste in ne e d of la nd disposa l a nd to ste r ilize the inf e c tious ma te r i a l s. The f o llowing se c tions review the basic ty pes of medical wast e i n ci nerat o r (MW I ) desi g n s used to incinerate medical
waste and the distribution of APCDs used on MW I s and summariz e the derivation of diox in TEQ

e mission f a c t or s f o r

MWI s a nd the na tiona l diox in TEQ e mission e stima te s f o r

r e f e r e nc e y e a r s 1987, 1995, and 2000.

3.3.1. Design Types of MWIs Opera ting in the United States
F or purposes of this document, EPA has cla ssified MW I s into three broad technolog y categ ories: modular furnaces usin g controlled air, modular furnaces using ex cess air, and rotary
kilns. Of the MW I s in use today , the vast ma jority are believed to be modular furnaces using
controlled air. EPA has estimate d that 97% are modular furnaces using controlled air, 2% are modular furnaces using ex cess air, and 1% ar e rotary kiln combustors (U.S . EP A, 1997a).

3-55

### Mod u l ar f u rn aces u s i n g con t rol l e d ai r. Modular furnaces have two separate combustion chambers mounted in series (one on t op of the other). The lower chamber is where the primary combustion of the me di cal wast e occurs. Medi cal wa ste is r a m- f e d into the pr ima r y chamber and underfire air is delivered beneath th e incinerator hearth to sustain g ood burning of
the waste. The primary combustion chamber is operated at below stoich iome tr ic le ve ls, he nc e
t h e t e rm s “cont rol l e d ai r” or “st a rved ai r.” W ith substoichiometric conditions, combustion occurs at relatively low temperatures (760 to 985°C). Under the conditions of low ox y g en and low temperatures, partial py roly sis of the wa ste occurs and volatile compounds are released. The combustion g a ses pass into a second chamber. Aux iliary fuel (such as natural g a s) is burned to sustain elevated temperatures (985 to 1,095°C) in this secondary chamber. The net
effect of ex posi n g t h e com bust i on g a ses t o an el evat ed t e m p erat ure i s m o re com p l e t e dest ruct i o n of

the or g a nic c onta mina n ts e n tr a i ne d in the c o mbustion g a se s e m a n a ting f r o m the pr ima r y combustion chamber. Combustion air at 100 to 300% in ex cess of stoichio metric requirements is usually added to the secondary ch amber. Gases ex iting the seconda ry chamber are directed to an incinerator stack (U.S. EPA, 1991b, 1997a; B uonicore , 1992b). B e cause of its low cost and g ood combustion performance, this desig n has been the most popular choice for MW I s and has accounted for more than 95% of sy stems insta lled over the past two decades (U.S . EP A, 1990b, 1991b; B uonicore, 1992b).
Mod u l ar f u rn aces u s i n g excess ai r. These sy stems use th e same modular furnace config uration as descri bed above for the controlled-air sy st ems. The difference is that the primary combustion chamber is operated at air le vels of 100 to 300% in ex cess of stoichiometric requirements, hence the name “ex cess air.” A secondary chamber is located on top of the

pr ima r y unit. Aux ilia r y f

u e l is a dde d to susta i n hig h te mpe r a t ur e s in a n e x c e ss- a i r e nvir onme n t.
Ex cess-ai r MW I s t y pi cal l y have sm al l e r capaci t y than do controlled-air units, and they are usually batch-fed operations. Th is me a n s tha t the me dic a l wa ste is r a m- f e d into the unit a n d

a llowe d to bur n c o mple te ly be f o re another batch of medical waste is added to the primary
combustion chamber. F i g u re 3-4 shows a schema tic of a ty pical modular furnace using ex cess ai r. Rot a r y kiln. I n terms of desig n a nd operational features, the rotary kiln technolog y used
in medical waste incineration is similar to that employ ed in both municipal and haz a rdous waste incineration (see description in S ection 3.1). B ecause of their relatively hig h capital and

ope r a ting c o sts, f e w r o ta r y kiln inc i ne r a tor s a r e in operation for medical waste treatment (U.S. EPA, 1990b, 1991b; B uonicore, 1992b).
MW I s can be operated in three modes: batch, intermittent, a nd continuous. B a tch incinerators burn a sing le load of waste, ty pica lly only once per day

. W a ste is loaded and ashes are removed manually

. I n termittent incinerators , which are loaded continuously and frequently

3-56

### with sma ll wa ste ba tc he s, ope r a te less than 24 hr/day , usually on a shif t ba sis. Eithe r ma nua l or automated charg i ng sy stems can be used, but the incinerator must be shut down for ash removal. Continuous incinerators are operated 24 hr/day and use automatic charg i ng sy stems to charg e waste into the unit in small, frequent batches. A ll continuous incinerato rs operate using a mechanism to automatically remove the as h from the incinerator (U.S. EPA, 1990b, 1991b).

3.3.2. Ch aracterization of MWIs f o r Ref eren ce Years 1987, 1995, an d 2000
Medical waste incineration re mains a poorly characteriz ed industry in the United States in terms of knowing the ex act number of fac ilities in operation over time , the ty pes of APCDs
i n st al l e d on t h ese uni t s , and t h e ag g r eg at e vol um e a nd weig ht of medical waste that is combusted in any g i ven y ear (U.S. EPA, 1997a). The primary reason for this lack of information is that

pe r mits we r e not g e ne r a lly r e quir e d f o r

the c ontr o l of polluta nt sta c k e missions f r o m MWI s until the early 1990s, when state reg u latory ag enci es beg a n setting limits on emissions of PM and other contaminants (F ederal Reg i ster, 1997a). Prior to that, only opacity was controlled.
The information available to characteriz e MW I s from 1987 and 1995 comes from national telephone survey s, stack emission permits, a nd data g a thered by EPA during public hearing s (F ederal Reg i ster, 1997a). F o r 2000, information was also provided by a memorandum
on emissions from MW I s (Strong and Hanks, 1999) and a limited telephone survey (McAloon, 2003). Strong and Hanks provide d information on MW I s in the United States, including the APCD being used by each facility

. A telephone survey was conducte d with the state ag encies in
each of these six states to obt ain the number of MW I s that were operating in 2000. EP A was able to obtain an updated list from four of the si x states, which are shown below, along with the dates they were contacted, th e number of MW I s operating in 1999, the updated number of MW I s for that state in 2000, and the percent of fac ilities closed over this time period for each state.

Sta t e Dat e cont act ed No. of MW I s 1999 2000 Pe r c e n ta g e of f

a c ilitie s closed from 1999 to 2000 I llinois J an. 16, 2003 97 13 86.6 L ouisiana J an. 16, 2003 92 24 73.91 Mary land Mi chi g an Dec. 2, 2002 Nov. 26, 2002 36 228 30 45 16.67 80.26

The g e om et ri c m ean of t h e cl osure percent a g e s for t h e four st at es was det e rm i n ed t o be
54.09 and the arithmetic mean wa s 64.36. Mary land had the lowest closure percent from 1999 to 2000; however, throug h discussions with repres entatives of Mary land state ag encies, it was

3-57

### determined that close to 70% of the facilitie s operating in 1999 would be shut down as of 2003.
I t was therefore assumed that the averag e closure percent of 64.36 was a fairly g ood estimate for
all states. This averag e was applied to the total number of facilities operating in 1999 from the Strong and Hanks (1999) memo randum to estimate the number of facilities operating in 2000.
The information obtained from thes e sources sug g e sts the following :

• The number of MW I s in operation for each reference y ear was approx imately 5,000 in 1987 (U.S. EPA, 1987c), 2,375 in 1995 (F ederal Reg i ster, 1997a), and 1,065 in 2000 (Strong and Hanks, 1999; McAloon, 2003).

• The amount of medical waste combuste d annually in the United States was approx imately 1.43 billion kg in 1987 (U.S . EPA, 1987c) and 0.77 billion kg in 1995 (F ederal Reg i ster, 1997a).

These estimates indicate that between 1987 and 1995 the total number of operating MWI s and the total amount of waste combusted decreas ed by more than 50%. F r om 1995 to 2000, the total number of operating MW I s decreased by appr ox imately 55%. A variet y of factors probably

c ontr i bute d to the r e duc tion in the numbe r of ope r a ting f a c ilitie s, inc l uding f e de r a l a nd sta t e
reg ulations and air pollution c ontrol requirements. I n 1997, EP A adopted emission g uidelines
for ex isting MW I s (incinerators constructe d on or before J une 20, 1996) and New Source
Performance Standards for new MW I s (incinerat ors constructed after J une 20, 1996). The Clean
Ai r Act requi res t h at st at es i m p l e m e nt t h e em i ssi on g u i d el i n es accordi n g t o a st at e pl an and t h at the y submit the sta t e pla n to EPA within one y e a r of EPA’ s pr omulg a tion of the g u ide line s ( i .e ., by September 15, 1998). The compliance schedule, however, allows up to three y ears from EPA approval of the state plan for MW I s to co mply , provided the plan includes enforceable increments of prog ress. All MW I s were requi r e d to be in c o mplia nc e within thr e e y e a r s of approval of their state plan or by September 15, 2002, wh ichever was earlier. Complia nc e is sta t e d to be e ithe r c o mple tion of r e tr of it of a i r pollution c ontr o ls or
shutdown of the f a c ility

. As a r e sult, ma ny f

a c ilitie s ha ve c l ose d down a nd hospita ls ha ve switched to less ex pensive medical waste treatment technolog ies, such as autoclaving (F ederal Reg i ster, 1997a). Autoclaving , or steam st eriliz ation, is one of the most common waste

manag e ment practices used today

. This process involves placing ba g s of infectious waste into a

se a l e d c h a m be r , some time s pr e ssur i ze d, a nd the n he a ting it by dir e c t c onta c t with ste a m to

ste r ilize the wa ste

. The actual controls used on MW I s on a facility -by -facility basis in 1987 are unknown, and EPA g e nerally assumes that MW I s were mostly uncontrolle d (U.S. EPA, 1987c). However, the modular desig n does cause some destruction of org a nic pollutants within the secondary

3-58

### combustion chamber. Residence time within th e secondary chamber is key to inducing the thermal destruction of the org a nic compounds. Residence time is the time that the org a nic compounds entrained within the flue g a ses are ex pos ed to elevated temper atures in the secondary

c h a m be r

. EPA ha s de monstr a t e d with f u ll- sc a l e MWI s tha t inc r e a sing r e side nc e time f r o m 1/4 sec to 2 sec in the secondary chamber can reduce org a nic pollutant emissions, including
CDDs/CDF s, by up to 90% (F ederal Reg i ster, 1997a). I n this reg a r d, residence time can be viewed as a method of air pollution control.
EPA estimates that about two- thirds of the medical wast e burned in MW I s in 1995 went
to facilities that had so me method of air pollution control (F ederal Reg i ster, 1997a).The ty pes of
APCDs installed and the methods used on MW I s include DSI , F F s , ESPs, W S s, and F F s combined with packed-bed scrubbers (composed of g r anular activated carbon). Some org a nic

c onstitue n ts in the f l ue g a se s c a n be a d sor b e d by the pa c k e d be d. Within the unc ontr o lle d c l a ss of MW I s , about 12% of the waste was combusted in facilities with desig n capacities of less than 200 lb/hr, with the majority of waste burned at facilities with capacities g r eater than 200 lb/hr. I n

c ontr o lle d f a c ilitie s, a n e stima te d 70% of the a g g r e g a t e a c tivity le ve l is a ssoc i a t e d with f a c ilitie s equipped with either W S s, F F s , or ESPs; 29.9% is associated with facilities that use DSI

c o mbine d with F F s; a nd le ss tha n 1% is a ssoc i a t e d with f a c ilitie s tha t ha ve a n F F /pa c k e d

- b e d APCD (AHA, 1995; F e deral Reg i ster, 1997a). Strong and Hanks (1999) provi ded information on the ty pes of APCDs used by facilities operating in 1999. Ten ty pes we re included in the memorandum , which included residence time as a ty pe of control technolog y

. The 10 ty pe s were 1/4-sec combusti on, 1-sec combustion, 2-sec combustion, low-efficiency W S
, moderate-efficiency W S , hig h -e fficiency W S , drylime injectF F
, dr y lime inje c t

- F F with CI , WS/dr y lime inje c t

- F F
, a nd SD/F F with CI

. Ta ble 3- 16 pr ovide s an estimated breakdown of these APCDs.

3.3.3. Estim ation of CDD/CDF Em issions f r om MWIs Emission tests reported for 22 MW I s (about 3% of the ex isting facilities operating in 2000) were collected for use in this document; e mission levels of diox in-like compounds at most
facilities are unmeasured. B ecause so few facilities have been evaluated, the estimation of
annual air emissions of CDDs/CDF s from MW I s is quite dependent on ex trapolations,

eng i neering judg ment, and assumptions. I n add ition, the information about the activity levels of
the s e f a c ilitie s is a l so quite limite d.

The analy s is divided MW I s into three de sig n ty pes on the basi s of mode of daily operation: batch, inter mittent, or continuous. This was done using the information from the inventory on desig n-rate d annual incineration capacity of each facility

. The smaller capacity

3-59

### Table 3-16. Estim a ted breakdow n of f

a c ilities by air pollution control device (AP CD)

AP CD Nu m b er of fac ilit ie s P ercen t of total
1/4-sec combustion 229 17.5
1-sec combustion 259 19.8
2-sec combustion 455 34.8
L o w-efficiency wet scrubber 208 15.9 Moderate-efficiency wet scrubber 75 5.7 Hig h -efficiency wet scrubber 16 1.2 Dry lime inject fabric filter 44 3.4 Dry lime inject fabric filter with carbon injection 7 0.5
W e t scrubber/dry lime inject fabric filter 14 1.1 Spray dry e r fabric filter with carbon injec tion 1 0.1

S o u r ce: S t ron g an d H a n k s (1999).



### units we r e a ssume d to be ba tc h ope r a tions, a nd the othe r s we r e c l a ssif i e d a s e ithe r inte r mitte nt or continuous, assuming a ratio of 3 to 1. The activity level of each f acility was estimated by multiply ing the desig n -rated annual incineration capacity of the MW I (kg / hr) by th e hours of operation (hr/y r). The annual hours of

ope r a tion we r e de te r mine d by a ssuming a c a p a c ity f

a c t or ( d e f ine d a s the f r a c tion of time tha t a unit operates over the y ear) for each desig n ty pe of MW I (Randall, 1995). Table 3-17 is a

summary of the estimated annual operating hours for each MW I desig n ty pe. I n e stima ting diox in e missions, the MWI s we r e divide d into two c l a sse s: those ha ving APCDs (controlled) and those lacking any APCD (uncontrolled). These two classes of MW I s are discussed below.
F or 1987, it is assumed that every MW I wa s uncontrolled. An EPA study of MW I s conducted at that time indicated that MW I s opera ting in 1987 did not need controls because they

we r e not subje c t to sta t e or f

e de r a l limits on e ithe r PM or or g a nic polluta nt e missions ( U .S. EPA, 1987c). The activity level estimate s were derived from data pres ented in that 1987 study

. This approach resulted in the following activity leve l assumptions for 1987: (a) 15% of the activity level (0.22 billion kg ) was incine rated annually by MW I s with capacities less than or equal to 200 lb/hr, and (b) 85% of the ac tivity level (1.21 billion kg ) was in cinerated annually by facilities with capacities g r eater than 200 lb/hr (see Table 3-18). F o r 1995, the activity levels were then
summed across facilities for each AP CD subclass (see Table 3-19).

3-60

### Table 3-17. Sum m a r y of annual ope r a ting hour s f o r e a c h m e dic a l w a ste i n ci n erator (MWI) typ e

MWI typ e Cap a city

ran g e ( l b/hr ) A nnual charging

hour s (hr/yr) Maxim u m annual charging

hour s (hr/yr) Cap a city fa c t o r

Continuous commercial > 1,000 7,776 8,760 0.89

Continuous onsite 501–1,000 >1,000 1,826 2,174 5,475 0.33 0.40

I n te r mitte nt # 

### 500 1,250 4,380 0.29

Bat c h C ase by case C ase by case C ase by case

S o u r ce: U

. S

. EPA (1990c).



### I n 1997, the amount of waste combusted by MW I s was estimated to be 0.8 million tons/y r (0.7 billion kg /y r) (NRC, 2000). This number represents a 9% decrease from 1995. I f we assume that this decrease occurred every two y ears from 1997 to 2000, the estimated amount of waste combusted by MW I s for 2000 would be 0.6 b illion kg /y r. This is a conservative estimate,

c onside r ing the la r g e numbe r of f

a c ilitie s tha t ha ve shut down or switc he d to le ss e x pe nsive medical waste treatment technolog ies. F or 2000 activity level es timates, the same distributions

among APCD classes were assu med as for 1995. These activity level estimates ar e presented in
Table 3-20. For all y ears, these activity levels were assig n ed a rating of low confidence because the data were judg ed to be possibly nonrepresentative.
The sta c k te st r e sults showing the a i r e mi ssions of diox in from 24 MW I s were obtained
and used to calculate 1987 and 1995 emission estimates. After revi ewing these test reports, EPA determined that 20 met the criteria for accep tability (see Section 3.1.3). I n some cases, C DD/ C DF cong ener-speci fi c dat a we re not reported or values were missing

. I n other cases, the protocols used in the laboratory analy s is were not described; therefore, no determination of the adequacy of the laboratory methods could be made. F or 2000, two additi onal test reports from
f

a c ilitie s ope r a ting in tha t y e a r we r e obta i ne d a nd we r e inc l ude d with the pr e v iously obta i ne d te st reports in order to calculate updated emission estimates. Each test report was included in its respect i v e MW I subcl a ss accordi n g t o i t s AP C D and was al so i n cl uded i n t h e overal l em i ssi on

e s tima te

.

3-61Table 3-18.TEQ emissions frommedical waste incinerators (MWIs) for reference year 1987



### 3-62MWIclassaNo. oftestedfacilitiesActivitylevel(kg/yr)TotalCDD/CDFemissionfactorb(g/kg)I-TEQDFemissionfactor(g/kg)TEQDF­WHO98emissionfactor(g/kg)AnnualCDD/CDFemissions(g/yr)AnnualI-TEQDFemissions(g/yr)AnnualWHO98­TEQDFemissions(g/yr)#200 lb/hr32.19e+089.25e!051.86e!061.98e!062.02e+044.08e+024.34e+02>200 lb/hr51.21e+096.05e!051.68e!061.78e!067.32e+042.03e+032.14e+03TOTAL81.43e+099.34e+042.44e+032.57e+03Table 3-19.TEQ emissions frommedical waste incinerators (MWIs) for reference year 1995MWIclass(air pollutioncontrol device[APCD])MWIsubclass(capacity orAPCDa)No. oftestedfacilitiesTotalCDD/CDFemissionfactor(ng/kg)I-TEQDFemissionfactor(ng/kg)TEQDF­WHO98emissionfactor(ng/kg)Activitylevel(kg/yr)AnnualCDD/CDFemissions(g/yr)AnnualI-TEQDFemissions(g/yr)AnnualTEQDF­WHO98emissions(g/yr)Uncontrolled#200 lb/hr39.25e+041.86e+031.98e+033.06e+072.83e+035.71e+016.06e+01>200 lb/hr56.05e+041.80e+031.78e+032.23e+081.35e+043.75e+023.97E+02ControlledWS/FF/ESP94.67e+047.22e+016.63e+013.71e+081.73e+032.68e+012.76E+01DSI/FF22.85e+026.784.611.46e+084.16e+019.90e!011.00E+00FF/PBS11.11e+051.35e+031.49e+036.99e+057.76e+019.44e!011.04e+00TOTAL7.71e+081.82e+044.59e+024.87E+02aSlash(es) indicatesdevicesused inconjunction.APCD (air pollutioncontrol device):DSI = Drysorbent injectionESP= Electrostatic precipitatorFF = Fabric filterPBS = Packed-bed scrubberWS=WetscrubberTable 3-20.TEQ emissions frommedical waste incinerators (MWIs) for reference year 2000



### 3-63MWIclass(air pollutioncontrol device[APCD])MWIsubclass(capacity orAPCDa)No. oftestedfacilitiesTotalCDD/CDFemissionfactor(ng/kg)I-TEQDFemissionfactor(ng/kg)TEQDF­WHO98emissionfactor(ng/kg)Activitylevel(kg/yr)AnnualCDD/CDFemissions(g/yr)AnnualI-TEQDFemissions(g/yr)AnnualTEQDF­WHO98emissions(g/yr)Uncontrolled#200 lb/hr39.25e+041.86e+031.98e+032.40e+072.22e+034.46e+014.75e+01>200 lb/hr56.05e+041.68e+031.78e+031.74e+081.05e+043.13e+023.10e+02ControlledWS/FF/ESP94.67e+046.44e+016.63e+012.88e+081.34e+042.08e+011.91e+01DSI/FF22.85e+024.564.611.14e+083.25e+017.73e–015.26e–01FF/PBS11.11e+051.35e+031.49e+035.40e+055.99e+037.29e+018.05e+01TOTAL6.01e+083.22e+043.57e+023.78e+02aSlash(es) indicatesdevicesused inconjunction.APCD:DSI = Drysorbent injectionESP= Electrostatic precipitatorFF = Fabric filterPBS = Packed-bed scrubberWS=Wetscrubber

### ______ The EPA stack testing method (EPA Met hod 23) produces a measurement of CDDs/
CDF s in units of mass concentration (ng / dscm) at standard temperature and pressure and 1 atm and adjusted to a measurement of 7% ox y g en in the flue g a s (U.S. EPA, 1995a). This concentration is assumed to repres ent conditions at the point of re l ease from t h e st ack i n t o t h e ai r and to be representative of rou tine emissions. The emission fact ors were derived by averag ing the emission factors across each tested facility in a desig n class. Th e emission factor for each

te ste d MWI wa s c a l c u la te d using the f o llowing e qua tion:

C × F
v 

### EF MW I 

### = (3-8) I

w 

### where:
EF MWI 

### = emission factor per MW I (averag e ng TEQ per kg medical waste burned)
C = averag e TEQ concent r at i on i n fl ue g a ses of tested MW I s (ng TEQ/dscm) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )
F
v 

### = a v e r a g e volume t r i c f l ue g a s f l ow r a te ( d sc m/hr ) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )
I
w 

### = averag e m e di cal wast e i n ci nerat i on rat e of t h e t e st ed MW I (kg / hr)

3.3.4. Sum m ary of CDD/CDF Em issions f r om MWIs
Annual diox in emissions were estimated by multiply ing the emission factor and activity level developed for each desig n class and then summing the calcula ted emissions for all classes. Tables 3-18, 3-19, and 3-20 summari z e the resulting national TEQ air emissions for reference

y ears 1987, 1995, and 2000, respectively

. These tables also indicate the activity level and the TEQ emission factor used in estimating annual TEQ emissions.
I n estimating annual TEQ emissions for each re ference y ear, a low confidence rating was assig ned to the estimate of the activity leve l, primarily because ve ry limited information is

a v a ila ble on a f

a c ility

- l e v e l ba sis f o r

c h a r a c t e r izing MWI s in te r m s of the f r e que nc y a nd dur a tion of operation, the actual waste volume handled, a nd the level of pollution control. The 1987 inventory of facilitie s was based on very limited info rmation. Althoug h the 1995 OAQPS inventory was more comprehensive than the 1987 inventory

, it was still based on a fairly limited

survey of operating facilities (approx imately 6%). The 2000 inventory included only two additional facilities and estimated an activity level based on a 1997 value and the distribution

among APCDs from the 1995 estimates.
The emission factor estimates were g i ven a low confidence rating because the reports of only 20 tested MW I facilities coul d be used to derive emissi on factors representing the 2,375 facilities operating in 1995 (i .e., less than 1% of the estimated number of operatin g facilities) and only two additional test reports were obtained for 2000. Even fewer tested facilities could be

3-64

### used to represent the larg er num ber of facilities operating in 1987 (8 tested facilities were used to represent 5,000 facilities). The limite d emission tests available cove r all desig n categ ories used here to develop emission factors. However, because of th e larg e number of facilities in each of these classes, it is very uncertain whether the few tested facilities in each class capture the true

va r i a b ility in e missions.
Table 3-20 shows the 2000 emissi ons estimate as being 378 g TEQ DF 

### -W HO 98 

### (357 g I

TEQ DF 

### ). The TEQ emissions are es timated to have been 487 g TEQ DF 

### -W HO 98 

### (459 g I

- TEQ DF 

### ) in 1995 (Table 3-19) and 2,590 g TEQ DF 

### -W HO 98 

### (2,440 g I

- TEQ DF 

### ) in 1987 (Table 3-18).
Because t h e act i v i t y l e vel and em i ssi on fact ors had l o w confi d ence rat i n g s , t h e em i ssi on

e stima te s f o r

a ll y e a r s we r e a ssig n e d a low c onf ide n c e r a ting

, i.e ., a Ca te g o r y C. F i g u r e s 3- 15 and 3-16 display the cong ener and cong ener g r oup profiles of MW I s w ithout APCDs and those equipped with W S s and F F s , respectively

.

3.3.5. Recen t EP A Regu latory Activities In Sept emb e r 1997, EPA promulgat e d fin a l regulat ion s un der t h e Clean Air Act Amen dmen t s limit i n g CD D / CD F st ack emission s from MWIs (Federal Regist er, 1997a). Th ese emission limits are specific to the sum of CDD and CDF emissi o n s (the sum o f tetr a - thr o ugh

oc t a

- C D D s an d CD F s )

. F o r eit h er n e w or exist i n g MW I s t h at w e re operat ion a l b e fore or aft e r J u n e 20, 1996, EPA limit s t h e t o t a l CD D / CD F con c en t r at ion in t h e st ack gases t o 2.3 n g / d scm. Th is would require t h e applicat ion of WSs, D S I o f a c ti va ted ca r b o n co mbi n ed wi th FFs a n d / o r SDs/FFs. EPA expects tha t ma ny f a ci li ti es tha t cur r ently o p erate on-site incine rato r s will switch to less expensive methods of treatment and dispos al of medical and infect ious waste when faced with the co mpliance co st s associated with the em ission standards for MW I s

. EPA projec t s t h at
, following full compliance with th ese standards, annual emissions from MWIs will be 5 to 7 g I

TEQ DF 

### /

yr.

3.4. CREMATORIA
3.4.1. Hum an Crem atoria
3.4.1.1 Em issions Data
B r emmer et al. (1994) measured CDD/CDF emissions at two crematoria in the
Net h erl a nds. The fi rst , a “col d ”-t y pe furnace wi t h di rect , uncool ed em i ssi ons, was cal cul a t e d t o
y i eld 2,400 ng I

- TEQ DF 

### per body

. I n the cold-ty p e furnaces , the coffin is placed inside at a temperature of about 300°C. The temperature of the chamber is then increased to 800 to 900°C using a burner and kept there for 2 to 2.5 hr. The second furnace, a “warm” ty pe in which flue

g a ses are cooled to 220°C prior to discha rg e, was calculated to y i eld 4,900 ng I

- TEQ DF 

### per body

. I n the warm-ty p e furnace, the co ffin is placed in a chamber preh eated to 800°C or hig h er for 1.2
to 1.5 hr. The chamber ex hausts from both furnace ty pes were incinerated in an afterburner at a

3-65Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09

Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.05 0.1 0.15 0.2 0.25



### F i gure 3-15. Congener and congener gr oup prof iles f or air em issions f r om

m e d i cal w a ste i n ci n erators w i th ou t ai r p o l l u ti on con t rol d e vi ces (n on d e tects set eq u a l to zero).

3-66Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09

Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.05 0.1 0.15 0.2



### F i gure 3-16. Congener and congener gr oup prof iles f or air em issions f r om

m e d i cal w a ste i n ci n erators eq u i p p e d w i th a w e t scru b b er an d f a b r i c f i l t er.

3-67

### temperature of about 850°C. The hig h er emissi on rate for the warm-ty p e furnace was attributed by the a u thor s to the f o r m a tion of CDDs/CDF s dur ing the inte ntiona l c ooling of the f l ue g a se s to 220°C.
J a g e r et al. (1992) (as reported in B r emmer et al., 1994) measured an emission rate of 28,000 ng I

- TEQ DF 

### per body for a crematorium in B e r lin, Germany

. No operating process inf o r m a tion wa s pr ovide d by B r e mme r e t a l . f o r

the f a c ility

. Mitchell and L o ader (1993) repor ted even hig her emission f actors for two crematoria in
the Unite d King dom. The f i r st f a c ility te ste d wa s ma nua lly ope r a te d a nd ha d pr ima r y a n d secondary combustion chambers preheated to 650°C and a residence time of 1 sec in the secondary combustion chamber. The second test ed facility was comput er controlled and had primary and secondary combustion chambers heat ed to 850°C and a residence time of 2 sec in the secondary combustion chamber. The measured stack g a s TEQ concentrations rang ed from 42 to 71.3 ng I

- TEQ DF 

### /m 3 

### (at 11% ox y g en) at the first facility and from 25.4 to 45.5 ng I

- TEQ /m 3 DF 

### (at 11% ox y g en) at the second facility

. Emissi on factors based on these test results and g a s
g e neration rates reported by B r emmer et al. (1994) were calculated to rang e from 70,000 to 80,000 ng I

- TEQ DF 

### /body (HMI P, 1995). Takeda et al. (1998) measured CDD/CDF emi ssions at 10 crematoria in J a pan. Althoug h there are more than 1,600 crematoria in J a pa n, the 10 tested facilitie s handle 4% of the
cremations carried out in J a pan annually

. A wi de rang e of CDD/CDF e missions were observed.
W h en nondetect values were treated as z e ro, the emission factor rang e was 42 to 62,000 ng I

TEQ DF 

### /body (mean of 9,200 ng I

- TEQ DF 

### /body ). W h en nondetect values were treated as one-half
the DL , the rang e was 450 to 63,000 ng I

- TEQ DF 

### /body (mean of 11,000 ng I

- TEQ DF 

### /body ).
To obtain more data on CDD/CDF emissions from crematoria in J a pan, Takeda et al. (2001) measured CDD/CDF emissions at 17 add itional crematoria. I n that study , all the
crematoria ex cept one had secondary combustion chambers. Additionally , one crematorium had a secondary combustion chamber but did not use it. One to four main chambers were connected to the secondary chambers, and the temper ature of the main chambers rang ed from

approx imately 650 to 1,150°C. I n most cases, only one body was cremated at time. However,
between two and four bodies were cremated at four sampling events. A coffin and any

accompany i ng materials were combusted along w ith the body

. Emission factors rang ed from 120 to 24,000 ng I

- TEQ DF 

### /body

. I n g e neral, as the averag e temperature in the main combustion
cham ber i n creased, C DD/ C DF em i ssi ons decreased. However, t h e crem at ori u m t h at had a secondary combustion chamber but did not use it had both hig h temperatures in the main combustion chamber and hig h CDD/ CDF emissions. Additionally , w i t h t h e ri se of t h e averag e temperature in the secondary combustion cham ber of the eig h t crematoria without dust
col l ect ors, C DD/ C DF em i ssi ons decreased. For cr ematoria with dust collectors, the relationship

3-68

### between the averag e temperature in the sec ondary combustion chambe r and CDD/CDF emissions

was not cl ear. EPA obtained test data from two crematoria for humans operating in the United States,
one at Camellia Memorial L a wn in California (CARB

, 1990a) a nd one at Woodlawn Cemetery in New York (U.S. EPA, 1999a). Additionally , EPA obtained test data fro m one crematorium for animals operating in the United States: Univers ity of Georg i a Veteri nary School (U.S. EPA, 2000a); however, it is not a ppropriate to use the emission factor s from this facility to characteriz e

em i ssi ons associ at ed wi t h hum an crem at i on. Te sting a t the Ca me llia Me mor i a l L a wn c r e m a t or ium, whic h is c l a ssif i e d a s a wa r m

- t y p e facility using the criteria of B r emmer et al. (1994), was conducted in 1990 (CARB , 1990a). The
combusted material at this fac ility consisted of the body , as well as 4 lb of cardboard, up to 6 lb of wood, and an unquantified amount of unspecified plastic wrapping

. The three emissions tests conducted at this facility

, which operates using an afterburner, y i elded an averag e emission factor of 543 ng TEQ DF 

### -W HO 98 

### /body (501 ng I

- TEQ DF 

### /body ). Table 3-21 presents the cong enerspe c i f i c e mission f a c t or s f o r

this f a c ility

. Testing at W oodlawn Cemetery , which has a crematorium with a primary combustion chamber, a secondary combusti on chamber, and a scrubber APCD , was conducted in 1995. Tests were run at three secondary combustion cham ber temperatures: 675, 870, and 980°C (U.S. EPA, 1999a). The combusted material consisted of the body , as well as a 10- to 100-lb casket
constructed of fiberboa rd, particle board, or wood and various body wra pping s and articles such as a plastic sheet, a cloth sheet, or clothes. F or this facility

, averag e emission factors of 362 and 709 ng TEQ DF 

### -W HO 98 

### /body cremated (348 and 638 ng I

- TEQ DF 

### /body cremated) were calculated,
based on emissions collected at th e scrubber inlet and outlet, respec tively

. The cong ener-specific

e mission f a c t or s f o r

this f a c ility a r e shown in Ta ble 3- 22.
I n 1995, 1,155 crematoria were re ported to be operating in th e United States; this number had decreased to approx imately 1,060 by 2000. To determine whether the emissions data
collected at the W oodlawn Cemetery facility are representative of a ty pical crematorium

ope r a ting in the Unite d Sta t e s, r e pr e se n ta tive s f r o m the Cr e m a tion Assoc i a tion of Nor t h Ame r ic a (CANA) were contacted to identify the ty pical operating conditions at U.S. crematoria. According to the C ANA representatives, all cr ematoria operating in the United S t ates have primary and secondary combustion chambers. Additionally , cremat oria with operating conditions that indicate the pres ence of an afterburner are c onsidered to contain secondary
combustion chambers. The primary and seconda ry combustion chambers at U.S. crematoria ty pically operate at between 675 and 870°C, but many operate at 980°C, as required by their respect i v e st at es.

3-69

### Table 3-21. Congener-specif i c prof ile f o r Cam e llia Mem orial Law n

crem atori u m

C o n g en er/co n g en er gr oup Mea n f a cility em issio n f a cto r (n g / b o d y )

As s u m i ng nonde t e c t set to zero As s u m i ng nonde t e c t s e t t o 1⁄2 d e tectio n lim it
2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 28.9 89.6 108 157 197 1,484 2,331 28.9 89.6 108 157 197 1,484 2,331
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 206 108 339 374 338 657 135 1,689

104 624 206 117 349 374 338 657 135 1,813

112 624

To t a l 2,3,7,8- CDD To t a l 2,3,7,8- CDF To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 4,396 4,574

501.8 544.1 4,396 4,725

508.6 550.9

T o tal T C D D T o tal P e C D D T o tal H x C D D T o tal H p C D D T o tal O C D D T o tal T C D F T o tal P e C D F T o tal H x C D F T o tal H p C D F T o tal O C D F 554 860 2,224 3,180 2,331 4,335 2,563 4,306 2,030

624 554 860 2,224 3,180 2,331 4,335 2,563 4,306 2,154

624

To t a l CDD/ CDF 23,007 23,131

S o u r ce: C A R B (1990a).



### 3-70

### Table 3-22. Congener-specif i c pr of ile f o r the Woodlaw n Cem e tery

crem atori u m

C o n g en er Me an e m i s s i on f a c t or , s c r ubbe r i n l e t ( n g/ body) Me an e m i s s i on f a c t or , scru b b er o u tlet (n g / b o d y )

Nonde t e c t s e t to zero N o n d e tect set to 1⁄2 d e tectio n lim it Nonde t e c t set to zero N o n d e tect set to 1⁄2 d e tectio n lim it
2,3,7,8- TCDD 1,2,3,7,8- Pe CD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 11 31 74 115

83 724 1,120 12 44 74 115

83 724 1,120 39 168 239 565 524 1,253 10,698 45 364 258 603 553 1,302 1,154
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 106 116 285 263 278 146 466 962 165 435 106 116 285 264 278 146 466 963 165 435 256 150 409 252 253 139 429 872 142 3,499 279 170 463 280 282 148 474 948 148 363

To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 348 362 356 376 638 709 780 961

S o u r ce: U

. S

. EPA (1999a).



### Only one or two f a c ilitie s in the Unite d Sta t e s inc o r por a t e the use of a n APCD, suc h a s a scrubber. Therefore, the inlet diox in emission factors rather than the outlet diox in emission
factors at the W oodlawn crematorium would be re presentative of a ty pical crematorium operating in the United States (telephone conversation between Allen Krobath, CANA, and K. Riley

, Versar, I n c., F e bruary 12, 2003, and telephone convers ation between Dale W a lter, Matthews Cremation, and K. Riley , Ve rsar I n c., F e bruary 13, 2003).
I n the previous inventory

, an av erag e emission factor of 17,000 ng I

- TEQ DF 

### /body (assuming nondetect values were z e ro) was deve loped, based on emission factors measured for 16 of the tested facilities, including the one at Camellia Memorial L a wn (CARB , 1990a), the 10
J a panese facilities (Takeda et al., 1998), the tw o Dutch facilities (B remme r et al., 1994), the one German facility (J ag er et al., 1992), and the two B r itish facilities (Mitc hell and L o ader, 1993). The more recent data provided by Takeda et al. (2001) for the 17 J a panese fac ilities support the emission factor of 17,000 ng I

- TEQ DF 

### /body

. However, an averag e emission factor developed

3-71

### using the da ta r e por te d f o r

the two U.S. c r e m a t or ia ( i .e ., the outle t va lue s f o r

the Ca me llia
Memorial L a wn facility and the inlet values for the W oodlawn Cemetery facility ) is 453 ng TEQ DF 

### -W HO 98 

### /body (425 I

- TEQ DF 

### /body cremated), assuming nonde tect values were z e ro. These values are two orders of mag n itude le ss than the overall averag e calculated above. An

ex amination of the differences in U.S. and fo reig n operating practices may provide a rationale
for t h e l a rg e di screpanci e s. B r emmer et al. (1994) reported an emission factor of 2,400 ng I

- TEQ DF 

### /body for a Dutch facility with a cold-ty p e furnace and an emission factor of 4,900 ng I

- TEQ DF 

### /body for another Dutch facility with a warm-ty p e furnace where flue g a ses were cooled to 220°C. Neither of the
U.S. facilities are considered to have cold-ty p e furnaces. Additionally , the flue g a ses at the
Ca me llia Me mor i a l L a wn c r e m a t or ium we r e not c oole d pr ior to e x iting the f u r n a c e

. At the
W oodlawn Cemetery facility , the fl ue g a ses were cooled from 681 to 860°C prior to entering the scrubber to 271 to 354°C by the time they ex ite d the scrubber and the furnace. The emissions were hig h er at the scrubber outlet than at the inlet (961 vs. 325 ng TEQ DF 

### -W HO 98 

### /body [ 780 vs.
319 I

- TEF /body ] ) ; however, the emissions were not of the same mag nitude as those reported by
B r emmer for the warm-ty p e facility (4,900 ng I

- TEQ DF 

### /body ). The J a g e r et al. (1992) report did
not inc l ude ope r a ting pr oc e ss inf o r m a tion; the r e f or e , the Ge r m a n f a c ility c ould not be c o mpa r e d
with the U.S. f a c ilitie s. Additiona lly , the e mission va lue s de r i ve d f r o m the Mitc he ll a nd L o a d e r (1993) emission concentrations were calculated using g a s g e ne ration rates from the B r emmer et al. report and, as such, may not be indica tive of crematoria in the United States.
I n the Takeda et al. (1998, 2001) reports, the burn time for the cremations varied from 47
to 117 min. The averag e burn time in the U.S. studies was 120 min. This shorter burn time may not be optimal for diox in reduction, resulting in hig her diox in emissions. Also, the secondary combustion chamber temperatur es rang ed from 250 to 950°C in the Takeda studies, ag ain resulting in hig her emission rates. I n fact, in Ta keda et al. (2001) two of the three runs that had the hig h est TEQ concentrations per body came fro m a crematorium that did not use a secondary
combustion chamber. Of the 31 crematoria samp led in Takeda et al. (2001), 26 had lower than 5,000 ng I

- TEQ DF 

### /body

. B ecause the W oodlawn facility is unique in that it incorporates an APCD, the sample data for the air stream entering the scrubber versus the stream ex iting the scrubber should be analy z ed.
A com p ari s on of t h e di ox i n concent r at i ons of t h ese ai r st ream s shows a si g n i f i cant i n crease i n diox in concentrations in the stream ex iting the sc rubber. This increase can be attributed to the decrease in temperature that occurred in the sc rubber. Upon ex iting the scrubber, the flue g a s temperatures were in the rang e of 271 to 354°C, compared with temperatures of between 681 and
860°C at the scrubber inlet. As di scussed in Section 2, these ex it fl ue g a s temperatures lie in the

3-72

### optimum te mpe r a t ur e r a ng e f o r

diox in f o r m a tion; the r e f or e , a n inc r e a se in diox in c onc e n tr a tions
would be ex pected. An analy s is of scrubber inlet diox in data indicates that th e averag e diox in concentrations increased with temperature (189, 445, and 503 ng TEQ DF 

### -W HO 98 

### /body at 681, 772, and 860°C, respect i v el y )

. Because t h e operat i n g t e m p erat ures are out si de t h e t e m p erat ure rang e for t h e formation of diox in (200 to 400°C), diox in concentrations should d ecrease as temperatures increase. F u rther analy s is of the data shows that as temperatures at the scrubber inlet increased, so did concentrations of PM, HCl, and lead (T able 3-23). The data also indicate that ox y g en levels decreased as the temper ature increased (U.S. EPA, 1999a). Given these data, one could specul a t e t h at as t h e t e m p erat ure i n creased, i n complete combustion conditions arose, leading to an i n crease i n di ox i n form at i on.

Tab l e 3-23. Op eration al d a ta f o r th e Wood law n Cem e tery crem atoriu m , scru b b er i n l e t

Par a m e t e r Me an val ue 675° C 870° C 980° C

P a rticu l ate m a tter (gr/d s cf @ 7 % O 2 

### ) Hy dr o c hl o r i c a c i d ( l b/ hr ) Lead (g/h r) Oxy g e n ( % ) 0.015 0.053 0.1 9.9 0.033 0.14 0.32 8.6 0.068 0.26 0.59 7.5

S o u r ce: U

. S

. EPA (1999a).



### Using data from U.S. crematoria, EPA reco mmends an averag e emission factor of 453 ng TEQ DF 

### -W HO 98 

### /body (425 ng I

- TEQ DF 

### /body ). This is derived from the scrubber inlet diox in
concentrations from the W oodlawn Cemetery st udy and the results from the Camellia Memorial
L a wn study

. These averag e c ong ener-specific emission are pr esented in Table 3-24, and the
CDD/CDF cong ener and cong ener g r oup emissi on profiles are presented in F i g u re 3-17.
B ecause the emission factor was derived using emissions data from onl y 2 of 1,060 crematoria,

t h e averag e em i ssi on fact or i s assi g n ed a l o w confi d ence rat i n g

.

3.4.1.2. A c t i v i t y Level In form at i o n A total of 323,371 cremations were perfo rmed in reference y ear 1987, 488,224 in 1995, and 629,362 in 2000. A hig h confidence rating is assig n ed to these ac tivity level estimates because they are based on comprehens ive data provided by CANA (CANA, 2006).

3-73

### Table 3-24. Congener-specif i c prof ile f o r the Cam e llia Mem orial Law n

crem atoriu m an d th e Wood law n Cem e tery crem atoriu m

Con g en er/ con g en er group M e a n fac ilit y e m ission fac t or ( n g/body)

Non d e tect set to zero Non d e tect set to 1⁄2 d e tecti o n l i m i t 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 20 60.3 91 136 140 1,104 1,725.5 20.5 66.8 91 136 140 1,104 1,725.5 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 156 112 312 318.5 308 401.5 300.5 1,325.5

134.5 529.5 156 116.5 317 319 308 401.5 300.5 1,388 138.5 529.5
Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 424.8 452.9 431.9 463.3

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 330 488 1,254.5 1,721.5 1,304.5 2,240.5 1,514.5 2,634 1,097.5

529.5 330 488 1,254.5 1,721.5 1,304.5 2,240.5 1,514.5 2,634 1,097.5

529.5
Total CDD/CDF 13,114.5 13,114.5

S o u r ces : C A R B (1990a); U

. S

. EPA (1999a).



### 3-74Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0

. 0 1 0

. 0 2 0

. 0 3 0

. 0 4 0. 05 0. 06 0. 0 7 0. 08 0. 09 0. 1

Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0. 05 0

. 1 0. 15 0

. 2 4D

2378

5D

12378

6D

123478

6D

123678

6D

123789

7D

1234678

8D

4F

2378

5F

12378

5F

23478

6F

123478

6F

123678

6F

123789

6F

234678

7F

1234678

7F

1234789

8F

4D

T

o t a

l

5D

T

o t a

l

6D

T

o t a

l

7D

T

o t a

l

8D

4F

T

o t a

l

5F

T

o t a

l

6F

T

o t a

l

7F

T

o t a

l

8F



### F i gure 3-17. Congener and congener gr oup prof iles f or air em issions f r om the Cam e llia Mem orial Law n crem atorium and Woodlaw n Cem e tery

crem atori u m .

S o u rces : C A R B (1990a); U

. S

. EPA (1999a).



### 3-75

### 3.4.1.3. Em ission Estim ates Combining the averag e emission rate of 453 ng W HO-TEQ 98 

### /body (425 ng I

TEQ DF 

### /body ) with the number of cremati ons in 1987, 1995, and 2000 (323,371; 488,224; and 629,362, respectively ) y i elds an es timated annual release of 0.15 g TEQ DF 

### -W HO 98 

### (0.14 g I

TEQ DF 

### ) in 1987, 0.22 g TEQ DF 

### -W HO 98 

### (0.2 g I

- TEQ DF 

### ) in 1995, and 0.29 g TEQ DF 

### -W HO 98 

### (0.27

g I

- TEQ DF 

### ) in 2000. An overall confidence rating of lo w was assig n ed to the emissions because the emission factor had a low rating

.

3.4.2. Anim al Crem atoria
3.4.2.1. Em issions Data Only one study that measured CDD/CDF emissions from animal cremation could be
located. I n 1999, CDD/CDF emissions from a newl y installed animal incineration unit located at the University of Georg i a Veterinary School were measured (U.S. EPA, 2000a). The incineration unit, which consists of a primary and a secondary combustion chamber, is used to dispose of animals (mostly cows and horses) used in ex perimentation. Emissions are uncontrolled, with the ex ception of an NF PA spark screen located at the stack outlet. B a sed on four test runs, the averag e TEQ emission factor was 0.12 TEQ DF 

### -W HO 98 

### /kg (0.11 ng I

- TEQ DF 

### /kg )
of ani m a l crem at ed. The averag e em i ssi on fact ors for these test runs are provided in Table 3-25 and a cong ener-specific profile based on these data is provided as F i g u re 3-18.

3.4.2.2. A c t i v i t y Level In form at i o n As part of the 2000 inventory

, OAQPS calcu lated a national anima l cremation activity level estimate of 81.9 million kg /y r for reference y ear 2000. This estimate was scaled from the 1999 activity level estimate by apply i ng the ratio of th e 2000 national human population (281,421,906) to the 1999 national human popula tion (249,440,000). The 1999 national activity
level was based on 1990 da ta provided by OAQPS’ Emission Standards Division. The 1999 and 2000 activity level estimates assume that animal mortality and cremation rates are constant and that the animal population is direc tly proportional to human population.

3.4.2.3. Em ission Estim ates Apply i ng the TEQ emission factor of 0.12 ng TEQ DF 

### -W HO 98 

### /kg (0.11 ng I

- TEQ DF 

### /kg ) of animal combusted to the activity level estima ted by OAQPS (81.9 million kg /y r) y i elds estimated annual emissions of 0.0098 g TEQ DF 

### -W HO 98 

### (0.009 g I

- TEQ DF 

### ) in 2000. This estimate does not include events such as the mass burning of an i m a l s affect ed by m a d cow di sease. These
estimates are based on ex tremely limited data and should be reg a rd ed as preliminary indications of possible emissions from this source; further tes ting is ne e d e d to c onf ir m the tr ue ma g n itude of
the e missions.

3-76

### Table 3-25. Congener-specif i c prof ile f o r the University of G e orgia Veteri n a ry S c h ool

C o n g en er/co n g en er g r o u p Mea n f a cility em issio n f a cto r (n g / kg o f a n im a l )

N o n d e tect set to zero N o n d e tect set to 1⁄2 d e tectio n lim it
2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD

OCDD 7.51e

! 

### 03 2.13e

! 

### 02 4.46e

! 

### 03 8.86e

! 

### 03 7.17e

! 

### 03 5.03e

! 

### 03 1.01e

! 

### 03 7.51e

! 

### 03 2.13e

! 

### 02 4.46e

! 

### 03 8.86e

! 

### 03 7.17e

! 

### 03 5.03e

! 

### 03 1.01e

! 

### 03
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF

OCDF 1.79e

! 

### 02 6.70e

! 

### 03 1.41e

! 

### 01 2.93e

! 

### 02 1.85e

! 

### 02 7.44e

! 

### 02 2.35e

! 

### 02 4.20e

! 

### 03 3.16e

! 

### 03 2.00e

! 

### 04 1.79e

! 

### 02 6.70e

! 

### 03 1.41e

! 

### 01 2.93e

! 

### 02 1.85e

! 

### 02 7.44e

! 

### 02 2.35e

! 

### 02 4.20e

! 

### 03 3.16e

! 

### 03 2.00e

! 

### 04

To t a l CDD/ CDF 0 .37 0.37

To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 0.11 0.12 0.11 0.12

S o u r ce: U

. S

. EPA (2000a).



### 3.5. SEWAG E SLUDG E INCINERATION The three principal combustion technolog ies us ed to incinerate sewag e sludg e in the United States are multiple-hearth incineration, fl uidiz e d-bed incinerati on, and electric furnace incineration (B runner, 1992; U.S. EPA, 1995a). All of these technolog ies are ex cess-air processes (i.e., they combust sewag e sludg e with ox y g en in ex cess of theoretical requirements). Approx imately 80% of ope rating sludg e incinerators are multip le-hearth desig n, about 20% are
fluidiz e d-bed incinerators, and fe wer t h an 1% are el ect ri c i n ci nerat o rs. Ot her t y pes of furnaces not widely used in the United States are sing le-h earth cy clones, rotary kilns, and hig h -pressure, wet-air ox idation units (U.S. EPA, 1997a; e- mail dated J uly 13, 1998, from K. Maw, Pacific Environmental Services, to G. Schweer, Versar, I n c.).
Mu l ti p l e -h earth i n ci n erators. These t y pes of furnaces consi s t of refract ory heart h s
arrang ed vertically in series, one on top of the other. Dried sludg e cake is fed to the top hearth of

t h e furnace. The sl udg e i s m echani cal l y m oved from one heart h t o anot her t h roug h t h e l e ng t h of

3-77Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

4D 2 378

5 D 12 378

6D 123 478

6D 123 678

6D 123 789

7D 1 234 678

8D

4F 23 7 8

5 F 12 378

5 F 23 478

6F 123 478

6F 123 678

6F 123 789

6F 234 678

7F 1 234 678

7F 1 234 789

8F



### F i gure 3-18. Congener prof ile f o r ai r em issions f r om the University of Georgi a an i m al crem atori u m .

S o u rce: U

. S

. EPA (2000a).



### the furnace. Moisture is evaporated from th e sludg e cake in the upper hearths. The center hearths are the burning z one, where g a s temperat ures reach 871°C. The bottom hearths are the
burn-out z one, where the sludg e solids become as h. A waste-heat boiler is usually included in the burning z one, where steam is produced to provide supplemental energ y at the sewag e treatment plant. Air pollution control measur es typically include a venturi scrubber, an imping e ment tray scrubber, or a combination of both. W e t cy clones and dry cy clones are also used (U.S. EPA, 1995a).
F l u i d i zed -b ed i n ci n erators. A fluidiz e d-bed incinerator i s a cy l i ndri cal refract ory -l i n ed shell with a steel plate structur e that supports a sand bed near the bottom of the furnace (B runner, 1992). Air is introduced throug h opening s in th e bed plate supporting the sand. This causes the sand bed to undulate in a turbulent air flow; hen ce, the sand appears to have a fluid motion when observed throug h furnace portals. Sludg e cake is added to the furnace at a position just above
this fluid motion of the sand bed. The fluid motion promotes mix ing in the combustion z one. S l udg e ash ex i t s t h e furnace wi t h t h e com bust i on g a ses; t h erefore, ai r pol l u t i on cont rol sy st em s

3-78

### ty pically consist of hig h-energ y venturi scrubbers or ventur i/imping e ment tray combinations (U.S. EPA, 1995a).
E l ectri c f u rn aces. Al so cal l e d i n frared furnaces, t h ese consi s t of a l ong , rect ang u l a r, refractory

- lined chamber. A belt convey e r sy st em moves the sludg e cake throug h the leng th of
the furnace. To promote combustion of the sl udg e, supplemental heat is added by electric infrared heating elements located just above the traveling belt within the furnace. Electric power is required to initiate and sustain combustion. Emissions are usually controlled with a venturi
scrubber or some other W S (B runner, 1992; U.S. EPA, 1995a).

3.5.1. Em issions Estim a tes f r om Sew age Sludge Incinerators
EPA me a sur e d CDD/CDF e missions a t thr e e multiple

- h e a r th inc i ne r a tor s a s pa r t of Tie r 4
of the National Diox in Survey (U.S. EPA, 1987a). During the pretest survey s, two of the
f

a c ilitie s we r e judg e d to ha ve “ a v e r a g e ” pote n tia l a nd one f a c ility wa s judg e d to ha ve “ h ig h” pote n tia l f o r

CDD/CDF e missions with r e spe c t to other sewag e sludg e in ci nerat o rs. T he resul t s of these tests include cong ener g r oup concentra tions in stack g a s but lack measurements for specific cong eners other than 2,3,7,8-TCDD a nd 2,3,7,8-TCDF

. The results show a wide

va r i a b ility in the e mission f a c t or s a t the se thr e e f a c ilitie s; tota l CDD/CDF e mission f a c t or s
rang ed from 90 to 3,400 ng /kg (averag e of 1,266 ng /kg )

. Total TEQ emissions could not be
determined for these facilities because of the lack of cong ener-specific data.
I n 1990, EPA measured CDD/CDF emissions (including all 17 tox i c cong eners) at another multiple-hearth incinerator and also at a fluidiz e d-bed incine rator (U.S. EPA, 1990d). Assuming nondetects were z e ro, the total CDD/ CDF emission factors for these two facilities were 79 and 846 ng /kg

, and the total averag e TEQ emission factors were 3.6 and 43.2 ng TEQ DF 

### WH O 98 

### /kg (2.4 and 43.3 ng I

- TEQ DF 

### /kg ) of dry sludg e. I n 1995, the Association of Metropolitan Sewerag e Ag encies (AMSA) submitted to EPA the results of stack tests conducted at an additional 13 sewag e sludg e incine rators (Green et al., 1995). Two of these data sets were
consi d ered not usabl e by EP A because ei t h er DL s or feed rat e s and st ack fl ow rat e s were not provided. As with the EPA- tested facilities (U.S. EPA, 1987a, 1990d), wide variability was observed in the emission factors for the 11 AM SA facilities. Assumin g nondetects were zero,
total CDD/CDF emission factors rang ed from 0 to 1,392 ng /kg (averag e of 217 ng /kg ) , and total

averag e TEQ emission factors rang ed from 0 to 16 ng TEQ DF 

### -W HO 98 

### /kg (averag e , 3.47 ng ) (3.46

ng I

- TEQ DF 

### /kg ) of dry sludg e. I n 1999, stack tests were conducted at a mu ltiple-hearth incinerator equipped with a venturi scrubber and a three-tray imping e ment conditioning towe r (U.S. EPA, 2000b). F our test runs were conducted; however, th e first test run was aborted, a nd the CDD/CDF results from the
f

our th te st r un we r e de te r mine d to be sta tistic a l outlie r s ( p >0.05). The back-half emission

3-79

### concentrations for test run 4 were 50 to 60% lower than those for te st runs 2 and 3. Overall, total
CDD/CDF emissions measured during test r un 4 were 48 ng /kg , whereas total CDD/CDF emissions measured during test runs 2 and 3 we re 120 and 116 ng /kg , respectively

. I t could not
be de te r mine d whe t he r the lowe r concent r at i ons associ at ed wi t h test run 4 were due to analy t e l o ss or whet her t h ey represent e d an accurat e refl ect i on of a chang e i n i n ci nerat o r em i ssi on rel eases. The averag e TEQ emission factor, ex cluding test run 4, was 3.28 ng TEQ DF 

### -W HO 98 

### /kg (3.23 ng I

- TEQ DF 

### / k g )

. The averag e TEQ em i ssi on fact or based on the data for the 11 AMSA facilities (Green et al., 1995) and the three facilities reported by EPA (U.S. EPA, 2000b, 1990d) is 6.74 ng TEQ DF 

### -W HO 98 

### /kg (6.65 ng I

- TEQ DF 

### /kg ) of dry sludg e, assuming nondetect values are

z e ro. F i g u re 3-19 presents the averag e cong ener and cong ener g r oup profiles based on these
data. Additionally , Table 3-26 presents the averag e cong ener and cong ener-speci fi c g r oup

e mission f a c t or s a nd the a v e r a g e TEQ e mission f a c t or s f o r

the se f a c ilitie s. Ta ble 3- 26 a l so presents 2,3,7,8-TCDD, 2,3,7,8-TCDF , and cong ene r-specific g r oup emission factors for the three facilities reported by EPA (U.S. EPA, 1987a). Studies from other countries have reporte d similar results. B r emmer et al. (1994) reported an emission rate of 5 ng I

- TEQ DF 

### /kg for a fluidiz e d-bed sewag e sludg e incinerator in the Netherlands that was equipped with a cy clone and a W S

. Cains and Dy ke (1994) measured
CDD/CDF emissions at two sewag e sludg e incine rators in the United King dom. The emission rate at an incinerator equipped with an ESP and a W S rang ed from 2.75 to 28 ng I

- TEQ DF 

### /kg

. The e mission r a te me a sur e d a t a f

a c ility e quippe d with only a n ESP wa s 43 ng I

- TEQ DF 

### /kg

. I n 1988, approx imately 199 sewag e sludg e incineration facilitie s combusted abo 0.865 million metric tons of dry sewag e sludg e (F eder al Reg i ster, 1993a). I n 1995, approx imately 257

sewag e sludg e incinerators (some of which were backup or alternate incinerators) combusted about 2.11 million dry metric tons of sewag e sludg e (e-mail dated J uly 13, 1998, from K. Maw,
P aci fi c Envi ronm ent a l S e rvi ces, t o G. Schweer, Versar, I n c.). Us ing trends in wastewater flow rates from the 1988 National Sewag e Sludg e Surv ey and the 1984 to 1996 Needs Survey s, EPA estimated that in 2000 approx ima tely 6.4 million metric tons of dry sewag e sludg e would be

g e nerated (U.S. EPA, 1999b). Of this amount , EPA projected that 22% (1.42 million metric tons) would be incinerated. According to EPA, sewag e sludg e g e nera tion would increase to 6.9 million dry tons in 2005 and 7.4 million dry tons in 2010; however, the percentag e of sewag e sludg e incinerated will decrease slig htly , to 20% in 2005 and 19% in 2010. EPA estimates th at approx imately 1.38 million metric tons of dry se wag e sludg e would be incine rated in 2005 and 1.41 million metric
tons will be incinerated in 2010. EPA believes that incineration as a disposal method for sewag e sludg e will decrease as a result of increasing cost s and public concerns a bout the environmental
and heal t h i m p act s associ at ed wi t h i n ci nerat i on.

3-80Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0. 0 5 0. 1 0

. 15 0. 2 0. 25 0

. 3

Ratio (congener group emission factor /total CDD/CDF emission factor)

0 0 .1 0 .2 0 .3 0 .4 4D 23 7 8

5D 12 378

6D 1 23 478

6D 1 23 678

6D 1 23 789

7 D 12 34 678

8D 123 46 789

4F

23 7 8

5F

12 378

5F

23 478

6F

12 34 7 8

6F

12 36 7 8

6F

12 37 8 9

6F

23 46 7 8

7F

12 34 678

7F

12 34 789

8 F

123 46 789

4D T o t al

5D T o t al

6D T o t al

7D T o t al

8D 12346789

4F T o t al

5F T o t al

6F T o t al

7F T o t al

8F 12346789



### F i gure 3-19. Congener and congener grou p prof iles f or air em issions f r om

sew age sl u d g e i n ci n erators.

3-81

### Table 3-26. CDD/CDF em ission f a ctor s f o r sew age sludge incinerators

Con g en er Mean em i ssi on f a ctor (ng/kg) f

o r U.S. EP A (1987a) ( 3 fac ilit ie s) Mean em ission f a ctor (ng/kg) f o r G reen et al. (1995) (11 f a cilities) U.S. EP A (1990d) (2 f a cilities) U.S. EP A (1999b) (1 f a cility)

N o nde t e c t set to zero Non d e tect set to 1⁄2 d e tecti o n lim it N o nde t e c t se t to zero Non d e tect set to 1⁄2 de t e c t ion lim it 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0.39 NR NR NR NR NR 46.2 0.44 NR NR NR NR NR 46.2 0.16 0.22 0.04 0.12 0.29 2.46 12.78 0.26 0.3 0.11 0.17 0.35 2.59 13.16 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 179 NR NR NR NR NR NR NR NR 109 179 NR NR NR NR NR NR NR NR 109 25.41 1.92 6.47 2.11 0.77 0.03 1.22 1.46 0.17 1.17 25.41 1.92 6.47 2.11 0.77 0.03 1.22 1.46 0.17 1.17

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 37.6 2.66 16.6 53.9 46.2 528 253

75.4 144 109 37.7 2.81 16.9 54 46.2 528 253

75.9 144 109 35.8 1.11 1.74 4.39 12.78 123.85 59.94 12.69

2.63 1.17 37.81 1.63 2.25 5.03 13.16 124.1

60.16 13.5

3.12 1.55
Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### NR NR NR NR 6.65 6.74 6.87 7.01
Total CDD/CDF 1,266 1,268 256 262
NR = No t rep o r ted



### 3-82

### A m e di um confi d ence rat i n g i s assi g n ed t o t h e averag e TEQ em i ssi on fact or because i t was derived from stack testing at 14 U.S. sewa g e sludg e incinerators. The 1988 activity level estimate (used as a surrog a te for the 1987 activity level) and the 2000 activ ity level estimate are assig n ed a hig h confidence rating because they are based on ex tensive EP A survey s to support rule-making activities. The 1995 ac tivity level estimate is assig n ed a medium confidence rating because assumptions were made for numerous facilities concerning hour s of operation, operating capaci t y , and desi g n capaci t y

. Using the above estimated amounts of sewag e sludg e incinerated per y ear and the averag e TEQ emission factor of 6.74 ng TEQ DF 

### -W HO 98 

### /kg (6.65 ng I

- TEQ DF 

### /kg ) , the e stima te of TEQ emissions to air is 5.8 g TEQ DF 

### -W HO 98 

### (5.8 g I

- TEQ DF 

### ) in 1987, 14.2 g TEQ DF 

### -W HO 98 

### (14 g ITEQ DF 

### ) in 1995, and 9.6 g TEQ DF 

### -W HO 98 

### /kg (9.4 g I

- TEQ DF 

### /kg ) in 2000. B ecause the emission
f

a c t or ha d a me dium c onf ide n c e r a ting

, the ove r a ll e mission e stima te s we r e a ssig n e d a me dium
confi d ence rat i n g for al l y ears.

3.5.2. Solid Waste f r om Sew age Sludge Incinerators
I n Table 5-16 of U.S. EPA (1987a), data are presented indicating that 2,3,7,8-TCDD was
not detected in the bottom ash or scrubber wate r filtrate from three sewag e sludg e incinerators. However, total CDDs for the three incinerators and the filtrate were nondetects, 20 ng /kg

, 10

ng /kg , and 0.3 ng /kg , respectively

. F or total CDF s , the respective valu es were nondetects, 70

ng /kg , 50 ng /kg , and 4 ng /kg

. No data were g i ven for any cong eners (other than 2,3,7,8-TCDD),

nor we r e the r e a n y da ta on the qua ntitie s of a sh or f

iltr a t e

.

3.6. TIRE COMBUSTION
Most di scarded t i r es are com bus te d in de dic a t e d tir e inc i ne r a tor s or c e m e n t kilns. Some
are combusted as aux iliary fuel in industria l boilers and in pulp and paper mill combustion
f

a c ilitie s. Additiona lly , tir e s ma y be uninte n tiona lly bur ne d in a n unc ontr o lle d f a shion a t la ndf ills ( ope n bur ning )

. This se c tion a ddr e sse s the tota l TEQ e missions tha t ma y r e sult f r o m the
combustion of tires in dedicated tire incinera tors, industrial boilers , and pulp and paper mill combustion facilities, but ex cludes cement kilns (a ddressed in Section 5.1)

. The open burning of tires is not discussed in this repor t due to the lack of information.
Emissions of CDDs/CDF s f r o m the inc i ne r a tion of discarded automobile tires were

m easured at a dedi cat ed t i r e i n ci nerat o r t e st ed by t h e C a l i f orni a Ai r R e sources Board (C AR B, 1991). The facility consists of two ex cess air furn aces equipped with steam boilers to recover the

energ y from the heat of combustion. W hole tires were fed to the inci neration units at rates

rang ing from 2,800 to 5,700 kg /hr during the three te st day s

. The facility was equipped with a
DS a nd a n F F f o r

the c ontr o l of e missions pr ior to e x iting the sta c k. Ta ble 3- 27 pr e se n ts the

c ong e n e r

- spe c i f i c e mission f a c t or s f o r

this f a c ility

. F i g u r e 3- 20 pr e se n ts CDD/CDF c ong e n e r

3-83

### Table 3-27. CDD/CDF air em ission f a ct ors f o r a tire com bustion f a cility

Con g en er/ con g en er group M e a n fac ilit y e m ission fac t or ( n g/kg)

Assu m i n g n o n d e tect set to zero Assu m i n g n o n d e tect set to 1⁄2 de t e c t ion lim it
2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0.149 0.006 0.018 0.055 0.036 0.379 4.156 0.149 0.026 0.023 0.062 0.048 0.379 4.156
2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.319 0.114 0.086 0.103 0.059 0.036 0.1 0.0 0.027 0.756 0.319 0.118 0.091 0.111 0.09 0.068 0.148 0.166 0.095 0.756
Total 2,3,7,8-CDD Total 2,3,7,8-CDF Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 4.799 1.6 0.282 0.281 4.843 1.962 0.312 0.320

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 0.153 0.032 0.391 0.695 4.156 1.204 0.737 0.71 0.119 0.802 0.153 0.032 0.391 0.695 4.156 1.204 0.737 0.71 0.186 0.802

Total CDD/CDF 8.999 9.067

S o u r ce: C A R B (1991).



### 3-84Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0 .1 0.2 0 .3 0.4 0 .5

Ratio (congener emission factor/t otal CDD/CDF emission factor)

0 0 .1 0.2 0 .3 0.4 0 .5



### F i gure 3-20. Congener and congener gro up prof iles f or air em issions f r om a ti re com b u s tor.

3-85

### and cong ener g r oup profile s based on these TEQ emission factors. F r om these data, the averag e emission factor is estimated to be 0.281 ng TEQ DF 

### -W HO 98 

### /kg (0.282 ng I

- TEQ DF 

### /kg ) of tir e s incinerated (when a ll nondetect values are treated as z e ro). This emission factor was used to estimate annual TEQ releases from the tire co mbustion source categ o ry for the y ears 1987, 1995,
and 2000. EPA assig n ed a low confidence rating to th e estimated TEQ emission factor because it is possible tha t it is not r e pr e se n ta tive of TEQ e missions f r o m a ll tir e c o mbustion f a c ilitie s. I t is also possible that this emission factor is an underestimation of emissions from this source categ ory because it was derived from the emissions of a facility equipped w ith very advanced air pollution control technolog y specifi c for the control of diox in e missions. These devices (DS/F F ) are capable of g r eater than 95% reduction a nd control of diox in-like compounds prior to discharg e from the stack into the air. B ecause other facilities may not be equipped with similar

a i r pollution c ontr o l sy ste m s, the TEQ e missions c ould be hig h e r tha n the e stima te s shown
above. F o r ex ample, Cains and Dy ke (1994) re ported much hig her emi ssion rates for two tire incinerators in the United King dom that were e quipped with only simple g r it arrestors. These emissions produced emission f actors of 188 and 228 ng I

- TEQ DF 

### /kg of tires combusted. EPA estimated that approx ima tely 500 million kg of tires were combusted in 1990 (U.S. EPA, 1992b). Of this total, 23% (115 milli on kg ) were combusted in cement kilns, and it is assumed that the remaining 385 million kg we re combusted in dedicated tire combustion facilities, industrial boile rs, and pulp and paper mill combustion facilities. This activity level was adopted for the y ears 1987 and 1995 and is assig n ed a medium confidence rating

. The Rubber Manufacturers Association ( 2002) reported that 281 million scrap tires weig hing approx imately 5.68 million metric tons were g e nerated in the United States in 2001. Approx imately 115 million of these sc rap tires were combusted as tire-derived fuel, or roug hly
2.32 million metric tons (2.32 billion kg ) of tires. Subtracting th e 23% of the tires burned in cement kilns y i elds a total of 1.8 billion kg of tir es estimated to have been combusted in facilities
other than cement kilns in 2001. This fig ure is used to represent the activity level for tire
combustion in 2000. This activity level is assig n ed a medium confidence rating

. Annual emissions for the reference y ears were estimated by multiply in g the activity level times the TEQ emission factor. The TEQ emission factor of 0.281 ng TEQ DF 

### -W HO 98 

### /kg (0.282

ng I

- TEQ DF 

### /kg ) of tires combusted was used to estimate annual emissi ons for all y ears. Multiply ing the emission factor by the activity level (385 million kg of tires) y i elds an estimate of 0.11 g TEQ DF 

### -W HO 98 

### /y r (0.11 g I

- TEQ DF 

### /y

r) emitted to the air in 1987 and 1995. Using the
same emission factor mu ltiplied by the estimated activity leve l of 1.8 billion kg tires combusted in 2000 g i ves an estimate of 0.51 g TEQ DF 

### -W HO 98 

### /y r (0.51 g I

- TEQ DF 

### /y

r )

. The e stima te d TEQ

3-86

### emissions to air from tire combustion for 1987, 1995, and 2000 are g i ven a low confidence rating
because of t h e l o w confi d ence rat i n g of t h e em i ssi on fact or.

3.7. COM B USTION OF WASTEWATER SLUDG E AT BLEACHED CHEM ICAL P U LP M I LLS Approx imately 20.5% of the wa stewater sludg es g e nerated at bleached chemical pulp
mills a r e de wa te r e d a nd bur ne d in ba r k boile r s a t the mills. The se sludg e s c a n c onta i n CDDs/CDF s and elevated levels of chloride. However, the level of heat input from sludg e in the
mix ed feed to bark boilers rarely ex ceeds 10% (NCAS I , 1995).
NCASI (1995) provided cong ene r-specific test results fo r four wood residue/sludg e boilers tested between 1987 and 1993. Sludg e comprise d 6 to 10% of the solids in the feed. The

averag e cong ener-speci fi c em i ssi on fact ors deri ved from t h e st ack t e st resul t s obt ai ned from these facilities are presented in Table 3-28. Th e averag e TEQ emission factor derived from the test results is 0.062 ng I

- TEQ DF 

### -W HO 98 

### (0.061 ng I

- TEQ DF 

### /kg ) of feed (i.e., sludg e and wood residue), assuming nondetect values were z e ro. The rang e in f acility -specific emission factors was wide (0.0004 to 0.118 ng I

- TEQ DF 

### /kg

, assuming nondetect values are z e ro).
NCASI (1995) also presented stack emission te st results for five other bark boilers. These boilers combusted only bark during the test s even thoug h the boilers normally fire bark in combination with sludg e and coal. These boile rs are discussed in Section 4.2.2 as industrial facilities burning wood scra p/residues. The averag e TEQ emi ssion factor for these facilities was
0.4 ng I

- TEQ DF 

### /kg of feed. The emissions test data presented in NCASI (1995), and discussed above, indicate that the CDD/CDF emission factors for bark/sludg e combustors are similar to the emission factor developed in Section 4.2.2 for industria l facilities burning only wood residues/scrap. B a sed on the fact th at wood residues comprise a far g r eater fraction of the feed to
the se ba r k /sludg e bur ne r s tha n doe s sludg e , the na tiona l TEQ e mission e stima te s de r i ve d in
Section 4.2.2 for industrial wood-bur ning facilities are assumed to include emissions from these bark/sludg e combustion units.

3.8. BIOG AS COMBUSTION Using a specially developed sa mpling apparatus, Schreiner et al. (1992) measured the
C DD/ C DF cont ent of a fl are com bust i n g ex haust g a ses from an anaerobic sewag e sludg e dig e stor in Germany

. The noz z l e of the apparatus was m oved throug h three cross-sections of the flame and cooling z one. The CDD/CDF content was 1.4 pg I

- TEQ DF 

### /sta nda r d c ubic me te r ( N m 3 

### ) at t h e bottom of the flare, 3.3. pg I

- TEQ DF 

### /Nm 3 

### at the top of the flare, and 13.1 pg I

- TEQ DF 

### /Nm 3 

### in the

m i ddl e of t h e fl are. C ong ener-speci fi c resul t s we re not reported. Using the theoretical ratio of

3-87

### Table 3-28. CDD/CDF em ission f a ctors f o r com bustion of bleached-kraf t

m ill sludge in w ood r e s idue boile r s

Con g en er Mean em i ssi on f a ctors (ng/kg f eed)

Non d e tect set to zero Non d e tect set to 1⁄2 de t e c t ion lim it 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0.005 0.005 0.012 0.05 0.035 0.301 1.189 0.013 0.012 0.022 0.056 0.043 0.302 1.192 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.104 0.022 0.019 0.069 0.043 0.036 0.004 0.274 0.081 0.187 0.107 0.029 0.027 0.071 0.046 0.041 0.012 0.275 0.083 0.188

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 0.101 0.03 0.599 0.956 1.189 0.56 0.469 0.748 1.102 0.187 0.108 0.109 0.6 0.958 1.192 0.56 0.47 0.748 1.102 0.188
Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 0.061 0.062 0.082 0.087
Total CDD/CDF 5.941 6.035

S o u r ce: N C A S I (1995).



### flare g a s volume to dig e stor g a s volume com busted, 78.6:1, and the averag e CDD/CDF content of the three measurements, 5.9 pg I

- TEQ DF 

### /Nm 3 

### , y i elds an emission rate of 0.46 ng I

- TEQ DF 

### /Nm 3 

### of dig e stor g a s combusted. During 1996, publicly owned treatment work s (POTW s ) in the United States treated

approx imately 122 billion L of wa stewater daily (U.S. EPA, 1997b)

. Althoug h reliable data are

3-88

### not readily available on the amount of sewag e sl udg e g e nerated by POTW s that is subjected to
stabiliz ation by anaerobic dig e stion, a reasonabl e approx imation is 25% of the total sludg e
g e nerated (i.e., the sludg e g e nera ted from treatment of about 30 tr illion L per day of wastewater). An estimated 196 kg of sludg e solids are g e nerate d for every 1 million L of wastewater subjected to primary and secondary treatment (W ater Pollution Control F e deration, 1990). Thus, multiply ing 30 billion L / day (25% of 122 billi on L ) by 196 kg /million L and 365 day s /y r y i elds
an annual estimate of 2 million metric tons of sludg e solids th at may be anaerobically dig e sted in
POTW s annually

. The volume of sludg e dig e stor g a s combusted in flares annually can be estimated using operat i on param e t e rs for a “t y p i cal ” anaerobi c di g e stor sy stem, as described in W a ter Pollution
Control F e deration (1990). Multiply ing the a nnual amount of sludg e solids of 2 million metric tons by the following paramete rs and appropriate c onversion factors y i elds an annual flared dig e stor g a s volume of 467-million Nm 3 

### :

• F r a c tion of tota l solids tha t a r e vola tile solids is 75%

. • R e duc tion of vola tile solids dur ing dig e stion is 50%

. • S pecific g a s production is 0.94 m 3 

### /kg vola tile solids r e duc e d

. • F raction of produced g a s that is flared is 66%.

Because t h ere are no di rect m easurem ent s of C DD/ C DF em i ssi ons from U.S

. anaerobi c sludg e dig e stor flares and because of uncertaintie s about the activity level for biog as combustion,

no na tiona l e missions e stima te ha s be e n de ve lope d f o r

inc l usion in the na tiona l inve ntor y

. However, a preliminary estimate of the potential annual TEQ emi ssions from this source can be obtained by multiply ing the emission factor of 0.46 ng I

- TEQ DF 

### /Nm 3 

### of dig e stor g a s flared by the estimated volume of g a s flared annua lly in the United States, 467 million Nm 3



### . This c a l c u la tion

y i elds an annual potential release in 2000 of 0.22 g

. This estimate should be reg a rded as a

pr e limina r y indic a tion of possible e missions f r o m this sour c e c a t e g or y ; f u r t he r te sting is ne e d e d

to c onf ir m the tr ue ma g n itude of the se e missions.

3-89Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmall municipal waste combustors(MWCs)operating in 2000



## 3-90Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)I.Large MWCs(>250 tpd/unit)HuntsvilleALMadisonMB/WW134588,154.49SD/FF/CI/SNCR0.0040.004HuntsvilleALMadisonMB/WW234588,633.51SD/FF/CI/SNCR0.0080.008LongBeachSERRFCALosAngelesMB/WW136095,572.00SD/FF/SNCR0.0280.031LongBeachSERRFCALosAngelesMB/WW1460154,264.93SD/FF/SNCR0.0140.015LongBeachSERRFCALosAngelesMB/WW2460164,072.92SD/FF/SNCR0.0310.033LongBeachSERRFCALosAngelesMB/WW3460160,371.15SD/FF/SNCR0.0180.023Stanislaus(Modesto)CAStanislausMB/WW1400131,607.90SD/FF/CI/SNCR0.0130.014Stanislaus(Modesto)CAStanislausMB/WW2400129,798.10SD/FF/CI/SNCR0.0090.01Wheelabrator Bridgeport,L.P.CTFairfieldMB/WW1750238,974.40SD/FF/CI0.0190.021Wheelabrator Bridgeport,L.P.CTFairfieldMB/WW2750237,183.53SD/FF/CI0.020.021Wheelabrator Bridgeport,L.P.CTFairfieldMB/WW3750231,472.07SD/FF/CI0.0240.027BristolRRFCTHartfordMB/WW232592,453.00SD/FF/CI/SNCR0.0040.004BristolRRFCTHartfordMB/WW232593,627.93SD/FF/CI/SNCR0.0040.004Mid-ConnecticutRRFCTHartfordRDF1675246,570.00SD/FF/SNCR0.0190.022Mid-ConnecticutRRFCTHartfordRDF2675251,454.04SD/FF/SNCR0.0410.046Mid-ConnecticutRRFCTHartfordRDF3675252,415.96SD/FF/SNCR0.0480.048SoutheasternConnecticutRRFCTNewLondonMB/WW1345122,528.01SD/FF/CI0.0150.016SoutheasternConnecticutRRFCTNewLondonMB/WW2345121,053.99SD/FF/CI0.0460.051Wheelabrator LisbonInc.CTNewLondonMB/WW125089,556.15SD/FF/CI/SNCR0.0010.001Wheelabrator LisbonInc.CTNewLondonMB/WW225089,452.85SD/FF/CI/SNCR0.0250.028Wheelabrator SouthBrowardFLFt.LauderdaleMB/WW1750259,426.57SD/FF/SNCR0.0230.025Wheelabrator SouthBrowardFLFt.LauderdaleMB/WW2750244,492.13SD/FF/SNCR0.0780.085Wheelabrator SouthBrowardFLFt.LauderdaleMB/WW3750252,013.30SD/FF/SNCR0.0460.051Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-91Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)Wheelabrator NorthBrowardFLBrowardMB/WW1750260,456.43SD/FF/SNCR0.0180.02Wheelabrator NorthBrowardFLBrowardMB/WW2750255,371.04SD/FF/SNCR0.0180.02Wheelabrator NorthBrowardFLBrowardMB/WW3750259,802.53SD/FF/SNCR0.070.076Dade Co. RRFFLDadeRDF1672172,792.98SD/FF/CI/SNCR0.3840.406Dade Co. RRFFLDadeRDF2672171,880.39SD/FF/CI/SNCR0.3930.419Dade Co. RRFFLDadeRDF3672167,673.72SD/FF/CI/SNCR0.0620.066Dade Co. RRFFLDadeRDF4672155,352.91SD/FF/CI/SNCR0.4440.475Hillsborough Co.RRFFLHillsboroughMB/WW1400116,426.35SD/FF/CI/SNCR0.0190.02Hillsborough Co.RRFFLHillsboroughMB/WW2400120,265.74SD/FF/CI/SNCR0.0230.025Hillsborough Co.RRFFLHillsboroughMB/WW3400121,674.90SD/FF/CI/SNCR0.0390.042McKayBayREFFLHillsboroughMB/WW125090,232.04SD/FF/CI/SNCR0.0140.015McKayBayREFFLHillsboroughMB/WW225090,232.04SD/FF/CI/SNCR0.0160.017McKayBayREFFLHillsboroughMB/WW325090,413.44SD/ESP/CI/SNCR0.0020.002McKayBayREFFLHillsboroughMB/WW425090,050.47SD/ESP/CI/SNCR0.0030.003LakeCo. RRFFLLakeMB/WW126482,586.03SD/FF/CI/SNCR0.0340.036LakeCo. RRFFLLakeMB/WW226483,262.97SD/FF/CI/SNCR0.0360.038Lee CountySolidWaste RRFFLLeeMB/WW1600197,620.93SD/FF/CI/SNCR0.1010.11Lee CountySolidWaste RRFFLLeeMB/WW2600197,203.07SD/FF/CI/SNCR0.110.12Pasco CountySolidWaste RRFFLPascoMB/WW135098,891.97SD/FF/CI/SNCR0.0120.012Pasco CountySolidWaste RRFFLPascoMB/WW2350102,727.33SD/FF/CI/SNCR0.0080.009Pasco CountySolidWaste RRFFLPascoMB/WW3350108,759.70SD/FF/CI/SNCR0.0040.004PinellasCountyRRFFLPinellasMB/WW11000299,275.82SD/FF/CI/SNCR0.0130.015PinellasCountyRRFFLPinellasMB/WW21000289,763.18SD/FF/CI/SNCR0.0740.083PinellasCountyRRFFLPinellasMB/WW31000301,717.00SD/FF/CI/SNCR0.0430.047Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-92Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)North CountyRRFFLWestPalmBeachRDF11000273,939.00SD/ESP0.2790.302North CountyRRFFLWestPalmBeachRDF21000288,988.00SD/ESP0.6810.747SavannahRRFGAChathamMB/WW125061,886.44SD/FF/CI/SNCR0.0290.032SavannahRRFGAChathamMB/WW225058,830.56SD/FF/CI/SNCR0.0230.025HonoluluRRFHIHonoluluRDF11080258,726.76SD/ESP0.8020.888HonoluluRRFHIHonoluluRDF21080256,019.24SD/ESP1.1811.318IndianapolisRRFINMarionMB/WW1787209,507.33SD/FF/CI/SNCR0.0250.027IndianapolisRRFINMarionMB/WW2787220,779.62SD/FF/CI/SNCR0.0250.028IndianapolisRRFINMarionMB/WW3787224,095.05SD/FF/CI/SNCR0.0050.005Haverhill RRFMAEssexMB/WW1825281,121.60SD/FF/CI/SNCR0.0480.051Haverhill RRFMAEssexMB/WW2825286,516.40SD/FF/CI/SNCR0.0630.067Wheelabrator NorthAndoverMAEssexMB/WW1750202,456.92SD/FF/CI/SNCR0.0060.007Wheelabrator NorthAndoverMAEssexMB/WW2750180,415.08SD/FF/CI/SNCR0.0060.006WheelabratorSaugusMAEssexMB/WW1750217,656.46SD/FF/CI/SNCR0.0060.006WheelabratorSaugusMAEssexMB/WW2750214,057.54SD/FF/CI/SNCR0.0040.005SEMASSRRFMAPlymouthRDF11000368,821.00SD/ESP/FF/CI0.0450.051SEMASSRRFMAPlymouthRDF21000372,224.92SD/ESP/FF/CI0.0480.052SEMASSRRFMAPlymouthRDF31000364,595.08SD/FF/SNCR0.0330.036Wheelabrator MillburyMAWorcesterMB/WW1750230,829.25SD/ESP/CI/SNCR0.0380.042Wheelabrator MillburyMAWorcesterMB/WW2750233,033.75SD/ESP/CI/SNCR0.0170.019Wheelabrator BaltimoreMDIndependentCityMB/WW1750242,224.16SD/ESP/CI/SNCR0.0430.047Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-93Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)Wheelabrator BaltimoreMDIndependentCityMB/WW2750241,753.99SD/ESP/CI/SNCR0.1760.179Wheelabrator BaltimoreMDIndependentCityMB/WW3750231,232.85SD/ESP/CI/SNCR0.1770.186MontgomeryCo. RRFMDMontgomeryMB/WW1600178,986.24SD/FF/CI/SNCR0.0960.107MontgomeryCo. RRFMDMontgomeryMB/WW2600170,879.15SD/FF/CI/SNCR0.090.091MontgomeryCo. RRFMDMontgomeryMB/WW3600170,131.61SD/FF/CI/SNCR0.0990.108Greater PortlandRegionRRFMECumberlandMB/WW125087,323.81SD/ESP/CI/SNCR0.0510.055Greater PortlandRegionRRFMECumberlandMB/WW225085,676.19SD/ESP/CI/SNCR0.1080.115PenobscotEnergyRecoveryMEPenobscotRDF1360108,975.08SD/FF0.0080.008PenobscotEnergyRecoveryMEPenobscotRDF2360110,899.92SD/FF0.0080.008Maine EnergyRecoveryMEYorkRDF1300123,654.50SD/FF/SNCR0.0180.02Maine EnergyRecoveryMEYorkRDF2300123,654.50SD/FF/SNCR0.0190.02KentCo. WTE FacilityMIKentMB/WW131390,813.23SD/FF/CI/SNCR0.0060.007KentCo. WTE FacilityMIKentMB/WW231388,925.77SD/FF/CI/SNCR0.0130.013CentralWayne EnergyMIWayneMB/WW330061,800.00SD/FF/CI/SNCR0.0050.005Greater DetroitRRFMIWayneRDF11100279,883.11SD/FF0.2590.287Greater DetroitRRFMIWayneRDF21100212,094.32SD/FF0.010.011Greater DetroitRRFMIWayneRDF31100201,288.58SD/FF0.1930.218WilmarthPlantMNBlue EarthRDF136094,983.00SD/FF/SNCR0.0280.03WilmarthPlantMNBlue EarthRDF2360108,339.00SD/FF/SNCR0.0320.034Red WingPlantMNGoodhueRDF136092,993.00DSI/FF0.0170.017Red WingPlantMNGoodhueRDF236089,211.00DSI/FF0.0660.069Covanta HennepinMNHennepinMB/WW1600182,903.45SD/FF/CI/SNCR0.0090.01Covanta HennepinMNHennepinMB/WW2600182,190.55SD/FF/CI/SNCR0.0490.052Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-94Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)GreatRiver EnergyMNSherburneRDF125075,878.19SD/FF0.0130.014GreatRiver EnergyMNSherburneRDF225075,122.55SD/FF0.0130.013GreatRiver EnergyMNSherburneRDF3500133,529.26SD/FF0.0220.024NewHanover Co. WTENCNewHanoverMB/WW3301126,709.00SD/FF/CI/SNCR0.0160.017Wheelabrator ConcordNHMerrimackMB/WW125091,065.04SD/FF/CI/SNCR0.0010.001Wheelabrator ConcordNHMerrimackMB/WW225092,550.96SD/FF/CI/SNCR0.0060.007CamdenRRFNJCamdenMB/WW135097,654.44SD/ESP/CI/SNCR0.0980.106CamdenRRFNJCamdenMB/WW235093,330.56SD/ESP/CI/SNCR0.2180.252CamdenRRFNJCamdenMB/WW335085,658.00SD/ESP/CI/SNCR0.0620.068EssexCo. RRFNJEssexMB/WW1900322,862.32SD/ESP/CI/SNCR0.070.078EssexCo. RRFNJEssexMB/WW2900327,332.25SD/ESP/CI/SNCR0.0490.054EssexCo. RRFNJEssexMB/WW3900335,288.43SD/ESP/CI/SNCR0.0390.043Gloucester CountyNJGloucesterMB/WW128890,774.74SD/FF/CI/SNCR0.0080.009Gloucester CountyNJGloucesterMB/WW228890,397.26SD/FF/CI/SNCR0.0090.01UnionCo. RRFNJUnionMB/WW1480169,630.18SD/FF/CI/SNCR0.0050.005UnionCo. RRFNJUnionMB/WW2480171,047.55SD/FF/CI/SNCR0.010.011UnionCo. RRFNJUnionMB/WW3480167,844.27SD/FF/CI/SNCR0.010.011HempsteadNYNassauMB/WW1835294,685.61SD/FF/SNCR0.0150.017HempsteadNYNassauMB/WW2835299,122.26SD/FF/SNCR0.4310.471HempsteadNYNassauMB/WW3835293,532.12SD/FF/SNCR0.0110.012Niagara FallsNYNiagaraMB/WW31100358,183.15SD/FF/CI/SNCR0.2090.225Niagara FallsNYNiagaraMB/WW41100355,338.85SD/FF/CI/SNCR0.1970.214OnondagaCo. RRFNYOnondagaMB/WW1330117,389.13SD/FF/CI/SNCR0.0020.002OnondagaCo. RRFNYOnondagaMB/WW233099,956.76SD/FF/CI/SNCR0.0040.004Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-95Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)OnondagaCo. RRFNYOnondagaMB/WW3330117,794.12SD/FF/CI/SNCR0.0070.007BabylonRRFNYSuffolkMB/WW1375112,323.03SD/FF/CI/SNCR0.0020.002BabylonRRFNYSuffolkMB/WW2375107,951.97SD/FF/CI/SNCR0.0070.008HuntingtonRRFNYSuffolkMB/WW1250102,526.89SD/FF/CI/SNCR0.0030.003HuntingtonRRFNYSuffolkMB/WW2250102,744.63SD/FF/CI/SNCR0.0070.008HuntingtonRRFNYSuffolkMB/WW3250110,853.48SD/FF/CI/SNCR0.0070.008AdirondackRRFNYWashingtonMB/WW125082,458.60SD/ESP/CI0.5090.556AdirondackRRFNYWashingtonMB/WW225079,860.40SD/ESP/CI0.4370.477Wheelabrator Westchester, L.P.NYWestchesterMB/WW1750226,329.03SD/FF/CI/SNCR0.0250.027Wheelabrator Westchester, L.P.NYWestchesterMB/WW2750217,185.24SD/FF/CI/SNCR0.0170.019Wheelabrator Westchester, L.P.NYWestchesterMB/WW3750206,044.73SD/FF/CI/SNCR0.0260.029Walter B. HallRRF(Tulsa)OKTulsaMB/WW1375111,998.10SD/FF/CI/SNCR0.0120.013Walter B. HallRRF(Tulsa)OKTulsaMB/WW2375113,501.52SD/FF/CI/SNCR0.0060.006Walter B. HallRRF(Tulsa)OKTulsaMB/WW3375113,849.38SD/FF/CI/SNCR0.0030.003MarionCo. WTEORMarionMB/WW127592,091.75SD/FF/CI/SNCR0.0040.005MarionCo. WTEORMarionMB/WW227592,288.25SD/FF/CI/SNCR0.0030.003Lancaster CountyPABainbridgeMB/WW1400125,595.02SD/FF/CI/SNCR0.0170.018Lancaster CountyPABainbridgeMB/WW2400127,240.06SD/FF/CI/SNCR0.0150.016Lancaster CountyPABainbridgeMB/WW3400128,049.91SD/FF/CI/SNCR0.0280.029Wheelabrator FallsRRFPABucksMB/WW1750264,839.58SD/FF/CI/SNCR0.0150.016Wheelabrator FallsRRFPABucksMB/WW2750259,729.42SD/FF/CI/SNCR0.0250.027AmericanRef-fuelofDelawareValleyPADelawareMB/RC1448179,845.19SD/FF0.1260.138AmericanRef-fuelofDelawareValleyPADelawareMB/RC2448190,795.79SD/FF0.0520.055Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-96Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)AmericanRef-fuelofDelawareValleyPADelawareMB/RC3448186,088.66SD/FF0.1810.197AmericanRef-fuelofDelawareValleyPADelawareMB/RC4448189,206.50SD/FF0.0450.05AmericanRef-fuelofDelawareValleyPADelawareMB/RC5448176,939.66SD/FF0.0230.025AmericanRef-fuelofDelawareValleyPADelawareMB/RC6448191,389.21SD/FF0.0290.032MontenayMontgomeryPAMontgomeryMB/WW1600204,290.69SD/FF/CI/SNCR0.1690.179MontenayMontgomeryPAMontgomeryMB/WW2600198,884.31SD/FF/CI/SNCR0.3540.372YorkCountyPAYorkMB/RC1448135,266.80SD/FF/CI/SNCR0.0230.025YorkCountyPAYorkMB/RC2448135,104.31SD/FF/CI/SNCR0.0250.028YorkCountyPAYorkMB/RC3448126,412.88SD/FF/CI/SNCR0.0230.025Foster Wheeler CharlestonRRFSCCharlestonMB/WW1300112,950.14SD/ESP/CI0.1510.16Foster Wheeler CharlestonRRFSCCharlestonMB/WW230098,453.86SD/ESP/CI0.150.16Nashville Thermal Transfer Corp.TNDavidsonMB/WW133067,181.87SD/FF/CI/SNCR00Nashville Thermal Transfer Corp.TNDavidsonMB/WW233072,257.44SD/FF/CI/SNCR00Nashville Thermal Transfer Corp.TNDavidsonMB/WW339085,979.69SD/FF/CI/SNCR00Alexandria/ArlingtonRRFVAAlexandriaMB/WW1325113,578.13SD/FF/CI/SNCR0.0070.008Alexandria/ArlingtonRRFVAAlexandriaMB/WW2325109,442.21SD/FF/CI/SNCR0.0220.024Alexandria/ArlingtonRRFVAAlexandriaMB/WW3325109,410.66SD/FF/CI/SNCR0.020.021I-95 EnergyRRFVAFairfaxMB/WW1750270,077.99SD/FF/CI/SNCR0.0110.011I-95 EnergyRRFVAFairfaxMB/WW2750271,967.16SD/FF/CI/SNCR0.0120.013I-95 EnergyRRFVAFairfaxMB/WW3750272,396.24SD/FF/CI/SNCR0.0060.006I-95 EnergyRRFVAFairfaxMB/WW4750271,628.61SD/FF/CI/SNCR0.0120.012Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-97Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)SPSAWaste ToEnergyVAPortsmouthRDF1500122,153.75SD/FF0.1230.133SPSAWaste ToEnergyVAPortsmouthRDF2500122,153.75SD/FF0.1110.12SPSAWaste ToEnergyVAPortsmouthRDF3500122,153.75SD/FF0.1030.111SPSAWaste ToEnergyVAPortsmouthRDF4500122,153.75SD/FF0.130.141Spokane Regional DisposalFacilityWASpokaneMB/WW1400141,392.12SD/FF/CI/SNCR0.0090.01Spokane Regional DisposalFacilityWASpokaneMB/WW2400143,927.88SD/FF/CI/SNCR0.0080.009LaCrosseCo.WILaCrosseRDF128822,727.86DSI/FF/H2O/SNCR0.3440.36LaCrosseCo.WILaCrosseRDF228821,718.14DSI/FF/H2O/SNCR0.3440.36Large MWC totals2.80e+00712.7313.815II.Small MWCs(<250 tpd/unit)JuneauRRFAKJuneauBoroughMOD/SA13510,975.85ESP0.4840.533JuneauRRFAKJuneauBoroughMOD/SA23510,975.85ESP0.4840.533Wallingford RRFCTNewHavenMOD/EA114043,903.39SD/FF0.0640.07Wallingford RRFCTNewHavenMOD/EA214043,903.39SD/FF0.0210.023Wallingford RRFCTNewHavenMOD/EA314043,903.39SD/FF0.0060.007BayResource ManagementCenterFLBayMB/RC124576,830.94ESP3.4423.786BayResource ManagementCenterFLBayMB/RC224576,830.94ESP4.6335.096MiamiInternationalAirportFLDadeMOD/SA16018,815.74Unc0.6490.714SouthernmostWTEFLMonroeMB/WW17523,519.67ESP0.3220.355SouthernmostWTEFLMonroeMB/WW27523,519.67ESP0.3220.355Pittsfield RRFMABerkshireMOD/EA112037,631.48WS/ESP0.9781.076Pittsfield RRFMABerkshireMOD/EA212037,631.48WS/ESP0.9781.076Pittsfield RRFMABerkshireMOD/EA312037,631.48WS/ESP0.9781.076Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-98Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)SpringfieldRRFMAHampdenMOD/EA112037,631.48DSI/FF0.0280.03SpringfieldRRFMAHampdenMOD/EA212037,631.48DSI/FF0.0280.03SpringfieldRRFMAHampdenMOD/EA312037,631.48DSI/FF0.0280.03Harford Co. WTE Fac.MDHarfordMOD/SA19028,223.61DSI/ESP1.3521.488Harford Co. WTE Fac.MDHarfordMOD/SA29028,223.61DSI/ESP1.3521.488Harford Co. WTE Fac.MDHarfordMOD/SA39028,223.61DSI/ESP1.3521.488Harford Co. WTE Fac.MDHarfordMOD/SA49028,223.61DSI/ESP1.3521.488Mid Maine Waste ActionCorp.MEAndroscogginMB110031,359.57SD/FF0.0240.027Mid Maine Waste ActionCorp.MEAndroscogginMB210031,359.57SD/FF0.0240.027JacksonCo. RRFMIJacksonMB/WW110031,359.57SD/FF1.1351.249JacksonCo. RRFMIJacksonMB/WW210031,359.57SD/FF1.1351.249CentralWayne Co.MIWayneRDF124978,085.32ESP0.0610.067CentralWayne Co.MIWayneRDF224978,085.32ESP0.0610.067Pope-DouglasWasteMNDouglasMOD/EA13611,289.44ESP0.2930.323Pope-DouglasWasteMNDouglasMOD/EA23611,289.44ESP0.2930.323RedWingSolidWaste BoilerFacilityMNGoodhueMOD/EA13611,289.44ESP0.2870.316RedWingSolidWaste BoilerFacilityMNGoodhueMOD/EA23611,289.44ESP0.2870.316Olmstead WTE FacilityMNOlmsteadMB/WW110031,359.57ESP1.4491.594Olmstead WTE FacilityMNOlmsteadMB/WW210031,359.57ESP1.4491.594FergusFallsMNOtter TailMOD/SA14714,739.00WS0.6210.683FergusFallsMNOtter TailMOD/SA24714,739.00WS0.6210.683PerhamRenewable RFMNOtter TailMOD/SA15717,874.95ESP0.370.407PerhamRenewable RFMNOtter TailMOD/SA25717,874.95ESP0.370.407Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-99Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)PolkCo.MNPolkMOD/SA14012,543.83ESP0.4330.476PolkCo.MNPolkMOD/SA24012,543.83ESP0.4330.476PascagoulaMSJacksonMOD/EA17523,519.67ESP0.6110.672PascagoulaMSJacksonMOD/EA27523,519.67ESP0.6110.672Livingston/ParkCountyMTParkMOD/SA13611,289.44Unc0.3890.428Livingston/ParkCountyMTParkMOD/SA23611,289.44Unc0.3890.428NewHanover Co.NCNewHanoverMB/WW110031,359.57SD/FF0.0240.027NewHanover Co.NCNewHanoverMB/WW210031,359.57SD/FF0.0240.027SES ClaremontNHSullivanMB/WW110031,359.57DSI/FF0.1130.124SES ClaremontNHSullivanMB/WW210031,359.57DSI/FF0.0950.104WarrenEnergyRFNJWarrenMB/WW120062,719.13SD/FF/CI0.0010.002WarrenEnergyRFNJWarrenMB/WW220062,719.13SD/FF/CI0.0010.002DutchessCo. RRFNYDutchessMB/RC120062,719.13DSI/FF0.0150.016DutchessCo. RRFNYDutchessMB/RC220062,719.13DSI/FF0.0270.029OswegoCo. WTENYOswegoMOD/SA35015,679.78SD/FF/CI0.0070.008OswegoCo. WTENYOswegoMOD/SA45015,679.78SD/FF/CI0.0240.026OswegoCo. WTENYOswegoMOD/SA15015,679.78SD/FF/CI0.0150.017OswegoCo. WTENYOswegoMOD/SA25015,679.78SD/FF/CI0.0150.017MacArthurWTENYSuffolkMB/RC124376,203.74DSI/FF0.0010.001MacArthurWTENYSuffolkMB/RC224376,203.74DSI/FF0.0010.001MiamiRRFOKOttawaMOD/SA13510,975.85Unc0.3790.417MiamiRRFOKOttawaMOD/SA23510,975.85Unc0.3790.417MiamiRRFOKOttawaMOD/SA33510,975.85Unc0.3790.417CoosBayIncineratorORCoosMOD/SA15015,679.78DSI/FF00Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-100Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)CoosBayIncineratorORCoosMOD/SA25015,679.78DSI/FF00CoosBayIncineratorORCoosMOD/SA35015,679.78DSI/FF00HarrisburgWTEPADauphinMB/WW124576,830.94ESP12.89414.184HarrisburgWTEPADauphinMB/WW224576,830.94ESP8.299.119Sumner Co.TNSumnerMB/RC110031,359.57ESP0.430.473Sumner Co.TNSumnerMB/RC210031,359.57ESP0.430.473CityofCleburneTXJohnsonMOD/SA13811,916.63DSI/ESP0.5260.579CityofCleburneTXJohnsonMOD/SA23811,916.63DSI/ESP0.5260.579CityofCleburneTXJohnsonMOD/SA33811,916.63DSI/ESP0.4110.452PanolaCo. WTETXPanolaMOD/SA14012,543.83WS0.4330.476Center RRFTXShelbyMOD/SA14012,543.83WS0.5540.609Davis/WasatchUTDavisMB/REF120062,719.13DSI/ESP1.2751.403Davis/WasatchUTDavisMB/REF220062,719.13DSI/ESP1.3841.522Arlington-PentagonVAArlingtonMOD/SA15015,679.78FF0.6970.766Arlington-PentagonVAArlingtonMOD/SA25015,679.78FF0.6970.766GalaxCitySWVAGraysonMB/WW/RC15617,561.36FF0.2410.265NASARefuse-firedSteamGeneratorVAHamptonCityMB/WW110031,359.57ESP0.6140.675NASARefuse-firedSteamGeneratorVAHamptonCityMB/WW210031,359.57ESP0.6140.675HarrisonburgVARockinghamMB/WW15015,679.78Unc0.1510.166HarrisonburgVARockinghamMB/WW25015,679.78Unc0.1510.166TacomaWAPierceFB/RDF115047,039.35DSI/FF0.0890.098TacomaWAPierceFB/RDF215047,039.35DSI/FF0.0890.098BarronCo.WIBarronMOD/SA15015,679.78ESP0.6920.761Table 3-5.National CDD/CDFTEQemissions (g/yr)for large andsmallmunicipal waste combustors(MWCs)operating in 2000 (continued)



## 3-101Facility nameStateCounty/cityMWC typeUnitno.MSWcapacity(tons/day)MSWcombusted(tons/yr)APCDEmissions (gITEQ/yr)Emissions(g WHO**DF**TEQ/yr)BarronCo.WIBarronMOD/SA25015,679.78ESP0.6920.761Small MWC totals2.60e+00663.58369.941All MWCsoperatingin2000(totals)3.06e+00776.383.8RRF = Resource recoveryfacility(steam-generatingfacility)MSW= Municipal solidwasteWTE = Waste-to-energy(facility)APCD (air pollutioncontrol device):MWCtype:CI = CarboninjectionFB/RDF = Fluidized-bed refuse-derived fuelDS = DryscrubberMB/REF = MassburnrefractoryDSI = Drysorbent injectionMB/WW= MassburnwaterwallESP= Electrostatic precipitatorMB= MassburnFF = Fabric filterMB/RC= MassburnrotarykilnSD = SpraydryerMOD/EA= Modular excessairSNRL= Selective noncatalytic reductionMOD/SA= Modular starved airUnc = UncontrolledRDF=Refuse-derivedfuelWS=Wetscrubber

### 4. COMB US T I ON S O URCE S OF CDDs/CDF s: P O WE R/E N E R G Y G E NE RAT ION

4.1. MOTOR VEHICLE F U EL COMBUSTION
B a llschmiter et al. (1986) re ported detecting CDDs/CDF s in used motor oil, thus

pr oviding some of the f i r st e v ide n c e tha t CDDs/CDF s mig ht be e mitte d by the c o mbustion processes i n g a sol i n e- and di esel -fuel ed eng i nes. I n complete combustion and the presence of a
chlorine source in the form of additives such as dichloroethane or pent achlorophenate in the oil or the fuel were speculated to lead to the fo rmation of CDDs/CDF s. The cong ener patterns found
in the use d oil sa mple s we r e c h a r a c t e r ize d by B a llsc h mite r e t a l . a s be ing simila r to the pa tte r n s found in fly ash and stack emissions from municipal waste incinerators. Since 1986, several studies have been c onducted to measure or estimate CDD/CDF
concentrations in emissions from vehicles. Alt houg h there is no standard approved protocol for measuring CDDs/CDF s in vehicle ex haust, some researchers have de veloped and implemented
several approaches for col l ect i n g and anal y z i n g tailpipe emissions. Other researchers have
estimated vehicle ex haust emissions of CDDs/CDF s indirectly from studies of tunnel air. The results of these two ty pes of studies are summariz e d in Sections 4.1.1 and 4.1.2.
Estimates of national annual CDD/CDF TEQ emissions from on-road and off-road motor
vehi cl es fuel ed wi t h l eaded g a sol i n e, unl eaded g a soline, and diesel fuel based on the results of those studies are presented in Section 4.1.3. I t s hould be noted, however, th at relatively few tests
on emissions from diesel- and unlead ed g a sol i n e-fuel ed vehi cl es are avai l a bl e, consi d eri n g t h e variety and number of such ve hicles currently in operation and the rang e of operational, technical, and environmental cond itions in which they are operate d. As a result, the emission
fact ors devel oped i n t h i s report for on-road and off-road m o t o r vehi cl es are qui t e uncert a i n

.

4.1.1. Tailpipe Em ission Studies Marklund et al. (1987) provided the first dir ect evidence of the pr esence of CDDs/CDF s in c a r e x ha ust by me a sur ing e missions f r o m ta ilp ipes of Swedish cars. Approx imately 20 to 220

pg I

- TEQ DF 

### /km driven from tetra- and penta-CDDs/CDF s were reported for four cars running on leaded g a soline. F or this study , an unleaded g a soline was used, with tetramethy l lead (0.15 g / L [ 0.57 g / g a l] ) and 1,2-dichloroethane (0.1 g / L as a scaveng e r) added. The fuel used may not have accurately represented commercia l fuels at that time, which ty pically contained a mix ture of chlorinated and brominated scaveng e rs (Marklund et al., 1990). Also, the lead content of the fuel used (0.15 g lead/L ) was the normal content for Sw edish fuels at the time, but it was hig her than that of leaded g a soline in the United States during the late 1980s (lowered to 0.1 g lead/g al [ 0.026 g lead/L ] effective J a nuary 1, 1986). The authors reported a stri king similarity between
the TCDF and PeCDF cong ener profiles in the car ex hausts and those found in emissions from municipal waste incinerators. F o r two cars running on unleaded g a soline, CDD/CDF emissions

4-1

### were below the detection limit (DL ) , which corresponded to approx imately 13 pg I

- TEQ DF 

### /km
driven. Table 4-1 presents a summary of the results of Marklund et al. (1987) and subsequent studies, which are discussed below. Tables 4-2 and 4-3 present the r e sults of ta ilpipe e mission studies reported for diesel -fuel ed cars and t r ucks, respect i v el y

. The results of studies of leaded

g a sol i n e-fuel ed cars are shown i n Tabl e 4-4 and t hose for unl eaded g a sol i n e-fuel ed cars i n Tabl es 4-5 and 4-6. F i g u res 4-1, 4-2, and 4-3 present cong ener a nd cong ener g r oup profiles for

em i ssi ons from di esel -fuel ed vehi cl es, l eaded g a sol i n e-fuel ed vehi cl es, and unl eaded g a sol i n efuel ed vehi cl es, respect i v el y

. Virtually no testing of vehicle emissions fo r CDDs/CDF s in the Unite d Sta t e s ha s be e n reported. I n 1987, the California Air Resources B o ard (CARB ) produced a draft report on the testing of ex hausts from four g a soline-fueled car s and t h ree di esel -fuel ed vehicles (one truck, one bus, and one car) (CARB

, 1987). However, CARB indicated to EPA that the draft report should not be cited or quoted to s upport g e neral conclusi ons about CDDs/CDF s in motor vehicle

ex haust s because of t h e sm al l sam p l e si z e of t h e st udy and because t h e use of l o w-resol u t i o n

r a the r tha n hig h

- r e solution ma ss spe c t r o me tr y in the study r e sulte d in hig h DL s a nd ina d e qua te selectivity in the presence of interferences (l etter dated J uly 1993, from G. L e w, California Air
Resources B oard, to J . Schaum, U.S. EPA).
C A R B st at ed t h at t h e resul t s of a si ng l e sa mple from the heavy

- duty diesel truck could be reported because cong eners from most of the hom olog ue g r oups were present in the sample at levels that could be detected by the analy ti cal method and there were no identified interferences in this sample. This test wa s conducted under steady

- state conditi ons (50 km/hr) for 6 hr with an

eng i ne with a fuel economy of 5.5 km/L

. The TEQ emission factor of this one sample was equivalent to 7,190 pg TEQ DF 

### -W HO 98 

### /L (7,290 pg I

- TEQ DF 

### /L ) fuel burned. An assumed fuel

economy of 5.5 km/L y i elds an emission factor of 1,307 pg TEQ DF 

### -W HO 98 

### /km (1,325 pg I

TEQ DF 

### /km). Assuming that nondetect values were z e ro, the TEQ emission factors were 3,280 pg TEQ DF 

### -W HO 98 

### /L (3,720 pg I

- TEQ DF 

### /L ) fuel burned and 596 pg TEQ DF 

### -W HO 98 

### /km (676 pg I

TEQ DF 

### /km) driven (letter dated J a nuary 11, 1996, fro m G. L e w, California Air Resources B o ard, to G. Schweer, Versar, I n c.). Hag l und et al. (1988) sampled ex haust g a ses from three vehicles (one car fueled with
l eaded g a sol i n e and one wi t h unl eaded g a sol i n e a nd a heavy

- duty diesel tr uck) for t h e presence of brominated dibenz o- p -diox i ns (B DDs) and ethy lene dibromide dibenz ofurans (B DF s). The authors concluded that the ethy lene dibromide scaveng e r added to the tested g a soline probably acted as a halog e n source. Tetra-B D F emissions were measured as 23,000 pg /km in the car with leaded g a soline and 240 pg /km in the car with unleaded g a soline. Tetra- and penta-emissions were measured as 3,200 and 980 pg /km, respectivel y , in the car with leaded g a soline. All
B DDs/B DF s were below DL s in the diesel truck emissions.

4-2Table 4-1.Descriptionandresults ofvehicle emissiontesting studies for CDDs andCDFs



### 4-3StudyCountryFuel typeScavengeraCatalystequippedNumberof testvehiclesTEQemission factorb(pg/kmdriven)Drivingcycle; samplinglocationCARB(1987);letterUnited StatesDiesel(truck)NoNR1676–1325c[597–1307]6-hrdynamometer testat50 km/hrdated January11, 1996,fromG.Lew,California AirResourcesBoard, to G.Schweer, Versar, Inc.Marklundetal. (1987)SwedenUnleadedNoYes2Not detected (<13)A10 (2 cycles); muffler exhaustLeadedYesNo4Approx. 20–220A10 (2 cycles); muffler exhaustBinghametal.(1989)NewZealandUnleadedNoNR1Not detected (<20)A10 (3 or 4 cycles); muffler exhaustLeadedYesNR41–39A10 (3 or 4 cycles); muffler exhaustMarklundetal. (1990)SwedenUnleadedLeadedUnleadedLeadedDiesel (truck)NoYesNoYesNoNoNoYesNoNR221210.36–0.392.4–6.30.361.1–2.6dNot detected (<18)cFTP-73 testcycle; before mufflerFTP-73 testcycle; before mufflerFTP-73test cycle; intailpipeFTP-73test cycle; intailpipeU.S. federalmode 13 cycle;before mufflerHagenmaier et al.GermanyUnleadedNoNo15.1c[6.0]Comparable toFTP-73test cycle; intailpipe(1990)UnleadedNoYes10.7c[0.8]Comparable toFTP-73test cycle; intailpipeLeadedYesNo1108c[129]Comparable toFTP-73test cycle; intailpipeDiesel (car)NoNR12.1c[2.5]Comparable toFTP-73test cycle; intailpipeOehme etal. (1991)(tunnelstudy)Norway–––e520f38fCars moving uphill (3.5%incline) at60 km/hrCars moving downhill (3.5%decline) atAvg =2809500f70 km/hrCar averageTrucks moving uphill (3.5%incline) at720f60 km/hrTrucks moving downhill(3.5%decline) atAvg= 5,10070 km/hrTruckaverageTable 4-1.Descriptionandresults ofvehicle emissiontesting studies for CDDs andCDFs (continued)



### 4-4StudyCountryFuel typeScavengeraCatalystequippedNumberof testvehiclesTEQemission factorb(pg/kmdriven)Drivingcycle; samplinglocationSchwind etal. (1991)Hutzinger etal. (1992)GermanyLeadedUnleadedYesNoNoNo115.2–118c[7.2–142]9.6–17.7c[10.2–18.1]Various test conditions(loadsandspeeds)Various test conditions(loadsandspeeds)UnleadedDiesel (car)NoNoYesNo111–2.6c[1–2.8]1–13c[1.2–14]Various test conditions(loadsandspeeds)Various test conditions(loadsandspeeds)Diesel (truck)NoNo113–15c[14–15]Various test conditions(loadsandspeeds)Gertler etal. (1996,1998) (tunnelstudy)United StatesDiesel (truck)––gMean= 172Meanofseven12-hrsamplesGullett andRyan(1997)United StatesDiesel (truck)No–1Mean= 29Meanoffive sample routesaExceptinMarklundetal. (1987), dichloroethaneand dibromoethane were used asscavengers.bValues are inunits ofI-TEQDF; valuesinbracketsare inunitsofTEQDF-WHO98.cResultsreported were inunitsofpgTEQ/Loffuel.For purposesofthistable, the fueleconomyfactor used byMarklundetal. (1990), 10 km/L(24miles/gal), was usedtoconvert the emissionrates intounits ofpgTEQ/kmdrivenfor the cars.For the diesel-fueledtruck,the fuel economyfactor reported inCARB(1987) for a 1984 heavy-dutydieseltruck,5.5 km/L(13.2 miles/gal), wasused.dTable reflectsthe rangeofsummaryresultsreported inMarklundetal. (1990);however, the congener-specific resultsfor thesingle runreported indicate anemissionrateofabout7.3 pgI-TEQDF/km.eTestswere conducted over portionsof4 days, withtraffic ratesof8,000–14,000 vehicles/day.Heavy-dutyvehicles(defined asvehiclesover7min length)ranged from4 to15%oftotal.fEmissionfactors are reportedinunits ofpgNordic TEQ/kmdriven; the values inunits ofI-TEQDF/kmare expected to be about 3 to 6% higher.gTestswere conducted over 5 days, withheavy-dutyvehicle ratesof1,800–8,700 vehiclesper 12-hr samplingevent.Heavy-dutyvehiclesaccounted for 21to28%ofallvehicles.NR =Not reported–= NodataTable 4-2.CDD/CDFcongener emissionfactors (pg/L)for diesel-fueledautomobiles



### 4-5Congener/congener groupAutomobile tailpipe emissionstudyresultsMean emission factors63 km/hraIdling(test no. 25)b57 km/hr(test no. 24)b57 km/hr(full load)(test no. 28)bAssumingnondetectsetto zeroAssumingnondetectsetto1⁄2 detectionlimit (DL)2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD7.99ND (5.1)ND (5.1)ND (5.1)44.144013.16.321.436281076352.44.111.4222.952522237.8211016656011.410.67.614.6108554011.410.68.215.210.6855402,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF20.5ND (5.1)7.16.56.7ND (5.1)ND (5.1)40.78.594.47917158.71217517.15215911.921418.11.83.44.130.8ND (0.4)18.97.11012361118568554.7312147.830588.47138.649.934.95.720.8108.28.8178.688.471.638.649.934.96.321.4108.28.8178.6Total2,3,7,8-CDDTotal2,3,7,8-CDFTotal I-TEQDF(nondetectsetto0)Total I-TEQDF(nondetect set to1⁄2 DL)Total TEQDF-WHO98(nondetectsetto0)Total TEQDF-WHO98(nondetect set to1⁄2 DL)501184.420.822.2c24.826.2846.8958.7100.7100.7103.1103.1558.8158.210.410.411.91.9809.81117.5129.6129.6140.4140.4679.1604.965.570.1681606.765.870.5Table 4-2.CDD/CDFcongener emissionfactors (pg/L)for diesel-fueledautomobiles (continued)



### 4-6Congener/congener groupAutomobile tailpipe emissionstudyresultsMean emission factors63 km/hraIdling(test no. 25)b57 km/hr(test no. 24)b57 km/hr(full load)(test no. 28)bAssumingnondetectsetto zeroAssumingnondetectsetto1⁄2 detectionlimit (DL)Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF37.419.723.688.5440.576.739.325.680.694.431721425618763543682155632121431222077525583626721013942281643565603,0931,205472241305195121116177540916525270179179195121116177540916525270179179Total CDD/CDF (nondetect set to0)Total CDD/CDF (nondetect set to1⁄2 DL)926.3926.33,9573,9579689687,0187,0183,2183,218aSource:Hagenmaier etal. (1990).bSource:Schwind etal. (1991);Hutzinger etal. (1992).cAnI-TEQDFemissionfactor of23.6 pg/Lisreported inHagenmaier etal. (1990);however, anI-TEQDFemissionfactor of22.2 pg/Liscalculated, based onreportedcongenerlevels.ND = Not detected(valueinparenthesis is the detectionlimit)Table 4-3.CDD/CDFcongener emissionfactors (pg/L)for diesel-fueledtrucks



### 4-7Congener/congener groupTrucktailpipe study resultsMean emission factors50 km/hr(test no. 40)a90 km/hr(full load)(test no. 42)a50 km/hrbAssumingnondetectsettozeroAssumingnondetectsetto1⁄2detection limit (DL)2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD255142814119135516185.76674353ND(560)ND(1,340)ND(2,160)ND(1,770)ND(2,640)116,000344,40013.77.76.611.36.738,731115,36910723136730744638,731115,3692,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF87451856844.7633754039753345129315.123715.4104ND(605)ND(4,750)ND(5,190)ND(8,210)ND(6,480)13,400ND(7,780)73,460ND(11,700)140,40046.726.32328.338.34,46928.724,63615.146,9811488198871,3971,1194,4691,32524,6361,96046,981Total2,3,7,8-CDDTotal2,3,7,8-CDFTotal I-TEQDF(nondetectsetto0)Total I-TEQDF(nondetect set to1⁄2 DL)Total TEQDF-WHO98(nondetectsetto0)Total TEQDF-WHO98(nondetect set to1⁄2 DL)1,5601,169.781818282478.7406.570707979460,400227,2603,7207,2903,2807,190154,14676,292.41,2901,150155,55883,7412,4802,450Table 4-3.CDD/CDFcongener emissionfactors (pg/L)for diesel-fueledtrucks(continued)



### 4-8Congener/congener groupTrucktailpipe study resultsMean emission factors50 km/hr(test no. 40)a90 km/hr(full load)(test no. 42)a50 km/hrbAssumingnondetectsettozeroAssumingnondetectsetto1⁄2detection limit (DL)Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF200321302001,3557632305245093972081176715535369473626876104ND(3,760)ND(3,020)ND(45,300)203,300344,00025,00047,900169,200150,700140,30013649.765.767,892115,2528,83116,29456,67050,41446,9327625537,62067,892115,2528,83116,29456,67050,41446,932Total CDD/CDF (nondetect set to0)Total CDD/CDF (nondetect set to1⁄2 DL)4,3404,3402,7782,7781,080,4001,106,440362,536.4371,220aSource:Schwind etal. (1991);Hutzinger etal. (1992).bSource:Letter dated July1993, fromG.Lew,California Air ResourcesBoard, toJ. Schaum, U.S.EPA;letter dated January11,1996, fromG.Lew,CaliforniaAir ResourcesBoard, to G. Schweer, Versar, Inc..ND = Not detected(valueinparenthesis is the detectionlimit)Table 4-4.CDD/CDFcongener emissionfactors (pg/L)for leadedgasoline-fueledautomobiles



### 4-9Congener/congener groupAutomotive tailpipe emissionstudyresultsMean emission factorsFTP cyclea63 km/hrbIdling(testno.12)cFull load(testno.13)c64 km/hr(testno.14)cRatedpower(testno.15)cFTP cycle(testno.22)cAssumingnondetectset tozeroAssumingnondetectset to 1⁄2detectionlimit (DL)2,3,7,8-TCDDND(14.4)128NR60141NR567681,2,3,7,8-PeCDDND (36)4254310646840731651681,2,3,4,7,8-HxCDDND (54)1881715206164169731,2,3,6,7,8-HxCDDND (54)2073235228306285891,2,3,7,8,9-HxCDDND (54)188NRNR206NR351071141,2,3,4,6,7,8-HpCDDND (54)503119136554111518277281OCDDND (90)4983805135491,1661,5816706762,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF43221.643.2ND (54)ND (54)ND (54)ND (54)ND (54)ND (54)ND (90)1,5421,081447856856ND (76)2734,051ND (76)230NR49263322NRNR170NR11156783671567060NR25NRNRNR1,6971,190492942942NR3014,460NR2537845243120NRNR158NR447214218225381375851,0332,3011091,128774425202330325283261,85736529774425202334329503321,86158536Total2,3,7,8-CDDND2,137$591$8652,352$1,3632,3151,4401,469Total2,3,7,8-CDF496.89,336$1,415$1,356$10,277$8036,0694,8324,901Total I-TEQDF( nondetect set to 0)65.91,075$52$300$1,184$56419$450Total I-TEQDF(nondetect set to1⁄2 DL)1021,080$52$300$1,184$56419$456Total TEQDF-WHO98(nondetectset to0)65.91,287$72$352$1,417$75454$532Total TEQDF-WHO98(nondetectset to1⁄2 DL)1111,291$72$352$1,417$75454$539Table 4-4.CDD/CDFcongener emissionfactors (pg/L)for leadedgasoline-fueledautomobiles (continued)



### 4-10Congener/congener groupAutomotive tailpipe emissionstudyresultsMean emission factorsFTP cyclea63 km/hrbIdling(testno.12)cFull load(testno.13)c64 km/hr(testno.14)cRatedpower(testno.15)cFTP cycle(testno.22)cAssumingnondetectset tozeroAssumingnondetectset to 1⁄2detectionlimit (DL)Total TCDD5,2204,5555178,1345,0124,5589214,1314,131Total PeCDDND(360)3,3386582,1613,6756,3893592,3692,394Total HxCDDND(540)1,8683546232,0561,9739961,1241,163Total HpCDDND (90)1,1641942971,2812,374988900906Total OCDDND (90)4983805135491,1661,581670676Total TCDF15,30050,7432,16720,51355,85729,3534,29025,46025,460Total PeCDF2,43011,5914523,60812,75710,5803,1656,3696,369Total HxCDFND(540)6,3081924776,94712,5533,1324,2304,268Total HpCDFND(270)5,642170NR6,2104,7672,9203,2853,307Total OCDFND (90)2301,115NR2534471,128529536Total CDD/CDF (nondetect setto0)Total CDD/CDF (nondetect set to1⁄2 DL)22,95023,94085,93785,9376,1996,199$36,326$36,32694,59794,59774,16074,16019,48019,48049,06749,210aSource:Marklundetal. (1990);valuesinthe table were calculated fromthe reported unitsofpg/kmtopg/Lusinga fueleconomyof9 km/Lfor leaded gasasreported inMarklundetal. (1990).bSource:Hagenmaier etal. (1990).cSource:Schwind etal. (1991);Hutzinger etal. (1992).ND = Not detected(valueinparenthesis is the reporteddetectionlimit)NR = Not reportedTable 4-5.CDD/CDFcongener emissionfactors (pg/L)forunleadedgasoline-fueledautomobiles without catalyticconverters



### 4-11Congener/congener groupAutomotive tailpipe emissionstudyresultsMean emission factorsFTP cyclea63 km/hrbFTP cycle(testno.21)c64 km/hr(testno.17)c64 km/hr(testno.20)c64 km/hr(testno.31/2)cAssumingnondetectset to zeroAssumingnondetectset to 1⁄2detectionlimit (DL)2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDDND (5)ND (3)ND (40)ND (40)ND (40)ND (40)ND (50)2.619.116.617.117.640.417624142484151928684431262829662807112542231216858.914.116.360.117.1197.82,63414.414.91838.51710377414.815.121.341.920.31067782,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF64ND (7)ND (7)ND (40)ND (40)ND (40)ND (40)ND (40)ND (40)ND (70)4444.520.741.921.237.854.327.916.611970403068624755278ND (1)37471723468346188452719477691848835ND (1)422224288295.2161.8135.2129.1113.236.982.141854.599110464.667.365.844.230.553.613220.432810465.167.969.247.633.956.913523.8334Total2,3,7,8-CDDTotal2,3,7,8-CDFTotal I-TEQDF(nondetectsetto0)Total I-TEQDF(nondetect set to1⁄2 DL)Total TEQDF-WHO98(nondetectsetto0)Total TEQDF-WHO98(nondetectsetto1⁄2 DL)ND646.426.26.426.9289.4427.950.950.960.260.21,2211,02496.496.41021025046941221221381389148291441441481482,948.32,417177177181181979910.499.5106997.4937.4103109Table 4-5.CDD/CDFcongener emissionfactors (pg/L)forunleadedgasoline-fueledautomobiles without catalyticconverters (continued)



### 4-12Automotive tailpipe emissionstudyresultsMean emission factorsAssumingnondetectFTP cycle64 km/hr64 km/hr64 km/hrAssumingset to 1⁄2(testno.(testno.(testno.(testno.nondetectdetectionCongener/congener groupFTP cyclea63 km/hrb21)c17)c20)c31/2)cset to zerolimit (DL)Total TCDD13435429706500304398398Total PeCDDND (3)481837784542170469469Total HxCDDND (40)305484496563114327330Total HpCDDND (10)93392147225301193194Total OCDDND (5)1768682806852,634774774Total TCDF1705697189234786,3791,5401,540Total PeCDFND (7)9315311,5134371,969897897Total HxCDFND (40)3781656152581,226440444Total HpCDFND (20)4762787734451,088510512Total OCDFND (7)119374194288991328328Total CDD/CDF (nondetect set to0)1833,9635,0766,4314,42115,1765,876Total CDD/CDF (nondetect set to2493,9635,0766,4314,42115,1765,8861⁄2 DLaSource:Marklundetal. (1990);the pg/Lvaluesinthe table were calculated fromthe reported unitsofpg/kmassuminga fueleconomyof10 km/Lforunleaded gas.bSource:Hagenmaier etal. (1990).cSource:Schwind etal. (1991);Hutzinger etal. (1992).ND = Not detected(valueinparenthesis is the reporteddetectionlimit)Table 4-6.CDD/CDFcongener emissionfactors (pg/L)for unleadedgasoline-fueledautomobileswithcatalyticconverters



### 4-13Congener/congener groupAutomotive tailpipe emissionstudytestresultsMeanemissionfactors63 km/hra64 km/hr(test no. 29)b64 km/hr(test no. 30)b64 km/hr(test no. 18)bAssumingnondetectset to zeroAssumingnondetectsetto1⁄2 detectionlimit (DL)2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD1.61.62.43.53.115.317032.65.36627.8275ND (7.9)ND (7.9)ND (7.9)6.4ND (7.9)78.1427144122141974.72.12.24.52.833.82675.633.24.53.833.82672,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF4.33.32.44.86.30.24.616.3ND (0.2)27.910.68.77.210.69.1ND (3.8)18.154.3ND (3.8)3812.75.16.24.53.92.18.2154.27.910635136575ND (1)51114015.77.55.56.26.61.87.7692.27815.77.55.56.26.62.37.9692.778Total2,3,7,8-CDDTotal2,3,7,8-CDFTotal I-TEQDF(nondetectsetto0)Total I-TEQDF(nondetect set to1⁄2 DL)Total TEQDF-WHO98(nondetectsetto0)Total TEQDF-WHO98(nondetect set to1⁄2 DL)197.570.17.27.27.87.8325.7156.61616.217.117.3511.5310.810.116.89.618.323426326.326.42828.1317.1200.214.915.6320.9201.416.617.9Table 4-6.CDD/CDFcongener emissionfactors (pg/L)for unleadedgasoline-fueledautomobileswithcatalyticconverters (continued)



### 4-14Congener/congener groupAutomotive tailpipe emissionstudytestresultsMeanemissionfactors63 km/hra64 km/hr(test no. 29)b64 km/hr(test no. 30)b64 km/hr(test no. 18)bAssumingnondetectset to zeroAssumingnondetectsetto1⁄2 detectionlimit (DL)Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF28.625.526.338.717052.653.433.327.127.95151565027515212271623813ND (15)3616342779296017410682101502519733284398314043.744.442.169.2267.3153.972.150.886.57843.746.342.169.2267.3153.972.150.886.578Total CDD/CDF (nondetect set to0)Total CDD/CDF (nondetect set to1⁄2 DL)483.4483.49289281,0871,0871,1331,133908909.9aSource:Hagenmaier etal. (1990).bSource:Schwind etal. (1991);Hutzinger etal. (1992).ND = Not detected(valueinparenthesis is the reporteddetectionlimit)R a t i o ( c o n g e n e r g r ou p e m i s s i on f a c t or / t o t a l CD D / CD F e m i s s i o n f a ct or ) 0 0. 05 0. 1 0. 1 5 0

. 2 0

. 25 0. 3 0. 35

TC D D

Pe CD D

Hx CD D

HpCD D

OC D D

TC D F

Pe CD F

Hx CD F

HpCD F

OC D F

Car s Tr u c ks



### F i gu re 4-1. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om die s e l- f ue le d ve hic le s (based on profi l e s cal cul a ted from emission factors [ nondetects equal one-half the detec tion limit] from Tables 4-2 and 4-3)

.

4-15Ra t i o (c on gene r gr o u p em issi on fa c t or /t o t a l C D D / CD F e m i ssi on fa ct o r ) 0 0. 1 0. 2 0. 3 0. 4 0. 5

TC D D

Pe C D D

Hx CDD

HpCDD

OC D D

TC D F

Pe C D F

Hx CDF

HpCDF

OC D F



### F i gu re 4-2. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om leaded gas-f ueled vehicles (based on profi l e s cal cul a ted from emission factors [ nondetects equal one-half the detection limit] from Table 4-4)

.

4-16 0. 6R a tio ( c on g ener group emi s sio n f a c t o r /tota l C DD/C D F emissio n 0 0. 0 5 0. 1 0. 1 5 0. 2 0. 2 5 0. 3 0. 35

TC DD

PeC D D

Hx C D D

Hp C D D

OC D D

TC DF

PeC D F

Hx C D F

Hp C D F

OC D F



### F i gu re 4-3. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om unle a de d gas- f ue le d ve hic le s (cataly tic converter e quipped vehicles; based on data from Table 4-6).

4-17

### B i ng ham et al. (1989) analy z ed the ex hausts of four cars using leaded g a soline (uniform lead and org a nics content of 0.45 g / L tetram ethy l lead, 0.22 g / L dichloroethane, and 0.2 g / L dibromoethane) and the ex haust of one car using unleaded g a soline. Analy tical results and DL s were reported for only 5 of the 17 tox i c CDD/CD F cong eners. TEQ emission rates for the cars using leaded fuel, based on detected cong eners only , rang ed from 1 to 39 pg I

- TEQ DF 

### /km.
CDDs/CDF s we r e not de te c t e d in the e x ha ust f r o m the ve hic l e using unle a d e d f u e l; the tota l TEQ emission rate for this car, based on one-half the DL s for the five reported cong eners, was 20 pg I

TEQ DF 

### /km.

Marklund et al. (1990) tested Swedish cars fueled with commercial fuels, measuring
CDD/CDF emissions before and afte r the muffler. B o th new and ol d vehicles were tested. The tests were done on three cars using unleaded g a so line and two cars using leaded g a soline (0.15 g
Pb/L with 1,2-dichloroethane and ethy lene dibromide scaven g e rs). CDDs/CDF s were not detected in the fuels at a DL of 2 pg I

- TEQ DF 

### /L but were detected at a level of 1,200 pg I

- TEQ DF 

### /L in the new semisy nthetic eng i ne l ube oil used in the eng i nes. The test driving cy cle used (31.7 km/hr as a mean speed, 91.2 km/hr as a max imum speed, and 17.9% of time spent idling ) y i elded
f u e l e c onomie s r a ng ing f r o m a ppr ox ima te ly 9 to 10 km/L ( 22 to 24 mile s/g a l) in the va r i ous c a r s. The reported rang es of emission factors were

• L eaded g a s, measured before muffler: 2.4 to 6.3 pg I

- TEQ DF 

### /km (21 to 60 pg I

TEQ DF 

### /L fuel consumed)

• L eaded g a s, measured in tailpipe: 1.1 to 2.6 pg I

- TEQ DF 

### /km (10 to 23 pg I

- TEQ DF 

### /L )

• U nleaded g a s, cataly s t-equipped, m easured in tailpipe: 0.36 pg I

- TEQ DF 

### /km (3.5 pg I

- TEQ DF 

### /L )

• U nleaded g a s, measured before muffler: 0.36 to 0.39 pg I

- TEQ DF 

### /km (3.5 pg I

TEQ DF 

### /L )

The TEQ levels in ex haust g a ses from older cars usi n g l e aded g a sol i n e were up t o si x time s g r e a t e r whe n me a sur e d be f o r e the muf f l e r tha n whe n me a sur e d a f te r the muf f l e r

. No
muffler-related difference was obser ved in new cars running on leaded g a soline or in old or new cars running on unleaded g a soline. Marklund et al. (1990) also analy z ed the emissi ons of a heavy

- duty

, di esel-fueled truck for
CDDs/CDF s. None were detected; however, the authors pointed out that the test fuel was a reference fuel and may not have been represen tative of commercial diesel fuel. Also, due to analy tical problems, a much hig h er DL (about 100 pg I

- TEQ DF 

### /L ) wa s r e a lize d in this die se l f u e l test than in the g a soline tests conducted (5 pg I

- TEQ DF 

### /L )

. F u r t he r unc e r ta inty wa s intr oduc e d
because t h e di esel em i ssi on sam p l e s were col l ect ed onl y before t h e m u ffl er.

4-18

### Hag e nmaier et al. (1990) ran a set of tests using conditions comparable to the F TP-73 test

cy cl e on g a sol i n e- and di esel -fuel ed eng i nes for l i g ht -dut y vehi cl es i n Germ any

. The fol l o wi ng

a v e r a g e TEQ e mission r a te s pe r lite r of f

u e l c onsume d we r e r e por te d:

• L eaded fuel: 1,287 pg TEQ DF 

### -W HO 98 

### /L (1,080 pg I

- TEQ DF 

### /L )

• U nleaded fuel (cataly s t equipped): 7.9 pg TEQ DF 

### -W HO 98 

### /L (7.2 pg I

- TEQ DF 

### /L )

• U nleaded fuel (not cataly s t equipped): 60.2 pg TEQ DF 

### -W HO 98 

### /L (50.9 pg I

- TEQ DF 

### /L )

• D iesel fuel: 24.8 pg TEQ DF 

### -W HO 98 

### /L (20.8 pg I

- TEQ DF 

### /L )

Schwind et al. (1991) published the major fi nding s of a German study of emissions of halog e nated dibenz o- p -diox i ns and dibenz ofurans from inte rnal combustion eng i nes running on commercial fuels. The full repor t was published in 1992 (Hutz i ng er et al., 1992). The study was conducted by the universitie s of Stuttg art, Tübing en, and B a y r euth for the F e deral Ministry for Research and Technolog y , the Research Associa tion for I nternal Combustion Eng i nes, and the
German Association for the Petroleum I ndustry a nd Coal Chemistry

. Te sts were conducted using

eng i ne test benches and rolling test benches under re presentative operating conditions. Tests were perform ed on l eaded g a sol i n e eng i nes, unl eaded g a soline eng i nes, diesel car eng i nes, and diesel truck eng i nes. The reported rang e of CDD/CDF e mission r a te s a c r oss the te st c onditions in units of pg I

- TEQ/L of fuel consumed are presented below.

• L eaded fuel: 72 to 1,417 pg TEQ DF 

### -W HO 98 

### /L (52 to 1,184 pg I

- TEQ DF 

### /L )

• U nleaded fuel (not cataly s t equipped): 102 to 181 pg TEQ DF 

### -W HO 98 

### /L (96 to 177 pg I

- TEQ DF 

### /L )

• U nleaded fuel (cataly s t equipped): 9.6 to 28 pg TEQ DF 

### -W HO 98 

### /L (10 to 26 pg I

TEQ DF 

### /L )

• D iesel fuel (cars): 12 to 140 pg TEQ DF 

### -W HO 98 

### /L (10 to 130 pg I

- TEQ DF 

### /L )

• D iesel fuel (trucks): 79 to 82 pg TEQ DF 

### -W HO 98 

### /L (70 to 81 pg I

- TEQ DF 

### /L

Tables 4-2 throug h 4-6 show the results fro m te sts with c o mme r c ia l f u e l s tha t we r e not conducted under normal opera ting conditions and for which c ong ener-specific emission results were presented in Hutz ing e r et al. (1992). Althoug h no specific details on the methodolog y used were provided, Hag e nmaier (1994) reported that analy s es of emissi ons of a diesel-fueled bus run on ei t h er t h e st eady

- st at e or t h e “Berl i n cy cl e” showed no C DDs/ C DFs present at a DL of 1 pg /L of fuel consumed for individual

cong eners.

4-19

### Gullett and Ry an (1997) re ported the results of the first pr og ram to sample diesel eng i ne emissions for CDDs/CDF s during actual hig hway and city driving

. The ex haust emissions from a
1991 F r eig htliner diesel tractor with a 10.3 L , si x

- cy linder Caterpillar en g i ne—representative of the first g e neration of computeriz ed fuel-c ontrolled vehicles manufactured in the United States—were sampled during both hi g h way and ci t y rout es. The averag e em i ssi on fact or for t h e three hig h way tests conducted (15.1 pg I

- TEQ DF 

### /km; rang e, 11.7 to 18.7 pg I

- TEQ DF 

### /km; sta nda r d deviation, 3.5 pg I

- TEQ DF 

### /km) wa s be low the a v e r a g e of the two c ity dr iving te sts by a

f

a c t or of 3 (49.9 pg I

- TEQ DF 

### /kg ; rang e, 3 to 96.8 pg I

- TEQ DF 

### /km). DL s were considered to be z e ro in the
cal cul a t i on of t h ese em i ssi on fact ors. The averag e of all five tests was 29 pg I

- TEQ DF 

### /km, with a standard deviation of 38.3 pg I

- TEQ DF 

### /km. This standard deviati on refl ect s t h e 30-fol d vari at i o n in the two c ity dr iving r oute te sts. Geueke et al. (1999) analy z ed diox in emissi ons from heavy

- duty vehicle diesel eng i nes in

Germany

. Table 4-7 shows the results of the an aly s is. I

- TEQ values rang ed from 2 to 18 pg I TEQ/m 3 

### , including one value so hig h that it coul d not be reproduced. Miy a bara et al. (1999) analy z ed CDDs/CDF s found in ve hicle ex haust particles from a g a soline eng i ne and a diesel

eng i ne in J a pan. Table 4-8 presents the data from three tests conducted on the ex haust particles deposited on the tailpipe of the g a soline eng i ne

. TEQ values rang ed from 3.44 to 5.32 pg TEQ DF 

### WH O 98 

### /g (3.46 to 5.33 pg I

- TEQ/g ) ex ha ust particles. Su spended particulat e matter (PM) was
also collected from an el ectrostatic precipitator (ESP) connect ed to a hig h way tunnel. The I

- TEQ for the suspended PM was 257.5 pg TEQ DF 

### -W HO 98 

### /g (241.6 pg I

- TEQ/g ), two orders of

mag n itude hig h er than the TEQ for ex haust partic le s de posite d on the ta ilpip es. Table 4-9 depicts
the data from three tests conducte d on the ex haust particles deposite d on the tailpipe of the diesel

eng i ne. TEQ values rang ed from 7.14 to 18.1 pg TEQ DF 

### -W HO 98 

### /g (7.13 to 14 pg I

- TEQ/g ) soot.

4.1.2. Tunne l Em ission Studie s Several European studies and one U.S. study evaluated CDD/CDF emissions from vehicles by measuring the presen ce of CDDs/CDF s in tunnel air. Th is approach has the advantag e of allowing the random sampling of ex haust from la rg e numbers of cars with a rang e of ag es and

ma inte na nc e le ve ls. The disadvantag e of this approach is th at it relies on indirect measurements ( r a the r tha n ta ilpipe me a sur e m e n ts)
, whic h ma y intr oduc e bia s a nd ma ke inte r p r e ta tion of the finding s difficult. Concerns have been raised th at tunnel monitors detect resuspended particulates that have accumulated over time, l eading to overestimates of emissions. Also, the driving patterns encountered in these tunnel studies are more or less steady

- state driving conditions, which may produce emission levels different fro m t hose of t h e t r ansi ent dri v i n g cy cl e and col d eng i ne st art s that are ty pical of urban driving conditions. Th ese studies are summariz e d below in chronolog ical
order.

4-20

### Table 4-7. Total dioxin em ission co ncentrations f r om heavy-duty diesel engines in G erm any

Sam p l e Conc e nt r at i o n i n e x haus t a 

### ( pg I

- TEQ/ m 3 

### ) Sam pl e vol um e (m 3 

### )

St a t i o na r y e n g i ne 1 ( S 1) 6.1 32.89

St a t i o na r y e n g i ne 2 ( S 2) 61 b 

### 10.35

St a t i o na r y e n g i ne 3 ( S 3) 18 c 

### 10.73

St a t i o na r y e n g i ne 4 ( S 4) 6.9 10.06

St a t i o na r y e n g i ne 5 ( S 5) 6.6 10.06

Tr uc k e n g i ne 1 ( V 1) 9.7 10.03

Tr uc k e n g i ne 2 ( V 2) 2.1 10.07

Tr uc k e n g i ne 3 ( V 3) 2 9 .99

a Detectio n lim it f o r sam p lin g : 4

. 1 p g /m 3 f o r statio n a ry sam p les, 4

. 5 p g /m 3 fo r t r uc k sa m p l e s.

b A n aly s is cou l d n o t be con f irm e d.

c Hig h an aly tical d e tectio n lim it (1 1 p g /m 3 ).

S o u r ce: G e u e k e et al . (1999).



### Rappe et al. (1988) reported the CDD/CD F content of two air samples (60 m 3 

### / s am pl e) collected from a tunnel in Hamburg

, German y , in J a nuary 1986 to be 0.44 and 0.59 pg TEQ DF 

### WH O 98 

### /m 3 

### (0.42 and 0.58 pg I

- TEQ DF 

### /m 3 

### ). Each sample was collected over a period of about
60 hr. The tunnel handled 65,000 vehicles per day

, of which 17% were classified as “heavy
traffic.” The cong ener-s pecific results of the two samples ar e presented in Table 4-10. Ambient air measured in September 1986 at a nearby hig h way in Ham burg was reported to contain
CDD/CDF levels two to six times lower than those measured in the tunnel.
L a rssen et al. (1990) and Oehme et al. (1991) re ported the results of a tunnel study in Oslo, Norway , performed during April and May of 1988. Oehme et al. estimated total vehicle emissions by measuring CDD/CDF concentrations in tunne l inlet and outlet air of both the uphill and the
downhill la ne s. Emission r a te s f o r

lig ht- duty a nd he a v y

- duty ve hic l e c l a sse s we r e e stima te d by counting the number of lig ht-duty and heavy

- duty vehicles passing throug h the tunnel on workday s and a weekend and assum i n g a l i n ear rel a tionship between the percentag e of the lig htor heavy

- dut y t r affi c and t h e overal l em i ssi on rat e

. Thus, t h e l i n ear rel a t i onshi p for each em i ssi on rate was based on only two poi nts (i.e., the weekday and th e weekend m easurem ent s ).

4-21

### Table 4-8. Levels of 2,3,7,8-chlorine -substituted congeners and total CDDs/CDF s in veh i cle exh a u s t p a rticles (p g/g) f o r gasolin e en gin e s an d suspe nde d par t ic ulat e m a t t e r ( S P M )

C o n g en er G a so lin e
SPM Sam pl e 1 Sam pl e 2 Sam pl e 3
2,3,7,8- TCDD Ot he r TCDD <4

. 4 6.21 <2

. 1 19 <1

. 2 7.41 <5

. 2 4,580
2,3,7,8- TCDF Ot he r TCDF 3.98 36.8 5.17 68.8 3.53 41.9 108 2,830
1,2,3,7,8- Pe CDD Ot he r Pe CDD <7

. 6 <7

. 6 <3

. 6 11.5 <2

. 1 4.25 40.8 1,240
1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF Ot he r Pe CDF 5.58 2.87 24.4 6.46 5.24 53.9 3.07 3.66 38.3 184 107 29,700
1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD Ot he r HxCDD 4.3 <3

. 8 <3

. 8

4.14 <1

. 8 2.66 <1

. 8 20.5 0.86 1.36 0.63 10.5 42.3 96.7 71 1,100
1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF Ot he r HxCDF 6.85 4.94 <1

. 9 <1

. 9 47.2 3.95 4.48 <0

. 9

4.94 23.7 2.26 2.35 <0

. 5

1.99 15.2 243 231

38.6 387 1,600
1,2,3,4,6,7,8- HpCDD Ot he r HpCDD <8

. 2 <8

. 2 11.4 11.3 7.64 9 1,700 1,360
1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF Ot he r HpCDF <1

. 9 <1

. 9 <1

. 9 12.7 1.06 8.36 7.41 0.5 4.88 1,330 143 778

OCDD OCDF 8.76 4.78 13.8 5.09 17 3.03 3,650 1450

To t a l CDD/ CDF 160.8 294 186.7 53,010.4

I

- TEQ 3.73 5.33 3.46 241.6 TEQ DF 

### -W H O 98 

### 3.72 5.32 3.44 257.5

S o u r ce: Mi y a bara et al . (1999).



### The e mission r a te s e stima te d in this study , in units of Nor d ic TEQ, a r e a s f o llows:

• L ig ht-duty vehicles using g a soline (appr ox imately 70 to 75% using leaded g a s): uphill, 520 pg TEQ/km; downhill, 38 pg TEQ/km; mean, 280 pg TEQ/km

4-22

### Table 4-9. Levels of 2,3,7,8-chlorine -substituted congeners and total CDDs/CDF s in veh i cle exh a u s t p a rtic les (p g/g) f o r d i esel en gin e s

C o n g en er D i esel
Sam pl e 1 Sam pl e 2 Sam pl e 3
2,3,7,8- TCDD Ot he r TCDD 2.81 267 < 14.4 117 <2 86.9 2,3,7,8- TCDF Ot he r TCDF 5.71 84.2 15.9 335 7.5 313 1,2,3,7,8- Pe CDD Ot he r Pe CDD 10.5 165 < 28.8 73.5 8.15 83.6 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF Ot he r Pe CDF 3.17 1.11 27.3 16.6

< 11.5 211 15.1 9.52 243 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD Ot he r HxCDD 3.39 4.59 2.14 40.9 < 17.3

< 17.3

< 17.3

28.1 4.01 4.6 <1

. 5 26.9 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF Ot he r HxCDF 1.29 <1

. 2 <1

. 2 <1

. 2

3.7 15.9 31.3

< 10.1

< 10.1 182 9.03 8.22 0.86 9.58 79 1,2,3,4,6,7,8- HpCDD Ot he r HpCDD 8.78 10.1 <3 6 <3 6 1.24 <1 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF Ot he r HpCDF <1 <1 <1 <8

. 6 <8

. 6 <8

. 6 4.69 <1

6.28
OCDD OCDF <2

. 8 <4

. 4 <2 3 <3 6 <0

. 5 4.25

To t a l CDD/ CDF 641.7 1 ,026.3 925.4

I

- TEQ 10.6 7 .14 1 4 TEQ DF 

### -W H O 98 

### 13.0 7 .14 18.1

S o u r ce: Mi y a bara et al . (1999).



### • H eavy

- duty diesel trucks: uphill, 9,500 pg TEQ/km; downhill, 720 pg TEQ/km; mean, 5,100 pg TEQ/km

The mean values are the averag es of the e mission rates corresponding to the two operating
modes: vehicles moving uphill on a 3.5% incline at an averag e speed of 37 mph and vehicles

4-23

### Table 4-10. CDD/CDF co ncentrations (pg/m 3 

### ) fr om Eur o pe an t unne l air st udie s

Congener/congener group G erm any a G erm any a B e lg ium b No rw a y (w ork d ays ) c, d No rw a y (w eek end) c, d

2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD ND (0 .0 1 ) 0.31 0.37 1.19 0.44 1.9 6.3 0.06 0.28 ND (0 .1 7 ) 0.66 ND (0 .1 7 ) 2 6.4 0.002 0.025 0.025 0.042 0.03 0.468 2.19 0.02 0.18 0.06 0.29 0.25 1.41 0.1 0.02 0.04 0.03 0.03 0.06 0.16 0.5
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 0.17 0.4 0.19 0.26 0.16 ND (0 .0 4 ) 0.12 1.2 ND (0 .1 6 ) ND (1 .3 ) 0.72 0.36 NR

0.13 0.15 ND (0 .0 5 ) ND (0 .0 5 ) 0.98 ND (0 .1 7 ) ND (1 ) 0.013 0.143 0.039 0.073 0.093 0.143 0.004 0.499 0.074 0.25 0.58 0.83 0.78 0.79 0.62 0.04 0.74 1.78 0.22 1.62 0.07 0.75 0.58 0.34 0.31 0.03 0.13 0.93 0.14 2.54

T o t a l 2,3,7,8- C D D T o t a l 2,3,7,8- C D F T o tal I- T E Q DF (n on det ect s e t t o 0) T o tal I- T E Q DF (n o n d e tect set to 1⁄2 DL ) T o tal T E Q DF -W H O 98 (n on det ect s e t t o 0) T o tal T E Q DF -W H O 98 (n o n d e tect set to 1⁄2 DL ) 10.51 2.5 0.58 0.59 0.73 0.74 9.40 2.34 0.42 0.44 0.55 0.58 2.78 1.33 0.096 0.096 0.106 0.106 2.31 8.0 0.91 0.91 1 1 0.84 5.82 0.48 0.48 0.49 0.49

T o tal T C DD T o tal P e CDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal P e CDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF 0.23 2.5 7.8 3.4 6.3 3.5 3.6 2. 1.9 ND (1 .3 ) 0.22 1.3 2.7 3.4 6.4 6.2 4.1 1.1 1.2 ND (1 ) NR NR NR NR NR NR NR NR NR NR 0.26 1.78 1.32 1.31 0.1 13.20 10.17

6.42 2.62 1.62 0.16 0.41 0.12 0.23 0.5 1.7 7.91 2.08 1.41 2.54

T o tal CDD/CDF (n o n d e tect set to 0 ) T o tal CDD/CDF (n o n d e tect set to 1⁄2 DL ) 31.2 31.9 26.6 27.1 NR NR 38.8 38.8 17.06 17.06

a S o u r ce: R a ppe et al . (1988).

b S o u r ce: Wev e rs et al . (1992).

c S o u r ce: O e h m e et al . (1991).

d Li st e d va l ue s a r e t he d i ffe r e nc e s b e t w e e n t he c o nc e nt r a t i o ns a t t he i nl e t a nd t he o ut l e t o f t he no r t hb o und t unne l l a ne s.

DL = Detectio n lim it ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it) NR = No t rep o r ted



### 4-24

### moving downhill on a 3.5% decline at an averag e speed of 42 mph. Althoug h Oehme et al.

r e por te d r e sults in units of Nor d ic TEQ, the r e sults in I

- TEQ DF 

### should be nearly identical (only about 3 to 6% hig h er) because the only diffe rence between the two TEQ schemes is the TEF assig ned to 1,2,3,7,8-PeCDF (0.1 in Nordic TEQ and 0.05 in I

- TEQ DF 

### ), a minor component of the

tox i c CDDs/CDF s measured in the tunnel air. Table 4-10 pr esents the cong ener-specific
differences in concentrations between th e tunnel inlet and ou tlet concentrations.
W e vers et al. (1992) measured the CDD/CD F content of air samp les taken during the winter of 1991 inside a tunnel in Antwerp, B e lg ium. B ackg r ound concentrations outside the
tunnel were also deter mined. Two to four sa mples were collected from each location with two
de vic e s: a sta nda r d hig h

- volume sa mple r with a g l a ss f i be r f

ilte r a nd a modif i e d two- pha se , hig h

volume sa mple r e quippe d with a g l a ss f i be r f

ilte r a nd a poly u r e tha n e f o a m ( P UF ) plug

. The
I

- TEQ DF 

### c onc e n tr a tion in the a i r sa mple d with the f ilte r with the PUF plug wa s 74 to 78% of the value obtained with the standard hig h -volume sa mpler. However, the results obtained from both
sets of devices indicated that the tunnel air had a CDD/CDF TEQ concentration about twice as

­ hig h as that of the outside air (filter with PUF : 80.3 fg I

- TEQ DF 

### /m 3 

### for tunnel air vs. 35 fg I TEQ DF 

### /m 3 

### for outside air; filter only : 100 fg I

- TEQ DF 

### /m 3 

### for tunnel air vs. 58 fg I

- TEQ DF 

### /m 3 

### for outside air). The authors presented the cong ener-specific results for only one tunnel air

m easurem ent ; t h ese resul t s are present e d i n Tabl e 4-10. During October and November of 1995, Ger tler et al. (1996, 1998) conducted a study at the F ort McHenry Tunnel in B a ltimore, MD. Th eir stated objective wa s to measure CDD/CDF
emission factors from in-use vehi c l e s ope r a ting in the Unite d Sta t es, with particular emphasis on heavy

- duty trucks. The air volume entering and l eaving the tunnel bore (the area that the traffic

g oes throug h) that is used by most of the heavy

- duty trucks (i.e., a pprox imately 25% of the vehicles using the bore are heavy

- duty trucks ) was measured, and the air was sampled for
CDDs/CDF s during seven 12-hr sa mpling periods. Three of the sa mple s we r e c o lle c t e d dur ing
da y time ( 6 a

. m. to 6 p.m.) a nd f our sa mple s we r e c o lle c t e d dur ing the nig h t ( 6 p.m. to 6 a

. m.)

. The ai r vol um e and concent r at i on m easurem ent s were combined with information on vehicle counts (obtained from videotapes ) and tunnel leng th to deter mine averag e emission factors. A total of 33,000 heavy

- duty trucks passed th roug h the tunnel during the seven sample runs (21.2 to 28.8% of all vehicles ). The emission factors, calcu lated on the assumption that all
CDDs/CDF s emitted in the tunnel were from heavy

- duty trucks, are presented in Table 4-11. The

averag e TEQ emission factor was reported to be 181.8 pg TEQ DF 

### -W HO 98 

### /km (172 pg I

TEQ DF 

### /km). The major uncertaintie s identified by the study authors were tunnel air volume

m easurem ent , sam p l e r fl ow vol um e cont rol

, and anal y t i cal m e asurem ent of C DDs/ C DFs.

4-25Table4-11.BaltimoreHarbortunnel study:estimatedemission factors (pg/km) forheavy-duty dieseltrucksa



### 4-26Congener/congener groupRun-specific emission factorsMeanemissionfactorsRun 2Run 3Run 5Run 6Run 8Run 9Run 102,3,7,8-TCDD24.561.6021.237.840.154.934.31,2,3,7,8-PeCDD40.220.615.45.638.4083291,2,3,4,7,8-HxCDD18.225.246.58.364.5012340.81,2,3,6,7,8-HxCDD37.528.264.319.615371.1186801,2,3,7,8,9-HxCDD53.656.591.648.4280126370146.61,2,3,4,6,7,8-HpCDD04017291112,4389632,080960.3OCDD03,3613,3821,1209,7305,8297,6204,434.62,3,7,8-TCDF094.367.6152.8155.873.461.786.51,2,3,7,8-PeCDF048.972.623.653.3043.334.52,3,4,7,8-PeCDF24.575.713146.68563.910876.41,2,3,4,7,8-HxCDF15.413920493.8124164166129.51,2,3,6,7,8-HxCDF0.375.173.75161.354.495.558.81,2,3,7,8,9-HxCDF27.714.875.6020.637.263.534.22,3,4,6,7,8-HxCDF15.282.515255.79386.811185.21,2,3,4,6,7,8-HpCDF12.6280445154313354308266.71,2,3,4,7,8,9-HpCDF058.560.831.1252.334.930.4OCDF0239401175416534370305Total2,3,7,8-CDD1743,9544,328.84,3281,334.17,02910,516.95,725.6Total2,3,7,8-CDF95.71,107.81,683.31,684783.61,3701,361.91,107.2Total I-TEQDF73.8174.8170.517095.7152.9302.5172.2Total TEQDF-WHO9893.9181.8174.817597.3147.2336.8182.4Table4-11.BaltimoreHarbortunnel study: estimatedemission factors (pg/km) forheavy-duty dieseltrucksa(continued)



### 4-27Congener/congener groupRun-specific emission factorsMeanemissionfactorsRun 2Run 3Run 5Run 6Run 8Run 9Run 10Total TCDD245014016531110997.3152.5Total PeCDD11021.983.335.6174016584.3Total HxCDD677075354.52,0091,6662,9711,161.5Total HpCDD08021,4981425,6961,9334,3772,064Total OCDD03,3613,3821,1209,7305,8297,6204,434.6Total TCDF09011,3146562,4161,007687997.3Total PeCDF1241191,15278.41,055282626490.9Total HxCDF13631985267.6444719619450.9Total HpCDF0223814144513354637383.6Total OCDF0239401175416534370305Total CDD/CDF1,2925,985.910,389.32,638.122,76412,43318,169.310,524.5Heavy-dutyvehiclesas% oftotalvehicles21.22222.63428.824.227.425.7aValuesarebasedonthedifferencebetweenthecalculatedchemicalmass entering thetunnel andthemass exiting thetunnel.All calculatednegativeemissionfactorswere set equal to zero.All CDD/CDF emissionswere assumed to result fromheavy-dutydiesel-fueled vehicles.Source:Gertler etal. (1996, 1998).

### EPA’s Office of Transportation and Air Quality (OTAQ) reviewed the Gertler et al. (1996) study (L orang , 1996) and found it to be tec hnolog ically well done; no major criticisms or comments on the test methodolog y or protocol were offered, nor did OTAQ find any reason to doubt the validity of the emission factor dete rmined by the study

. OTAQ noted that the particulate emission rate for h eavy

- duty vehicles measured in the study (0.32 g /mile) was lower than the g e neral particulate emission rate used by EPA (about 1 g /mile) and, thus, may
underestimate CDD/CDF e missions under different driving cond itions. OTAQ cautioned that the reported emission factor should be reg a rded only as a conservativ e estimate of the mean emission factor for the interstate trucking fleet under the driving conditions of the tunnel (i.e., speeds on the order of 50 mph, with those of the entering traffi c slig htly hig her and those of the ex iting traffic slig htly lowe r )

. F i g u re 4-4 g r aphically presents the results of the studies by Rappe et al. (1988), Oehme et al. (1991), W e vers et al. (1992) , and Gertler et al. (1996, 1998). The fig u re compares the

cong ener profiles (i.e., cong en er concentrations or emissi on f a c t or s nor ma lize d to tota l
concentration or emission fact or of 2,3,7,8-substituted CDDs a nd CDF s ) reported in the four
studies. The dominant cong eners in the Rappe et al ., W e vers et al., and Ger t l e r et al . st udi es are OCDD; 1,2,3,4,6,7,8-HpCDD; OCDF ; and 1,2,3,4,6,7,8-HpCD F

. W ith the ex ception of OCDD,

t h ese cong eners are al so t h e m a j o r cong eners report e d by Oehm e et al

. The Oehm e et al . st udy
also differs from the other tunnel studies in th at the total of 2,3,7,8-substituted CDF s far ex ceeds the total of 2,3,7,8-substituted CDDs (by a factor of 2), whereas the other three observed just the opposite.

4.1.3. National Em ission Estim a tes
Estimates of national CDD/CD F TEQ emissions for reference y ears 1987 and 1995 are presented in this section only fo r on-road vehicles using g a soline and diesel fuel. F o r reference

y ear 2000, EPA’s Office of Air Quality Planning and Standards (OAQPS) developed national
CDD/CDF TEQ emission estimates for on-hig h way g a soline and di esel vehicles, off-hig hway

g a soline and diesel equipment, di esel railroad equipment, and dies e l c o mme r c ia l ma r i ne ve sse ls.

4.1.3.1. Activity Inform ation for On-Road V e hicles Reference y ear 2000 activity information for on- hig h way g a soline and diesel vehicles was estimated by OAQPS as county

- le vel vehicle miles driven (V MD). The estimates include calculations by month, road ty pe, and vehicle ty pe. To develop the VMD, OAQPS relied on data supplie d by the F e de r a l Hig h wa y Administr a tion ( F HWA)

.

4-28Ratio(congener conc./total2378CDD/CDF conc.) 0.7

0.6

0.5

0.4

0.3

0.2

0.1

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Congen er num b er

No r w a y (R o w 1 ) a Germany ( R ow 2) b Ger m an y ( R ow 3) a
Belgiu m ( R o w 4) c Balti m ore, U S A ( R o w 5 ) d



### F i gur e 4- 4. Tunne l air c o nc e n t r at ions (cong ener numbers refer to the cong eners in order as listed in Table 4-7).

a S o u r ce: O e h m e (1991).

b S o u r ce: R a ppe et al . (1988).

c S o u r ce: Wev e rs et al . (1992).

d S o u r ce: G e rt l e r et al . (1996, 1998)



### .



### F o r on-hig h way g a soline-driven vehicles, OAQPS c a l c u la te d a na tiona l a c tivity le ve l of 4,071 billion km for 2000. The activity level for each vehicle ty pe was

Vehi cl e t y pe B illion kilome te r s L i g ht-duty vehicles 2,574.95 L i g ht-duty trucks 1 1,004.23 L i g ht-duty trucks 2 342.79 Heavy

- duty vehicles 131.97 Motorcy c les 17.70

4-29

### F o r on- hig h wa y die se l

- f u e l e d ve hic l e s, OAQPS e stima te d a na tiona l a c tivity le ve l of 359
billion km for 2000. The activity level for each vehicle ty pe was

Vehi cl e t y pe B illion kilome te r s L i g h t-duty vehicles 6.44 L i g ht-duty trucks 1 6.44 2B -heavy diesel vehicles 33.80 L i g ht heavy

- duty vehicles 25.75 Medium heavy

- duty vehicles 59.55 Heavy heavy

- duty vehicles 217.26 B u ses heavy

- duty vehicles 9.66

F o r reference y ear 1995, F HW A reported that 1,448 billion total vehicle miles (2,330 billion km) were driven by automobiles and moto rcy c les in the United States. Trucks accounted for 1,271 billion km (790 billion miles) and buses accounted for 10 billion km (6.2 billion miles) (U.S

. DOC, 1997). I n 1992, diesel-fueled trucks accounted for 14.4% of total truck vehicle kilometers driven (VKD); g a soline-fueled truc ks accounted for the remaining 85.6% (U.S . DOC, 1995a). Apply i ng this factor of 14.4% to the 1995 truck estimate of 1,271 b illion km results in an estimate of 183 billion km driven by diesel-fueled trucks in 1995. All other VKD (2,947 billion km) are assumed to be by g a soline-fueled vehicles (nondiesel trucks, all automobiles, all buses, a nd all motorcy c les); alt houg h a fraction of buses and automobiles use diesel fuel, the ex act numbers are not known. I t is further assumed that all of these kilometers were driven by unleaded g a so line-fueled vehicles because in 1992 only 1.4% of the g a soline supply was leaded fuel (EI A , 1993). Us e of leaded fuel should have declined further by 1995 because its use in motor vehicles for hi g h way use in the United S t ates was prohibited as of December 31, 1995 (Federal Reg i ster, 1985a).
F o r reference y ear 1987, an estimated 3,092 billion km were driven in the United States, of which trucks accounted for 887 billion km (U.S . DOC, 1995b). Diesel-fuel ed trucks accounted
for 17.2% of total truck kilomete rs driven (U.S. DOC, 1995a). Apply i ng this factor of 17.2% to
the 1987 truck kilometer estimate of 887 billion results in an estimate of 153 billion km driven by
diesel-fueled trucks. All other VKD (2,939 billion) are assumed to have been by g a soline-fueled
vehicles. L eaded g a soline accounted for 24.1% of the g a soline supply in 1987 (EI A , 1993); thus,
708 billion km are estimated to have been driven by leaded g a soline-fueled vehicles. The remaining 2,231 billion km are es timated to have been driven by unleaded g a soline-fueled

ve hic l e s. The se mile a g e e stima te s a r e g i ve n a hig h c onf ide n c e r a ting be c a u se the y a r e ba se d on
U.S. Census B ureau transportation studies.

4-30

### 4.1.3.2. Activity In form ation for Off-Road Uses Althoug h on-road vehicles are the larg est users of g a soline and diesel fuel, certain sectors of the economy account for sig n ificant amounts of farm, railroad, marine vessel, and other off-hig hway uses. Reference y ear 2000 activity information for off-hig hway g a soline and diesel equipment was estimated by OAQPs from NONROAD model runs prepared for the National
Emissions I nventory

. For off-hig hway g a solin e-driven equipment, OAQP S calculated a national activity level of 23,091.01 million L for 2000. The ac tivity level for each equipment ty pe was

Vehi cl e t y pe Million lite r s L a wn and g a rden equipment, 4-stroke eng i nes 8,100.78 Pleasure craft, 2-stroke eng i nes 3,607.50 Commercial equipment, 4-stroke eng i nes 3,255.45 Recreational equipment, 2-stroke eng i nes 2,032.77 Recreational equipment, 4-stroke eng i nes 1,782.93 Pleasure craft, 4-stroke eng i nes 1,374.10 L a wn and g a rden equipment, 2-stroke eng i nes 1,192.40 I ndustrial equipment, 4-stroke eng i nes 579.16 Construction and mining equipm ent, 4-stroke eng i nes 473.18 Ag ricultural equipment, 4-stroke eng i nes 306.62 I ndustrial equipment, 4-stroke eng i nes; other oil field equipment 124.92 Construction and mining equipm ent, 2-stroke eng i nes 102.21 Commercial equipment, 2-stroke eng i nes 79.49 L og g i ng equipment, 4-stroke eng i nes 37.85 L og g i ng equipment, 2-stroke eng i nes 26.50 Airport g r ound support equipmen t, 4-stroke eng i nes 7.57 Railroad, 4-stroke eng i nes 3.79 Ag ricultural equipment, 2-stroke eng i nes 3.40 I ndustrial equipment, 2-stroke eng i nes 1.14

F o r reference y ear 2000, OAQPS calculate d national activity levels of 40,125.37 million
L

for off-hig hway diesel-drive n vehicles, 12,491.86 million L for dies el railroad equipment, and 7,684.39 million L for diesel commercial marine vessels. F o r diesel commercial ma rine vessels, the national activity level co mprises port emissions (5,905.24 milli on L ) and underway emissions (1,968.41 million L )

. The activity level for each ty pe of diesel ra ilroad equipment was:

Die se l loc o motive ty pe Million lite r s Class I locomotives 10,561.30 C l a s s II/ III l o c o m o t i v e s 700.30 Yard locomotives 794.94 Passeng er trains 230.91 Commuter trains 215.77

4-31

### The fol l o wi ng parag r aphs defi ne each of t h e off-road fuel uses l i s t e d at t h e beg i nni ng of this section and present distillate fuel sales (in liters) in each s ector for reference y ears 1987 and 1995 (EI A , 1992, 1997a). F o r these sectors, the major ity of “distillate fuel” sales are diesel fuels;
a small fraction are fuel oils. The activity le vel information for reference y ears 1987 and 1995 is provided for informational purposes only because emission estimates for these y ears could not be
calculated due to the lack of emission factors. Farm fuel use includes sales for use in tractors, irrig a tion pumps, and other ag ricultural

m achi n ery , as wel l as fuel used for crop dry i ng , i n sm udg e pot s, and for space heat i n g of building s

. Sales were 11,352.45 milli on L in 1987 and 13,158.1 million L in 1995. Railroad fuel use includes sales to railroads for any us e, including diesel fuel for use in locomotives and fuel used for heating buildin g s operated by railroads

. Sales were 10,788.42 L in 1987 and 12,980.18 L in 1995. Marine vessel fuel use inc l ude s sa le s f o r

the f u e ling of c o mme r c ia l or pr iva t e boa ts suc h as pl easure craft

, fi shi n g boat s , t u g boat s , and oceang o i n g vessel s , i n cl udi ng vessel s operat e d by oil companies. Ex cluded are sales to the U. S. Armed F orces. Sale s were 7,059.79 L in 1987 and 8,854.08 L in 1995. Off-highway fuel use includes sales for use in constr uction equipment, including , e.g ., earthmoving equipment, cranes, stationary g e nerators, and ai r com p ressors, and sal e s for nonconstruction off-hig hway uses such as log g i ng

. S a les were 5,905.24 L in 1987 and 8,225.7 L
in 1995.

4.1.3.3 Em ission Estim ates Using the results of the studies discusse d in Section 4.1.1, sepa rate national annual

e mission e stima te s we r e de ve lope d f o r

ve hic l e s bur ning le a d e d g a soline

, unle a d e d g a soline

, a n d
di esel fuel

. Leaded gasoline. The lite r a tur e indic a t e s tha t CDD/CDF e missions oc c u r f

r o m f u ll combustion in vehicles using leaded g a soline, and t h at consi d erabl e vari a tion occurs depending

, at least in part, on the ty pes of scaveng e rs used. Marklund et al. (1987) re ported emissions rang ing from 20 to 220 pg I

- TEQ DF 

### /k m from four cars fuel ed wi t h a reference unl eaded fuel t o whi c h l e ad (0.5 g /leaded g a l) and a chlorinated scaveng e r were added. Marklund et al. (1990) reported much
lower emissions in the ex haust of cars using a co mmercial leaded fuel (0.5 g / L ) containing both 1,2-dichloroethane and ethy lene dibromide as scaveng e rs (1.1 to 6.3 pg I

- TEQ DF 

### /km)

. The
difference in the emission meas urements in the 1987 and 1990 studies was attributed to the
different mix of scaveng e rs used in the two studies, which may have r e sulte d in pr e f e r e n tia l
formation of mix ed chlorinated and brominated diox ins and furans.

4-32

### Hag e nmaier et al. (1990) reporte d TEQ emissions of 1,080 pg I

- TEQ DF 

### /L f

u e l (approx imately 129 pg TEQ DF 

### -W HO 98 

### /km [ 108 pg I

- TEQ DF 

### /km]) f r o m a c a r f

u e l e d with a commercial leaded fuel (lead content not repor ted). B i ng ham et al. (1989) reported emissions

rang ing from 1 to 39 pg I

- TEQ DF 

### /km from four cars using g a soline with a lead content of 1.7 g / L
in New Z ealand. The German study reported by Schwind et al. (1991) and Hutz ing e r et al. (1992) measured emissions of 52 to 1,184 pg I

- TEQ DF 

### /L (approx imately 7.2 to 142 pg TEQ DF 

### -W HO 98 

### /km [ 5.2 to 118 pg I

- TEQ DF 

### /km] ) for cars under various simulate d driving conditions. The tunnel study by Oehme et al. (1991) estimated that emissions from cars running primarily on leaded

g a soline (70 to 75% of the cars) rang ed from 38 to 520 pg Nordic TEQ/km. The averag e emission factor (see Table 4-4) was 532 pg TEQ DF 

### -W HO 98 

### /L (450 pg I

TEQ DF 

### /L )
, a s r e por te d f o r

the ta ilpipe e mission studie s pe r f o r m e d using c o mme r c ia l le a d e d f u e l (Marklund et al., 1990; Hag e nmaier et al., 1990; Schwind et al., 1991), which presented analy tical
results for all 17 tox i c CDD/CDF cong eners. A ssuming an averag e fuel economy of 10 km/L

, this
emission factor was a pprox imately 53 pg TEQ DF 

### -W HO 98 

### /km (45 pg I

- TEQ DF 

### /km)

. A low

c onf ide n c e r a ting is a ssig n e d to this e mission f actor because it is based on European fuels and emission control technolog ies, which may have differed from U.S. leaded-fuel and eng i ne technolog ies, and because the factor is based on tests with only nine cars. Combining this averag e emission factor (53 pg TEQ DF 

### -W HO 98 

### /km [ 45 pg I

- TEQ DF 

### /km], assuming nondetect values were z e ro) with the estima te for kilometers driven by leaded g a solinefueled vehicles in 1987 (708 billion km) sug g e sts that 37.5 g TEQ DF 

### -W HO 98 

### (31.9 g I

- TEQ DF 

### ) were emitted from vehicles using leaded fuels in 1987. Althoug h some on-road vehicles used leaded fuel in 1995, further use of leaded fuel in motor vehicles for hig h way use in the United
S t ates was prohibited as of December 31, 1995 (Fed eral Reg i ster, 1985a). I n 1992, the last y e ar for which data are available on consumption of leaded g a soline by on-road vehicles, only 1.4% of the g a soline supply was leaded g a soline (EI A , 1993)

. A conservative assumption that 1% of the total VKD in 1995 (29.5 billion km of a total of 2,947 billion km) was by leaded g a soline-fueled vehicles, in conjunction with th e emission factor of 53 pg TEQ DF 

### -W HO 98 

### /km (45 pg I

- TEQ DF 

### /km)

, y i elds an annual emission of 1.6 g TEQ DF 

### -W HO 98 

### (1.3 g I

- TEQ DF 

### ) in 1995. These emission

e stima te s a r e a ssig n e d a low c onf ide n c e r a ting on the ba sis of the low r a ting f o r

the e mission
fact or. Unleaded gasoline. The lite r a tur e doc ume n ting r e sults of Eur ope a n studie s indic a t e s tha t
CDD/CDF emissions from vehicles burning unl eaded fuel s are l o wer t h an em i ssi ons from

ve hic l e s bur ning le a d e d g a s with c h lor i na te d sc a v e n g e r s. I t a l so a ppe a r s, ba se d on the limite d data available, that cataly s t-equipped cars have lower emi ssion factors than do noncataly s tequipped cars. Marklund et al. (1987) did not de tect CDDs/CDF s in emi ssions from two cataly s tequipped cars running on unleaded g a soline at a DL of 13 pg I

- TEQ DF 

### /km. Marklund et al. (1990)

4-33

### reported emission factor s of 0.36 and 0.39 pg I

- TEQ DF 

### /km for two noncataly s t-equipped cars and an emission factor of 0.36 pg I

- TEQ DF 

### /km for one cataly s t-equipped car

. Hag e nmaier et al. (1990) reported an emission factor of 5.1 pg I

- TEQ DF 

### /km for one noncataly s t-equipped car and 0.7 pg I

TEQ DF 

### /km for one cataly s t-equipped car. Schwind et al. (1991) and Hutz ing e r et al. (1992) reported emission factor s of 9.6 to 17.7 pg I

- TEQ DF 

### /km for several noncataly s t-equipped cars tested under various conditions; th e reported emission factor rang e for cataly s t-equipped cars was 1 to 2.6 pg I

- TEQ DF 

### /km. All automobiles running on unleaded g a solin e in the United States are equipped with

cat al y s t s

. The averag e em i ssi on fact or report e d for t h e t a i l p i p e em i ssi on st udi es perform ed on cataly s t-equipped cars (Hag enmaier et al. 1990; Sc hwind et al., 1991; Hutz ing e r et al., 1992) was
15.6 pg TEQ DF 

### -W HO 98 

### /L (14.9 pg I

- TEQ DF 

### /L ) ( c a l c u la te d f r o m the me a n e mission f a c t or in Ta ble 4-6). A l o w confi d ence rat i n g i s assi g n ed t o t h i s em i ssi on fact or because t h e European fuel s and emission control technolog y used may have differed from U.S. fuels and technolog y and also
because t h e em i ssi on fact or rang e i s based on t e st s wi t h onl y t h ree cat al y s t

- equi pped cars. OAQPS calculated emissions for reference y ear 2000 for diox ins and furans from

g a sol i n e-fuel ed vehi cl es usi n g t h e final version of the MOB I L E6 model. On-road emissions were calculated by converting the emission factor of 15.6 pg TEQ DF 

### -W HO 98 

### /L (14.9 pg I

- TEQ DF 

### /L ) to a millig ram-per-mile basis using a conversion factor of 3.78e–09 a nd assuming a fuel economy of
21.5 miles/g a l. The new emission factor was th en multiplied by the corresponding county

- level VMD in miles per y ear. The off-hig hway g a so line equipment emission estimates for reference

y ear 2000 were developed by multiply ing the mean emission factor of 15.6 pg TEQ DF 

### -W HO 98 

### /L (14.9 pg I

- TEQ DF 

### /L ) by 2000 activity estimates devel oped from NONROAD model runs prepared
for the National Emissions I nventory

. The ac tivity estimates represen t county

- level g a soline consumption in g a llons. The emission fact or was converted from picog r ams per liter to millig rams per g a llon by multiply ing by a conve rsion factor of 3.78e–09. The use of these methodolog ies resulted in national estimates for refe rence y ear 2000 of 7 g TEQ DF 

### -W HO 98 

### (6.7 g
I

- TEQ DF 

### ) for on-hig h way g a soline vehicles and 0.36 g TEQ DF 

### -W HO 98 

### (0.35 g I

- TEQ DF 

### ) for offhig hway g a soline equipment. Apply i ng the same emission factors from Gertler et al. (1996, 1998) and assuming an
averag e fuel economy of 10 km/L y i el ds an emission factor of 1.6 pg TEQ DF 

### -W HO 98 

### /km (1.5 pg I

TEQ DF 

### /km). Apply i ng this emission factor to the estimate derived for VKD in 1995 by all

g a soline-fueled vehicles (2,947 billion km) sug g e sts that 4.7 g TEQ DF 

### -W HO 98 

### (4.4 g I

- TEQ DF 

### ) were emitted from vehicles using unleaded fuels in 1995. Apply i ng the same emission factors to the estimate derived above for VKD in 1987 by unl eaded g a soline-fueled vehicles (2,231 billion km) sug g e sts that 3.6 g TEQ DF 

### -W HO 98 

### (3.3 g I

- TEQ DF 

### ) may have been emitted in 1987. The

4-34

### e mission e stima te s f o r

a ll r e f e r e nc e y e a r s we r e a ssig n e d a low c onf ide n c e r a ting on the ba sis of
the low r a ting g i ve n to the e mission f a c t or

. Di esel f u el

. L imited data are availabl e upon which to base an evaluation of the ex tent of
CDD/CDF emissions resulting from diesel fuel combustion, and th ese data address only emissions
from on-road vehi cl es; no em i ssi ons dat a are av ai l a bl e for off-road di esel uses (const r uct i o n vehicles, farm vehicles, and stati onary equipment). Two U.S. tailp ipe studies have been reported:
CARB (1987) and Gullett and Ry an (1997). CARB reported a rela tively hig h emission factor of 676 pg I

- TEQ DF 

### /km (nondetect values assumed to be z e ro) for one heavy

- duty truck with a fuel

economy of 5.5 km/L at 50 km/hr. Gullett and Ry an reported a rang e of emission factors for one
diesel truck tested on six hig hway or c ity driving routes of 3 to 96.8 pg I

- TEQ DF 

### /km (mean of 29

pg I

- TEQ DF 

### /km)

. The results of several tailpip e studies conducted in Europe have also been published. Marklund et al. (1990) reported no e missions at a DL of 100 pg I

- TEQ DF 

### /L (or 18 pg I

- TEQ DF 

### /km, assuming a fuel economy of 5.5 km/L ) for one tested truck. Schwind et al . (1991) and Hutz ing e r et al. (1992) reported emission factors of 32 to 81 pg I

- TEQ DF 

### /L (or 6 to 15 pg I

- TEQ DF 

### /km, assuming a fuel economy of 5.5 km/L ) for a truc k eng i ne run under vari ous simulated driving
conditions. Hag e nmaier (1994) reported no emissions from a bus at a DL of 1 pg /L fuel consumed for individual cong eners. F o r diesel-fueled cars, Hag e nmaier et al. (1990) reported an emission factor of 24 pg I

- TEQ DF 

### /L (or approx imately 2.4 pg I

- TEQ DF 

### /km) for one tested car.
Schwind et al. and Hutz ing e r et al. repor ted emission factors of 5 to 13 pg I

- TEQ DF 

### /km f o r

a

c a r
eng i ne run under various s imulated driving conditions. The tunnel study by Oehme et al. (1991) g e ne rated an estimated mean emission factor of 5,100 pg TEQ/km and a rang e of 720 to 9,500 pg TEQ/km (in units of Nordic TEQ) for dieselfueled trucks. I nsufficient information was pr ovided in Oehme et al. to enable an ex act calculation of emissions in units of I

- TEQ DF 

### or TEQ DF 

### -W HO 98 

### . However, based on the information that was provided, the mean emission factor in units of TEQ is approx imately 5,250 to 5,400 pg I

- TEQ DF 

### /km. The se indir e c tly e stima te d e mission f a c t or s a r e c onside r a b ly la r g e r tha n those reported in eng i ne studies by Marklund et al. (1990), Schwind et al. (1991), and Hutz ing e r et al. (1992); the CARB (1987) dies el truck emission factor falls at the low end of the rang e. Althoug h ag g r eg ate samples representing se veral thousand heavy

- duty diesel vehicles
were collected in Oehme et al . (1991), several characteristics of the study introduce considerable

unc e r ta inty with r e g a r d to the use of the study ’ s r e sults a s a ba sis f o r

e stima ting e missions in the
Uni t e d S t at es: (a) heavy

- dut y vehi cl es represent e d only 3 to 19% of total vehicle traffic in the tunnel; (b) the majority of the lig ht-duty vehicl es were fueled with leaded g a soline, the combustion of which, as noted in Table 4-4, can release considerable am ounts of CDD/CDF s ; and

4-35

### (c) technolog y differences likely ex isted be tween the 1988 Norweg ian and the 1987 and 1995 U.S.
vehi cl e fl eet s. The tunnel study conducted in B a ltimore, MD, by Gertler et al. (1996, 1998) shares the disadvantag es of all tunnel studies relative to studies that direc tly measured CDDs and CDF s in tailpipe emissions. Specifically , tunnel studies rely on indirect measurements (rather than tailpipe

m easurem ent s ), whi c h m a y i n t r oduce bi as, and t h e em i ssi on fact ors cal cul a t e d from t h ese st udi es reflect driving conditions of onl y the vehicle fleet using the t unnel and not necessarily of the
overall vehicle fleet under ot her driving conditions. However, the Gertler et al. st udy does have streng ths that ar e l acki n g i n t h e Oehm e et al

. (1991) tunnel study , and it has a dvantag es over the two U.S. di esel truck tailpipe studies, including : (a) the study was c onducted (fairly recently ) in the Un ited S t ates and thus reflects current U.S. fuels and technolog y , (b) virtually no vehicle using the tunnel used leaded g a soline, (c) the tunnel walls and streets were cleaned 1 week prior to the start of sampling and, in addition, the study analy z ed road dust and determined th at resuspended road dust contributed only about
4% of the e stima te d e mission f a c t or s, ( d ) he a v y

- duty ve hic l e s c o mpr i se d, on a v e r a g e , a r e la tive l y larg e proportion (25.7%) of vehicles using the tunnel, and (e) a larg e number of heavy

- duty vehicles—approx imately 33,000—passed throug h the tunnel dur ing the sampling period, which

g e ne r a te s c onf ide n c e tha t the e mission f a c t or is r e pr e se n ta tive of inte r sta te tr uc ks.
Conside r ing the str e ng ths a nd weaknesses of the available e mission factor data from the tailpipe and tunnel studies, the mean TEQ emi ssion factor reported by Gertler et al. (1996, 1998)—182 pg TEQ DF 

### -W HO 98 

### /km (172 pg I

- TEQ DF 

### /km) —is a ssume d to r e pr e se n t the be st c u r r e nt

e stima te of the a v e r a g e e mission f a c t or f

o r

on- r o a d die se l

- f u e l e d tr uc ks. This e mission f a c t or is
assi g n ed a l o w confi d ence rat i n g because i t m a y not be represent a t i v e of em i ssi on rat e s for t h e entire fleet of diesel-fuel ed trucks under the wide array of driving conditions encountered on the
road.
F o r reference y ear 2000, OAQPS developed national CDD/CDF TEQ emission estimates
for on-hi g h way di esel vehi cl es, off-hi g hway di esel equi pm ent , di esel rai l r oad equi pm ent , and
die se l c o mme r c ia l ma r i ne ve sse ls. F or on-hig hway diesel vehicles, OAQPS combined the
calculated mean emission factor s from Gertler et al. (1996, 1998) with the OAQPS estimate for
VMD. The picog r am-per-kilome ter emission factors were firs t converted to a milig ram-per-mile basis using a conversion factor of 1.61e–09. OAQPS estimated nationa l emissions of 65.4 g TEQ DF 

### -W HO 98 

### (61.7 g I

- TEQ DF 

### ) from on-hig h way diesel-fueled ve hicles for reference y ear 2000.
For al l y ears, t h e em i ssi ons from di esel vehi cl es were assi g n ed a l o w c onfidence rating because

t h e em i ssi on fact ors were assi g n ed a l o w confi d ence rat i n g

. For off-hig hway diesel equipment, OT AQ developed the NONR OAD emissions model to estimate emissions from nonroad (off-road) equi pment ty pes. However, the NONROAD model

4-36

### does not contain emission factors for calculatin g CDD/CDF emissions. To calculate emissions for 2000, OAQPS estimated fuel consumption, as reported by the May 2002 “L ockdown C” draft version of NONROAD, and multiplied th is estimate by an averag e fu el efficiency of 7 miles/g a l
and the emission factor from Gertler et al . (1996, 1998). The NONROAD model does not contain

a c tivity e stima te s f o r

c o mme r c ia l ma r i ne ve sse ls a nd r a ilr oa d e quipme n t. OAQPS developed estimates for c ounty

- level diesel consump tion, in g a llons, for diesel

c o mme r c ia l ma r i ne ve sse ls a nd die se l r a ilr oa d e quipme n t a nd multiplie d the se e stima te s by a n
averag e fuel efficiency of 7 miles/g a l and th e emission factor from Gertler et al. (1996, 1998). The results from using these methodolog ies sug g e st that 22 g TEQ DF 

### -W HO 98 

### (21 g I

- TEQ DF 

### ), 4.3 g TEQ DF 

### -W HO 98 

### (4 g I

- TEQ DF 

### ), and 6.8 g TEQ DF 

### -W HO 98 

### (6.4 g I

- TEQ DF 

### ) we r e e mitte d f r o m of f

hig hway diesel equipment, dies e l c o mme r c ia l ma r i ne ve sse ls, and diesel railroad equipment, respectively

, in reference y ear 2000.
The use of the same emission factors from Gertler et al. (1996, 1998) and an assumption of an averag e fuel economy of 10 km/L re sults in an emission factor of 1.6 pg TEQ DF 

### -W HO 98 

### /km (1.5 pg I

- TEQ DF 

### /km). Apply i ng this factor to the estimate for VKD in 1995 in the United States by diesel-fueled trucks (183 billion km) sug g e sts that 33.3 g TEQ DF 

### -W HO 98 

### (31.5 g I

- TEQ DF 

### )
were emitted from diesel-fueled trucks in 1995. Combining the same emi ssion factors with the estimate derived above for VKD in 1987 by diesel -fueled trucks (153 billion km) sug g e sts that
27.8 g TEQ DF 

### -W HO 98 

### (26.3 g I

- TEQ DF 

### ) were emitted from diesel-fueled trucks in 1987. For 1987 and 1995 off-road diesel emissions, EP A used the emission factor from Gertler et al. (1996, 1998) and multiplied it by an averag e fuel efficiency of 2.98 km/L (U.S. EPA, 2003b)
and a conversion factor of 1.61e–09 g

- km/pg

- mile to obtain e mission factors of 0.51 ng I

TEQ DF 

### /L and 0.54 ng TEQ DF 

### -W HO 98 

### / L

. These em i ssi on fact ors are assi g n ed a l o w confi d ence rating because they possibly are nonrepresentativ e of the source. Multiply ing these emission factors by the 1987 activity factors for o ff-hig hway equipment (17,278.61 million L ) , marine vessels (7,068.35 million L ) , and railroad use (10,801.5 million L ) , EPA estimated the following
emissions for 1987: 8.8 g I

- TEQ DF 

### (9.4 g TEQ DF 

### -W HO 98 

### ) for off-hig hway equipment, 3.6 g I

TEQ DF 

### (3.8 g TEQ DF 

### -W HO 98 

### ) for marine vessels, and 5.5 g I

- TEQ DF 

### (5.8 g TEQ DF 

### -W HO 98 

### ) for
railroad use. Similarly , using the 1995 activ ity factors for off-hig hway equipment (21,409.71
million L ) , marine vessels (8,864.81 million L ) , and railroad use (12,995.91 million L ) , EPA estimated the following emissions for 1995: 11 g I

- TEQ DF 

### (12 g TEQ DF 

### -W HO 98 

### ) for off-hi g hway equipment, 4.5 g I

- TEQ DF 

### (4.8 g TEQ DF 

### -W HO 98 

### ) for marine vessels, and 6.6 g I

- TEQ DF 

### (7 g TEQ DF 

### -W HO 98 

### ) f o r

r a ilr oa d use

. The se e mission e stima te s a r e g i ve n a low c onf ide n c e r a ting because the emission factor may possibl y be nonrepresentative of the source.

4-37

### 4.2. WOOD COMBUSTION
F o r reference y ear 1987, wood energ y consump tion is estimated to have been 2,437 trillion
B r itish thermal units (B tu), or 3.2% of the total pr imary energ y consumed in the United States. I n 1995, wood fuel (including black liquor solids) provided about 2.6% (2,350 trillion B t u) of the total primary energ y consumed (EI A , 1997b). W ood energ y consumption in 2000 is estimated to have been 2,473 trillion B t u, or 2.5% of the total primary energ y consumed (EI A , 2003a). The industrial sector is the larg est consumer of w ood fuel, accounting for 65% of total consumption in 1987, 72% in 1995, and 80% in 2000; the residen tial sector accounted for 35% of total consumption in 1987, 25% in 1995, and 18% in 2000; and the commercial sector accounted for

approx imately 2% of total consumption in all thr ee reference y ears (EI A, 2003a). These energ y consumption estimates appear to include the energ y value of black liquor solids, which are combusted in recovery bo ilers by wood pulp mills. I n 1987, 1995, and 2000, the

energ y values of combusted black liquor so lids were 950, 1,078, and 998 tr illion B t u, respectively (American Paper I n stitute, 1992; American F o re st and Paper Associa tion, 1997; letter dated Aug ust 5, 2002, from W . Gillespie, National Counc il of the Paper I ndustry for Air and Stream
I m provement, to C. Peck, Versar, I n c.). Subtr acting the estimates of black liquor energ y values from the 1987, 1995, and 2000 national totals fo r wood fuel y i elds 1,487, 1,272, and 1,475 trillion
B t u, respectively

. Assuming that 1 kg of ove n-dried wood (2.15 kg of g r een wood) provides

approx imately 19,000 B t u (EI A , 1994), an es timated 78.3, 66.9, and 77.6 milli on metric tons of oven-dried wood equi valents were burned for ener g y purposes in 1987, 1995, and 2000, respectively

. Of these totals, an estimate d 44.8, 31.4, and 23 million metric tons were consumed by the residential sector a nd an estimated 33.2, 32.6, and 51.5 million metric tons were consumed by the industrial sector in 1987, 1995, and 2000, respectively

. The following subsections discuss the resu lts of relevant emission studies for the
residential and industria l sectors and present annual TEQ e mission estimates for reference y e ars 1987, 1995, and 2000.

4.2.1. F l ue Em issions f r om Wood Com bustion (Residential)
Several studies have provided direct measurement of CDDs/CDF s in flue g a s emissions from wood-burning stoves and fireplaces (S chatowitz et al., 1993; Vikelsoe et al., 1993; B r emmer et al., 1994; B r öker et al., 1992; L a unhardt and Thoma, 2000; Environment Canada, 2000). The
fi ndi ng s of each of t h ese st udi es are sum m a ri z e d bel o w.

4.2.1.1. Em issions Data
Schatowitz et al. (1993) measured the C DD/CDF content of flue g a s emissions from several ty pes of wood bur ners used in Switz erland: a house hold stove (6 kW ), automatic chip

4-38

### furnaces (110 to 1,800 kW ), and a wood stick boiler (35 kW ). Emissions were measured from the combustion of a variety of wood fuels (natur al beech wood, natural wood chips, uncoated chipboard chips, and waste wood chips from build ing demolition). The results from the testing of
the household stove are most rele vant for assessing releases fro m residential combustion. The
household stove was tested with the stove door both open and cl osed. The open-door stove can be assumed to be representative of fireplaces because both have an uncontrolle d draft. Althoug h the

cong ener and cong ener g r oup analy tical results were not reported, the fo llowing emission factors (dry weig ht for wood, wet weig ht for household waste) and emission ra tes (corrected to 13%

ox y g en) for the household stoves and furnaces were reported.

Stoves

• O pen-door burning of beech wood sticks: 0.77 ng I

- TEQ DF 

### /kg (0.064 ng I

- TEQ DF 

### /Nm 3 

### )

• C losed-door burning of beech wood sticks: 1.25 ng I

- TEQ DF 

### /kg (0.104 ng I

- TEQ DF 

### /Nm 3 

### )

• C losed-door burning of hous ehold waste: 3,230 ng I

- TEQ DF 

### /kg (114.4 ng I

- TEQ DF 

### /Nm 3 

### )

Furnaces

• N atural wood chips: 0.79 to 2.57 ng I

- TEQ DF 

### /kg

• C hipboard chips (uncoated): 0.29 to 0.91 ng I

- TEQ DF 

### /kg

• W aste wood chips from building demolition: 26 to 173.3 ng I

- TEQ DF 

### /kg

Vikelsoe et al. (1993) studied emissions of CDD/CDF cong ener g r oups from residential
wood stoves in Denmark. The wood fuels used in the ex periments were seasoned birch, beech,

a nd spr u c e , e quilibr a te d to 18% a b solute moistur e

. F our dif f

e r e nt ty pe s of stove s ( i nc luding one

ex perimental stove) were eval uated under both normal and optimal operating c onditions (i.e., well controlled, with carbon monox ide [ C O] emissions as low as possible). Total CDD/CDF emissions varied widely for the 24 fuel/stove ty pe/operating condition co mbinations. Emissions from spruce were about twice as hig h as those from birch and beech. Surprising ly , the optimal

ope r a ting c ondition le d to sig n if ic a n tly hig h e r CDD/CDF emissions for two stove ty pes but not
for the other stoves. The predominant cong en er g r oup for all ex periments was TCDF

. The weig hted averag e emission factor and the flue g a s concentration for wood stoves (considering

4-39

### wood and stove ty pes) we re reported to be 1.9 a nd 0.18 ng Nordic TEQ/Nm 3 

### , respect i v el y

. Because Vi ckel soe et al . di d not m easure cong ener l e vel s , t h e report e d em i ssi on fact or and
emission rate were estima ted by assuming the same cong ener distribution in each cong ener g r oup that had been found for muni cipal waste incinerators.
B r emmer et al. (1994) reported results of testing performed with a cast-iron wood- burning
stove with a combustion chamber lined with fire refractory clay

. Measurements were conducted at three loads (max imum, averag e, and minimum) using clean wood as fuel

. The emission factors

rang ed from 1 to 3.3 ng I

- TEQ DF 

### /kg (averag e of about 2.2 ng I

- TEQ DF 

### / k g )

. Brem m e r et al . al so reported results of testin g conducted with a fireplace of a ty pe that is common in the Netherlands. Measured emission factors from the burning of clean wood rang ed from 13 to 28.5 ng I

- TEQ DF 

### /kg (averag e of about 20 ng I

- TEQ DF 

### /kg )

. The authors noted that th e measured emission factors for fireplaces were considerably hig h er than thos e reported by others (see B r öker et al., 1992, below)
and assi g n ed “g reat uncert a i n t y ” t o t h e em i ssi on fact ors. B r öker et al. (1992) reported re sults of a series of three tests with a wood stove and a fireplace. The averag e, minimum, and max imu m emission factors measured for the wood stove tests rang ed from 0.53 to 0.94 ng I

- TEQ DF 

### / k g

. The g e om et ri c m ean of t h e t wo averag e val u es was 0.71 ng I

- TEQ DF 

### /kg

. The a v e r a g e of the minimum a nd ma x imum e mission f a c t or s me a sur e d f o r the fireplace tests rang ed from 0.2 to 1.06 ng I

- TEQ DF 

### /k g

. The g e om et ri c m ean of t h ese t wo
averag e values is 0.46 ng I

- TEQ DF 

### /kg

. L a unhardt and Thoma (2000) c onducted an investig ation on org a nic pollutants from a domestic heating sy stem using various solid bi ofuels. Tests were c onducted using a multifuel
furnace desi g n ed for dom est i c appl i cat i ons. Tabl e 4-12 shows t h e averag e di ox i n concent r at i on i n the flue g a s for the four fuels used (spruce wood, wheat straw, hay

, and triticale). The concentrations in the flue g a s rang ed from 52 to 891 pg TEQ/m 3



### .

Table 4-12. Average CDD/CDF concentration in f l ue gas w h ile burning w ood and crop s

F u el Con cen trati o n (p g T E Q / m 3 

### ) N um be r of t r ials
Spruce wood 52 7

W h eat straw 656 5
Hay (set-aside land) 891 4

Tri t i cal e (whol e crop) 52 5

So ur c e : La unha r d t a nd T ho m a ( 2000).



### 4-40

### Environment Canada (2000) c onducted a study on the release of diox ins and furans into the atmosphere by residential wood combustors. The study analy z ed two wood stoves believed to be representative of stoves used in Canada: a conventional w ood stove that was popular in the early 1980s and an advanced combustion, noncat aly tic, EPA-certified wood stove. Each stove was tested using hard maple and black spruce wood. Results from the study rang ed from 0.222 to
0.952 ng I

- TEQ/kg wood (see Table 4-13). B ecause th ese tests took place in North America using indig e nous wood, and they included the analy s is of an EPA-certified wood stove, the mean value of the Environment Canada study (0.5 ng I

- TEQ /kg wood) was used to determine the national
emissions estimate for resi dential burning of clean wood in fi replaces and stoves. This emission factor is assig n ed a low confidence rating because it is judg ed to be nonrepresentative of all
residential wood combustion (e.g ., home fireplaces).
Several studies have reported that combustion of treated or manufactured wood in stoves
and fi repl aces can resul t i n si g n i f i cant l y hi g h er C DD/ C DF em i ssi on fact ors. A few researchers (e.g ., Vikelsoe et al., 1993) ha ve reported hig h CDD/CDF emi ssion rates when pentachlorophenol (P CP )-contaminated wood is combusted in resi dential wood stoves and furnaces. The European
I nventory (Quab and F e rmann, 1997) used the results of these studi es to derive best estimates of
CDD/CDF emission factors for combustion of “slig htly contaminated wood (ex c luding PCP)” and
“PCP-contaminated wood”: 50 and 500 ng I

- TEQ DF 

### /kg , respectively

. Althoug h it is likely that
there is some residential combustion of these ty pes of wood in the United States, there are no corresponding activity level data upon which to base a national annual estimate of emissions.

4.2.1.2. A c t i v i t y Level In form at i o n I n 1987, 22.5 million households in the United States burned wood (EI A , 1991). W ood was used as the primary heating fuel in 5 milli on of those households and as a secondary source for aesthetic purposes (i.e., in fireplaces ) in 17.4 million (EI A , 1991, 1997b). L ower numbers were reported for 1995; wood was reported to be used as the primary fuel in only 3.53 million households (EI A , 1997b). More rural, low-in come households consumed wood as a primary heating fuel than did other sectors of the popul ation. The majority of these households used wood-burning stoves as the primary heating a ppliance. Althoug h fireplaces were the most common ty pe of wood-burning equipment in the residential sector, only 7% of fireplace users reported using fireplaces for heating an entire home (EI A , 1991, 1994). Residential wood consumpti on was 852 trillion B t u (44.8 million metric tons), or 35% of total U.S. wood energ y consumption, in 1987 and 596 trillion B t u (31.4 milli on metric tons), or 25% of total U.S. wood energ y consumpti on, in 1995 (EI A , 1997b). An estimated 433 trillion B t u (23 million metric tons) of wood were consumed in residences in 2000 (EI A , 2003a). These production estimates are g i ven hi g h confidence rating s because they are based on recent

g overnment survey data.

4-41Table 4-13.CDD/CDFconcentrations (pg TEQ/kg wood) in emissions fromresidential wood stoves in CanadaU.S.EPA-certifiedConventionalMapleSpruceMapleSpruceRunCongenerRun 1Run 2Run 3Run 1Run 2Run 31Run 2Run 3Run 1Run 2Run 32,3,7,8-TCDD21221425682110916875566370661,2,3,7,8-PeCDD1081381174166573456472739411,2,3,4,7,8-HxCDD211617101814813977101,2,3,6,7,8-HxCDD211617101814813977101,2,3,7,8,9-HxCDD211617101814813977101,2,3,4,6,7,8-HpCDD222122112121OCDD1000000110102,3,7,8-TCDF1291341279547552838362716181,2,3,7,8-PeCDF2224231213176445252,3,4,7,8-PeCDF243371350186149302857866541733



### 4-421,2,3,4,7,8-HxCDF223123121323271110167181,2,3,6,7,8-HxCDF1518208131510864782,3,4,6,7,8-HxCDF171714813107864781,2,3,7,8,9-HxCDF101011813104864781,2,3,4,6,7,8-HpCDF2121222211111,2,3,4,7,8,9-HpCDF211122111011OCDF000000010000TOTAL8481,009997485497628297331269227198238MeanEmissionFactor951537299221Source:EnvironmentCanada(2000).

### OAQPS developed emission estima tes for residential wood combustion from the results of a study by EPA’s Emission F actor and I nventory Group (U.S. EPA, 2001a). The activity data for
residential wood combustion were based on the ty pe of combustion unit, and the activity data for wood stoves and fireplaces with inserts were estimated on the ba sis of total amount of wood consumed in a y ear. OAQPS used 1997 national ac tivity data to ex trapolate an estimate for 1999 by apply i ng a g r owth rate factor based on wood energ y consumption data from the Energ y I n f o r m a tion Administr a tion ( E I A )

. Ac tivity da ta f

o r

f

i r e pla c e s we r e e stima te d on the ba sis of

num ber of hom es i n t h e U.S

. wi t h usabl e fi repl aces, as report e d by t h e U.S

. C e nsus Bureau. OAQPS assumed that the ex tent of wood cons umption in residential combustion units is directly related to ambient te mperature (with more wood cons umption in colder climates).
Historical climate data were used to assig n each U.S. count y to one of five climate z ones, as de f i ne d by the Na tiona l Clima tic Da ta Ce nte r

. Ea c h c lima te zone wa s the n a ssig n e d a pe r c e n ta g e of total national wood cons umption on the basis of information contained in the EI A’s Residential Energ y Consumption database. The consumption in each climate z one was th en allocated to individual counties in that

z one. Each county was desig n ated as urban or ru ral to reflect unit locati on preferences reported in the 1999 American Housing Survey , which estimate d that 68% of fireplaces are found in urban areas, compared with 32% in rural areas. An estimated 69% of wood st oves are found in rural areas, compared with 31% in urban areas. F i replaces with inserts were ev enly split between urban
and rural areas. I n each z one, the total urba n and rural county wood consumption was summed and an adjustment was made with in the z one for each county ’ s cons umption if the urban and rural
totals did not match the ex pected percentag e . Th ese steps resulted in final cordwood consumption by county , which was converted to tons of wood consumed using a conversion factor of one cord of wood equaling 1.163 tons.
W ood consumption estimates for stoves and fireplaces with inserts were further categ oriz ed to account for the different desig n s of units that ex ist in the marketplace. Different desig ns of stoves and inse rts have been found to have different levels of emissions. According to data received from the Hearth P r oducts Association, the three prima ry ty pes of units currently in use are noncertified (92% of the stoves manufactured), certified non cat al y t i c (5.7%), and cert i f i e d cataly tic (2.3%). These proportions were applie d to the national, state, and county cordwood

c onsumption e stima te s pr ior to the a pplic a tion of e mission f a c t or s.

4-43

### Ac tivity le ve ls we r e e stima te d to be a s f o llows:

Ac tivity le ve l W ood combustion categ ory ( million me tr ic tons/y r ) Fireplaces 2.79 Fireplaces with inserts, certified cataly tic 0.92 Fireplaces with inserts, certified noncataly tic 0.47 Fireplaces with inserts, noncertified 7.64 Noncataly tic wood stoves 0.26 Cataly tic wood stoves 0.64 Conventional wood stoves 10.60

4.2.1.3. Em ission Estim ates
The emission factor used to determine national emission estima tes (0.5 ng I

- TEQ/kg wood) was obtained from Environm ent Canada (2000) because it was the most comprehensive and recent study

. Combining this emission factor with the mass of wood consumed in residences in 1987, 1995, and 2000 y i elds annual TEQ air emissi ons from this source of approx imately 22, 15.7, and 11.3 g I

- TEQ DF 

### , r e spe c tive l y

. The se e stima te s a r e g i ve n a low c onf ide n c e r a ting f o r

a l l

y ears because t h e em i ssi on fact or was j udg ed t o be of l o w confi d ence.

4.2.2. Stac k Em issions f r om Wood Com bustion (Industr ial)
4.2.2.1. Em issions Data Cong ener-specific measurements of CDDs/CDF s in st ack emissions from industrial woodburning furnaces were measured by CARB at four facilities in 1988 (CARB , 1990b, c, d, e).
Measurements of CDD/CDF cong ener g r oups and 2,3,7,8-TCDD and 2,3,7,8-TCDF were reported for one facility by EPA (U.S. EPA, 1987a ). The National Council of the Paper I ndustry
for Air and Stream I m provement (NCASI ) presen t e d cong ener-speci fi c em i ssi on fact ors for fi ve boilers tested during burns of bark and wood residue (NCASI , 1995). The averag e cong enerspecific emission factors derived from the four CARB and five NC AS I st udi es are present e d i n Table 4-14. Averag e cong ener and cong ener g r oup profiles are presented in F i g u re 4-5a for the
four CARB studies and in F i g ure 4-5b for the five NCASI studies.
CARB (1990b) measured CDDs/CDF s in the emissions from a quad- cell wood-fired boiler used to g e nerate electricity

. The fuel c onsisted of coarse wood waste and sawdust from nonindustrial log g i ng operations. The ex haust g a ses passed throug h a multicy c lone before entering the stack. F r om this study , the aver a g e TEQ e mission f a c t or f

or

tota l CDDs/CDF s wa s calculated to be 0.64 ng I

- TEQ DF 

### /kg of wood burned.

4-44Table 4-14.CDD/CDFmean emission factors (ng/kg wood) for industrial wood combustors



### 4-45Congener/congener groupFourfacilities testedbyCARBFivefacilities testedbyNCASINinefacilities testedbyCARBandNCASINondetect set tozeroNondetect set to1⁄2detectionlimitNondetectset to zeroNondetect set to1⁄2detectionlimitNondetect set tozeroNondetect set to1⁄2detectionlimit2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD0.0070.0440.0420.0860.0790.9026.0260.0160.0540.0550.0960.1320.9056.0260.0660.110.1790.1910.5220.6351.3170.0680.1120.1830.1930.5240.6371.3170.040.0790.1150.1380.3210.7453.3290.0460.0840.1230.1430.3420.7480.3292,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF0.6730.790.7410.7610.9410.3430.452.5080.261.5870.6730.790.7410.7680.9410.350.4912.7490.3441.590.7070.1450.1590.1080.0710.0640.0150.0720.0170.0490.7190.1490.1640.1110.0730.0670.0170.0740.020.060.6840.4060.3890.3750.4180.1780.1921.0620.1130.6740.690.4090.3920.3790.4190.1830.2091.1550.1520.681Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF0.1511.0391.7482.9366.0264.2759.757.4283.7471.5880.1541.0391.7482.9366.0264.2759.757.4283.9881.591.6281.9581.7921.121.3174.5321.5480.5360.1110.0491.6291.981.7961.1321.3174.5521.5490.5430.1160.060.9691.5211.6631.8213.3294.3534.933.3161.580.6740.971.5331.6651.8230.3294.3644.933.321.6740.681Total I-TEQDFTotal TEQDF-WHO980.820.840.850.870.40.460.410.470.560.60.580.62TotalCDD/CDF38.6938.9314.5914.6724.1621.29CARB=CaliforniaAirResourcesBoardNCASI = National Council for Air and StreamImprovementSources:CARB(1990b, c, d, e);NCASI (1995).R a t i o (m ea n c o

ngene r gr ou p em i s s i on f a c t o r /t o t a l C D D / C D F em i s s i on f a c t o r )
0 0 .0 5 0 .1 0 .1 5 0 .2 0 .2 5

TC D D

PeC D D

Hx CD D

HpC D D

OC D D

TC D F

PeC D F

Hx CD F

HpC D F

OC D F



### F i gure 4-5a. Congener and congener gr oup prof iles f or air em issions f r om indust r ial wood c o m bust o r s (nondetects set equal to z e ro).

S o u r ces : C A R B (1990b, c, d, e)



### .



### 4-46 0 .3Rat i o (m ea n c on g ener g r o u p e m i s s i on f a c t or/t o t a l CD D / CDF e m i s s i on f a c t or)
0 0. 0 5 0. 1 0. 1 5 0. 2 0. 2 5

TC DD

Pe CD D

HxC D D

Hp C D D

OC D D

TC D F

Pe CD F

HxC D F

Hp C D F

OC D F



### F i g u re 4

- 5 b

. C o n g en er a n d co n g en er g ro u p p ro f iles f o r a i r em issio n s f ro m b l ea ch ed K ra f t m ill b a rk co m b u s to rs (n on d etects set eq u al to zero)

.

S o u rce: N C A S I (1995).



### 4-47 0. 3

### I n the second study (CARB , 1990d), CDDs/CDF s in the emissions from two spreaderstoke r wood- f i r e d boile r s ope r a te d in pa r a lle l by a n e l e c t r i c utility f

o r

g e ne r a ting e l e c t r i c ity we r e

m easured. The ex haust g a s st ream from each boi l e r was passed t h roug h a dedi cat ed ES P
, aft e r whic h the g a s str e a m s we r e c o mbine d a nd e mitte d to the a tmosphe r e thr oug h a c o mmon sta c k.
Stack tests were conducted when the facility burned fuels allowed by ex isting permits and when it
burned a mix ture of permitted fuel supplemented by urban wood waste at a ratio of 7:3. F r om this

study , the averag e TEQ emission factor for to tal CDDs/CDF s was calculated to be 0.82 ng I TEQ DF 

### /kg of wood burned.

I n the third study (CARB , 1990e), CDDs/CDF s in the emissions from twin fluidiz e d-bed combustors desig ned to burn wood chips for the g e neration of electricity we re measured. The air pollution c ontr o l de vic e ( A PCD) sy ste m c onsiste d of a mmonia inje c tion f o r

c ontr o lling nitr og e n

ox ide s a nd a multic y c lone a nd ESP f o r

c ontr o lling PM. Dur i ng te sting

, the f a c ility bur ne d wood

wa ste s a nd a g r i c u ltur a l wa ste s a llowe d by e x isting pe r mits. F r om this study , the a v e r a g e TEQ
emission factor for total CDDs/CDF s was calculated to be 1.32 ng I

- TEQ DF 

### /kg of wood burned.
I n the fourth study (CARB , 1990f), CDDs/C DF s in the emissions from a quad-cell woodfired boiler were measured. During testing

, the fuel consisted of wood chips and bark. The flue

g a se s pa sse d thr oug h a multic y c lone a nd a n ESP be f o r e e n te r i ng the sta c k. F r om this study , the

averag e TEQ emission factor for total C DDs/CDF s was calculated to be 0.5 ng I

- TEQ DF 

### /kg of
wood burned.
NCASI (1995) presented stack e mission test results for five boilers burning bark or wood

r e sidue s. One of the se f a c ilitie s, whic h wa s e quippe d with a multic y c lone , nor ma lly bur ne d ba r k
in c o mbina tion with sludg e a nd c o a l

. Anothe r f

a c ility , whic h wa s e quippe d with a n ESP,

nor ma lly f

i r e d pulve r i ze d c o a l

. The othe r thr e e f a c ilitie s we r e spr e a d e r

- stoke r s e quippe d with multicy c lones or ESPs. Althoug h stack g a s flow rates were obtained durin g these tests, accurate
measurements of the amounts of bark and wood fi red were not made and had to be estimated from steam production rates. The averag e TEQ emi ssion factor for these facilities was 0.46 ng TEQ DF 

### WH O 98 

### /kg (0.4 ng I

- TEQ DF 

### /kg of feed).
The mean of the emission factors derived fro m the four CARB studies and five NCASI studies—0.6 ng TEQ DF 

### -W HO 98 

### /kg wood (0.56 ng I

- TEQ DF 

### /kg wood), assuming nondetect values

were z e ro—is used in this document as the mo st representative of i ndustrial wood combustion. This emission factor was assig ned a medium c onfi d ence rat i n g

. However, t h ese m ean em i ssi on factors may not be appr opriate for the combustion of waste wood containing elevated chlorine

content. NCASI (1995) concl uded that CDD/CDF emissions fro m facilities burni ng salt-laden wood residue may be considerab ly hig her than those from f acilities burning salt-free wood. Umweltbundesamt (1996) re ported the results of stack g a s testing at approx imately 30 facilities of vary ing desig n ty pe s burning various ty pes of wood fuel. The author noted that

4-48

### CDD/CDF emissions were elevat ed when the combustion conditi ons were poor, as evidenced by elevated CO emissions, or when the fuel cont ained elevated chlorine levels. Umweltbundesamt

at t r i but ed t h e correl a t i on bet ween el evat ed C DD/ C DF em i ssi ons and el evat ed chl o ri ne cont ent of
the fuel to the fire-retardant effects of chlori ne, which may have inhib ited complete combustion.
The chlorine content of untreated wood and bark were reported as 0.001 to 0.01% by weig ht and
0.01 to 0.02% by weig ht, respectively

. Chipboard can contain up to 0.2% chlorine by weig ht because of the binding ag ents used to manufact ure the chipboard. P r eservative-treated wood and PVC-coated wood were reported to contain chlorine contents as hig h as 1.2 and 0.3% by weig ht, respect i v el y

. The facility tested by EPA in 1987 (U.S. EP A, 1987a) was located at a lumber products plant that manufactured overlay panels and other lumber wood pr oducts. Nearly all the wood fed to the lumber plant had been stored in sea wa ter adjacent to the facility and therefore had a sig nificant concentration of inorg a nic chloride

. The wood-fired boiler tested was a three-cell dutch oven equipped with a waste heat boiler. The feed wood was a mix ture of bark, hog g e d wood, and g r een and dry planer shaving s

. The ex haust g a ses from the boiler passed throug h a

c y c l one a nd f a br ic f ilte r ( F F ) pr ior to disc ha r g e f r o m the sta c k. F r om this study , a n a v e r a g e emission factor for total CDDs/CDF s of 1,020 ng /kg wood burned (rang e, 552 to 1,410 ng /kg ) was reported for the three collected samples. An averag e TEQ emission factor of 17.1 ng
I

- TEQ DF 

### /kg wood burned (rang e, 7.34 to 22.8 ng /kg ) was estimated by EPA using measured

cong ener g r oup concentrations and concen trations of 2,3,7,8-TCDD and 2,3,7,8-TCDF

. Similar emission factors were reported by L u the et al . (1998) from testing conducted during the 1990s at four Canadian coastal, salt-laden wood-fueled bo ilers—1.4, 2.6, 17.4, and 27.6 ng I

- TEQ DF 

### /kg
wood combusted. The overall averag e of the five tested fac ilities in Canada and th e United States was 13.2

ng I

- TEQ DF 

### /kg of wood combusted. The confidence rating assig ned to this emission factor is low because it is based on reporting of limited cong ener data at one U. S. facility and testing at four
non-U.S. sources and because the fraction of sa lt-laden wood combusted acr oss facilities is likely to have been hig h ly variable.
F o r reference y ear 2000, NCASI provided c ong ener-specific estimates of CDD/CDF releases from the pulp and paper industry

, incl uding emissions from wood residue-fired boilers (letter dated Aug ust 5, 2002, from W . Gillespie, Nationa l Council of the Paper I ndustry for Air
and Stream I m provement, to C. P eck, Versar, I n c.). The e mission factors were taken from
“NCASI Handbook of Chemical Specific I n form ation for SARA (Superfund Amendments and
Reauthoriz ation Act) Section 313 F o rm R Reporting

. ” The fact ors provided in the handbook were

c o mpile d f r o m va lid te st da ta supplie d to NCAS I by a variety of s ources, including NCASI member companies that had performed the tests in response to a reg u latory prog ram. Data from

4-49

### 11 bark and wood residue-fired boilers used by the forest products industry we re used to calculate
an emissions estimate. Concentrations of e missions from the wood residue-fired boilers were
0.017 : 

### g TEQ DF 

### -W HO 98 

### /ton wood (see Table 4-15).

Table 4-15. NCASI CDD/CDF TEQ concentrations a nd em issions f o r w ood resi d u e -f i red b o i l ers

C o n g en er Wo o d -f ired b o iler em issio n s Wo o d -f ired b o iler a s h n o t la n d f illed (7 2 % o f to ta l a s h la n d f illed ) TEQ DF 

### -WH O 98 

### co n cen tra t io n s (m ed ia n μg /to n ) E m issio n s ( n g/ yr ) TEQ

co n cen tra t io n s (n g / kg ) E m issio n s ( n g/ yr )
2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD 1,2,3,4,6,7,8,9- OCDD 0 0 0 4.00e

! 

### 04 5.00e

! 

### 04 1.05e

! 

### 03 5.69e

! 

### 04 0 0 0 1.68e + 0 7 2.10e + 0 7 4.41e + 0 7 2.39e + 0 7 1.84e + 0 0 1.73e + 0 0 3.25e

! 

### 01 4.28e

! 

### 01 2.60e

! 

### 01 4.01e

! 

### 01 1.90e

! 

### 02 3.06e + 08 2.88e + 08 5.41e + 07 7.12e + 07 4.33e + 07 6.71e + 07 3.96e + 06
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF 1,2,3,4,6,7,8,9- OCDF 4.40e

! 

### 03 7.50e

! 

### 04 5.00e

! 

### 03 9.00e

! 

### 04 7.00e

! 

### 04 2.10e

! 

### 03 9.00e

! 

### 04 2.80e

! 

### 04 1.10e

! 

### 04 2.10e

! 

### 05 1.85e + 0 8 3.15e + 0 7 2.10e + 0 8 3.78e + 0 7 2.94e + 0 7 8.82e + 0 7 3.78e + 0 7 1.18e + 0 7 4.62e + 0 6 8.82e + 0 5 4.20e + 0 0 3.35e

! 

### 01 3.23e + 0 0 2.21e

! 

### 01 1.60e

! 

### 01 5.40e

! 

### 02 3.80e

! 

### 02 4.10e

! 

### 03 1.30e

! 

### 03 5.40e

! 

### 04 7.06e + 08 5.56e + 07 5.37e + 08 3.68e + 07 2.66e + 07 8.98e + 06 6.32e + 06 6.82e + 05 2.16e + 05 1.64e + 05

TOTAL 1 .72e

! 

### 02 7.42e + 0 8 1 .32e + 0 1 6 .19e + 0 8 (ash n o t lan d filled )

2.21e + 09 (ash lan d filled )
NC A S I = Nation a l C o u n c il f o r A i r an d S t ream Im prov em en t

So ur c e : Le t t e r d a t e d A ugust 5
, 2002, f r om W. Gilles p ie, Nation a l C o u n c il of th e P a per In du s t ry f o r A i r an d Stream Im prov em en t, to C . P eck , Vers ar, In c.



### 4.2.2.2. A c t i v i t y Level In form at i o n I n 1987, 33.2 million metric tons of wood were burned for fuel in industrial furnaces. I n 1995, industrial wood consumption totaled 32.6 million metric tons

. EI A (2003b) estimated that industrial wood consumption to taled 1988 trillion B t u (104.6 million me tric tons) in 2000. This

4-50

### total becomes 51.5 million metric t ons with the removal of kraf t black liquor combustion. The majority of wood fuel consumed in the industria l sector consists of wood waste (chips, bark, sawdust, and hog g e d fuel). Consumption in the i ndustrial sector is dominated by two industries: paper and allied pr oducts and lumber and wood products (EI A , 1994). These activity level estimates are assig n ed a hig h confidence ratin g because they are based on recent g overnment
survey data.

Activity level data on combus tion of salt-laden wood are not normally collected, even thoug h the associated emission fact or is g r eater than the factor associated with nonsalt-laden
wood. Nonetheless, attempts ha ve been made to estimate this activity level. NCASI combined the results from a 1995 survey of combustion units in the pulp and paper industry with those from an ad hoc telephone survey of mills in the Paci fic Northwest (Oreg on and W a shing t on) to produce
a conservative estimate of the amount of salt-laden wood burned at U.S. pulp and paper mills in
1995: 254,000 metric tons (0.8% of the estimated 32.6 million metric tons of industrial wood consumed that y ear). NCASI suspected that a similar fraction of industrial wood combusted in 1987 by pulp and paper mills was salt laden (letter dated October 8, 1998, from W. Gillespie, National Council of the Paper I ndus try for Air and Stream I m prove ment, to G. Schweer, Versar,
In c

. )

. F o r purposes of the NCASI survey , salt-lade n wood was defined as wood that had been transported, stored, or otherwise ex posed to saltwater prior to be ing processed as fuel. None of the three responding mills in Oreg on reported the use of salt-laden wood. Eig h t of the 13 responding mills in W a shing t on reported some com bustion of salt-laden w ood. Of the total wood
consumed in the W a shing t on mills, 17% was estimated to be salt-laden wood. As noted above, the majority of industr ial wood combustion (97%) occurs in two
industries: the paper and allie d products industry and the lumb er and wood products industry

. The relative amount of wood combusted by each of these two industries was the same in 1990 and 1992, the only y ears for which these statistics ar e readily available (EI A , 1991, 1994). I t can be assumed that the percentag e of total wood combusted nationally by the lumber and wood products industry that is salt laden is th e same percentag e as for the paper and allied products industry

, 0.8%; therefore, the total percenta g e of wood combusted by industr y that is salt laden is 1.6%.
F o r reference y ears 1987, 1995, and 2000, this e quates to 0.5, 0.5, and 0.8 million metric tons,

r e spe c tive l y

. The se a c tivity le ve l e stima te s a r e a ssig n e d a low c onf ide n c e r a ting be c a use the y a r e possibly nonrepresentative of th e activity levels for the sour ce categ ory combusting salt-laden
wood.

4.2.2.3. Em ission Estim ates Appl y i ng t h e averag e TEQ em i ssi on fact or from the four CARB and five NCASI studies (0.6 ng TEQ DF 

### -W HO 98 

### /kg wood [ 0.56 ng I

- TEQ DF 

### /kg wood] ) to the estimated quantities of nonsalt-laden wood burned by i ndustrial facilities in 1987 (33.2 million metric tons), 1995 (32.6

4-51

### million metric tons), and 2000 (51.5 million metric tons) y i elds estima ted TEQ emissions to air of
19.9 g TEQ DF 

### -W HO 98 

### (18.6 g I

- TEQ DF 

### ) in 1987, 19.6 g TEQ DF 

### -W HO 98 

### (18.3 g I

- TEQ DF 

### ) in 1995, and 30.9 g TEQ DF 

### -W HO 98 

### (28.8 g I

- TEQ) in 2000. Appl y i ng t h e averag e TEQ em i ssi on fact or from the five studies on boilers combusting salt-laden wood (13.2 ng I

- TEQ DF 

### /kg wood) to the estimated quan tities of salt-la den wood burned by industrial facilities in 1987 (0.5 million metric tons), 1995 ( 0.5 million metric tons), and 2000 (0.8 million metric tons) y i elds estimate d TEQ emissions to air of 6.6 g I

- TEQ DF 

### in both 1987 and 1995 and 10.6 g I

- TEQ DF 

### in 2000. Total emissions for 1987, 1995, and 2000 are estimated to have been 26.5, 26.2, and 41.5

g TEQ DF 

### -W HO 98 

### (25.2, 24.9, and 39.4 g I

- TEQ DF 

### ), respectively

. Of the 2000 estimate, NCASI estimated that 0.74 g TEQ DF 

### -W HO 98 

### /y r of diox ins were emitted from pulp and paper wood-fired boilers (letter dated Aug ust 5, 2002, from W . Gille spie, National Council of the Paper I ndustry for
Air and Stream I m provement, to C. Peck, Versar, I n c.). As noted above, the total emissions are
based on tests conducted at nine facilities in two i ndustries that account for 97% of total industrial
wood fuel combustion. The remaining 3% of i ndustrial combustion and the combustion of wood by the c o mme r c ia l se c t or ( f o r

whic h no r e lia ble a c tivity le ve l e stima te s a r e a v a ila ble ) ma y not be well represented by the emission factors used a bove, particularly if poor ly controlled combustors or treated wood (e.g ., treated with PCP or pl astics) are burned. The emission estimates for 1987, 1995, and 2000 are g i ven a low confidence level because the activity level estimates were
assi g n ed a l o w confi d ence rat i n g

.

4.2.3. Solid Waste f r om Wood Com bustion (Re side n tial and Industr ial)
The measurement of CDDs/CDF s in chimn ey soot and bottom ash from wood-burning stoves and fireplaces has been re ported by several researchers (B umb et al., 1980; Nestrick and
L a mparski, 1982, 1983; Clement et al., 1985; B ach er et al., 1992; Van Oostam and W a rd, 1995; and Dumler-Gradl et al., 1995).
B u mb et al. (1980) detect ed TCDDs (nondetect to 0.4 : 

### g / kg ), Hx CDDs (0.2 to 3 : 

### g/ k g)
, HpCDDs (0.7 to 16 : 

### g / kg ), and OCDD (0.9 to 25 : 

### g / kg ) in residues from the wall of a home fireplace and from the firebrick of another home fireplace; for lack of a suitabl e analy tical method,
anal y s i s was not perform ed for P e C DDs. Nei t h er of t h e fi repl aces sam p l e d by Bum b et al . had burned preservative-treated wood.
Nestrick and L a mparski (1982, 1983) ex panded th e research of B u mb et al. by conducting

a survey of CDD concentrations in chimney s oot from residential wood- burning units in three
rural areas of t h e Uni t e d S t at es. S a m p l e s were col l ect ed from t h e base of si x chi m n ey s i n each of the three study areas. Samples were not coll ected from units where any ty pe of treated or
manufactured wood had been burned. F o r lack of a suitable analy tical method, analy s is was not performed for PeCDDs. The results of this su rvey are summariz e d in Table 4-16. There was

4-52

### Table 4-16. CDD/CDF concentr ations (ng/kg) in residen tial chim ney soot f r om

w ood stoves and f i replaces

U.S. Ca na dia n Ca na dia n Co ng ener/

co ng ener g r o u p U.S. east reg io n a U.S. w e st reg io n a centra l reg io n a Germ a n f a rm ho use b w ood st ov e c Ca na dia n f i repla ce c w ood st ov e d

2,3,7,8- T C D D 1,2,3,7,8- P e CD D 1,2,3,4,7,8- H x CD D 1,2,3,6,7,8- H x CD D 1,2,3,7,8,9- H x CD D 1,2,3,4,6,7,8- H p CD D OCDD 66 NR 250 e 250 e 208 1,143 2,033 13.3 NR 522 e 522 e 282 1,653 2,227 66 NR 1,831 e 1,831 e 1,450 6,160 13,761 150 70 35 60 30 90 90 NR NR NR NR NR NR NR NR NR NR NR NR NR NR N D ( 12) 70 N D ( 10) 625 281 948 530

2,3,7,8- T C D F 1,2,3,7,8- P e CD F 2,3,4,7,8- P e CD F 1,2,3,4,7,8- H x CD F 1,2,3,6,7,8- H x CD F 1,2,3,7,8,9- H x CD F 2,3,4,6,7,8- H x CD F 1,2,3,4,6,7,8- H p CD F 1,2,3,4,7,8,9- H p CD F OCDF NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR 930 560 590 330 400

70 200 490

40 70 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR 235 58 68 51 57

8 24 97 20 41

T o t a l 2,3,7,8- CD D 3,950 5,219 21,437 525 NR NR 2,454 T o t a l 2,3,7,8- CD F NR NR NR 3,680 NR NR 659 T o tal I

- T E Q Df $ 150 $ 165 $ 286 720 NR NR 211 T o tal T E Q DF -WHO 98 $ 98 $ 163 $ 81 355 NR NR 246

T o tal T C DD T o tal PeCDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal PeCDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF 1,987 NR 2,183 2,104 2,033 NR NR NR NR NR 269 NR 4,273 3,243 2,227 NR NR NR NR NR 1,511 NR 14,243 12,603 13,761 NR NR NR NR NR 3,900 880 600 200

90 13,400

6,100 3,200

720

70 N D ( 10) N D ( 10) N D ( 50) 100 200 N D ( 10) N D ( 10) N D ( 50) N D ( 50) N D ( 50) ND (1 0 ) 500 1,700

500 400 300 1,400 1,700

400 100 11 608 3,450 1,550

530 1,010

948 482 154 41

T o t a l CD D / CD F 8 ,307 10,012 42,118 29,160 300 7,000 8,784

a Sour ce: Nestr i ck and L a m p ar sk i ( 1982, 1983) ; m ean v a lues listed, six sam p les collected in each r e g i on. b S our c e : Ba c h e r e t

a l . ( 1992)

.
c S our c e : Cl e m e n t e t

a l . ( 1985)

. d S our c e : V a n O o st da m a nd W a r d ( 1995) ; m e a n of t w o sa m p l e s, nonde t e c t v a l u e s a s sum e d t o be z e r o.

e A n a l y t i c a l m e t hod c oul d not di st i n g u i s h be t w e e n c ong e n e r s; l i s t e d v a l u e i s t h e sum of bot h c ong e n e r s.

N D = N o t de t e c t e d ( v a l ue i n pa r e nt he si s i s t h e r e por t e d de t e c t i on l i m i t ) NR = No t rep o r ted



### 4-53

### wide variation in the results acr oss soot samples, with standard deviations for cong eners and

cong ener g r oups often equal to or ex ceeding the m ean value; however, CDDs in each cong ener g r oup

we r e de te c t e d in the soot f r o m a lmost a ll sa mple d units. The authors concluded that the results did not appear to present any easily discernible pa tterns with respect to g e og raphic reg i on, furnace operational parameters , or wood fuel ty pe. They attri buted the wide variability observed to differences in desig n of the units, which affected the sa mpling point or the c onditions a t the sa mpling point, and possible contamination of the fuel wood. Clement et al. (1985) analy z ed chimney soot and bottom ash from re sidential wood stoves
and fi repl aces i n C a nada. The C DD/ C DF cong ener concent r at i ons are present e d i n Tabl e 4-16 (soot ) and Table 4-17 (bottom ash). CDD/CDF cong eners we re detected in all sa mples analy z ed, althoug h the relative amounts of the different cong ener g r oups varied considerably and inconsistently between wood-burning unit ty pes and between ash a nd soot samples from the same unit.

Table 4-17. CDD/CDF concentrations (n g/kg) in bottom ash f r om residential

w ood stoves and f i replaces

C o n g en er/co n g en er gr oup Canadi an w ood

s t ove as h Canadi an w ood

s t ove as h Canadi an

w ood s t ove as h Canadi an f i rep la ce a s h

T o tal T C D D T o tal P e C D D T o tal H x C D D T o tal H p C D D T o tal O C D D T o tal T C D F T o tal P e C D F T o tal H x C D F T o tal H p C D F T o tal O C D F ND ( 10) ND ( 10) ND ( 50) 300 2,600 9,100 2,200 1,000

700 ND ( 50) 100 3,000 10,000

1,200

900 400 4,600 9,300 1,000

100 100 200 700 500 100 100 200 500 300 ND ( 50) ND ( 10) ND ( 10) 300 2,000 3,100 ND ( 10) ND ( 10) 100 400 100

To t a l CDD/ CDF 15,900 30,600 2,700 6,000

a N o v a l u es w e re report e d f o r i n di v i du al con g e n e rs or f o r t o t a l 2,3,7,8- C D D
, 2,3,7,8- C D F
, or t o t a l T E Q

.

ND = No t d e tected (v alu e in p a ren t h e sis is th e rep o r ted d e tectio n lim it)

S o u r ce: C l em en t et

al . (1985).



### Cle m e n t e t a l . a l so pr e se n te d tota l CDD/CDF c onc e n tr a tion da ta f

o r

bottom a sh f r o m open-air burning of wood. No analy s es were repor ted for individual cong eners. The results for the cong ener g r oups are shown below. The quan tity of ash produced by the open-air burning test

wa s not pr ovide d; he nc e , it is not possible to r e a d ily de te r mine the qua ntitie s of CDDs/CDF s disposed of.

4-54

### Cong ener g r oup Concentration (μg / kg ) TC DDs 0.8 P e C DDs 4.2 Hx C DDs 7.2 HpC DDs 11 OC DD 10 TCDF s 2.2 PeCDF s 7.6 Hx CDF s 8.2 HpC DFs 11 OC DF 1.7

B acher et al. (1992) characteriz ed the fu ll spectrum (mono throug h octa substitution) of
CDD/CDF and B DD/B D F cong eners in the soot from an old farmhouse in southern Germany

. The chimney carried smoke from an oven that ha d used untreated wood at the rate of about
5 m 3 

### /y r for more than 10 y r

. The sample was taken during the annual cleaning by a chimney

sweep. The only B D F detected was mono-B D F (230 ng /kg )

. No B DDs, B C DDs, or B C DF s were detected at a DL of 20 ng /kg

. The results for the te tr a

- thr oug h oc ta

- C DDs/CDF s a r e pr e se n te d in
Table 4-16. The results indicat e that CDFs ex ceeded the CDDs in each cong ener g r oup ex cept

octa. Also, the lower-chlorinated cong ener g r oups ex ceeded the hig h e r-chlorinated cong ener
g r oups for both the CDDs and the CDF s

. The TEQ content of the chimney soot was 755 ng TEQ DF 

### -W HO 98 

### /kg (720 ng I

- TEQ DF 

### /kg ) , of which less than 30% was due to CDDs.
Van Oostdam and W a rd (1995) analy z ed soot from two wood stoves in B r itish Columbia,
Canada. The averag e TEQ concentration was 246 ng TEQ DF 

### -W HO 98 

### /kg (211 ng I

- TEQ DF 

### /kg )

. The cong ener-specific results are presented in Table 4-16. The soot from a wood stove burning
salt-laden wood in a coastal ar ea was found to have an I

- TEQ DF 

### content of 7,706 ng I

- TEQ DF 

### /kg

, or 20 to 90 times more than the concentrations f ound in the soot from the other two tested stoves. Dumler-Gradl et al. (1995) analy z ed chimney soot samples collected by chimney sweeps from 188 residences in B a varia, Germany

. Th e summary results of the survey , the larg est published survey of its kind to date, are presente d in Table 4-18. As in Nestrick and L a mparski (1982, 1983) and Clement et al. (1985), CDDs/CDF s we re detected in all sa mples; however, there

wa s wide va r i a b ility in tota l TEQ c onc e n tr a tions within a nd a c r oss unit ty pe /f ue l ty pe

c o mbina tions.
The W a shing t on State Department of Ecol og y (1998) reported C DD/CDF cong ener data
f

o r

a sh f r o m hog f u e l boile r s a t thr e e pa pe r mills. The da ta we r e c o mpile d a nd e v a l ua te d to
determine total I

- TEQ con centrations and loading

. Nondetect values were included as z e ro, onehalf the DL , or at the DL

. The results, assumin g nondetect values are at z e ro, are shown below.

4-55

### Table 4-18. CDD/CDF concentrations in chim ney soot (Bavaria, G erm any)

U n it ty p e F u el ty p e N u m b er o f

sa m p les C o n cen tra tio n ( ng I

- TEQ DF 

### /kg )

Mi ni m um M e a n M ax i m um

Ov e n Wo o d 33 10.4 2 ,015 15,849

Ti l e d s t o v e Wo o d 39 4 3 ,453 42,048

He a t i n g s y s t e m Wo o d 9 16.9 1 ,438 20,450

Ov e n Wo o d / c o a l 2 7 77.3 2 ,772 10,065

Ti l e d s t o v e Wo o d / c o a l 5 53.1 549 4,911

O v en W ood

, wood /coal,
waste 5 116.3 6 ,587 10,652

S o u r ce: D u m l er- G radl et al . (1995).



### I

- TEQ DF 

### I

- TEQ DF 

### L o c a tion Ty pe of residual (ng / kg ) (m g / day ) Dai s howa Am eri ca,

Port Ang e les M ix ed ash 0.31 0.012 F t . J a mes F ly ash 35.4 0.544 Ray onier F ilter ash 12,640 68.9 Vacuum filter and g r ate 1,150 6.27 F ilter ash 2,299 12.5 F l y ash 225 1.23

Pohlandt and Marutz ky (1994) presented CDD/CDF concentra tion data for various ty pes of ash (bottom, furnace, boiler, and fly ) from 12 wood-burning boilers. The fly ash samples from two wood-working industry boilers appeared to ha ve the g r eatest concentrations of CDDs/CDF s. Tabl e 4-19 l i s t s t h e averag e cong ener concent r a tion f o r

the two boile r s. Thr e e boile r bottom a sh samples contained detectable amounts of only total HpCDDs /HpCDF s and OCDD/OCDF

. All the other boiler samples were from boilers that burned copper/ chrome/boron-impreg n ated woods. These samples had total TEQs (a ssumed to be I

- TEQs) rang ing from 0.07 to 89 ppt, the hig hest being for the fly ash samples (52 and 89 ppt). The quantities produced by the boilers that were

te ste d we r e not r e por te d; he nc e , it is not possible to r e a d ily de te r mine the qua ntitie s of
CDDs/CDF s disposed of. The results of analy s es of two ash sa mples from wood-burning facilities in New Hampshire were reported in a facsimile dated J a nuary 23, 2001, from Andrew Carpenter, Resource Manag e ment, I nc., to St ephen Schwartz , Versar, I n c. B o th sa mple s we r e f r o m the

4-56

### Table 4-19. CDD/CDF concentrations (n g/kg) in f l y ash f r om w ood-w orking indust r y

C o n g en er/co n g en er g ro u p Ave r age

co n cen tra t io n I -T E Q DF 

### TEQ DF 

### -WH O 98 

### 2,3,7,8- TCDD T o tal T C D D <1 5 1,730 <1 5

– <1 5

– 1,2,3,7,8- Pe CDD T o tal P e C D D 100 1,250 50

– 100

– 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD T o tal H x C D D 130 150 140 750 13 15 14

– 13 15 14

– 1,2,3,4,6,7,8- HpCDD T o tal H p C D D 280 470 3

– 3

– To t a l OCCD 300 0.3 0 .03
2,3,7,8- TCDF T o tal T C D F 130 1,300 13

– 13

– 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF T o tal P e C D F 100 120 790 5 60

– 5 60

– 1,2,3,4,7,8- HxCDF 1,2,3,7,8,9- HxCDF 1,2,3,6,7,8- HxCDF T o tal H x C D F 40 40 <1 0 150 4 4 <1

– 4 4 <1

– 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF T o tal H p C D F 320 <1 0 570 3 <0

. 1

– 3 <0

. 1

– To t a l OCDF 60 0.06 0.006

Es t i m a t e d TEQ 89–90 89–90

S o u rce: Poh l an dt an d Maru t z k y (1994).



### burning of clean (i.e., untreated) wood chips, sawdust, and bark. Th e first sample was a combination of fly ash and bottom ash. The second sample was fly ash only , but it was a combination of fly ash from two wood-burning bo ilers. F o r the first sample, none of the 2,3,7,8­ substituted cong eners were detected at DL s that rang ed from 0.98 ng /kg for 2,3,7,8-TCDD and 2,3,7,8-TCDF to 9.8 ng /kg for OCDD and OCDF

. (A ll other cong eners had a DL of 4.9 ng /kg

. )
F o r the second sample, all but two cong eners were below DL s (which rang ed from 0.379 to 0.831

ng /kg )

. The two cong eners that ex ceeded DL s were OCDD, at 1.261 ng /kg

, and 1,2,3,4,6,7,8­ HpCDF , at 1.022 ng /kg

. F or this sample, a ssuming that the nondetected cong eners were not

4-57

### present , t h e I

- TEQ DF 

### concentration was 0.011 ng /kg

. The quantities of the ash produced were not reported.
I n a CARB report of emissions from a wood waste-fired incinera tor (CARB , 1990b), data

are g i ven for CDDs and CDF s for four ash sa mples. The concentra tions of 2,3,7,8-substituted
C DD/ C DF cong eners for each of t hose four t e st s were al l bel o w t h e DL s ex cept for OC DD, whi c h was detected in three samples at concentra tions of 14, 18, and 32 ng /kg , and 2,3,7,8-TCDF , which was detected in one sample at a concentration of 2.2 ng /kg

. The DL s for each CDD and CDF

cong ener rang ed from 0.63 ppt (for 2,3,7,8-TCDD) to 9.5 ppt (for HpCDF cong eners). Total
C DD and C DF val u es were g i ven for each of t h e f our sam p l e s. However, t hose val u es assum e d that nondetected cong eners were at the DL leve l. Consequently , the total CDD and total CDF values were biased hig h. The averag e of the four total CDD values was 28.8 ng /kg (rang e, 20.3 to 44 ng /kg )

. The averag e of the four total CD F values was 21.9 ng /kg (rang e, 16 to 26.9 ng /kg )

. I n CARB (1990d), data are presented for C DDs/CDF s for several sa mples of ESP waste
ash from a wood-fired boiler. The report provi de s sa mple r e sults f o r

2 we e k s of sa mpling conducted at the facility

. During the first week, the boiler burned fuels that were allowed by the facility permit; during the second week, the boiler burned a mix tu re containing 70% permitted
fuel and 30% urban wood wastes. F o r the six samp les collected over the 3 day s of the first week,

many of the concentrations of CDD/CDF cong en ers in the ESP ash were below the DL s. The reported CDD concentrations in ESP waste ash rang ed from 24 to 264 ng /kg , and the CDF concentrations rang ed from 12 to 151 ng /kg

. However, those values assumed that nondetected

cong eners were present at the de tection level. One sample did not have any nondetect values for
CDDs. The total CDD concentration for this sample was 264 ng /kg , or about 11.4 ng /kg TEQ DF 

### WH O 98 

### (8.3 ng /kg I

- TEQ DF 

### ). The TEQ DF 

### -W HO 98 

### and I

- TEQ DF 

### CDF c onc e n tr a tions f o r

this sample were both less than 1.5 ng /kg

. These va lues were less than 1 ng /kg for the other five samples. All of the samples had some nondetects for the CDF analy s is.
Six samples were also collected over 3 day s during the second week of sampling

, when the 70/30 permitted/urban wood waste mix was burned. F or the samp les from the second week, the
CDD concentrations in ESP waste ash ra ng ed from 1,365 to 3,190 ng /kg , and the CDF concentrations rang ed from 2,866 to 11,282 ng /kg

. The study authors assumed that nondetected

c ong e n e r s we r e pr e se n t a t the de te c tion le ve l; howe v e r , this is a r e a sona ble e stima te f o r

this da ta set because there was only one nondetect value. Table 4-20 presents the averag e cong ener concentrations for these samples. The report did not present quantities of ESP ash produced by
the boile r ; the r e f or e , it is not possible to r e a d ily de te r mine the qua ntitie s of CDDs/CDF s dispose d
of.

4-58

### Tab l e 4-20. CDD/CDF con cen tration s (n g/k g ) in electrostatic p recip i tator w a ste ash fr om wood- f ir e d indust r ial boile r

Con g en er/ con g en er grou p Average

con cen trati o n I -T E Q DF 

### TEQ DF 

### -WH O 98 

### 2,3,7,8- TCDD T o tal T C D D 17.85 239 17.85

– 17.85

– 1,2,3,7,8- Pe CDD T o tal P e C D D 30.67 226.83 15.33

– 30.67

– 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD T o tal H x C D D 20.33 26.33 23.33 300 2.03 2.63 2.33

– 2.03 2.63 2.33

– 1,2,3,4,6,7,8- HpCDD T o tal H p C D D 325 706.67 3.25

– 3.25

– To t a l OCDD 786.67 0.79 0.08

To t a l CDD 2 ,439.17 44.22 58.85
2,3,7,8- TCDF T o tal T C D F 285 2,713.33 28.5

– 28.5

– 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF T o tal P e C D F 154.5 641.67 2,666.67 7.73 320.83

– 7.73 320.83

– 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF T o tal H x C D F 244.83 179.67 296.67 7.28 1,520 24.48 17.97 29.67

0.73

– 24.48 17.97 29.67

0.73

– 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF T o tal H p C D F T o tal O C D F 147.67 21.33 248.33

48.33 1.48 0.21

– 0.05 1.48 0.21

– 0

To t a l CDF 7 ,196.67 431.64 431.6

Es t i m a t e d TEQ 475.64 490.44

S o u rce: C A R B (1990d).



### Appendix I I in L uthe et al. (1998) shows TEQ concentrations (assumed to be I

- TEQ DF 

### ) i n ashes collected from APCDs from “salt- laden” wood steam boilers. The I

- TEQ DF 

### content of ashes from three of the primary multiclone hoppe rs varied sig nificantly : 0.0978, 0.186, and 9.375

4-59

### μg /kg

. Two samples of ash were taken from the secondary multiclone hoppers. The secondary
multic lone r e move s dust f r o m the pr ima r y multic lone e missions; the r e f or e , the a sh is f i ne r tha n

primary dust. The I

- TEQ DF 

### values for the ash samples were 1.073 and 20.879 μg /kg

. The I TEQ DF 

### values for two samples taken from the ESP that collected dust from the secondary multiclone emissions, which th erefore was finer than multic lone dust, were 3.926 and 8.044

μ g / k g

. No dat a were g i ven for i ndi vi dual cong en ers. I n fact , because t h e reference di scusses onl y

“ diox i ns,” it is unc le a r whe t he r the TEQ da ta a r e f or

CDDs or f

or

CDDs plus CDF s. Qua ntitie s of collected ash were not g i ven. Table I I in a report by L u the et al. (1996) pres ents data for the “TEQ s” (assumed to be I

TEQs) on particulates from a secondary collecti on device for boilers at four paper mills burning
salt-laden wood. Eig ht da ta points were g i ven (two for each mill), the averag e of which was 3.6

μg /kg

. The rang e of values was 1.3 to 8 μg /kg

. As in L u the et al. (1998), no data were g i ven for individual cong eners. I t is also unclear whethe r the TEQ data were for CDDs or for CDDs plus
CDF s. Qua ntitie s of c olle c t e d a sh we r e not g i ve n. Table 5-16 in the National Diox in Survey (U .S. EPA, 1987a) contains data indicating that
the bottom ash from wood combustion from one source (it is not indicated whether it was a boiler) contained 140 ng /kg of 2,3,7,8-TCDD, 138,200 ng /kg of CDDs, and 7,400 ng /kg of CDF s

. F or a second wood combustion source, the ash containe d no detectable 2,3,7,8-TCDD, but it did contain about 125 ng /kg of CDDs and nonde tectable levels of CDF s

. The F F dust from the second source contained 100 ng /kg of 2,3,7,8-TCDD, 1,143,600 ng /k g of CDDs, and 315,600 ng /kg of CDF s

. Spe c i f i c da ta f

o r

c ong e n e r s a nd f o r

a sh/dust qua ntitie s we r e not g i ve n. NCASI also provided information on emissions from wood residue boiler ash for reference

y ear 2000 (letter dated Aug u st 5, 2002, from W

. G illespie, National Council of the Paper I ndustry
for Air and Stream I m provement, to C. Peck, Ve rsar, I nc.). As with the boiler emissions,
emission factors for the boiler ash were ta ken from “NCASI Handbook of Chemical Specific
I nformation for SARA Section 313 F orm R Re porting

. ” Total TEQ concentrations were estimated to be 13.2 ng /kg

. B ecause 72% of the total ash produced is landfilled, emission estimates were 2.21 g TEQ DF 

### -W HO 98 

### /y r for ash landfilled and 0.62 g / y r for ash not landfilled (see Table 4-15). I t is not known at this time whethe r the amount of diox in in nonlandfilled ash results
i n an envi ronm ent a l rel ease. Therefore, this value was not included in the inventory

.

4.3. OIL COMBUSTION
The two ma jor c a t e g or ie s of f

u e l oils tha t a r e bur ne d by c o mbustion sour c e s a r e distilla te oils a nd r e sidua l oils. The se oils a r e f u r t he r disting u ishe d by g r a d e : numbe r s 1 a nd 2 a r e distilla te

4-60

### oils, 5 a nd 6 a r e r e sidua l oils, a nd 4 is e ithe r distilla te oil or a

mix tur e of distilla te a nd r e sidua l
oils. Number 6 fuel oil is sometimes referred to as B unker C. Distillate o ils are more volatile and
less viscous than residual oils. Th ey have neg lig ible nitrog en a nd ash content and usually contain less than 0.3% sulfur (by weig ht ). Distillate oils are used mainly in domestic and small

c o mme r c ia l a pplic a tions. The he a v ie r r e sidua l oils ( 5 a nd 6) , be ing mor e visc ous a nd le ss vola tile than distillate oils, must be heated for ease of handling and to fac ilitate proper atomiz ation.
B ecause residual oils are produced from the residue after the lig hter fractions (g asoline, kerosene,

a nd distilla te oils) a r e r e move d f r o m the c r ude oil, the y ma y c onta i n sig n if ic a n t qua ntitie s of a sh, nitrog en, and sulfur. Re sidual oils are used mainly in u tility , industrial, a nd larg e commercial applications (U.S. EPA, 1995a).

4.3.1. Institutional/Com m ercial a nd Residential Oil Com b ustion
No te sting inf o r m a tion on the CDD/CDF c onte n t of a i r e missions f r o m institutiona l/

c o mme r c ia l or r e side ntia l oil- f i r e d c o mbustion units in the United States could be located. However, EPA (U.S. EPA, 1997a) estimated CDD/CDF cong ener g r oup and TEQ emission
f

a c t or s using a v e r a g e CDD/CDF c onc e n tr a tions r e por te d f o r

soot sa mple s f r o m 21 distilla te f u e l
oil-fired furnaces used fo r central heating in Canada and a pa rticulate emission factor for distillate fuel oil combustors (300 mg /L oil) obtained from AP-42 (U.S. EPA, 1995a). The TEQ emission
factor estimate in U.S. EPA (1997a) was derived using the cal culated emission factors for 2,3,7,8­ TCDD, 2,3,7,8-TCDF , and the 10 cong ener g r oups. Thes e emission factors are presented in Table 4-21 and the cong ener g r oup profile is presented in F i g u re 4-6.
F o r reference y ear 1987, assuming a barrel of o il contains 42 g a llons, distillate fuel oil
sales to the residential sect or and the commercial sector totaled 28.1 billion L (177 million barrels) and 16.2 billion L (102 million barrels), re spectively (EI A , 1999). Residual oil sales to
the commercial sector in 1987 totaled 6.7 billion L (42 million ba rrels) (EI A , 1999). Using the emission factor presented in Table 4-21 (150 pg I

- TEQ DF 

### /L oil combusted [ 190 pg TEQ DF 

### WH O 98 

### /L oil combusted] ), EPA estimated that 4.22 g I

- TEQ DF 

### (5.35 g TEQ DF 

### -W HO 98 

### ) were
emitted in 1987 for the residential sector. F o r the institutional/commercia l sector, EPA estimated TEQ emissions of 1.34 g I

- TEQ DF 

### (1.54 g TEQ DF 

### -W HO 98 

### ) for residual oil and 3.24 g I

- TEQ DF 

### (3.73 g TEQ DF 

### -W HO 98 

### ) for distillate oil for 1987, using an emission factor of 200 pg I

- TEQ DF 

### /L oil combusted (230 pg TEQ DF 

### -W HO 98 

### /L oil combusted) (see S e ction 4.3.2). B ecause the representativeness of the emi ssion factor to 1987 emissions is uncertain and may not be

r e pr e se n ta tive

, this e stima te is a ssig n e d a low c onf ide n c e r a ting

.

4-61

### Table 4-21. Estim ated CDD/CDF em ission f a ctors f o r oil- f i red residential f

u rn aces

C o n g en er/

co n g en er g ro u p Me an f a cility

em issio n

fa c t o r ( p g/ L oi l ) WHO- TEF E m issio n fa c t o r ( p g

TEQ DF 

### ­ WHO 98 

### /L

o il) I-T E F Em i s s i on fa c t o r ( p g I

- TEQ DF 

### /L

o il)
2,3,7,8- TCDD T o tal P e C D D T o tal H x C D D T o tal H p C D D OCDD 56 82 66 63 66 1 1 0.1 0.01 0.0001 56 82

7 1 0 1 0.5 0.1 0.01 0.001 56 41

7 1 0
2,3,7,8- TCDF T o tal P e C D F T o tal H x C D F T o tal H p C D F OCDF 53 420 170

73 30 0.1 0.05 0.1 0.01 0.0001 5 21 17

1 0 0.1 0.05 0.1 0.01 0.001 5 21 17

1 0

TOTAL 190 149

S o u rce: U

. S

. EPA (1997a).



### F o r reference y ear 1995, a low confidence es timate of potential na tional TEQ emissions from this source categ ory was made using the sa me emission factors as for the 1987 estimates.
Distillate fuel oil sales to th e residential and co mmercial sector tota led 26.2 and 13.5 billion L

, respectively

, in 1995 (EI A , 1997a). Apply i ng the respective emission factors to these fuel oil
sales estimates results in es timated emissions of 3.93 g I

- TEQ DF 

### (4.98 g TEQ DF 

### -W HO 98 

### ) for t h e residential sector and 2.7 g I

- TEQ DF 

### (3.11 g TEQ DF 

### -W HO 98 

### ) f o r

the institutiona l/c omme r c ia l
sector in 1995. Residual oil sales to the co mmercial sector in 1995 totaled 3.7 billion L (23 million barrels) (EI A , 1999). Apply i ng the emission factor of 200 pg I

- TEQ DF 

### /L oil c o mbuste d (230 pg TEQ DF 

### -W HO 98 

### /L oil combusted) (see Section 4.3.2) y i elds TEQ emissions of 0.73 g I TEQ DF 

### (0.84 g TEQ DF 

### -W HO 98 

### ) for residual oil in 1995.
F o r reference y ear 2000, EPA/OAQPS develope d national emission es timates for residual
oil a nd distilla te oil c onsume d in institutiona l/c omme r c ia l he a ting a nd distilla te oil c onsume d in residential heating

. EPA used state-level 2000 activity data (EI A , 1999), which were allocated to ­

4-62

### F i gure 4-6. Congener group prof ile f o r ai r em i ssi on s f r om resi d en ti al oi l

- f u el ed f u rn aces.

S o u rce: U

. S

. EPA (1995b).



### counties by the 1999 y ear county

- to-state proportion of employ me nt for numerous SI C codes, as
identified in the U.S. Census B ureau’s 2000 censu s. EPA estimated that 2.82 billion L of residual
oil and 12.7 billion L of distillate oil were consumed in institu tional/commercial heating in 2000. Apply i ng the emission factor of 200 pg I

- TEQ DF 

### /L oil combusted (230 pg TEQ DF 

### -W HO 98 

### /L oil combusted) (see Section 4.3.2) to these activity levels y i elds TEQ emissions of 0.56 g I

- TEQ DF 

### (0.65 g TEQ DF 

### -W HO 98 

### ) for residual oil and 2.53 g I

- TEQ DF 

### (2.92 g TEQ DF 

### -W HO 98 

### ) f o r

distilla te oil for 2000. EPA/OAQPS estimated that 23.9 billion L of distillate oil were consumed for residential heating in 2000. Using the emission factors discussed above from U.S. EPA (1997a), EPA/OAQPS estimated emissions of 3.59 g I

- TEQ DF 

### (4.54 g TEQ DF 

### -W HO 98 

### ) f r o m distilla te oil used for residential heating in 2000.

4-63

### 4.3.2. Utility Se c t or and Industr ial Oil Com bustion
Pr e limina r y CDD/CDF e mission f a c t or s we r e r e por te d f o r

oil- f i r e d utility boile r s using the
results of boiler tests conducted over several y ears (U.S. EPA, 1997a). The data are for a

com posi t e of vari ous furnace confi g urat i ons and AP C D sy st em s. Tabl e 4-22 l i s t s t h e m e di an emission factors presented by EPA. The cong ener and cong ener g r oup profiles based on these data are presented in F i g u re 4-7. The median I

- TEQ DF 

### emission factor was reported to be 366 pg TEQ DF 

### -W HO 98 

### /L (314 pg I

- TEQ DF 

### /L ) oil burned.
I n 1993, the Electric Power Research I n stitute (EPRI ) sponsored a project to g a ther
inf o r m a tion of c onsiste nt qua lity on powe r pla n t e missions. The F i e l d Che mic a l Emissions Measurement (F CEM) project included testing of two cold-sided, ESP-equipped, oil-fired power plants for CDD/CDF emissions (EPRI , 1994). The averag es of the cong ener and cong ener g r oup emission factors reported for th ese two facilities are presented in Table 4-22. The averag e TEQ emission factor was 93.6 pg TEQ DF 

### -W HO 98 

### /L (83.1 pg I

- TEQ DF 

### /L ) oil burned when nondetect
val u es were t r eat ed as z e ro. The TEQ emission factors reported by EPRI (1994) were less than the median TEQ emission factor reported by EPA by a factor of 3 to 4 (U.S. EPA, 1997a). F o r purposes of this

assessm ent , t h e EP A m e di an and EP R I m ean e m i ssi on fact ors were averag ed, for an em i ssi on factor of 230 pg TEQ DF 

### -W HO 98 

### /L (200 pg I

- TEQ DF 

### /L ). Althoug h the estimated emission factors
are assumed to be the current be st estimates for utility /industrial o il burning , they are assig n ed a
low c onf ide nc e r a ting

. Residual fuel oil sales to taled 77.3 billion L in 1987 and 46.6 billion L in 1995 (EI A
, 1992, 1997a). Vessel bunkering was th e larg est consumer (48% of sales), followed by electric
utilities and the industrial sector

. A hig h confidence rating is assig n ed to these production
estimates. Application of the TEQ emission factor of 230 pg TEQ DF 

### -W HO 98 

### /L (200 pg I

TEQ DF 

### /L ) to these residual fuel oil sales resu lts in estimated TEQ emissions of 17.8 g TEQ DF 

### WH O 98 

### (15.5 g I

- TEQ DF 

### ) for 1987 and 10.7 g TEQ DF 

### -W HO 98 

### (9.3 g I

- TEQ DF 

### ) for 1995.
F o r reference y ear 2000, OAQPS developed na tional emission estimate s for residual and distillate oil consumption for the industrial s ector. OAQPS used stat e-level 2000 activity data (EI A , 2003a), which were allocated to coun ties by the 1999 county

- to-state proportion of employ ment for numerous SI C codes, as iden tified by the 2000 census. OAQPS estimated that
7.33 billion L of residual oil and 31.5 billion L of di stillate oil were consum ed in the industrial
sector in 2000. OAQPS combined these national ac tivity levels with the emission factor of 230

pg TEQ DF 

### -W HO 98 

### /L (200 pg I

- TEQ DF 

### /L ) to estimate 2000 TEQ emissions of 1.69 g TEQ DF 

### WH O 98 

### (1.47 g I

- TEQ DF 

### ) from residual oil consumption and 7.25 g TEQ DF 

### -W HO 98



### 4-64

### Table 4-22. CDD/CDF em ission f actors (pg/ L oil) f o r oil-f i red utility/industrial b o i l ers

C o n g en er/co n g en er g ro u p U.S. EPA ( 1997a)

me d i a n

em issio n f a cto r a,b 

### EPRI ( 1994) m e an e m i s s i on f a c t or a,c



### N o n d e tect set to

zero N o n d e tect set to 1⁄2 d e tectio n lim it

2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 117 104 215

97 149 359 413 0 24.7 63.3 65.8 79.7 477 2,055 26.6 43.1 108

79.3 102 546 2,141

2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 83 77 86 109

68 104

86 169 179 179 0 64.1 49.3 76.5 35.4

0 23.8 164 0 0 35.7 73.9 59.6 94.9 45.2 37.7 42.2 218 137 139

To t a l 2,3,7,8- CDD To t a l 2,3,7,8- CDF To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 1,454 1,140

314.6 366.1 2,765.5 413.1

83.1 93.6 3,046 883.2 147.4 166.9

T o tal T C D D T o tal P e C D D T o tal H x C D D T o tal H p C D D T o tal O C D D T o tal T C D F T o tal P e C D F T o tal H x C D F T o tal H p C D F T o tal O C D F 102 104 145 359 413

90 131 172

27 179 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR

To t a l CDD/ CDF 1 ,722 NR NR

a A s s u m e s a den s i t y f o r res i du al f u el oi l of 0.87 k g / L

. b Nu m b er o f f

acilities n o t rep o r ted

.
c Bas e d on t w o col d

- s i d ed pow er pl an t s eq u i p p e d w ith electro static p r ecip itato rs.

NR = No t rep o r ted



### 4-65

### F i gu re 4-7. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om indust r ial oil- fue le d boile r s .

S o u rce: U

. S

. EPA (1995b; 1997a).



### 4-66

### (6.3 g I

- TEQ DF 

### ) from distillate oil combustion. Emissi on estimates for all re ference y ears are

a ssig n e d a low c onf ide n c e r a ting on the ba sis of the low r a ting f o r

the e mission f a c t or

.

4.3.3. Used Oil Com bustion
The emission factors derived by EPA (U.S. EPA, 1997a) and EPRI (1994) were based on

c o mbustion of vir g in oil by utility boile r s. Sig n if ic a n tly g r e a t e r e mission f a c t or s ha ve be e n reported by B r emmer et al. (1994) for combustion of used oil by smaller combustion units in the
Netherlands. F l ue g a ses from a g a ra g e stove consisting of an atomiz er fueled by spent lubricating oil from diesel eng i nes (35 mg Cl

! 

### /kg ) were reported to contain 0.1 ng I

- TEQ DF 

### /Nm 3 

### (2,000 pg I

TEQ DF 

### /kg ) oil burned. The flue g a ses from a hot wa te r boile r c onsisting of a rotary cup burner fueled with the org a nic phase of rinse water from oil tanks (340 mg Cl

! 

### /kg ) contained 0.2 ng
I

- TEQ DF 

### /Nm 3 

### (4,800 pg I

- TEQ DF 

### /kg ) oil burned. The flue g a ses from a steam boiler consisting of a rotary cup burner fueled by processed spent oil (240 mg Cl

! 

### /kg ) contained 0.3 ng I

- TEQ DF 

### /Nm 3 

### (6,000 pg I

- TEQ DF 

### /kg ) oil burned. The emission factor for a ferry burning heavy fuel oil containing 11 ng /kg org a nic chlorine was 3,200 to 6,500 pg I

- TEQ DF 

### /kg oil burned. F r om these data, B r emmer et al. derived an averag e emission factor for combustion of used oil of 4,000 pg I

TEQ DF 

### /kg oil burned.

B r emmer et al. (1994) also reported measur ing CDD/CDF emissions from a river barg e and a container ship fueled with g a s oil (less th an 2 ng /kg org a nic chlorine). The ex haust g a ses contained from 0.002 to 0.2 ng I

- TEQ DF 

### /Nm 3 

### . F r om these data, B r emmer et al. derived an averag e emission factor for inland oil -fueled vessels of 1,000 pg I

- TEQ DF 

### /kg oil burned.
The a pplic a b ility of the se e mission f a c t or s to use d oil c o mbustor s in the Unite d Sta t e s is

unc e r ta in. The r e f or e , e stima te s of pote n tia l e missions f r o m use d oil c o mbustion in the Unite d
Sta t e s a r e not be ing de ve lope d a t this time

.

4.4. COAL COMBUSTION During 2000, coal consumption accounted for approx imately 18.9% of the energ y consumed in the United States from all sources (EI A , 1999). Of the 980 million metric tons of coal consumed in 2000, 891 million metric tons (90.9%) were consumed by electric utilities, including independent power pr oducers; 85.4 million metric tons ( 8.7%) were consumed by the industrial sector, including 26.2 million metric tons consumed by coke plants; and 3.7 million metric tons (0.4%) were cons umed by residential and co mmercial sources (EI A , 1999).
I n 1995, coal consumption (872 million metric tons) accounted for approx imately 22% of the energ y consumed from all sources in the Un ited States (U.S. DOC, 1997). Of this total,

4-67

### 88.4% (771 million metric tons) were consumed by electric utilities; 11% ( 96 million metric tons) were consumed by the industrial sector, including consumption of 30 million metric tons by coke plants; and 0.6% (5.3 million metric tons) were consumed by residential and commercial sources (EI A , 1997b).
I n 1987 a total of 759 million metric tons of co al were consumed by electric utilities (651 million metric tons), coke plan ts (33.5 million metric tons), ot her industries (68.2 million metric tons), and the residential and commercial sectors (6.3 milli on metric tons) (EI A , 1995).
All of the above estimates are a ssig n ed a hig h confidence rating because they are based on
det a i l e d st udi es speci fi c t o t h e Uni t e d S t at es. The following two sections discuss the resu lts of relevant emission studies for the utility /industrial and reside ntial sectors and present annual TEQ emission estimate s for reference

y ears 1987, 1995, and 2000.

4.4.1. Utilitie s and Industr ial Boile r s F e w studies have been perform ed t o m easure C DD/ C DF concen trations in emissions from coal-fired plants. Those studies did not have the cong ener specifi c ity or DL s ne c e ssa r y to f u lly
characteriz e this potential s ource (U.S. EPA, 1987a; NATO, 1988; W i enecke et al., 1992). The results of more recent testing of coal-fired utility and industrial boile rs in the Netherlands (B remmer et al., 1994), the United King dom (Cains and Dy ke, 1994; CRE, 1994), Germany (Umweltbundesamt, 1996), and the Un ited States (Rig g s et al., 1995; EPRI , 1994) have achieved
lower DL s. B r emmer et al. (1994) reported the results of emission meas urements at two coal-fired
f

a c ilitie s in the Ne the r la nds. The e mission f a c t or r e por te d f o r

a

pulve r i ze d c o a l e l e c t r i c powe r plant equipped with an ESP and a wet sc rubber for sulfur removal was 0.35 ng I

- TEQ DF 

### / k g coal combusted (0.02 ng I

- TEQ DF 

### /Nm 3 

### at 11% ox y g en). The emission factor reported for a g r assdry i ng chain g r ate stoker equipped w ith a cy clone APCD was 1.6 ng I

- TEQ DF 

### /kg coal fired (0.16

ng I

- TEQ DF 

### /Nm 3 

### at 11% ox y g en). Cains and Dy ke (1994) reported an e mission factor of 102 to 109 ng I

- TEQ DF 

### / k g of coal at

a

sma ll- sc a l e f a c ility in the Unite d King dom tha t wa s e quippe d with a n APCD c onsisting of only

a g r it arrester. CRE (1994) repor ted results of testing at 13 commercial and indus trial coal-fired boilers in the United King dom, with TEQ e mission factors rang ing from 0.04 to 4.8 ng I TEQ DF 

### /kg coal combusted (mean value, 0.6 ng I

- TEQ DF 

### /kg )

. CRE a l so r e por te d te sting r e sults f o r one coal-fired power plant: 0.06 ng I

- TEQ DF 

### /kg of coal combusted. Umweltbundesamt (1996) reported that the I

- TEQ DF 

### c onte n t of sta c k g a se s f r o m 16 c o a l

- bur ning f a c ilitie s in Ge r m a n y

4-68 ­

### rang ed from 0.0001 to 0.04 ng I

- TEQ DF 

### /m 3 

### ; however, the data provide d in that report did not
enabl e em i ssi on fact ors t o be cal cul a t e d.
I n 1993, the U.S. Department of Energ y (DOE ) sponsored a project to assess emissions of
haz a rdous air pollutants at coal -fired power plants. As part of the project, CDD/CDF stack

e missions we r e me a sur e d a t se ve n U.S. c o a l

- f i r e d powe r pla n ts. The pr e limina r y r e sults of the project, concentrations in stack emissions, we re reported by Rig g s et al. (1995) and are
summariz e d in Table 4-23. The levels reported for individua l 2,3,7,8-substituted cong eners were ty

pically very low (less th an or equal to 0.033 ng /Nm 3 

### ) or not detected. I n g e neral, CDF levels were hig h er than CDD levels. OCDF and 2,3,7,8-TCDF were the most frequently detected

cong eners (at four of the seven pl ant s ). Tabl e 4-24 present s charact eri s t i c s of t h e fuel used and

t h e AP C D em pl oy ed at each pl ant

. R i g g s et al . coul d not at t r i but e vari at i ons i n em i ssi ons bet ween pl ant s t o any speci fi c fuel or operat i onal charact eri s t i c

. As mentioned in Section 4.3.2, EPRI sponsored the F C EM project to g a ther information
of

c onsiste nt qua lity on powe r pla n t e missions. Te sting f o r

CDD/CDF e missions wa s pe r f o r m e d on four coal-fired power plants equipped with cold-sided ESPs. Two plants burned bituminous
coal and two burned sub-bituminous coal. The results of the testing were integ r ated into the final results of the DOE project di scussed above (Rig g s et al., 1995) and published in 1994 (EPRI

, 1994). The averag e cong ener and cong ener g r oup emission factors deri ved from this 11-facility data set, as reported in EPRI (1994), are presented in Tabl e 4-25. Cong ener and cong ener g r oup profiles for the data set are pres ented in F i g ure 4-8. Assuming nondetect values were z e ro, the

averag e emission factor was 0.078 ng TEQ DF 

### -W HO 98 

### /kg (0.079 ng I

- TEQ DF 

### /kg ) coal combusted.
A me dium c onf ide n c e r a ting is a ssig n e d to th e emission factors derived from the DOE and EPRI

st udi es because t h ey were based on recent t e st i n g at U.S

. power pl ant s

. Because t h e EP R I and DOE dat a charact eri z ed em i ssi ons from uni t s wi t h onl y col d -si d ed ESPs, the r e ha s be e n unc e r ta inty r e g a r d ing the a pplic a b ility of the e mission f a c t or s de r i ve d f r o m these data to units with hot-sided ESPs. I n J uly 1999, EPA conducted te sting of stack emissions

a t a c o a l

- f i r e d utility e quippe d with a hot- side d ESP. The pr e limina r y r e sults of this te sting
i ndi cat ed t h at t h e TEQ em i ssi on f actor for hot-sided ESPs is of the same order of mag n itude as the averag e TEQ emission factors derived above.

4-69Table 4-23.CDD/CDFconcentrations (pg/Nm3) in stack emissions fromU.S. coal-fired power plants



### 4-70Congener/congener groupPlant1Plant2Plant3Plant4Plant5Plant6Plant72,3,7,8-TCDDND (3.5)ND (3.5)1ND (2)ND (3.3)ND (2.6)ND (1.7)1,2,3,7,8-PeCDDND (0.56)ND (4.8)ND (1.8)ND (10)ND (4.7)ND (3.2)ND (1.8)1,2,3,4,7,8-HxCDDND (0.56)ND (5.7)ND (3.6)ND (10)ND(15.4)ND (2.7)ND (2)1,2,3,6,7,8-HxCDDND (0.44)5ND (1.8)ND (10)ND (9.9)ND (4.2)ND (1.4)1,2,3,7,8,9-HxCDDND (0.56)4.9ND (1.8)ND (10)ND(12.1)ND (4.3)ND (1.2)1,2,3,4,6,7,8-HpCDDND (1.7)29ND (1.8)ND (10)ND (26.4)4.32.4OCDDND (12)32ND (14)ND (20)ND(131)2021.62,3,7,8-TCDFND (1.7)8.17.8ND (2)ND (3.3)130.71,2,3,7,8-PeCDFND (1)ND (5.7)7.2ND (10)ND (3.2)ND (5.7)ND (1.1)2,3,4,7,8-PeCDF2.4ND (19)6.6ND (10)ND (3.2)ND (4.8)ND (1.4)1,2,3,4,7,8-HxCDF3.3168.4ND (10)ND(16.4)ND (5.1)ND (1.8)1,2,3,6,7,8-HxCDF1.1ND (5)2.9ND (10)ND (5.8)ND (4)ND (1.3)1,2,3,7,8,9-HxCDFND (0.44)11ND (1.8)ND (10)ND (8.8)ND (6.9)ND (1.5)2,3,4,6,7,8-HxCDFND (2)ND (4.2)3ND (10)ND(16.4)ND (2.5)ND (2)1,2,3,4,6,7,8-HpCDF2296ND (10)ND (23)ND (30)ND (2.2)1,2,3,4,7,8,9-HpCDFND (0.63)ND (6.1)ND (3.6)ND (10)ND(15.4)ND (5)ND (2.1)OCDF5.6332.4ND (20)ND(131)ND (19)11.4Total2,3,7,8-CDD070.910024.324Total2,3,7,8-CDF14.497.144.3001312.1Total TCDD1.81212NR6.7ND (2.6)ND (55)Total PeCDDND (1)4.46ND (10)ND (4.7)ND (3.2)ND (32)Total HxCDD1.3182.7ND (10)ND(26.3)ND (4)ND (24)Total HpCDD3.445ND (2.4)ND (10)ND(26.4)ND (14)ND (8.1)Total OCDDND (12)32ND (14)ND (20)ND(131)2021.6Total TCDFND (5.2)2978ND (2)ND (3.3)88ND (37)Total PeCDF5.43361ND (10)ND (6.6)143Total HxCDF7.63929ND (10)ND(16.4)ND (5)ND (27)Total HpCDF4.3349ND (10)ND(29.5)ND (20)2.9Total OCDF5.6332.4ND (20)ND(131)ND (19)11.4TotalCDD/CDF29.4279.4200.106.712238.9ND = Not detected; value inparenthesis is the detectionlimitNR= Not reported; suspected contaminationproblemSource:Riggsetal. (1995).

### Table 4-24. Characteristics of U.S. coal-f ired pow er plants tested by the U.S. Dep a rtm e n t of E n ergy

Pl ant no. C oal t y pe C o a l ch lo rin e

co n t en t (m g / kg ) T em p era tu re (°C ) a


### ESP FF FGD St ac k

1 B i t um i no us 800 160 – – 160

2 B i t um i no us 1,400 130 – – 130

3 S ub- bi t um i no us 300 – 150 – 150

4 S ub- bi t um i no us 390 – 70 130 75

5 B i t um i no us 1,400 130 – 120 40

6 L i g ni t e 400 170 – 170 110

7 B i t um i no us 1,000 150 – – 150

a T e m p eratu r e at pollu tion con t rol dev i ce an d s t ack

.

ESP = Electro static p r ecip itato r FF = Fab r ic f ilter FG D = Fl ue ga s d e sul f ur i z a t i o n sy st e m

S o u r ce: R i g g s et al . (1995).



### Apply i ng the TEQ emission factor of 0.078 ng TEQ DF 

### -W HO 98 

### /kg (0.079 ng I

- TEQ DF 

### /kg ) coal combusted to the consumption totals of 651, 771, and 891 million metric tons of coal consumed by U.S. utility sectors in 1987, 1995, and 2000, respectively

, y i elds estimated annual emissions by the utility sector of 50.89 g TEQ DF 

### -W HO 98 

### (51.4 g I

- TEQ DF 

### ) in 1987, 60.1 g TEQ DF



### WH O 98 

### (60.9 g I

- TEQ DF 

### ) in 1995, and 69.5 g TEQ DF 

### -W HO 98 

### (70.4 g I

- TEQ DF 

### ) in 2000.
The se e mission e stima te s a r e a ssig n e d a me dium c onf ide n c e r a ting be c a use the e mission f a c t or rating for this categ ory was judg ed to be medium. No testing results could be located fo r CDD/CDF content in air emissions from
commercial and industrial coal-fi red combustion units in the United States. I t is uncertain whether the data collected in the European studies (B remmer et al., 1994; CRE, 1994) accurately represent U.S. sources, but the data sug g e st th at emission factors for commercial/industrial sources mig ht be hig h e r tha n those r e por te d f o r

U.S. c o a l

- f i r e d utilitie s. The r e f or e , no na tiona l e mission

e stima te ha s be e n de r i ve d f o r

this c a t e g or y

. Howe ve r , pr e limina r y e stima te s of pote n tia l na tiona l TEQ emissions from this source categ ory can be derived for 1987, 1995, and 2000 using the total
coal consum pt i on for each of t hose reference y ear s, ex cl udi ng consum pt i on by coke pl ant s , and the averag e emission factor, 0.6 ng I

- TEQ DF 

### /kg coal combusted.

4-71

### Table 4-25. CDD/CDF em ission f a ctors (ng/kg coal) f o r c oal-f ired utility/industrial
powe r plant s a



### C o n g en er/co n g en er g ro u p N o n d etect set to zero N o n d e tect set to 1⁄2 d e tectio n lim it
2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.005 0 0 0.004 0.004 0.216 0.513 0.018 0.016 0.034 0.028 0.035 0.241 0.644
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.109 0.007 0.074 0.098 0.014 0.013 0.043 0.354 0.087 0.158 0.117 0.021 0.084 0.12 0.03 0.038 0.06 0.385 0.112 0.281

To t a l I

- TEQ DF 

### To t a l TEQ DF 

### -W H O 98 

### 0.078 0.078 0.124 0.131

T o tal T C D D T o tal P e C D D T o tal H x C D D T o tal H p C D D T o tal O C D D T o tal T C D F T o tal P e C D F T o tal H x C D F T o tal H p C D F T o tal O C D F 0.051 0.014 0.03 0.063 0.513 0.154 0.18 0.104 0.064 0.158 0.052 0.015 0.03 0.074 0.644 0.158 0.18 0.104 0.064 0.281

To t a l CDD/ CDF 1 .331 1.602

a Elev en

- f acility d a ta set.

S o u rce: EPR I (1994).



### 4-72

### F i gu re 4-8. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om indust r ial/ut ilit y c oal- f ue le d c o m bust o r s ( nondetects set equal to z e ro ).

S o u rce: EPR I (1994).



### 4-73

### Apply i ng the emission factor to the estimated combustion for 1987, 1995, and 2000 (68.2, 66, and 59.14 million metric tons, re spectively ) y i elds 40.9 g I

- TEQ DF 

### /kg for 1987, 39.6 g I

TEQ DF 

### /kg for 1995, and 35.4 g I

- TEQ DF 

### /kg coal combusted for 2000. These estimates should be

reg a rded as preliminary indications of possibl e emissions from commerc ial/industrial coal-fired
boile r s; f u r t he r te sting is ne e d e d to c onf ir m the tr ue ma g n itude of the se e missions. The se emission estimates are assig n ed a Categ o ry D uncer tainty rating because th e emission factor has been judg ed to be clearly nonrepresentative of commercial and industria l coal-fired combustion
units.

4.4.2. Residential Coal Com bustion
I n the residential sector, coal is usually combusted in underfed or hand-stoked furnaces. Other coal-fired heating units include hand-fed room heaters, metal stoves, and metal and

m a sonry fi repl aces. S t oker-fed uni t s are t h e m o st com m on desi g n for warm -ai r furnaces and for boilers used for steam or hot water production. Most coal combusted in these units is either
bituminous or anthracite. These units operate at relatively low te mperatures and do not efficiently

c o mbust the c o a l

. Coa l g e ne r a lly c onta i ns sma ll qua ntitie s of c h lor i ne ; the r e f or e , the pote n tia l f o r C DD/ C D F form at i on ex i s t s

. Ty pi cal l y , coal -fi red resi dent i a l furnaces are not equi pped wi t h P M

or

g a se ous polluta nt c ontr o l de vic e s tha t ma y limit e missions of a n y CDDs/CDF s f o r m e d ( U .S. EPA, 1997b). No testing results for C DD/CDF content in air emissions from

r e side ntia l/c omme r c ia l c o a l

- f i r e d c o mbustion units in the Unite d Sta t e s c ould be loc a t e d ; however, several relevant st udies have been performed in European countries. Thub et al. (1995) measured flue g a s con centrations of CDDs/CDF s from a household
he a ting sy ste m in Ge r m a n y tha t wa s f i r e d with e ithe r sa lt lig nite c o a l ( t ota l c h lor i ne c onte n t of 2,000 ppm) or normal lig nite coal (total chlorine content of 300 ppm). CDDs/CDF s were detected in the flue g a ses g e nerated by combustion of both fuel ty pes (see Table 4-26). The cong ener
pr of ile s a nd pa tte r n s we r e simila r f

o r

both f u e l ty pe s, with OCDD the domina n t c ong e n e r a n d
TCDF the dominant cong ener g r oup. However, the e missions were hig h er by a factor of 8 for the “salt” coal (0.109 ng I

- TEQ DF 

### /m 3 

### [ 2.74 ng I

- TEQ DF 

### /kg ] ) than for the “normal” coal (0.015 ng I

TEQ DF 

### /m 3 

### [ 0.34 ng I

- TEQ DF 

### /kg ] )

. Using the r e sults of te sting pe r f o r m e d by the Coa l Re se a r c h Esta blishme n t in the Unite d King dom, Eduljee and Dy ke (1996) estimated emission factors for residential coal combustion units of 2.1 ng I

- TEQ DF 

### /kg for anthracite coal and 5.7 to 9.3 ng I

- TEQ DF 

### /kg (midpoint, 7.5 ng
I

- TEQ DF 

### /kg ) for bituminous coal.

4-74

### Table 4-26. CDD/CDF em ission f actors (ng/kg coal) f o r residential coal

com b u s tors

C o n g en er “Sal t ” lig n ite a 

### “Nor m a l ” lig n ite a 

### A n th ra cite b 

### Bi t um i nous b


### 2,3,7,8- TCDD 1,2,3,7,8- Pe CDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.58 0.73 0.63 0.6 0.4 3.24 16.19 0.06 0.08 0.06 0.09 0.06 0.59 2.42 1.6 NR NR NR NR NR 77 2.4 NR NR NR NR NR 120
2,3,7,8- TCDF 1,2,3,7,8- Pe CDF 2,3,4,7,8- Pe CDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2.49 2.24 2.09 0.38 1.86 0.07 1.01 2.59 0.25 0.63 0.5 0.43 0.31 0.13 0.36 0.02 0.12 0.95 0.06 0.3 42 NR NR NR NR NR NR NR NR 4.2 63 NR NR NR NR NR NR NR NR 6.3

To t a l 2,3,7,8- CDD c 

### To t a l 2,3,7,8- CDF c 

### To t a l I

- TEQ DF c 

### 22.37 13.6

2.74 3.38 3.2 0.34 NR NR 60 NR NR 98.5

T o tal T C D D T o tal P e C D D T o tal H x C D D T o tal H p C D D T o tal O C D D T o tal T C D F T o tal P e C D F T o tal H x C D F T o tal H p C D F T o tal O C D F 14.23 14.15 11.14

7.06 16.19 80.34 29.21 12.72

3.87 0.63 9 2.22 1.81 0.82 2.42 20.33

8.98 3.78 1.27 0.3 61.6 31 60 57 77 412 340 130

32

4.2 92.4 46 90 86 120 613 550 190

47

6.3

To t a l CDD/ CDF 189.5 50.9 1 ,205 1,841

a S o u r ce: T h u b et al . (1995); l i s t e d res u l t s repres en t m ean s of t h ree f l u e g a s s a m p l e s

. b S o u r ce: U .S . EPA (1997a); bas e d on av erag e part i c u l at e C D D / C D F con cen t r at i o n s f r om ch i m n e y s oot s a m p l e s collected f r om s e v e n coal ov en s an d particu l ate em is s i on f

actors f o r an th racite an d bitu m i n o u s coal com b u s tion

.

c Valu es as reported in s o u r ces

.

NR = No t rep o r ted



### 4-75

### CDD/CDF emission factors were estimated (U.S. EPA, 1997a) for coal-fired residential
furnaces usi n g averag e part i c ul at e C DD/ C DF con cent r at i ons from chi m n ey soot sam p l e s col l ect ed
from seven coal ovens and PM emission factor s obtained from AP-42 th at are speci fi c t o anthracite and bituminous coal combustion (U .S. EPA, 1995a). The TEQ emission factors estimated (60 and 98.5 ng I

- TEQ DF 

### /kg anthracite and bituminous co al, respectively ) were derived using the calculated emission factors fo r 2,3,7,8-TCDD, 2,3,7,8-TCDF , and the 10 cong ener
g r oups (U.S. EPA, 1997a). EP A stated that the estimated factors should be considered represent a t i v e of m a x i m u m em i ssi on fact ors becau se soot m a y not be represent a t i v e of t h e P M

a c t ua lly e mitte d to the a tmosphe r e

. The se e mission f a c t or s a r e pr e se n te d in Ta ble 4- 26; c ong e n e r
g r oup profiles are presented in F i g u re 4-9. Althoug h the cong ener g r oup profiles of the m easurements by Thub et al. (1995) and the estimates by EPA (U.S. EPA, 1997a) are similar, the TEQ emission factors of the two studies differ by factors of 175 to 289. The emission fact ors used by Eduljee and Dy ke (1996) to estimate national annual TEQ emissions fro m residential coal combustion in the United King dom fall in
between the other two sets of es timates but are still about one to two orders of mag n itude g r eater than the estimated emission factor for industrial and utility coal combustors (see Section 4.4.1).
F or 1987 and 1995, preliminary estima tes of potential national TEQs were derived using the emission factors from Eduljee and Dy ke (1996)

. U.S. EPA (1997a) reported that 72.5% of the coal consumed by the residential sector in 1990 was bituminous a nd 27.5% was anthracite. Assuming that these relative proportions re flect the actual usag e in 1987 and 1995, then application of the emission factors from Eduljee and Dy ke (2.1 ng I

- TEQ DF 

### / k g ant h raci t e coal and
7.5 ng I

- TEQ DF 

### bituminous coal) to the consumption va lues of 6.3 and 5.3 million metric tons in 1987 and 1995, respectively (U.S. DOC, 1997), results in estimated TEQ emissions of 37.9 and
32.0 g I

- TEQ DF 

### in 1987 and 1995, respectively

. Thes e estimates should be reg a rded as preliminary indications of possible emissions from this source categ ory because the emission factor is judg ed to be clearly nonrepresentative of the sources. F urther testing is needed to

c onf ir m the tr ue ma g n it ude of these emissions.
F or 2000, OAQPS developed nati onal emission estimates for coal combustion for

r e side ntia l he a ting

. The a c tivity le ve l f o r

r e side ntia l c o a l c o mbustion wa s ta ke n f r o m sta t e

- le ve l 2000 activity data (EI A , 2003a). B ecause EI A no long er disag g r eg ates coal consumption into anthracite versus bituminous/lig nite, OAQPS estimated each state’s coal consumption using the state’s 1999 proportion of anthrac ite versus bituminous/lig nite to total coal consumption. Emissions were allocated to the county level as a proportion of state popul ation in states that consume anthracite coal and bituminous and lig nite coal for residential heating

. OAQPS estimated that in 2000, 67,400 metric tons of an thracite coal and 343,000 metric tons of

4-76

### F i gure 4-9. Congener group prof ile f o r ai r em i ssi on s f r om residential

c oal- f ue le d c o m bust o r s .

S o u rce: U

. S

. EPA (1997a).



### bituminous and lig nite coal were consumed for re sidential heating

. Apply i ng the TEQ emission factors of 2.1 ng I

- TEQ DF 

### /kg anthracite coal combusted and 7.5 ng I

- TEQ DF 

### /kg bituminous coal combusted (Eduljee and Dy ke, 1996) to these pr oduction factors y i elds preliminary estimates of annual emissions of 0.14 g I

- TEQ DF 

### of anthracite coal and 2.6 g I

- TEQ DF

### of bituminous/subbituminous coal in 2000. These emission estimates are assig n ed a Categ o ry D uncertainty rating because the emission factor has been judg ed to be clearly nonrepresenta tive of residential coal
combustion.

4.4.3. Solid Wastes f r om Coal Com bustion
A limited amount of CDD/CDF concentration data have been de veloped for utility industry solid wastes (U.S. EPA, 1999c), and these data are for wastes that are comanag e d (i.e., combinations of fly ash, bottom ash, boiler slag , and flue g a s desulfuriz ation wa ste s)

. A tota l of 15 samples were taken from 11 dis posal si t e s. The averag e concent r at i on for each of t h e C DD

4-77

### and CDF cong eners is presented in the second colu mn of Table 4-27. I t should be noted that most
of the concentration values shown in Table 4-27 represent DL s. Consequently , the values

ove r e stima te a c t ua l c onc e n tr a tions.
U.S. EPA (1999d) indicates that approx imately 63 million tons (assumed to be short tons, i.e., 2,000 pounds) of larg e-volume utility coal co mbustion solid wastes were produced in 1995. Of this amount, about 67% wa s landfilled and the balance wa s disposed of in surface impoundments. The concentration data presente d in Table 4-27 are for only the 53 million tons that were comanag e d (about 84% of the total wastes). F or purposes of this analy s is it is assumed

t h at t h e C DD/ C DF concent r at i ons i n t h e com a nag e d wast es are t h e sam e as for t h e ent i r e wast e
qua ntity

. Combining the c onc e n tr a tion da ta with the 63 million tons of tota l wa ste y i e l ds the tota l quantities of each cong ener disposed of in 1995. Th ese data are presented in the fourth column of
Table 4-27. As indicated in Section 4.4 of this document, total consumpti on of coal for electric utility boilers in 1987 was 98.4% of 1995 cons umption. Consequently , the quantities of
CDDs/CDF s disposed of in 1987 is assumed to be 98.4% of the 1995 values. These values are presented in column 3 of Table 4-27. The 1995 cong ener quantities are converted into I

- TEQ DF 

### and TEQ DF 

### -W HO 98 

### val u es i n col u m n s 5 and 6. Because di sposal of t h ese wast es does not

c onstitute a n e nvir onme n ta l r e le a se , the va lue s a r e not inc l ude d in the inve ntor y

.

4-78

### Table 4-27. CDD/CDF concentrations and am ounts disposed of in solid w a stes fr om c oal- f ir e d ut ilit ie s

C o n g en er Me an

co n cen tra t io n a 

### (n g / kg ) Di s pos e d of in so lid

wa s t e i n 1987 ( g/ yr ) b 

### Di s pos e d of in so lid w a ste i n 1995 ( g/ yr ) c 

### I

- TEQ DF 

### / yr 1995 (g ) TEQ DF 

### ­ WHO 98 

### /y r

1995 ( g) 2,3,7,8- TCDD d 

### 0.17 10 10 9.72 9.72 1,2,3,7,8- Pe CDD d 

### 0.25 14 14 7.15 14.3 1,2,3,4,7,8- HxCDD d 

### 0.35 20 20 2 2 1,2,3,6,7,8- HxCDD d 

### 0.28 16 16 1.6 1 .6 1,2,3,7,8,9- HxCDD e 

### 0.3 1 7 1 7 1 .72 1 .72 1,2,3,4,6,7,8- HpCDD f 

### 0.59 33 34 0.34 0.34 OCDD g 

### 10.54 593 603 0.6 0 .6 2,3,7,8- TCDF h 

### 0.19 11 11 1.09 1.09 1,2,3,7,8- Pe CDF d 

### 0.17 10 10 0.49 0.49 2,3,4,7,8- Pe CDF d 

### 0.17 10 10 4.86 4.86 1,2,3,4,7,8- HxCDF e 

### 0.25 14 14 1.43 1.43 1,2,3,6,7,8- HxCDF d 

### 0.18 10 10 1.03 1.03 2,3,4,6,7,8- HxCDF d 

### 0.28 16 16 1.6 1 .6 1,2,3,7,8,9- HxCDF d 

### 0.24 14 14 1.37 1.37 1,2,3,4,6,7,8- HpCDF e 

### 0.29 16 17 0.17 0.17 1,2,3,4,7,8,9- HpCDF d 

### 0.35 20 20 0.2 0 .2 OCDF i 

### 0.59 33 34 0.03 < 0 .01
TOTAL 35.41 41.98

a S o u rce: U

. S

. EPA (1999c, T a bl e 2- 9).

b A s s u m e s th at s o lid w a s t e qu an tity f o r 1987 w a s 98.4% of 1995 qu an tity , bas e d on total u tility coal u s e in th os e y ears (s ee Section 4.4).

c B a sed o n EP RI estim ate o f 6 3 m illio n to n s /y r o f larg e- v o lu m e u tility co al co m b u s tio n so lid w a stes. See Sectio n 3.3 of U .S . EPA (1999d). A s s u m e s al l w a s t e ch aract eri s t i c s w e re t h e s a m e as f o r com a n a g e d w a s t es

. d A ll 17 an aly s es w ere n o n d etects

.
e Six t een of th e 17 an aly s es w ere n o n d etects

. f Elev en of th e 17 an aly s es w e re n o n d etects

. g Fiv e of th e 17 an aly s es w ere n o n d etects

. h Fou r teen of th e 17 an aly s es w ere n o n d etects

. i Fif t een of th e 17 an aly s es w ere n o n d etects

.



### 4-79

### 5. COMB US T I ON S O URCE S OF CDDs/CDF s: OT HE R HIG H -T E M P E RAT URE S O URCE S

5.1. CEMENT K I LNS
This se c tion a ddr e sse s CDD/CDF e missions f r o m Por tla nd c e m e n t kilns. The s e f a c ilitie s use hig h temperatures to convert mineral feed stocks into Portland cem ent and other ty pes of
construction materials. F o r pur poses of this analy s is, cement kilns are divided into two
categ ories: those that burn haz a rdous waste as a supplementary fu el and those that do not. F o r the 1987 and 1995 estimates, the haz a rdous waste- burning cement kiln categ ory was further divided into kilns with inlet air pollution cont rol device (APCD) temper atures above 232°C and those with APCD temperatures below 232°C. Cement kiln technolog y , the derivation of TEQ
emission factors for cement kilns that burn haz a r dous waste as supplementa l fuel and those that do not, and the derivation of annual TEQ air e missions (g /y r) for reference y ears 1987, 1995, and
2000 are discussed below.

5.1.1. P r ocess Description of P o rtland Cem e nt K ilns
I n the United States, the primary cement pr oduct is Portland cement. Portland cement is

a

f

i ne , g r a y powde r c onsisting of a

mix tur e of f

our ba sic ma te r i a l s: lime , silic a , a l umina

, a nd ir on compounds. Cement production invol ves heating (py r oprocessing ) the raw materials to a very
hi g h t e m p erat ure i n a rot a ry (rot a t i n g ) ki l n t o i nduce chem i cal react i ons t h at produce a fused
material called clinker. The cement clinker is then g r ound into a fine powder and mix ed with

g ypsum to form the Portland cement.
The cem ent ki l n i s a l a rg e, st eel , rot a t i n g cy l i ndri c al furnace l i n ed wi t h refract ory material. The kiln is alig ned on a slig ht ang l e, usually a slope of 3 to 6 deg r ees, which allows the materials to pass throug h the kiln by g r avity

. Th e kiln rotates at about 50 to 70 revs/hr, and the
rotation induces mix ing and the downward movement of mix ed materials. The upper end of the kiln, known as the cold end, is g e nerally where the raw materials, or meal, are fed into the kiln. Midpoint injection is practiced at some facilities. The lower end of the kiln, known as the hot end, is where the combustion of primary fuels (usually coal and petroleum coke) occurs, producing a hig h temperature. The cement kiln operates using countercurrents: hot combustion

g a ses are convected up throug h the kiln while th e raw materials pass down toward the lower end. As the meal moves throug h the cement kiln and is heated by hot combustion g a ses, water is vaporiz ed and py roprocessi ng of materials occurs.
The c e m e n t kiln c onsists of thr e e the r ma l z ones to produce cement clinker. Z one 1 is at the upper end of the kiln where the raw meal is a dded. Temperatures in th is z one ty pically rang e from ambient up to 600°C. I n this area of the k iln, moisture is evaporated from the raw meal.

5-1

### Z one 2 is known as the calcining z one. Calcining occurs when the hot g a ses from the

c o mbustion of pr ima r y f

u e l s dissoc i a t e c a l c i um diox ide f r o m the lime stone a nd f o r m c a l c i um

ox ide. I n this z one, temperatures rang e from 600 to 900°C. Z one 3, the burning or sintering

z one, is the lowest and hottest reg i on of the k iln. Here, temperatures in ex cess of 1,500°C induce
the calcium ox ide to react with silicates, iron, and aluminum in the raw materials to form the
cement clinker. The formation of clinker actually occurs close to the combustion of primary fuel.
The chem i cal react i ons t h at occur i n z one 3 are referred to as py roprocessing

. The cement clinker, which leaves the kiln at the hot end, is a g r ay , g l ass-hard material
consi s t i n g of di cal ci um si l i cat e, t r i cal ci um si l i cat e, cal ci um al um i n at e, and t e t r acal ci um aluminoferrite. At this point, the temperature of the clinker is about 1,100°C. The hot clinker is then dumped onto a moving g r ate, where it cools as it passes under a series of cool-air blowers. After it is cooled to ambient temperature, the clinker is g r ound into a fine powder and mix ed with

g y psum to produce the Portland cement product.
Cement kilns can be either we t process or dry process. I n the we t pr oc e ss, the r a w materials are g r ound and mix ed with water to form a slurry , which is fed into the kiln throug h a

pump. This is an older process. A g r eater amount of heat energ y is needed in the wet process kiln than in other ty pes of kilns. These kilns consume about 5 to 7 trilli on B t u per ton of clinker product to evaporate the additional wa ter. I n the dry process, a preheater is used to dry the raw

m eal before i t ent e rs t h e ki l n. A t ypi cal preheat er consists of a vertical tower containing a series of cy clone-typ e vessels. Raw meal is added at the top of the tower and hot ex haust g a ses from the kiln operation preheat the meal, thus lowering the fuel consumption of the kiln. Dry kilns are now the most popular ty pe of cement kiln. Portland cement clinker production in the Unite d States is estimated to have been 52 billion kg in 1987 (U.S. DOC, 1996), 67.6 billion kg in 1995 (U.S. DOC, 1996), and 75.2 billion kg in 2000 (PCA, 2001). The 2000 estimate is ba sed on the assumption that of the annual

max imum clinker capacity reporte d for that reference y ear (PCA, 2001), only 90% was actually produced (e-mail dated J a nuary 31, 2003, from Gart h Hawkins, Portland Ce ment Association, to
Kari e R i l e y , Versar, I n c.).

5.1.2. Cem e nt K ilns That Burn Hazardous Waste The hig h temperatures achieved in cement k ilns make the kilns an attractive technolog y for combusting haz a rdous waste as supplemental fuel. Sustaining the relatively hig h combustion temperatures that are needed to form cement clinker (1,100 to 1,500°C) requires the burning of a fuel with a hig h energ y output. Therefore, coal or petroleum coke is ty pic a lly use d a s the pr ima r y fuel source. Because m u ch of t h e cost of ope rat i n g t h e cem e nt ki l n at hi g h t e m p erat ures i s associated with the consumption of fossil fu els, some cement kiln operators burn haz a rdous

5-2

### liquid and solid waste as supplemental fuel. I n 2000, approx imately 60% of all fac ilities burned
haz a rdous waste as the primary fuel to offset the amount of coal/coke purchased and burned by the kiln (PCA, 2001). Org a nic haz a rdous waste ma y have a heating value similar to that of coal (9,000 to 12,000 B t u/lb for coal). The kiln opera tor may charg e the waste g e nerator a disposal
fee to combust the haz a rdous waste; this fee also offsets the cost of kiln operation. The hig h

energ y and ig nitable wastes include diverse s ubstances, such as waste oils, spent org a nic solvents, sludg es from the paint and coating s indus try , waste paints and coating s from auto and truck assembly plants, and sludg es from the pe troleum refining industry (Greer et al., 1992).
The conditions in the cement kiln mimic conditi ons of hazardous wast e incineration. F o r

e x a m ple

, the g a s r e side nc e time in the bur ning zone is ty pic a lly 3 se c a t te mpe r a t ur e s in e x c e ss of 1,500°C (Greer et al., 1992). The method of intr oducing liquid and solid haz a rdous waste into
the kiln is a ke y f

a c t or in the c o mple te c ons umption of the waste during the combustion of the primary fuel. L i quid haz a rdous waste is either injected separately or blended with the primary
f u e l ( c oa l)

. Solid wa ste is mix e d a nd burned along with the primary fuel.
Trial burns have consis tently shown that destruction a nd removal efficiencies of 99.99 to 99.9999% can be achieved for very stable org a nic wastes using cement kilns (Greer et al., 1992).
Haz a rdous waste was combusted at 34 of the 212 kilns operating in 1995 (F ederal Reg i ster, 1996a) and at 33 of the 201 kilns operating in 2000 (e-mail correspondence dated F e bruary 24, 2003, between M. B e noit, Cement Kiln Recy clin g Coalition, and K. Riley

, Versar, I n c.; PCA, 2001). Other ty pes of supplemental fuel used by these facilities include natural g a s, fuel oil, automobile tires, used motor oil, sawdust, and scrap wood chips.

5.1.3. Air P o llution Control Devices The py roprocessing of raw meal in a cement k iln also produces fine part i c ul at es, referred

to a s c e m e n t kiln dust ( C KD)

. CKD is c o lle c t e d a nd c ontr o lle d with f a br ic f ilte r s ( F F s )
, electrostatic precipitators (ESPs), or both. Acid g a ses such as sulfur diox ide (SO 2 

### ) can be form ed during py roprocessing of the sulfur-laden min erals and fuels, but the minerals have hig h

a l ka linity , whic h pa r tia lly ne utr a lize s SO 2 

### g a ses. Most APCDs used at cement kilns in 1987 and
1995 were considered to be hot-sided control de vices. A hot-sided control device is one that operates at kiln ex haust g a s te mperatures above 232°C (some EPA rules use different definitions
for hot-sided control devices fo r different industries). Most APCDs currently used at cement kilns are cold-sided devices (i.e., they operate at kiln ex haust g a s temperatures below 232°C.
Re duc ing the te mpe r a t ur e a t the inle t of the APCD is one factor that has been shown to
ha ve a sig n if ic a n t impa c t on limiting diox in f o r m a tion a nd e missions a t c e m e n t kilns ( U .S. EPA, 1997c). Emissions testing at a Portland cemen t kiln showed that CDDs/CDF s were almost

ent i r el y absent at t h e i n l e t t o a hot -si d ed ES P
, but m easurem ent s t a ken at t h e ex i t showed

5-3

### conclusively that diox ins were formed within the hot-sided ESP (U.S. EPA, 1997c). Reducing
the kiln ex haust g a s temperature in the APCD to below 232°C has been shown to substantially
limit CDD/CDF formation. L o wer temperatures are believed to prevent the post-combustion cataly tic formation of CDDs/CDF s. Consequently , a number of cement kilns have added ex haust

g a s-quenching units upstream of the APCD to r e duc e the inle t APCD te mpe r a t ur e , the r e b y reducing CDD/CDF stack concentrations. A quenc hing unit usually consists of a water spray

sy ste m within the f l ue duc t.

5.1.4. CDD/CDF Em issions Data The g e neral st rat e g y used t o deri ve em i ssi on fact ors for t h i s report was t o di vi de each
source categ ory on the basis of desig n and ope ration. However, because cement kilns are relatively uniform in terms of kiln desig n, r a w f e e d ma te r i a l , ope r a ting te mpe r a t ur e s , a n d APCDs, they have been categ oriz ed, as not ed above, only on the basis of whether or not
haz a rdous waste is burned as a supplementary fuel.
CDD/CDF emissions data from tests c onducted between 1989 a nd 1996 were obtained for 16 cement kilns burning haz a rdous waste and 15 cement kilns burning nonhaz a rdous waste (U.S

. EP A, 1996b). More recent CDD/CDF emi ssions data were also obtained from tests conducted in 2000 at 3 cement kilns burning haz a rdous waste (U.S. EPA, 2002a) and from tests
conducted in J une and J u ly of 1999 at one facility burning nonhaz a rdous waste (B ell, 1999). The majority of stack emissions data from cement k ilns burning haz a rdous wa ste were derived during

tr ia l bur ns a nd ma y ove r e stima te the CDD/CDF e missions tha t most kilns a c h ie ve dur ing nor ma l operations. Stack emissions data from kilns burning nonhaz a rdous waste were derived from

te sting dur ing nor ma l ope r a tions.

5.1.4.1. Em issions Data for 1989 Through 1996 (U.S. EPA, 1996b) The averag e TEQ emission factors for this period, based on the data reported by EPA in 1996 (U.S. EPA, 1996b), were 0.000941 to 232 ng TEQ DF 

### -W HO 98 

### /kg (averag e of 22.48 ng TEQ DF 

### -W HO 98 

### /kg [ 20.91 ng I

- TEQ DF 

### /kg ] ) clinker produced for cement kilns burning haz a rdous waste and 0.000012 to 2.76 ng TEQ DF 

### -W HO 98 

### /kg (averag e of 0.29 ng TEQ DF 

### -W HO 98 

### /kg [ 0.27 ng
I

- TEQ DF 

### /kg ] ) clinker produced for cement kilns burning nonhaz a rdous waste. These data show that the averag e emission f actor for kilns burning haz a rdous waste was about 90 times g r eater than that for kilns burni ng nonhaz a rdous waste. However, it should be noted that the averag e emission factor for kilns burning haz a r dous waste was derived from “near worst case” testing of haz a rdous waste-burning kilns. As discussed in Section 5.1.8, a

c o mpa r ison of CDD/CDF c onc e n tr a tions in CKD sa mple s shows a simila r r e la tionship ( i .e ., the
CDD/CDF TEQ concentration of the CKD from kilns burning haz a rdous waste was about 100

5-4

### times hig h er than that of the dust from kilns bur ning nonhaz a rdous waste). Althoug h the averag e emission factors for the two g r oups of kilns differ substantially , the emission factors for individual kilns in the two g r oups overlap. Theref ore, other aspects of the desig n and operation
of

the kilns—in pa r tic ula r , the te mpe r a t ur e of the APCD equipment (as discussed in Section 5.1.3)—were likely affecting CDD/CDF emissions. Previous attempts to understand these differe nces using parametric testing of cement kilns y i elded mix ed results. EPA (U.S . EPA, 1997c) conducted a limited comparison of
C DD/ C D F TEQ st ack g a s concent r at i ons (n g TEQ/dscm) between cement kilns burning
haz a rdous wastes and those not burning haz a rdous wastes. Those comparisons were made at 14

c e m e n t kilns. With the e x c e p tion of the f u el being burned, operatin g conditions (e.g ., APCD temperature) were the same or similar for each set of comparisons. B a seline conditions used coal as the only primary fuel. The results of these comparisons found:

• s even kilns in which the baseline (i.e., no combustion of haz a rdous waste) CDD/CDF TEQ stack g a s concentrations were about the same as those for the burning of haz a rdous wastes,

• t wo kilns in whic h the ba se line CDD/CDF I

- TEQ DF 

### st ack g a s concent r at i ons were about double those for the burning of haz a rdous wastes, and

• f ive kilns in which the haz a rdous waste CDD/CDF I

- TEQ DF 

### st ack g a s concent r at i ons

we r e substa ntia lly g r e a t e r ( 3

- to 29- f o ld g r e a t e r ) tha n those f o r

the ba se line ope r a ting conditions.

Subsequently , EPA’s Office of Research a nd Development (ORD) conducted analy s es of

t h e avai l a bl e em i ssi ons dat a t o eval uat e , on a cong ener-speci fi c basi s, whet her t h ere were sig n ificant differences in emi ssion factors between (a) kilns bur ning haz a rdous waste and those burning nonhaz a rdous waste, (b) kilns with APCD inlet temperatures g r eater than 232°C and those with temperatures less than 232°C, (c) haz a rdous waste-burning and nonhaz a rdous wasteburning facilities with AP CD inlet temperatures g r eater than 232°C, (d) haz a rdous waste-burning
and nonhaz a rdous waste-burning f acilities with APCD in let temperatures less than 232°C, (e)
haz a rdous waste-burning facilitie s with APCD inlet temperatur es less than and g r eater than 232°C, and (f) nonhaz a rdous waste-bur ning facilities with APCD inle t temperatures less than and

g r eater than 232°C. The results of all analy s es showed sig n ificant differences in the sample

m ean val u es ( p <0.05).
Gi ven t h e st rong em pi ri cal evi d ence t h at real differences ex isted, ORD decided to address the kilns burning haz a rdous wast e separately from those burning nonhaz a rdous waste to develop
a CDD/CDF emissions inventory and to subdivi de the haz a rdous waste-burning categ ory into

5-5

### subcateg ories by APCD inlet temperature (i.e ., less than 232°C and g r eater than 232°C). APCD
inle t te mpe r a t ur e da ta we r e a v a ila ble f o r

88 te st runs at 14 cement kilns. The number of test runs conducted at individual kilns rang ed from 1 to 26. Each test run was treated as an individual facility and each was classified according to APCD inlet temperature and whether or not
haz a rdous waste was burned. The emission factor for each cement kiln test run was calculated using eq 5-1.

= C × F
v 

### (5-1) EF CK



### ______ I

cl



### where:
EF CK 

### = cement kiln emission factor (burni ng or not burning haz a rdous waste)

(ng TEQ/kg of clinker produced)

C = TEQ or CD D / CD F c onc e n tr a tion in kiln e x ha ust g a se s ( n g TEQ/dsc m) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )

F
v 

### = volume t r i c kiln e x ha ust g a s f l ow r a te ( d sc m/hr ) ( 20°C, 1 a tm; a d juste d to 7% O 2 

### )

I cl 

### = averag e cement kiln clinker production rate (kg / hr)

After developing the emission f actor for each cement kiln test run, the overall averag e cong enerspeci fi c em i ssi on fact or was deri ved for al l t e st runs i n each subcat eg ory usi n g eq 5-2.

EF CK 1 

### + EF CK 2 

### + EF CK 3 

### + ....... + EF CK N 

### EF
av gCK 

### _______________________________ (5-2)
= N

where:
EF
a vgC K 

### = averag e emission factor of test ed cement kilns burning haz a rdous waste as supplemental fuel a nd with APCD inlet temperatures either g r eater than or less than 232°C (ng TEQ/kg clinker)

N = number of cement kiln test runs

TEQ emission values for haz a r dous waste-burning cement kilns with APCD inlet temperatures

g r eater than 232°C and less than 232°C were 30.7 and 1.11 ng TEQ DF 

### -W HO 98 

### /kg c linke r produced, respectively

.

5-6

### 5.1.4.2. Em issions Data for 1999 and 2000 (B ell, 1999; U.S. EPA, 2002a)
The results of a test conducted in 1999 fo r a cement kiln burning nonhaz a rdous waste (B ell, 1999) showed averag e TEQ DF 

### -W HO 98 

### and I

- TEQ emission fact ors of 0.14 ng /kg clinker produced. This value is within the rang e of emission factor values developed using the 1989 throug h 1996 data (U.S. EPA, 1996b).
I n 1999, EPA’s Office of Solid W a ste and Emerg e ncy Response (OSW ER), under the
National Emission Standards for Haz a rdous Ai r Pollutants (NESHAPs), promulg a ted F i nal
Standards for Haz a rdous Air Pollutants for Haz a rdous W a ste Combustors (F ederal Reg i ster, 1999a). During the development of this rulema king , a database of na tional emission estimates
for haz a rdous waste combustors (HW C s), includi ng haz a rdous waste-burning cement kilns, was
established. I n this database EPA identified 30 haz a rdous wa ste cement kilns operating in 1997. Twenty -four of the 30 kilns ha d provided emissions sampling da ta to EPA, including diox in

concent r at i ons. Usi n g t h e m o st recent sam p l i n g dat a for each ki l n, al ong wi t h i m put ed rel ease

e s tima te s f o r

the missing six kilns a nd the a ssumption tha t c e m e n t kilns we r e ope r a ting 24 hr/day , 365 day s /y r, OSW E R developed a nati onal emissions estimate of 13 g TEQ/y r for 1997. A number of parties soug ht j udicial review of the 1999 rule, and in 2001 the standards
were vacated. I n terim standa rds were issued in 2002 until EP A could issue revised final
standards in 2004. The ex isting national emi ssions database was upda ted to include new sampling data and data for newl y operational HW Cs and to remove e i g h t of the c e m e n t kilns tha t were identified as no long er bur ning haz a rdous waste. F r om this updated data base (U.S. EPA, 2002a), EPA was able to devel op new emission estimates for 2000.

5.1.4.3. Em ission Factor Estim ates for Cem e nt Kilns Burning Hazardous Waste
F o r reference y ears 1987 and 1995, EPA es timated the TEQ emission factor by subdividing the emissions da ta reported in 1996 (i.e., for 1989 throug h 1996) (U.S. EPA, 1996b) by inlet APCD temperature above and below 232°C. F o r cement kilns operating at temperatures above 232°C, the TEQ emission factor was 30.7 ng TEQ DF 

### -W HO 98 

### /kg clinker produced, and for cement kilns operating at temperatures belo w 232°C, the TEQ emission factor was 1.11 ng TEQ DF 

### -W HO 98 

### /kg clinker produced. These emission fact ors are presented in Table 5-1 and the

averag e cong ener profi l e i s presented in F i g u re 5-1.
B ecause a vast majority of the facilities had reduced thei r APCD inlet temperature to below 232°C by 2000, and because only a few new test reports applicable to reference y ear 2000 were available, EPA removed th e 232°C divider and combined the emission factor results (i.e., 1989 throug h 1996 data) (U.S. EPA, 1996b) for fac ilities that were still operating in 2000 with

5-7

### T a b l e 5-1. CDD/CDF em ission f a ctors (n g/k g clin k e r p r od u ced ) f o r cem e n t k iln s b u r n i n g h a zard ou s w a ste f o r ref eren ce years 1987 an d 1995

C o ngener/
congener group Mean emission f a ctor ( n ondet ect val ues set equal t o z ero)

AP CD i n l e t t e m p e r a t u r e >232°C A P C D in let temp eratu re <232°C
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 3.38 4.28 4.85 6.93 9.55 27.05 18.61 0.02 0.13 0.29 0.42 0.4 3.16 1.08
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 36.26 13.36 23.48 22.24

8.46 0.96 13.33

7.73 2.16 2.51 3.24 0.23 0.65 0.55 0.27 0.06 0.52 0.34 0.16 0.37

Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### 28.58 30.7 1.04 1.10

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 406.76 608.65 845.99 192.99

18.61 295.72 127.99

50.75

8.36 2.51 1.78 0.89 0.69 0.42 1.08 11.52

3.83 1.88 0.47 0.37

T o tal CDD/CDF 2,558.33 22.93
A P CD = A i r p o llu tio n co n t ro l d e v i ce

S o u r ce: U

. S

. EPA (1996b).



### the newer data reported (U.S. EP A, 2002a). Therefore, emission tests from five facilities (U.S. EPA, 1996b) were not used to estimate the 2000 emission factor because the facilities no long er burned haz a rdous waste in 2000. Using this appr oach, a conservative TEQ emission estimate of

5-8Ratio (co n g e n e r em issio n f acto r /to tal CDD/CDF em issio n f acto r )
0 a 0.005 0.01 0.015 0.02



### F i gu re 5-1. Con g en er p r of i l e f o r ai r em i ssi on s f r om cem en t k i l n s b u r n i n g h a zard ou s w a ste f o r ref eren ce years 1987 an d 1995 (nondetect set equal to

z e ro).

5.95 ng TEQ DF 

### -W HO 98 

### /kg (5.49 ng I

- TEQ/kg ) clinker produced was developed for reference y ear 2000. The cong ener-specific emi ssion factors are presented in Table 5-2 and the averag e
cong ener and cong ener g r oup profile s are presented in F i g u re 5-2.

5.1.4.4. Em ission Factor Estim ates for Cem e nt Kilns Burning Nonhazardous Waste
B ecause only one test report a pplicable to reference y ear 2000 was located for a cement kiln burning nonhaz a rdous waste (B ell, 1999), and the results from the tests were similar to the results reported by EPA in 1996 (U.S. EPA, 1996b) , EPA combined the results from the two data sets to obtain a TEQ emission factor estimate of 0.27 ng TEQ DF 

### -W HO 98 

### /kg (0.26 ng I

- TEQ/kg ) clinker produced for reference y ears 1987, 1995, and 2000. The cong ener-specific emission factors are presented in Table 5-3 and the av erag e cong ener and cong ener g r oup profiles are presented in F i g u re 5-3.

5-9

### T a b l e 5-2. CDD/CDF em ission f a ctors (n g/h r ) f o r cem en t k iln s b u r n i n g h a zard ou s w a ste f o r ref eren ce year 2000

C ong ener/cong ener g r oup Mean em ission factor
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 9,533 32,510 48,483 78,043 66,369 446,105 142,108
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 63,866 37,470 77,981 59,340 48,179 33,967 47,458 47,762 15,098 12,418

Total I

- T E Q DF 

### (g /y r) Total TE Q DF 

### -W H O 98 

### (g /y r) 16.6 18.8

S o u r ces : U

. S

. EPA (1996b, 2002a).



### 5.1.4.5. Confidence Ratings of Em ission Factor Estim ates The TEQ em i ssi on fact ors are g i ven a l o w confi d ence rat i n g for al l subcat eg ori e s and al l

y ears. The emission factor for nonhaz a rdous wa ste-burning kilns was g i ven a low rating because

te st da ta we r e a v a ila ble f o r

only 16 f a c ilitie s. The te ste d f a c ilitie s ma y not be r e pr e s e n ta tive of
routine CDD/CDF emissions from all kilns bur ning nonhaz a rdous waste. Althoug h a hig h er percentag e of the kilns burning haz a rdous wa ste (with reported APCD temperature data) had been tested, g r eater uncertainty ex ists about wh ether the emissions are representative of normal
operat i ons because t h e t e st s used t r i a l burn pro cedures and because a g r eat er m a j o ri t y of t h e operating facilities had reduced thei r APCD temperatures to below 232°C. According l y , a low confidence rating is also assig n ed to the estima ted emission factors for kilns burning haz a rdous

waste.

5.1.5. Activity Level Inf o rm ation
I n 1987, approx imately 52 billion kg of cemen t clinker were produced in the United States (U.S. DOC, 1996). I n 1995, approx imately 67.6 billion kg of clinker were produced in the

5-100.00 0
4D 2 378

5 D 12 378

6D 1 2 3 478

6D 1 2 3 678

6D 1 2 3 789

7 D 12 34 678

8D

4F 23 7 8

5F

12 378

5F

23 478

6F 1 2 3 478

6F 1 2 3 678

6F 1 2 3 789

6F 2 3 4 678

7 F 12 34 678

7 F 12 34 789

8F R a t i o ( c ong e n e r e m i s s i on f a c t or / 2 3 7 8

- C D D / C

D F

e m i s s i on f a c t o r )

0

. 0 10 0

. 0 2 0 0 .03 0 0. 0 4 0 0

. 0 50 0

. 06 0

R a t i o ( c o n g e n e r gr o u p e m i s s i o n f a c t o r / t o t a l C D D / C D F e m i s s i o n f a c t o r )

0 0 .1 0

. 2 0 .3 0

. 4 0 .5

4 D T o t a l

5 D T o t a l

6 D T o t a l

7 D T o t a l

8D

4 F T o t a l

5 F T o t a l

6 F T o t a l

7 F T o t a l

8F



### F i gu re 5-2. Con g en er p r of i l e f o r ai r em i ssi on s f r om cem en t k i l n s b u r n i n g h a zard ou s w a ste f o r ref eren ce year 2000.

5-11

### T a b l e 5-3. CDD/CDF em ission f a ctors (n g/k g clin k e r p r od u ced ) f o r cem e n t k iln s n o t b u r n i n g h a zard ou s w a ste f o r ref eren ce years 1987, 1995, an d 2000 a



### C o ngener/congener group Mean emission f a ctor

N o ndetect set to z ero N o n d e tect set to 1⁄2 d e tection limit
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.01 0.03 0.03 0.04 0.04 0.39 0.64 0.02 0.04 0.04 0.05 0.06 0.39 0.64
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.73 0.1 0.22 0.17 0.05 0.01 0.08 0.13 0 0.22 0.73 0.11 0.23 0.18 0.06 0.02 0.08 0.14 0.02 0.24

Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### 0.26 0.27 0.29 0.31

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 1.89 1.92 5.51 0.78 0.64 7.72 2.06 0.56 0.23 0.22 1.89 1.92 5.51 0.78 0.64 7.72 2.06 0.56 0.23 0.24

T o tal CDD/CDF 21.53 21.55

a T h e s a m e C DD/C D F em is s i on f actor w a s as s u m e d f o r all th ree y ears

.

S o u r ces : U

. S

. EPA (1996b); Bel l (1999).



### United States (U.S. DOC, 1996), and of this amount, 61.3 billion kg were produced by cement kilns burning nonhaz a rdous waste (Memora ndum dated Aug u st 23, 1995, from E. Heath, Research Triang le I n stitute, to J

. W ood, U.S. EPA); therefore, approx imately 6.3 billion kg were produced by cement kilns burning haz a rdous waste. B a sed on the fact that 9.3% of the clinker

5-12R a t i o ( c on ge ne r e m i s s i on f a c t or / 2 3 7 8

- C D D / C

D F e m i s s i on f a c t or )

0. 0 0 0 0

. 050 0

. 10 0 0

. 1 50 0. 200 0

. 25 0 0

. 3 00

4D 237 8

5D 1 237 8

6D 12 347 8

6D 12 367 8

6D 12 378 9

7D 1 2 3 467 8

8 D 12 34 678 9

4 F 237 8

5F

1 237 8

5F

2 347 8

6F 12 347 8

6F 12 367 8

6F 12 378 9

6F 23 467 8

7F 12 34 6 7 8

7F 12 34 7 8 9

8F

12 34 678 9

R a t i o ( c o n g e ne r g r o u p e m i s s i on f a c t o r / t o t a l C D D / C D F e m i s s i on f a c t or )

0. 0 0 0 0

. 0 5 0 0

. 1 0 0 0

. 1 50 0

. 20 0 0

. 2 50 0. 30 0 0

. 3 5 0

4D T o t a l

5D T o t a l

6D T o t a l

7D T o t a l

8D 12 34 67 89

4F T o t a l

5F T o t a l

6F T o t a l

7F T o t a l

8 F

12 34 67 89



### F i gu re 5-3. Con g en er p r of i l e f o r ai r em i ssi on s f r om cem en t k i l n s b u r n i n g n o n h a zard ou s w a ste f o r ref eren ce years 1987, 1995, an d 2000.

5-13

### produced in 1995 was from cement kilns burning haz a rdous waste, it is assumed that

approx imately 4.8 billion kg of the clinker produced in 1987 were from cement kilns burning
haz a rdous waste.
I n 2000, cement kilns produced approx imately 75.2 billion kg of clinker. This amount is based on the assumption that cement kilns ope rated at 90% of the max imum annual clinker capacity of 83.6 billion kg (e -mail dated J a nuary 31, 2003, fro m Garth Hawkins, Portland Cement Association, to Karie R iley

, Versar, I n c.). B a sed on the annual clinker capacities of individual cement kilns, approx imately 11.5 b illion kg of clinker (15%) were produced by cement kilns burning haz a rdous waste and appr ox imately 63.7 billion kg of clinker (85%) were produced by cement kilns not burning haz a rdous waste (PCA, 2001). The activity level estimates for 1995 and 2000 are g i ven a hig h confidence ratin g because they are based on comprehensive

survey data, but the rating for 1987 is medium b ecause of uncertainty concerning the proportion produced by haz a rdous waste-bur ning kilns (U.S. EPA, 1996b).

5.1.6. National CDD/CDF Em ission Estim a tes
5.1.6.1. Estim ates for Reference Y e ars 1987 and 1995
Na tiona l e s tima te s of CDD/CDF a i r e missions ( g TEQ/y r ) f r o m a ll Por tla nd c e m e n t kilns for reference y ears 1987 and 1995 were made by multiply ing the averag e TEQ emission factors by an estimate of the annual activity level (cement clinker produced) for each of the three subcateg ories (haz ardous waste-burning kilns with APCD inlet temperatures g r eater than 232°C
and less than 232°C and kilns bur ning nonhaz a rdous waste). Of the 10 haz a rdous waste-burning
kilns with APCD te mpe r a t ur e da ta , 8 f a c ilitie s ( 80% ) ha d APCD inle t te mpe r a t ur e s g r e a t e r tha n 232°C and 2 facilities (20%) had AP CD inlet temperatures less th an 232°C. The percentag e s of
haz a rdous waste-burning kilns w ith input temperatures less th an and g r eater than 232°C were assumed to represent the actual distribution of ac tivity level in the industry

. These percentag e s, coupled with the TEQ emission factors presente d in Table 5-1 and Table 5-3 (haz ardous waste
cement kilns and nonhaz a rdous waste cement kiln s, respectively ) a nd the activity levels established in Section 5.1.5, were used to calcu late the annual nationa l TEQ emission estimates
shown in Table 5-4. Overall, 131 g TEQ DF 

### -W HO 98 

### (122 g I

- TEQ DF 

### ) were produced by cement kilns in 1987. Of this amount, 116.7 g TEQ DF 

### -W HO 98 

### (108.6 g I

- TEQ DF 

### ) were produced by haz a rdous wasteburning cement kilns with inlet APCD te mperatures g r eater than 232°C, 1.1 g TEQ DF 

### -W HO 98 

### (1 g I

- TEQ DF 

### ) were produced by cement kilns burni ng haz a rdous waste with inlet APCD temperatures less than 232°C, and 12.7 g TEQ DF 

### -W HO 98 

### (12.3 g I

- TEQ DF 

### ) were produced by cement kilns burning nonhaz a rdous waste.

5-14

### T a b l e 5-4. Nati on al em i ssi on esti m a tes f o r cem en t k i l n s f o r ref eren ce years 1987 and 1995

Category TEQ emission f a ctor ( n g/ kg cl i nker) A c tivity level (b illion k g clinker/yr) Annual TEQ em i ssi on (g/yr)

I-T E Q DF 

### TEQ DF 

### ­ WHO 98 

### I-T E Q DF 

### TEQ DF 

### ­ WHO 98 

### R e f erence year 1987

Haz a rdous waste >232° C Haz a rdous waste <232° C Nonhaz a rdous waste 28.58 1.04 0.26 30.7 1.11 0.27 3.8 1 47.2 108.6 1 12.3 116.7 1.1 12.7

T O T A L 5 2 122 131

R e f erence year 1995

Haz a rdous waste >232° C Haz a rdous waste <232° C Nonhaz a rdous waste 28.58 1.04 0.26 30.7 1.11 0.27 5.04 1.26 61.3 144 1.3 15.9 154.7 1.4 16.6

T O T A L 67.6 161 173



### I n 1995, a total of 173 g TEQ DF 

### -W HO 98 

### (161 g I

- TEQ DF 

### ) were produced by cement kilns. Of this amount, 154.7 g TEQ DF 

### -W HO 98 

### (144 g I

- TEQ DF 

### ) were produced by haz a rdous wasteburning cement kilns with inlet APCD te mperatures g r eater than 232°C, 1.4 g TEQ DF 

### -W HO 98 

### (1.3 g I

- TEQ DF 

### ) were produced by cement kilns burni ng haz a rdous waste with inlet APCD temperatures less than 232°C, and 16.6 g TEQ DF 

### -W HO 98 

### (15.9 g I

- TEQ DF 

### ) were produced by cement kilns burning nonhaz a rdous waste. The overall rating for these emission estimates is low because the emission factors had a
low c onf ide n c e r a ting

.

5.1.6.2. Estim ates for Reference Y e ar 2000
Na tiona l e s tima te s of CDD/CDF a i r e missions ( g TEQ/y r ) f r o m a ll Por tla nd c e m e n t kilns for reference y ear 2000 were made by multiply ing the averag e TEQ emission factors by an estimate of the annual activity level (cement clinker pr oduced) for the nonhaz a rdous waste
categ ory

. The TEQ emission factors presente d in Table 5-3 (above) and the activity levels
established in Section 5.1.5 were used to calcu late the annual nationa l TEQ emission estimates
shown in Table 5-5. F o r 2000, 17.2 g TEQ DF 

### -W HO 98 

### (16.6 g I

- TEQ DF 

### ) we r e e mitte d by c e m e n t kilns not burning haz a rdous waste. The emission estimates for cement kilns not burning
haz a rdous waste in 2000 have an overall low confidence rating b ecause of the small number of

te ste d f a c ilitie s pr oviding the ba sis f o r

the e mission f a c t or

. The e mission f a c t or ma y not be

5-15

### representative of emissions from cement kilns not burning haz a rdous waste. However, the

act i v i t y l e vel i s g i ven a hi g h confi d ence ra t i n g because i t i s based on m easured dat a

. I n reference y ear 2000, 22 cement kilns burni ng haz a rdous waste as supplemental fuel

we r e ope r a tiona l in the Unite d St ates, and most had been stack tested and evaluated for diox in
emissions. Using the measured data from the stack tests, EPA estimated that 18.8 g TEQ DF 

### WH O 98 

### (16.6 g I

- TEQ DF 

### ) were released from all cement k ilns burning haz a rdous waste in 2000. The emission estimates for cement kilns burning haz a rdous waste in 2000 have an overall hig h
confi d ence rat i n g because t h e em i ssi on fact ors ha ve a hi g h confi d ence rat i n g due t o t h e l a rg e numbe r of te ste d f a c ilitie s pr oviding the ba sis f o r

the e mission f a c t or

. The a c tivity le ve l is g i ve n a hig h confidence rating because the amount of clinker produced by cement kilns burning
haz a rdous waste is known.

5.1.7. EP A Regulatory Activities
I n 1999 EPA promulg a ted national emission st andards for new and ex isting cement kilns burning and not burning haz a rdous waste (F eder al Reg i ster, 1999a, b). A number of parties, representing both industrial and e nvironmental communities, requested judicial review of the rule affecting cement kilns and incine rators burning haz a rdous waste and challeng ed EPA’s emission standards and several imp lementation provisions. On J u ly 24, 2001, the U.S. Court of Appeals
for the District of Columbia Ci rcuit vacated the emission standard s. I n response to this action, EPA proposed new standards affec ting cement kilns and incinerato rs burning haz a rdous waste on April 20, 2004 (Federal Reg i ster , 2004), which were made fi nal in December 2005 (Federal Reg i ster, 2005).
With r e g a r d to diox in e missions, the r e g u la tions a r e spe c if ic to the I

- TEQ c onc e n tr a tion
in the c o mbustion g a se s le a v ing the sta c k. Ex isting a nd ne w c e me nt kilns e ithe r c o mbusting or not combusting haz a rdous waste as supplemental fuel cannot emit more than 0.2 ng I

- TEQ/dscm.
I n addition, the temperature of the combustion g a ses measured at the inlet to the APCD cannot

ex ceed 232oC. The rule required owners or opera tors of facilities to test for CDDs/CDF s every 21⁄2 y ears. EPA ex pects this rule to reduce I

- TEQ DF 

### e missions f r o m e x isting a nd ne w f a c ilitie s by
more than 30% over the nex t several y ears (F ederal Reg i ster, 1999a, b, 2004, 2005).

5.1.8. Solid Waste f r om Cem e nt Ma nuf acturing: Cem e nt K iln Dust
EP A charact eri z ed C KD (t he sol i d resi dual ma te r i a l g e ne r a te d dur ing the ma nuf a c t ur ing of cement) in a report to Cong ress (U.S. EPA, 1993a) that was based in part on a 1991 survey of cement manufacturers conducted by the Portland Cement Associati on (PCA). Survey responses were recei ved from 64% of t h e act i v e cem ent ki l n s i n t h e Uni t e d S t at es. On t h e basi s of t h e

5-16

### T a b l e 5-5. Nati on al em i ssi on esti m a tes f o r cem en t k i l n s f o r ref eren ce year 2000

T e sted f a cility ID Haz a rdous w a ste

b u r n i n g k iln s E stimate in g I-T E Q/yr E stimate in g WHO-T E Q/yr

200 0.61 0.67
201 0.01 0.01
203 3.77 4.24
204 3.15 3.63
205 0.14 0.16
206 1.12 1.39
207 0.05 0.06
208 0.88 1.26
228 0.06 0.07
300 3.45 3.53
302 0.23 0.27
303 0.13 0.16
318 0.27 0.30
319 0.50 0.59
322 0.04 0.04
323 0.06 0.07
403 0.32 0.38
404 0.06 0.07
473 0.11 0.12
491 1.59 1.75
680 0.01 0.01
681 0.06 0.07

T o tal Haz a rdous waste burning k ilns 16.6 18.8

T o tal Non- haz a rdous waste burning k ilns 16.6 17.2

All cem ent k ilns 33.2 36.0

S o u r ce: U

. S

. EPA (2002a).



### 5-17

### survey responses, EPA estimated that in 1990 the U.S. cement industry g e nerated about 12.9 million metric tons of g r oss CKD and 4.6 million me tric tons of net C KD, of which 4.2 million
metric tons were land-di sposed. The m a t e ri al col l ect ed by the APCD sy ste m is c a lle d g r oss CKD (or as-g enerat ed C KD); i t i s ei t h er recy cl ed back i n t o t h e ki l n sy st em or rem oved from t h e sy st em for di sposal (becom i n g net C KD or as-m anag ed C KD)

. As discussed below, low levels of diox in
ha ve be e n me a s ur e d in CKD. This ma te r i a l is dispose d of in pe r mitte d la ndf ills a nd the r e f or e is
not considered to be an environmental release and is not included in the inventory of diox in

r e le a s e s pr e s e n te d in this r e por t. Howe ve r , f o r

inf o r m a tiona l pur pose s only

, e s tima te s of the
amount of diox in in CKD were devel oped for the reference y ears 1987, 1995, and 2000. The PCA recently provided current estimates of the amount of CKD removed from the manufacturing process for benefi cial reuse and long -term ma nag e ment units (i.e., landfill disposal) in 1990, 1995, and 2000 (e-mails date d J a nuary 31 and March 18, 2003, from Garth Hawkins, Portland Cement Associa tion, to Karie Riley

, Versor, I n c. ). Possible beneficial reuses
inc l ude munic i pa l wa ste da ily c ove r ma te r i a l , munic i pa l wa ste la ndf ill f i na l c ove r ma te r i a l , soil

sta b iliza tion f o r

r o a d wa y s or othe r str u c t ur e s , wa ste ne utr a liza tion/sta b iliza tion/solidif ic a tion (food wastes, haz a rdous wastes, etc.), and ag ri cultural soil amendment. The PCA estimated that the amount of CKD beneficially reused on or off site was 752 million kg in 1990, 652 million kg in 1995, and 575 million kg in 2000. The amount of CKD disposed of annually in landfills was estimated to be 2.7 billion kg in 1990, 3.1 billion kg in 1995, and 2.2 billion kg in 2000.
I n its report to Cong ress (U.S. EPA, 1993a), EPA also included the results of sampling and analy s is of CKD and cli nker conducted in 1992 and 1993. The purposes of the sampling and
anal y s i s effort s were t o (a) charact eri z e t h e C DD/ C D F cont ent of cl i nker and C KD, (b) det e rm i n e the relationship, if any

, between the CDD/CDF c ontent of CKD and the use of haz a rdous waste
as fuel , and (c) det e rm i n e t h e relationship, if any

, between th e C DD/ C D F cont ent of C KD and the use of wet-process a nd dry

- process cement kilns. Clinker samples were collected from five cement kilns burning nonhaz a rdous waste and
six kilns burning haz a rdous waste. CDDs/CDF s were not detected in any of the samples. Tetrathroug h octa-chlorinated CDDs/C DF s were detected in the g r oss CKD samples obtained from 10 of the 11 kilns and in the net CKD samples obt ained from 8 of the 11 kilns. The CDD/CDF
content rang ed from 0.008 to 247 ng I

- TEQ DF 

### /kg for g r oss CKD and from 0.045 to 195 ng I TEQ DF 

### /kg for net CKD. Analy s es for seven PCB cong eners were also conducted, but no

cong eners were det ect ed i n any clinker or CKD sample.
Mean CDD/CDF concentrations in net CKD g e nerated by the kilns burning haz a rdous waste were hig h er (35 ng I

- TEQ DF 

### /kg ) tha n in ne t CKD g e ne r a te d by the f a c ilitie s bur ning
nonhaz a rdous waste (0.003 ng I

- TEQ DF 

### /kg )

. These calculations of mean values treated nondetect
values as z e ro. I f the nondetects had been ex cluded from the calculation of the means, the mean ­

5-18

### for net CKD from kilns burning haz a rdous waste would increase by a factor of 1.2 and the mean for net CKD from kilns burning nonhaz a rdous wast e would increase by a factor of 1.7. One sampled kiln had a net CKD TEQ concentration of more than tw o orders of mag n itude g r eater than the TEQ levels found in samples from any other kiln. I f this kiln were considered aty p ical of the industry (U.S. EPA, 1993a) and were not included in the calculation, then the mean net
CKD concentration for haz a rdous waste-bur ning kilns would decrease to 2.9 ng I

- TEQ DF 

### /kg

. CDD/CDF c ong e n e r da ta f

o r

CKD f r o m Holna m , I n c ., Se a ttle , WA, we r e pr e s e n te d in a report by the W a shing t on State Department of Ecolog y (1998). The da ta were compiled and
evaluated to determine total I

- TEQ concentrations and loading s

. Nondetect values were included

a s e ithe r ze r o, one

- h a l f of the de te c tion limit ( D L ) , or a t the DL

. The r e sults of thr e e se pa r a te tests of CKD were as follows, assumin g that nondetect values were z e ro:

I

- TEQ I

- TEQ Date (ng / kg ) (mg / day ) 05/15/96 0.038 0.0038 10/21/97 0.67 0.0674 10/21/97 0.95 0.0948

EPA provided data for ashes from an ESP connect ed t o a cem ent ki l n and an FF connected to a lig htweig ht ag g r eg ate (L W A ) k iln (U.S. EPA, 1999e). The averag e cong ener

c onc e n tr a tions f o r

the a s h sa mple s a r e liste d in Tabl e 5-6. The averag e concent r at i ons for t h e

cem ent ki l n were det e rm i n ed from t w o di fferent wast e st ream s, each wi t h fi ve sam p l e burns. The averag e concent r at i ons for t h e L W A ki l n were det e rm i n ed usi n g one wast e st ream wi t h t h ree sample burns.
The amount of CDDs/CDF s associated with CKD was calculated for informational purposes only

. National estimate s were divided among cement k ilns burning haz a rdous waste and those burning nonhaz a rdous waste for both CKD that was beneficially reused and CKD that

wa s se nt la ndf ills. The a c tivity le ve ls use d in the e s tima te s we r e those pr ovide d by the PCA ( e

mail dated March 18, 2003, from Gart h Hawkins, Portland Cement Association, to Karie Riley

, Versar, I n c.). The 1990 activity levels provided by PCA were us ed for reference y ear 1987. The
CDD/CDF c onc e n tr a tions in CKD use d in the e s tima te s we r e 35 ng I

- TEQ DF 

### /kg f o r

c e me nt kilns burning haz a rdous waste (which includes th e hig h value discussed above) and 0.003 ng I TEQ DF 

### /kg for cement kilns burning nonhaz a rdous waste.

As shown in Table 5-7, by combining the a ppr opr ia te a c tivity levels and CDD/CDF

c onc e n tr a tions, na tiona l e s tima te s of CDDs/CDF s in CKD we r e de ve lope d f o r

r e f e r e nc e y e a r s 1987, 1995, and 2000. F o r cement kilns burning ha z a rdous waste, approx imately 4.2 g I

- TEQ DF



### 5-19 ­

### T a b l e 5-6. CDD/CDF con cen tration s (n g/k g ) in ash sam p les f r om cem en t k iln electrostatic p recip i tator an d ligh t w e igh t aggregate (LWA) k iln f a b r ic filt e r

C o ngener Ce m e nt k iln LWA k iln C e men t k iln L W A k iln Avg.

conc. Avg.

c o nc . I

- TEQ WHOTEQ I

- TEQ W H O

- TEQ
2,3,7,8- T C DD Total TC D D 1,2,3,7,8- PeCDD Total P e C D D 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD Total H x C D D 12,2,3,4,6,7,8- HpCDD Total H p C D D OCDD 0.429 36.1

0.886 54.9

1.03 2.36 2.47 173

17.7 55.2 21 3.97 333

17.3 467

15.4 35.6 56.6 500 133 300 133 0.429

– 0.443

– 0.103 0.236 0.247

– 0.177

– 0.021 0.429

– 0.886

– 0.103 0.236 0.247

– 0.177

– 0.0021 3.97

– 8.65

– 1.54 3.56 5.66

– 1.33

– 0.133 3.97

– 17.3

– 1.54 3.56 5.66

– 1.33

– 0.133

T o tal T C DD T E Qs 1.66 2.08 24.8 33.5
2,3,7,8- T C DF Total TC D F 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF Total P e C D F 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF Total H x C D F 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF Total H p C D F OCDF 4.65 18.1

1.04 2.59 31.8

2.13 0.869 0.523 2.14 9.26 1.84 0.739 3.06 1.43 833 4630

100 267 2930

267 100 7.8 133 1230

167

22.6 2670 39.2 0.465

– 0.0518 1.3

– 0.213 0.0869 0.0523 0.214

– 0.0184 0.00739

– 0.00143 0.465

– 0.0518 1.3

– 0.213 0.869 0.0523 0.214

– 0.0184 0.00739

– 0.000143 83.3

– 5 133

– 26.7 10

0.780 13.3

– 1.67 0.226

– 0.0392 83.3

– 5 133

– 26.7 10

0.780 13.3

– 1.67 0.226

– 0.00392

T o tal T C DF T E Qs 2.41 3.19 274 274

– = N o dat a av ai l a bl e



### in 1987, 3.6 g I

- TEQ DF 

### in 1995, and 3.3 g I

- TEQ DF 

### in 2000 were produced from CKD that was beneficially reused, a nd approx imately 14.9 g I

- TEQ DF 

### in 1987, 17.7 g I

- TEQ DF 

### in 1995, and 12.8

g I

- TEQ DF 

### in 2000 were produced from CKD that was dis posed of in a landfill. F o r cement kilns burning nonhaz a rdous waste, approx imately 0.0019 g I

- TEQ DF 

### in 1987, 0.0016 g I

- TEQ DF 

### in 1995, and 0.0014 g I

- TEQ DF 

### in 2000 were produced from CKD that was beneficia lly reused, and

5-20

### T a b l e 5-7. CDD/ CDF esti m a tes i n cem en t k i l n d u s t (CKD) f o r ref eren ce years 1987, 1995, and 2000

Category CDD/ CDF concentration (ng I-TEQ DF 

### /k g of

CK D) CKD benef i cially reused on or

o ff s i t e C K D sen t to a lan d f ill f o r disposal

Activity level

(million k g t o ns CK D/ yr ) Annual TEQ CDD/ CDF concentration (g/yr) A c tivity level (million k g ton s CK D/ yr ) Annual TEQ CDD/ CDF concentration (g/yr)

R e f erence year 1987

H W k ilns NHW k i l n s 35 0.003 120 632 4.2 0.0019 426 2,230 14.9 0.0067

R e f erence year 1995

H W k ilns NHW k i l n s 35 0.003 104 547 3.6 0.0016 505 2,642 17.7 0.0079

R e f erence year 2000

H W k ilns NHW k i l n s 35 0.003 94 480 3.3 0.0014 365 1,858 12.8 0.0056

HW = Hazardou s w a s t e NHW = Non h azardou s w a s t e



### approx imately 0.0067 g I

- TEQ DF 

### in 1987, 0.0079 g I

- TEQ DF 

### in 1995, and 0.0056 g I

- TEQ DF 

### in 2000 were produced from CKD that was disposed of in a landfill. EPA is currently developing CKD storag e and disposal requirements. I n 1999, a proposed rule for the standards for the manag e ment of CKD was developed by EPA (F ederal Reg i ster, 1999a). Under the rule, CKD woul d remain a nonhaz a rdous waste, provided that proposed manag e ment standards are met, which would protect g r oundwater and control releases of fug itive dust. Additionally , the rule propos es concentration limits on various pollutants in CKD used for ag ricultural purpos es (F ederal Reg i ster, 1999c).

5.2. LIG H TWEIG H T AG G R EG ATE K I LNS
L

W A ki l n s heat raw m a t e ri al s such as cl ay , shal e, or sl at e t o ex pand t h e part i c l e s t o form lig htweig ht materials for use in concrete products. I n 1995, onl y 5 of the more than 36 L W A kilns in the United States were burning haz a rdous waste; in 2000, 9 L W A kilns were burning
haz a rdous waste. L W A kilns are estimated to have emitted 3.3 g I

- TEQ DF 

### to air in 1990 (F ederal Reg i ster, 1998a) and 2.4 g I

- TEQ DF 

### in 1997 (F ederal Reg i ster, 1999a); these estimates are used in this report for reference y ears 1987 and 1995, respectively

.

5-21

### The CDD/CDF emission factors for 2000 are base d on the data for five L W A kilns tested in 2000 (U.S. EPA, 2002a). They were calculate d using the process described in Section 3.2.3. The averag e emission factor for the L W A kilns was 1.986 ng TEQ DF 

### -W HO 98 

### /kg (2.063 ng
I

- TEQ DF 

### /kg ) of waste feed, assumin g nondetect values of z e ro. These are assig n ed a low
confi d ence rat i n g because t h e em i ssi on fact or m a y not be represent a t i v e of em i ssi ons from t h e
source cat eg ory

. The amount of haz a rdous waste combusted using L W A kilns in 2000 was conservatively estimated to be 903,000 metr ic tons, based on estima ted activity levels de rived for each halog e n acid furnace (HAF ) in 2000. Data were available for all of the nine facilities operating in 2000. A conservative estimate for the averag e annual quantity burned per HAF (100,280 metric tons/y r) was derived by assuming that pl ants operate continuously thr oug hout the y ear and are alway s running at 80% of capacity

. This quantity , mu ltiplied by the total unive rse of nine facilities,

y i elded the final estimate. B ecause the activity level was not derived from a survey but was

e s tima te d, it is g i ve n a low c onf ide n c e r a ting

. Equation 3-5 (Chapter 3, Section 3.2.4), used to calculate annual TEQ emissions for
dedicated haz a rdous waste incine rators, was also used to calcu late annual TEQ emissions for
L

W A kilns. Multiply ing the averag e TEQ emi ssion factors by the total estimated amount of liquid haz a rdous waste burned in 2000 y i elds an annual emissions estimate. F r om this procedure, the emissions from all L W A kilns burni ng haz a rdous waste as supplemental fuel were estimated as 1.86 g TEQ DF 

### -W HO 98 

### (1.79 g I

- TEQ DF 

### ) for 2000. B ecause of the low confidence

r a ting f o r

the e mission f a c t or , the ove r a ll c onf ide n c e r a ting f o r

the e mission e s tima te s is low.

5.3. ASP H ALT MIXING P L ANTS Asphalt consists of an ag g r eg ate of g r av el, sand, and filler mix ed with liquid asphalt

c e m e n t or bitume n. F ille r ty pic a lly c onsists of lime stone , mine r a l stone powde r , a nd some time s ash from power plants and municipal waste com bustors. The ex act composition of an asphalt
f

o r m ula tion de pe nds on how it will be use d. The a g g r e g a t e typic a lly c onstitute s mor e tha n 92% by weig ht of the total asphalt mix ture. The com ponents of the ag g r eg ate are dried, heated to a
temperature rang ing from 135 to 163°C, and then mix ed and coated with the bitumen at an asphalt mix ing installation. “Old ” asphalt (i.e., asphalt from disman tled bridg e s and roads) can be heated and disag g r eg ated to its orig inal components and reused in the manufacture of new asphalt (U.S. EPA, 1996c). “Hot mix ” asphalt pavi ng materials can be manufactured by batch
mix plants, continuous mix plants, parallel-flow drum mix plants, and counterflow drum mix plants (U.S. EPA, 1998c).
B r emmer et al. (1994) reported the CDD/CD F emissions factor for an asphalt mix ing plant in the Netherlands as 47 ng I

- TEQ DF 

### per metric ton of produced asphalt. No cong ener5-22

### specific emission factors were reported. The mix ing plant heated old asphalt to about 150°C in an individual recy cling drum with kiln ex haus t g a se s tha t we r e mix e d with a m bie n t a i r a n d heated to a temperature of 300 to 400°C. Paralle l to this recy cling drum was the main drum,
whi c h dri e d and heat ed t h e ag g r eg at e (sand and g r a v e l/g r a nite c h ipping s) to a te mpe r a t ur e of
about 220°C. The kiln ex haust g a ses leaving the recy cling drum were le d along the main burner
of the main drum for incineration. The old as phalt, the minerals from the main drum, and new bitumen from a hot storag e tank (about 180°C) we re mix ed in a mix er to form new asphalt. Natural g a s fueled the plant during the sample collection period, and 46% of the feed was old asphalt. The plant’s APCD sy stem consisted of cy clones and an F F

. Umweltbundesamt (1996) re ported lower emission factors for three tested facilities in
Ge r m a n y tha t we r e a l so e quippe d with F F s

. The s e thr e e f a c ilitie s we r e f u e l e d by oil or buta n e
g a s and used old asphalt at rates rang ing from 30 to 60% of the feed. The emission factors calculated from the stack g a s concentrations, g a s flow rates, and hourly throug hputs for these
three facilities were 0.2, 3.5, and 3.8 ng I

- TEQ DF 

### /metric ton of asphalt produced, respectively

. EPA conducted stack emissions testing at tw o hot-mix asphalt production plants in the United States (U.S. EPA, 2000g ). The Midwest Research I n stitute performed emission tests on
outlet of FFs that controlled emissions from the counter-flow rotary dry e r process used at the asphalt plant in Clay ton, NC, and from the parallel -flow rotary dry e r process used at the asphalt plant in Cary , NC. I n both processes, virg in a g g r eg ate of various siz e s was fed to the drum by cold-feed controls in proportions dictated by the final mix specifications. Ag g r eg ate was delivered at the opposite end of the burner in th e counter-flow continuous drum mix process and at the same end as the burner in the parallel-fl ow continuous drum mix pr ocess. EPA developed

a v e r a g e TEQ e mission f a c t or s f r o m the te ste d f a c ilitie s to r e pr e s e n t hot- mix a s pha lt pla n ts in

g e neral (U.S. EPA, 2000g ). The averag e TEQ e mission factor for hot-mix asphalt plants was
1.40e

– 

### 03 ng I

- TEQ (1.46e

– 

### 3 ng TEQ DF 

### -W HO 98 

### /kg ) asphalt produced. Table 5-8 summariz e s the TEQ emission factors for hot-mix asphalt plants.
B ecause only two U.S. facilities have been te sted, these emission factors are g i ven a low
confi d ence rat i n g

. I t i s l i k el y t h at t h ese em i ssi on fact ors are not represent a t i v e of C DD/ C D F emissions from all ty pes of as phalt production facilities in the Un ited States; nevertheless, they are sufficient to derive a preliminary estima te of annual emissions from asphalt production
facilities in the United States for 2000. Approx imately 500 million tons of hot-mix as phalt paving materials were produced at

approx imately 3,600 active asphalt pl ants in the United States in 1996 (U.S. EPA, 1998c). This activity level was used to repr esent reference y ear 2000. The activity level is g i ven a hig h
confidence level because it was based on a comprehensive surv ey

. A preliminary estimate of annual TEQ air releases for 2000 was calculated by multiply ing the activity level (in kilog r ams)

5-23

### T a b l e 5-8. Con g en er-sp eci f i c em i ssi on f a ctors (ng/kg asphalt produced) derived f r om the testing of air em issions at tw o hot-m ix asphalt plants in the Un i t ed S t ates

Con g en er Mean em i ssi on f a ctor
I- TEQ DF 

### TEQ DF 

### -WH O 98 

### 2,3,7,8-TCDD 1,2,3,7,8-PeCD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 9.53e–05 7.03e–05 1.91e–05 5.90e–05 4.45e–05 2.18e–05 1.13e–05 9.53e–05 1.41e–04 1.91e–05 5.90e–05 4.45e–05 2.18e–05 1.13e–06 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 4.40e–05 9.75e–05 1.91e–04 1.81e–04 5.44e–05 8.62e–05 3.81e–04 2.95e–05 1.22e–05 2.18e–06 4.40e–05 9.75e–05 1.91e–04 1.81e–04 5.44e–05 8.62e–05 3.81e–04 2.95e–05 1.22e–05 2.18e–07
Total TEQ 1.40e–03 1.50e–03

S o u r ce: U

. S

. EPA (2000g ).



### by the averag e emission factor of 1.40e–03 ng I

- TEQ (1.46e–3 ng TEQ DF 

### -W HO 98 

### /kg ) asphalt produced. Approx imately 0.70 g I

- TEQ (0.73 g TEQ DF 

### -W HO 98 

### ) we r e e mitte d into the a i r f

r o m asphalt plants in the United States in 2000. This estimate is assig n ed a low confidence level
because t h e em i ssi on fact ors are g i ven a l o w confi d ence l e vel rat i n g

.

5.4. P ETROLEUM REF I NING CATALYST REG E NERATION
Re g e ne r a tion of spe n t c a t a l y s t f r o m the r e f o r ming process at petroleum refineries is a potential source of CDDs/CDF s, according to limited testing conducted in the United States (Amendola and B a rna, 1989; Kirby

, 1994), Canada (Maniff and L e wis, 1988; Thompson et al., 1990), and the Netherlands (B remmer et al., 1994)

. This section summariz e s the cataly s t

reg e neration process, re levant studies performed to date, and the status of EPA reg u latory investig ations of this source.

5-24

### Ca ta ly tic r e f o r ming is the pr oc e ss use d to pr oduc e hig h

- o c t a n e r e f o r m a t e s f r o m lowe r

octane reformates for blending of hig h -octane g a solines and avi a t i on fuel s. The reform i n g process occurs at hig h temperature and pre ssure and requires the use of a platinum or platinum/rhenium cataly s t. Du r i ng the r e f o r ming pr oc e ss, a c o mple x mix tur e of a r oma tic compounds, known as coke, is formed and deposited onto the cataly s t. As coke deposits onto the cataly s t, its activity is decreased. The hig h co st of the cataly s t nece ssitates its reg e neration.
Ca ta ly st r e g e ne r a tion is achieved by removing the coke depos its via burning at temperatures of 399 to 454°C and then reactivating the cataly s t at elevated temperatures (454 to 538°C) using chlorine or chlorinated compounds (e.g ., methy l ene chloride, 1,1,1-trichlor oethane, and ethy lene dichloride; most refineries use ch lorine of perchloroethy l ene). B u rning of the coke produces kiln

ex haust g a ses that can contain CDDs and CDFs along with other combustion products. B ecause kiln ex haust g a ses, if not vent ed directly to the atmosphere, may be scrubbed with caustic or water, internal effluents ma y become contaminated with CDDs/CDF s (Kirby , 1994; SAI C
, 1994).
Three basi c cat al y s t reg e nerat i on processes are used: sem i -reg e nerat i v e, cy cl i c , and
continuous. During the semi-reg e ne rative process, the entire cataly tic reformer is taken off line.
I n t h e cy cl i c process, one of t w o (or m o re) reform i n g react ors i s t a ken off l i n e for cat al y s t

reg e nerat i on; t h e rem a i n i n g react or(s) rem a i n s on l i n e so t h at reform i n g operat i ons cont i nue. I n the continuous process, ag ed cataly s t is con tinuously removed from one or more on-line stacked
or si de-by

- si de react ors, reg e nerat e d i n an ex t e rn al reg e nerat o r, and t h en ret u rned t o t h e sy st em ; the reforming sy stem, consequen tly , never shuts down (SAI C, 1994).
I n 1988, a study by the Canadian Ministry of the Environment (Maniff and L e wis, 1988) detected concentrations of CDDs rang ing from 1.8 to 22.2 μg /L and CDF s rang ing from 4.4 to
27.6 μg /L in an internal waste stream of spent caustic at a petroleum refinery

. The hig h est concentration of 2,3,7,8-TCDD was 0.0054 μg /L

. CDDs were also observed in the refinery ’s biolog ical sludg e at a max imum concentration of 74.5 μg /kg

, and CDF s were observed at a

max imum concentration of 125 μg /kg

. The con centration of CDDs/CDF s in the final combined refinery plant effluent was below the DL s. Amendola and B a rna (1989) repor ted detecting trace levels of hex a - to octa-CDDs and
CDF s in untreated wastewaters (up to 2.9 pg I

- TEQ DF 

### /L ) and wastewater sludg es (0.26 to 2.4 ng
I

- TEQ DF 

### /kg ) a t a r e f i ne r y in Ohio. The le ve ls of de te c t e d tota l CDDs/CDF s in the wa ste w a t e r and sludg e were much lower (<3 ng /L and <1 μg /kg

, r e spe c tive l y ) tha n the le ve ls r e por te d by
Maniff and L e wis (1988). No CDDs /CDF s were detected in the fi nal treated effluent (less than
0.2 ng I

- TEQ DF 

### /L ). The data collected in the study were acknowledg ed to be too limited to
enabl e i d ent i f y i ng t h e source(s) of t h e C DDs/ C DF s within the refinery

. The study authors also
present e d i n an appendi x t o t h ei r report t h e resul t s of anal y s es of wast ewat er from t h e cat al y s t

5-25

### reg e neration processes at two ot her U.S. refineries. I n bot h cases, unt reat ed wast ewat ers

c onta i ne d CDDs/CDF s a t le ve ls r a ng ing f r o m hig h pic o g r a m s to low na nog r a ms pe r lite r ( r e sults were reported for cong ener g r oup totals, not specific cong ener s). However, CDDs/CDF s were not detected in the only tr eat ed effl uent sam p l e co llected at one refinery

. Thompson et al. (1990) reported total C DD and CDF concentrations of 8.9 ng /m 3 

### and 210

ng /m 3 

### , respect i v el y , i n st ack g a s sam p l e s from a C a nadi an pet r ol eum refi nery ’s reform i n g operation. They also observed CDDs/CDF s in th e picog r am- to nanog ram-per-liter rang e in the
internal washwater from a scrubber of a periodic/cy clic reg e nerator.
B eard et al. (1993) conducted a series of benchtop ex periments to investig ate the

m echani s m ( s) of C DD/ C D F form at i on i n t h e cat al y tic reforming process. A possible pathway
for the formation of CDF s was found, but the resu lts could not ex plain th e formation of CDDs. Analy s es of the kiln ex haust g a s from burni ng coked cat al y s t s reveal ed t h e presence of
unchlorinated dibenz ofuran in quantities up to 220 μg /kg of cataly s t. Chlorination ex periments
indicated that dibenz ofuran and, possibly

, bipheny l and similar hy drocarbons act as CDF precursors and can become chlorinated in the cataly s t reg e neration pro cess. Corrosion products on the steel piping of the process plant seem e d to be the most like l y c h lor i na ting a g e n t.
I n May 1994, EPA’s Office of W a ter conducte d a sampling and analy tical study of

cat al y s t reg e nerat i on wast ewat er for C DDs/ C DFs at three petroleum refining plants (Kirby

, 1994). The study objectives were to determine the analy tical me thod best suited for determining
C DDs/ C DFs i n refi nery wast ewat er and t o screen and charact e ri z e wast ewat er di scharg es from several ty pes of refor ming operations for CDDs/CDF s. The report for this study (Kirby , 1994)

a l so pr e s e n te d r e sults submitte d volunta r ily to EPA by two othe r f

a c ilitie s. The sa mple d inte r n a l untreated wastewaters and spent caustics were found to contain a wide rang e of CDD/CDF concentrations, 0.1 pg I

- TEQ DF 

### /L to 57.2 ng I

- TEQ DF 

### /L

. The study results also showed that 90%
of t h e TEQ was cont ai ned i n t h e wast ewat er t r eatment sludg es g e nerate d during the treatment of

wast ewat er and caust i c from t h e reg e nerat i on process. I n 1995, EPA issued a notice of its proposed intent to not desig n ate spent reformer

c a t a l y s ts a s a liste d ha za rdous wa ste unde r RCRA (F e d e r a l Re g i ste r , 1995b). The fina l rule wa s issued in Aug u st 1998 (F ederal Reg i ster, 1998b). The Ag ency ’s assessment of current

manag e ment practices associated with recy cling of reforming cataly s t found no sig n ificant risks
to human health or the environment. The Ag ency estimated that 94% of the approx imately 3,600 metric tons of spent reformer cataly s t sent off s i t e by refi neri es were bei n g recy cl ed for t h ei r
pr e c i ous me ta l c onte n t. EPA ma de no de te r mina tion of the “ lista bility ” of spe n t c a u stic r e sidua ls
f

o r m e d dur ing r e g e ne r a tion of spe n t r e f o r ming c a t a l y s t, but it did ide n tif y

the pote n tia l a i r rel eases from t h e com bust i on of t h e reform i n g cat aly s t prior to reclamation as possibly being of

concern. The Ag ency requested comments on (a ) opportunities for removing diox in prior to

5-26

### discharg e of scrubber water into the wastewater treatment sy stem, (b) opportunities to seg r eg ate this wa ste s tr e a m , a nd ( c ) pote n tia l he a lth r i sks a ssociated with insertion of diox in-contaminated media back into the refinery process (such as th e coker). I n this proposed rulemaking , EPA also

note d the possibility of diox in r e le a s e s to a i r dur ing r e g e ne r a tion ope r a tions. As pa rt of its re g u la tory inve stig a tion unde r RCRA, EPA’s Offic e of Solid Wa ste commissioned a study to analy z e and discuss ex isting data and information concerning
CDD/CDF formation in the treatme nt of cataly tic reformer wa stes. This report (SAI C, 1994)

a l so ide n tif ie d pote n tia l pr oc e ss modif i c a tions tha t ma y pr e v e n t the f o r m a tion of CDDs/CDF s. The report’s authors concluded th at, althoug h the available data indicate that CDDs/CDF s can be

g e nerated during the cataly s t reg e neration proce ss, t h e avai l a bl e dat a i ndi cat e t h at C DD/ C D F

concent r at i ons i n t r eat ed wast ewat er and i n sol i d wast e are m i n i m a l

. R e l eases t o ai r coul d resul t from vented kiln ex haust g a ses at some facilities. I n additi on, the CDDs/CDF s formed could possibly be reintroduced into other refining operations (e.g ., the coke r) and resulting products.
I n 1998, emissions from the caustic scrubber used to treat g a ses from the ex ternal

reg e neration unit of a refinery in California were tested (CAR B
, 1999). This facility uses a continuous reg e neration process. The reactor is not taken off line during reg e neration; rather, small amounts of cataly s t are continuously withdr awn from the reactor and are reg e nerated. The emissions from the reg e neration un it are neutraliz ed by a caustic scrubber before being vented to the atmosphere. The cataly s t r ecirculation rate during the th ree tests rang ed from 733 to 1,000
lb/hr

. All 2,3,7,8-substituted CDDs/CDF s were detected in each of the three samples collected. The averag e emission factors in units of nanog rams per barrel of reformer feed are presented in
Table 5-9. The cong ener profile is presented in F i g u re 5-4. Th e samples showed a wide rang e in
concentrations of the CDD/CDF cong eners (up to a fivefold difference); however, the cong ener profile was consistent in all samples. The concentrations of the individual furan cong ener g r oups were alway s hig h er than the concentrations of the corresponding diox in cong ener g r oup. The

averag e TEQ DF 

### -W HO 98 

### emission factor for these three tests was 3.18 ng TEQ/barrel and the

averag e I

- TEQ DF 

### was 3.04 ng TEQ/barrel.
I n 1991, stack testing was performed on th e ex haust from one of the three semireg e nerative cataly tic reforming units of a refi nery in California (Rad ian Corporation, 1991). At
the s e units, a c a u stic solution is intr oduc e d to the e x ha ust to ne utr a lize HCl e missions f r o m the

c a t a l y s t be ds pr ior to r e le a s e to the a tmos phere. The tested unit was considered to be representative of the other units. Each unit is periodically taken off line ( a ppr ox ima te ly onc e a
y ear) so the cataly s t beds can be reg e nerate d. The tested unit has a feed capacity of 7,000 barrels/day

. Approx imately 59,500 pounds of cat aly s t were reg e nerated during the tested

reg e neration cy cle, which lasted for 62 hr.

5-27

### The a v e r a g e e mission f a c t or s f o r

this f a c ility ( i n units of na nog a m s pe r ba r r e l of r e f o r m e r feed) are present e d i n Tabl e 5-9 and t h e cong en er profile is presented in F i g u re 5-4. The majority of the 2,3,7,8-substituted C DD cong eners were not detected during testing

. I n contrast, the majority of the 2,3,7,8-substituted CDF c ong eners were detected. The averag e TEQ DF 

### WH O 98 

### emission factor (assuming nondetect values were z e ro) was 1.04e–03 ng TEQ/barrel and

t h e averag e I

- TEQ DF 

### emission factor was 1.01e–03 ng TEQ/barre l. These values are three orders of mag n itude less than the emi ssion factor reported in CARB ( 1999). The calculation of these
emission factors involved several assumptions: the unit is reg e nerated once per y ear, the unit operates at capacity (7,000 barrels/day ), and the facility operates 362 day s /y r. The averag e of the two facility emission factors, 1.59 ng TEQ DF 

### -W HO 98 

### /barrel (1.52 ng I TEQ DF 

### /barrel) of reformer feed, is assumed to apply to all reference y e ars (1987, 1995, and 2000) and is assig n ed a low confidence rating

. Only one continuous and one semireg enerative unit in
the Unite d Sta t e s ha ve be e n te ste d. Combine d, the s e two f a c ilitie s r e pr e s e n t le ss tha n 1% of the cataly tic reforming capacity in U.S. petrol eum refineries in 1987 (3.805 million barrels/day ), 1995 (3.867 million barrels/day ), and 2000 (3.770 million barrels/day ) (EI A , 2002a). The

averag e emission factor develope d above assumes that emissions are proportional to reforming capacity ; however, they may be mo re related to the amount of c oke burned, the APCD equipment present, or other process parameters. The national daily averag e cataly tic reformin g capacities in the United States were 3.805, 3.867, and 3.770 million barrels per day for 1987, 1995, and 2000, respectively (EI A , 2002).
These were assi g n ed a hi g h confi d ence rat i n g b ecause t h ey are based on com p rehensi v e survey s of industry

. I f it is conserva tively assumed that all units opera ted at full capacity in all three

y ears, then apply i ng the averag e emission factor s of TEQ/barrel y i elds annual emissions of 2.21 g TEQ DF 

### -W HO 98 

### (2.11 g I

- TEQ DF 

### ) in 1987, 2.24 g TEQ DF 

### -W HO 98 

### (2.14 g I

- TEQ DF 

### ) in 1995, and
2.19 g TEQ DF 

### -W HO 98 

### (2.09 g I

- TEQ DF 

### ) in 2000. These emissions have a low confidence rating
because t h ey are based on an em i ssi on fact or wi t h a l o w confi d ence rat i n g

.

5.5. CIG ARETTE SM OK ING
B u mb et al. (1980) were the first to report that cig a rette smoking is a source of CDD
emissions. Subsequent studies by Muto and Ta kiz a wa (1989), B a ll et al. (1990), and L ö froth and
Z e bühr (1992) also reported the presence of CDDs as well as CDF s in cig a rette smoke. A study by Matsueda et al. (1994) re ported on the CDD/CDF content of tobacco from 20 brands of cig a rettes from seven countries. Althoug h a wi de rang e in the concentrations of total
CDDs/CDF s a nd tota l TEQs we r e r e por te d in the s e studie s , simila r c ong e n e r pr of ile s a n d
pat t e rns were report e d. The fi ndi ng s of each of t h ese st udi es are descri bed i n t h i s sect i on. ­

5-28

### T a b l e 5-9. CDD/CDF em ission f a ctors (ng/barrel) a 

### f o r p e trol eu m catal y ti c

r e f or m i ng unit s

C o ngener/congener
group Semiregenerative unit C onti nuous regeneration unit

Nondet ect set to z ero N o n d e tect set to 1⁄2 d e tection limit Nondet ect set to z ero Nondet ect set t o 1⁄2 d e tection limit

2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND 5.69e



### ! 05 4.22e



### ! 05 ND ND 7.02e



### ! 04 2.55e



### ! 03 2.35e



### ! 05 9.58e



### ! 05 8.09e



### ! 05 5.52e



### ! 05 5.10e



### ! 05 7.02e



### ! 04 2.55e



### ! 03 1.61e



### ! 02 2.87e



### ! 01 3.47e



### ! 01 8.45e



### ! 01 5.56e



### ! 01 3.02e+00 1.71e+00 1.61e



### ! 02 2.87e



### ! 01 3.47e



### ! 01 8.45e



### ! 01 5.56e



### ! 01 3.02e+00 1.71e+00

2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2.32e



### ! 04 4.68e



### ! 04 1.09e



### ! 03 1.06e



### ! 03 1.07e



### ! 03 ND 1.24e



### ! 03 2.94e



### ! 03 8.32e



### ! 04 1.01e



### ! 03 2.32e



### ! 04 4.68e



### ! 04 1.09e



### ! 03 1.06e



### ! 03 1.07e



### ! 03 6.82e



### ! 05 1.24e



### ! 03 2.94e



### ! 03 8.32e



### ! 04 1.01e



### ! 03 6.10e



### ! 01 1.72e+00 2.33e+00 4.70e+00 3.58e+00 4.34e



### ! 01 3.10e+00 1.59e+01 1.45e+00 3.75e+00 6.10e



### ! 01 1.72e+00 2.33e+00 4.70e+00 3.58e+00 4.34e



### ! 01 3.10e+00 1.59e+01 1.45e+00 3.75e+00

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### 3.35e



### ! 03 9.94e



### ! 03 1.01e



### ! 03 1.03e



### ! 03 3.56e



### ! 03 1.00e



### ! 02 1.07e



### ! 03 1.12e



### ! 03 6.78e+00 3.76e+01 3.04e+00 3.18e+00 6.78e+00 2.18e+01 3.04e+00 3.18e+00

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F ND 3.56e



### ! 04 1.28e



### ! 03 1.39e



### ! 03 2.55e



### ! 03 2.70e



### ! 03 5.12e



### ! 03 7.85e



### ! 03 4.88e



### ! 03 1.01e



### ! 03 2.35e



### ! 05 3.56e



### ! 04 1.28e



### ! 03 1.39e



### ! 03 2.55e



### ! 03 2.70e



### ! 03 5.12e



### ! 03 7.85e



### ! 03 4.88e



### ! 03 1.01e



### ! 03 6.84e+00 5.61e+00 8.18e+00 6.58e+00 1.71e+00 4.68e+01 3.30e+01 2.96e+01 2.11e+01 3.75e+00 6.84e+00 5.61e+00 8.18e+00 6.58e+00 1.71e+00 4.68e+01 3.30e+01 2.96e+01 2.11e+01 3.75e+00

Total C D D / C D F 2.71e



### ! 02 2.72e



### ! 02 1.63e+02 1.63e+02

a O n e barrel as s u m e d t o be equ i v a l e n t t o 139 k g

.

ND = No t d e tected

S o u r ces : R a di an C o rporat i o n (1991); C A R B (1999).



### 5-29Rat i o (m ean co n g en er em i ssi o n f act o r / t o t a l CDD/ CDF em i ssi o n f act o r )

0 a 0.02 0.04 0.06 0.08 0.1 0 .12

Rat i o (m ean co n g en er em i ssi o n f act o r / t o t a l CDD/ CDF em i ssi o n f act o r )

0 a 0.05 0.1 0 .15 0 .2 0.25 0.3



### F i gu re 5-4. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om p e trol eu m catal y ti c ref orm i n g u n i ts (nondetect set equal to z e ro)

.

S o u r ces : C A R B (1999); R a di an C o rporat i o n (1991).



### 5-30 0 .35

### No studies published to date have demonstrated a mass balance, and it is not known
whet her t h e C DDs/ C DFs m easured i n ci g a ret t e sm oke are t h e resul t of form at i on duri n g t obacco combustion, volatiliz ation of CDDs/CDF s present in the unburned tobacco, or a combination of

t h ese t w o source m echani s m s

. The com bust i on pr ocesses operating during cig a rette smoking are complex and could be used to justify both sour ce mechanisms. As reported by Guerin et al. (1992), during a puff on a cig a rette, g a s-phase te mperatures reach 850°C at the core of the firecone, and solid-phase temperatures reach 800°C at the co re and 900°C or g r eater at the char
line

. Thus, te mpe r a t ur e s a r e suf f i c i e n t to c a u se a t le a s t some de str u c tion of CDDs/CDF s initia lly present in the tobacco. B o th solid- and g a s-pha se temperatures rapidly decline to 200 to 400°C
within 2 mm of the c h a r line

. F o rmation of CDDs/CDF s has been reported in combustion studies with other media in this temperature rang e of 200 to 900°C. Howeve r, it is known that a process likened by Guerin et al. (1992) to steam distillation takes place in the reg i on behind the char line because of hig h

, localiz ed concentrations of water and temperatures of 200 to 400°C. At least 1,200 tobacco constituents (e.g ., nicotine, n-para ffin, some terpenes) are transfe rred intact from the tobacco into the smoke stream by distillation in this reg i on, a nd it is plausible that CDDs/CDF s present in the unburned tobacco would be subject to similar distillation.
B u mb et al. (1980), using low-resolution ma ss spectrometry , analy z ed the CDD content
of

ma instr e a m smoke f r o m the bur ning of a

U.S. br a nd of unf ilte r e d c i g a r e tte

. A pa c k a g e of 20
ci g a ret t e s was com bust e d i n each of t w o ex peri m e nt s. Approx i m a t e l y 20 t o 30 puffs of 2 t o 3 sec duration were collected from each cig a rette on a silica column. Hex a -, hepta-, and octa-CDDs
were detected at levels of 0.004 to 0.008, 0.009, and 0.02 to 0.05 ng /g , respectively

. Muto and Takiz a wa (1989) employ ed a con tinuous smoking apparatus to measure CDD

cong ener concent r at i ons i n t h e m a i n st ream sm oke g e nerated from the combustion of one kind of filtered cig a rette (brand not repor ted). The apparatus pulled air at a constant continuous rate (rather than a pulsed rate) throug h a burning cig a re tte and collected the smoke on a series of traps (g lass fiber filter, poly u rethane foam, and XAD-I I re sin). The CDD content of the smoke as well as the CDD content of the unburned cig a rette a nd the ash from the burned cig a rettes were also analy z ed using low-resolution mass spectrometry

. The results are presented in Table 5-10, and the cong ener g r oup profiles are presented in F i g u re 5-5. Table 5-11 and F i g u re 5-6 present the

ma instr e a m smoke r e sults on a ma ss- pe r

- c ig a r e tte ba sis to e n a b le c o mpa r ison with the r e sults of
other studies. The major CDD cong ener g r oup found was Hp CDD, which accounted for 84% of total CDDs found in the cig a rette, 94% of total CDDs found in smoke, and 99% of total CDDs found
in the ash. The 2,3,7,8-HpCDDs also accounted for the majority of the measured TEQ in the

5-31

### Table 5-10. CDD concentrations in Jap anese cigarettes, sm oke, and ash

C o ngener/congener group C i garette (pg/g) C o ncentrations

Mainstream smoke (ng/m 3 

### ) As h (pg/g)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND (0.5) ND (0.5) 2.01 a

a

a 

### 1343

257 ND (0.22) 0.43 2.15 a

a

a 

### 783 240 ND (0.5) ND (0.5) 0.56 a

a

a 

### ND (0.5) ND (0.5)
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### 1602.01 NR

13.9 13.7 1025.58 NR 8.5 8.3 0.56 NR

0.06 0.06

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 44.9 ND (0.5) 13.41 1629

257 NR NR NR NR NR 68 1.51 7.51 4939

240 NR NR NR NR NR 4.63 ND (0.5) 5.01 3211 ND (0.5) NR NR NR NR NR


### Total CDD/CDF 1944 5256 3221

a Valu e rep o r ted o n ly f o r to tal 2

, 3
, 7
, 8

- su b s titu ted Hx CDDs.

ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it) NR = No t rep o r ted

S o u r ce: Mu t o an d T a k i zaw a (1989)

.



### 5-32

### F i gu re 5-5. CDD p r of iles f o r Jap an ese cigarettes, sm ok e, an d ash

.

S o u r ce: Mat s u e da et al . (1994).



### cig a rettes and smoke; however, none were measured in the ash. Althoug h no PeCDDs were
det ect ed i n t h e ci g a ret t e , t h ey were det ect ed a t low le ve ls in the smoke, indicating probable formation during combustion. On the basis of th e similarities in the cong ener g r oup profiles for the three media, the study authors concluded that most of the CDDs found in the cig a rette smoke
result from volatiliz ation of CDDs/CDF s present in the unburned cig a rette rather than being formed during combustion.
B a ll et al. (1990) measured the CDD/CDF cont ent of mainstream smoke for the 10 bestse lling Ge r m a n c i g a r e tte br a nds. The inte r n a tiona l te st a ppr oa c h ( 1 puf f /min; puf f f

l ow r a te of
35 mL /2 se c ) wa s e m ploy e d with a n a ppa r a tus tha t smoke d 20 c i g a r e tte s a t a time in thr e e successive batches and ha d a l a rg e col l ect i on devi ce. The averag e TEQ cont ent (on bot h an I TEQ DF 

### and a TEQ DF 

### -W HO 98 

### basis) in mainstream smoke for the 10 brands tested, normaliz ed to a mass-per-cig arette basis, wa s 0.09 pg /cig arette (i .e., 16.5 times less than the value reported by
Muto and Takiz a wa, 1989, for a J a panese cig a re tte brand). However, the cong ener g r oup

5-33 ­

### Table 5-11. CDD/CDF concentrations (pg/cig) in cigarette sm oke,

n o rm al i zed to a p er-ci garette b a si s a

Congener/congener grou p Mu t o a n d T a k i zaw a (1989) (1 Jap an es e b r an d ) (m ain s tream

sm o k e ) Bal l et al . (1990) (avg. of 10 G erm an bra nds) (m ain s tream

sm o k e ) L ö froth an d Z e bühr (1992) ( 1 Sw edish bra nd) (m ain s tream

sm o k e ) L ö froth an d Z e bühr (1992) ( 1 Sw edish bra nd) (s ides tream s m ok e)
2,3,7,8- T C D D ND (0 .0 4 ) ND (0 .0 3 ) 0.028 0.07 1,2,3,7,8- PeC D D 0.075 ND (0 .0 3 ) 0.15 0.32 1,2,3,4,7,8- H x C D D 0.376 0.06 0.1 0.19 1,2,3,6,7,8- H x C D D b 0.05 0.34 0.6 1,2,3,7,8,9- H x C D D b 0.04 0.25 0.55 1,2,3,4,6,7,8- H p C D D 137 1.3 6.05 12.2 OCDD 42 3.4 22.1 38.8
2,3,7,8- T C D F NR 0.19 1.2 c 2.1 c 1,2,3,7,8- PeC D F NR 0.13 0.34 c 0.8 c 2,3,4,7,8- PeC D F NR 0.04 0.34 0.6 1,2,3,4,7,8- H x C D F NR ND (0 .0 3 ) 1.3 c 3.8 c 1,2,3,6,7,8- H x C D F NR 0.03 0.48 1.2 1,2,3,7,8,9- H x C D F NR 0.03 0.14 0.39 2,3,4,6,7,8- H x C D F NR 0.05 0.21 0.5 1,2,3,4,6,7,8- H p C D F NR 0.16 10 23.5 1,2,3,4,7,8,9- H p C D F NR 0.03 2.6 5 OCDF NR 0.11 3.2 10.7

T o t a l 2,3,7,8- C D D 179.45 4.85 29.02 52.7 T o t a l 2,3,7,8- C D F NR 0.77 19.81 48.6 T o tal I- T E Q DF 1.49 0.09 0.9 1.96 T o tal T E Q DF -W H O 98 1.49 0.09 0.96 2.08

T o tal T C DD 11.9 0.51 0.61 0.67 T o tal P e CDD 0.264 0.14 1.07 2.14 T o tal Hx CDD 1.31 0.53 2.52 5.2 T o tal Hp CDD 864 2.9 12.3 21.3 T o tal OCDD 42 3.4 22.1 38.8 T o tal T C DF NR 1.41 4.5 5.75 T o tal P e CDF NR 0.83 3.23 6.35 T o tal Hx CDF NR 0.35 5.3 12.9 T o tal Hp CDF NR 0.27 19.8 47.8 T o tal OCDF NR 0.11 3.2 10.7

T o t a l C D D / C D F 919.47 10.45 74.63 151.6

a Em i s s i on s cal cu l a t e d as s u m i n g 0.0035 m 3 of s m ok e are i n h a l e d per 20 ci g a ret t e s s m ok ed (Mu t o an d T a k i zaw a, 1992).

b Mu t o an d T a k i zaw a (1989) report e d a v a l u e on l y f o r t o t a l 2,3,7,8- H x C D D s (0.38 pg / c i g ).

c Co n cen tratio n s listed in clu d e th e co n t rib u tio n o f a co elu tin g n o n

- 2
, 3
, 7
, 8

- su b s titu ted co n g e n e r.

ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it) NR = No t rep o r ted



### 5-341

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0 TC D D Pe C D D Hx C D D Hp C D D OC D D TC D F Pe C D F Hx C D F Hp C D F OC D F

J a p a n e se M a i n st r e a m ( r o w 1 ) Ge rm a n M a i n s t re a m ( r o w 2 )

Sw e d i s h M a i n s t r e a m ( r o w 3 ) Sw e d i s h Si d e s t r e a m ( r o w 4 )



### F i gu re 5-6. Con g en er grou p p r of i l e s f o r m a i n stream an d si d e stream cigarette sm oke

.

S o u r ce: Mat s u e da et al . (1994).



### pr of ile s we r e simila r to those r e por te d by Muto a nd Ta kiza wa , with HpCDD a nd OCDD the dominant cong ener g r oups found.
L ö froth and Z e bühr (1992) measured the CDD/CDF content of mainstream and sidestream smoke from one common Swedish cig a re tte brand. The cig a re tte brand was labeled

as g i ving 17 mg carbon monox ide, 21 mg tar, and 1.6 mg nicotine. The international test

a ppr oa c h wa s use d, a nd the smoke wa s c o lle c t e d on g l a ss f i be r f

ilte r s f o llowe d by two pol y u ret h ane pl ug s. The anal y t i cal resul t s for m a i n st ream and si dest ream sm oke are present e d i n Table 5-11. The TEQ content in mainstream sm oke, normaliz ed to a ma ss-per-cig arette basis, was 0.96 pg TEQ DF 

### -W HO 98 

### /cig arette (0.9 pg I

- TEQ DF 

### /cig arette) (i.e., a bout two times less than the value reported by Muto a nd Takiz a wa, 1989, and 10 times g r ea ter than the averag e value reported by B a ll et al., 1990). As in the Muto a nd Takiz a wa and B a ll et al. studies, the dominant

cong ener g r oups were HpCDDs and OCDD; howev er, HpCDF s were also relatively hig h in

5-35

### comparison with the other cong ener g r oup tota ls. The sidestream smoke contained 2.08 pg TEQ DF 

### -W HO 98 

### /cig arette (1.96 pg I

- TEQ DF 

### /c ig a r e tte )
, or twic e tha t of ma instr e a m smoke

. Using hig h -resolution mass spectrometry

, Mats ueda et al. (1994) analy z ed the CDD/CDF
content of tobacco from 20 brands of commercia lly available cig a rettes collected in 1992 from
J a pan, the United States, Taiwan, China, the Un ited King dom, Germany

, and Denmark. Table 5­ 12 presents the study results. The total CDD/CDF content rang ed from 109 to 1,136 pg /pack,

­ a nd tota l TEQ DF 

### -W HO 98 

### content rang ed from 1.9 to 14 pg /pack (1.4 to 12.6 pg /pack on an I TEQ DF 

### basis). The Chinese cig a rette brand cont a i ne d sig n if ic a n tly lowe r CDDs/CDF s a nd TEQs than did any other brand of cig a rette. F i g u re 5-7 depicts the cong ener g r oup profiles for the

averag e results for each country

. A hig h deg r ee of similarity is seen among the CDF cong ener
g r oup profiles of the tested cig a rette brands. The J a panese a nd Taiwanese cig a rettes show CDD

cong ener g r oup profiles different from t hose of the other countries’ cig a rettes.
B r own (2002) estimated that 440 billion cig a rette s were consumed in the United States in
2000. I n 1995, approx imately 487 billi on cig a rettes were consumed in the United States and by
U.S. overseas armed forces personnel. I n 1987, approx imately 575 billion cig a rettes were
consumed. According to The Tobacco I n stitute (1995), per capita U.S. cig a rette consumption, based on the total U.S. population ag ed 16 a nd over, was a record hig h of 4,345 in 1963, declining to 2,415 in 1995 and 1,563 in 2000 (USDA, 1997; U.S. Census B u reau, 2000). The activity level estimates by B r own (2002) were adopted, and a hi g h confidence rating is assig n ed because they are based on known consumption rates.
The available emission factor data presented above provide the basis for two methods of estimating the amount of TEQs that may have been released to the air in the United States in 2000, 1995, and 1987 from the combustion of cig a rettes. The confidence rating assig n ed to the emission factor is low because of the very limited amount of testing performed to date. F i rst, an
annual emission estimate fo r 2000 of 0.19 g TEQ (on a TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### basis) is
obt ai ned i f i t i s assum e d t h at (a) t h e averag e TEQ content of seven bra nds of U.S. cig a rettes reported by Matsueda et al. (1994)—6.3 pg TEQ DF 

### -W HO 98 

### /pack (5.5 pg I

- TEQ DF 

### /pa c k )

— is

r e pr e s e n ta tive of c i g a r e tte s smoke d in the Unite d S t at es, (b) C DDs/ C DFs ar e not formed and the

cong ener profile reported by Matsueda et al. (1994) is not altered during combustion of
ci g a ret t e s, and (c) al l C DDs/ C DFs cont ri but i n g t o t h e TEQ are rel eased from t h e t obacco duri n g smoking

. The available emission factor data presented above provide the basis for two methods of estimating the amount of TEQs that may have been released to the air in the United States in 2000, 1995, and 1987 from the combustion of cig a rettes. The confidence rating assig n ed to the emission factor is low because of the very limited am ount of testing performed to date. F i rst, an

5-36

### Table 5-12. CDD/CDF concentrations (p g/pack) in tobacco cigarette brands f

r om various countries

U.S. (avg. of 7 bra nds) Jap an (avg. of 6 bra nds) United K i ng do m (avg. of 3 bra nds) Ta iw a n ( 1 bra nd) China ( 1 bra nd) Denm a r k ( 1 bra nd) G erm any ( 1 bra nd)
2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 1.2 1.6 6.9

a

a 52.7 589.3 0.5 1.4 4.8

a

a 17.8 244 1.7 3.1 6.1

a

a 23.9 189.5 1 3.3 12.2

a

a 26.4 272.7 ND 1.1 1.1

a

a 2.2 28.2 0.5 0.8 6.2

a

a 53.3 354.3 1.1 3.3 5.7

a

a 32.7 288.6

2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 18.2 8.7

b 8.1

c

c

c 17.6

d 24.6 4.8 5.3

b 8.1

c

c

c 11.1

d 10.5 15.6 21.2

b 17

c

c

c 13.6

d 8.3 11 16

b 12.9

c

c

c 13.2

d 13.9 1.2 1.5

b 2.2

c

c

c 1.5

d 0.5 2.2 4.3

b 4.3

c

c

c 7

d 10.5 7.9 14.4

b 13.2

c

c

c 12.9

d 13.9

T o t a l 2,3,7,8- C D D 651.7 268.5 224.3 315.6 32.6 415.1 331.4 T o t a l 2,3,7,8- C D F 77.2 39.8 75.7 67 6.9 28.3 62.3 T o tal I- T E Q DF 7.1 3.8 8.8 7.7 1.1 3.4 6.9 T o tal T E Q DF -W H O 98 7.3 4.3 10.1 9.1 1.7 3.4 8.3

T o tal T C DD 47.1 296.3 85.1 329 9.7 17 49.5 T o tal P e CDD 27.6 33.6 62.9 150.5 5.2 9.8 40.8 T o tal Hx CDD 40.6 29.2 49.2 99.4 5.4 26.7 40.6 T o tal Hp CDD 108.7 40 47.7 62 3.8 93.1 60.2 T o tal OCDD 589.3 244 189.5 272.7 28.2 354.3 288.6 T o tal T C DF 183.8 102.1 348.9 372.1 35.4 97.8 233.4 T o tal P e CDF 57.7 45.9 134.5 149.1 11.2 35.5 97.5 T o tal Hx CDF 29.1 26.4 51.3 45.8 7.8 18.1 40.8 T o tal Hp CDF 27.3 16.6 19 18.5 1.7 11.1 21.2 T o tal OCDF 24.6 10.5 8.3 13.9 0.5 10.5 13.9

T o t a l C D D / C D F 1 ,135.8 844.6 996.4 1513 108.9 673.9 886.5

a Valu e rep o r ted o n ly f o r to tal 2

, 3
, 7
, 8

- su b s titu ted Hx CDDs.

b Valu e rep o r ted o n ly f o r to tal 2

, 3
, 7
, 8

- su b s titu ted P e CDFs.

c Valu e rep o r ted o n ly f o r to tal 2

, 3
, 7
, 8

- su b s titu ted Hx CDFs.

d Valu e rep o r ted o n ly f o r to tal 2

, 3
, 7
, 8

- su b s titu ted Hp CDFs.

S o u r ce: Mat s u e da et al . (1994).



### annual emission estimate fo r 2000 of 0.19 g TEQ (on a TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### basis) is
obt ai ned i f i t i s assum e d t h at (a) t h e averag e TEQ content of seven bra nds of U.S. cig a rettes

5-370.6

0.5

0.4

0.3

0.2

0.1

0 TC D D Pe C D D Hx CDD Hp CDD OCDD TC D F Pe C D F Hx CDF Hp CDF OCDF

J a pa n (c olu m n 3 ) Ch in a ( co l u m n 1 ) D e nm ar k ( co l u m n 2 )

G e r m any ( c o l um n 4) U nite d K i ng do m ( c o l um n 5) U n ite d S t ate s ( c o l um n 6)



### F i gure 5-7. Congener group prof iles f o r cigarette tobacco f r om various

cou n t ri es.

S o u r ce: Mat s u e da et al . (1994).



### reported by Matsueda et al. (1994)—6.3 pg TEQ DF 

### -W HO 98 

### /pack (5.5 pg I

- TEQ DF 

### /pa c k )

— is

r e pr e s e n ta tive of c i g a r e tte s smoke d in the Unite d S t at es, (b) C DDs/ C DFs ar e not formed and the

cong ener profile reported by Matsueda et al. (1994) is not altered during combustion of
ci g a ret t e s, and (c) al l C DDs/ C DFs cont ri but i n g t o t h e TEQ are rel eased from t h e t obacco duri n g smoking

. The second method of estimating is based on the assumption th at the TEQ emission rates for a common Swedish brand of cig a rette reporte d by L ö froth and Z e bühr (1992) for mainstream smoke (0.96 pg TEQ DF 

### -W HO 98 

### /cig arette [ 0.9 pg I

- TEQ DF 

### /cig arette] ) and si destream smoke (2.08

pg TEQ DF 

### -W HO 98 

### /cig arette [ 1.96 pg I

- TEQ DF 

### /c ig a r e tte ]) a r e r e pr e s e n ta tive of the e mission r a te s for U.S. cig a rettes. F o r 2000, the tw o methods y i eld estimates of 0.11 g TEQ DF 

### -W HO 98 

### (0.1 g I TEQ) and 0.67 g TEQ DF 

### -W HO 98 

### (0.63 g I

- TEQ DF 

### ). F o r 1995, the two methods y i eld estimates of
0.2 g (on a TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### basis) and 1.48 g TEQ DF 

### -W HO 98 

### (1.41 g I

- TEQ DF 

### ). F o r

5-38 ­

### 1987, the two methods y i eld estimates of 0.14 g TEQ DF 

### -W HO 98 

### (0.12 g I

- TEQ DF 

### basis) and 1.75

g TEQ DF 

### -W HO 98 

### (1.67 g I

- TEQ DF 

### ).
F o r purposes of this report, the best estimate s of annual emissions ar e assumed to be the

averag e of the annual emissions estimated by the two methods for 2000, 1995, and 1987 (0.4 g

, 0.8 g , and 1 g TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### , respect i v el y )

. These em i ssi ons are assi g n ed a l o w confidence rating because the emission factor has a low confidence rating

. Althoug h these

e mission qua ntitie s a r e r e la tive l y sma ll whe n c o mpa r e d with the e mission qua ntitie s e s tima te d
for various industrial combusti on source categ ories, they are sig n ificant because humans are directly ex posed to cig a rette smoke.

5.6. P YROLYSIS OF BROMINATED F L AME RETARDANTS The py roly sis and photoly s is of brominat ed phenolic derivatives and poly b rominated bipheny l ethers used as flame reta r d a n ts in pla s tic s ( e spe c ia lly t hose used in electronic devices),

tex tiles, and paints can g e nerate considerable amounts of poly b rominated dibenz o- p -di o x i ns (B DDs) and dibenz ofurans (B DF s) (W atanab e and Tatsukawa, 1987; Thoma and Hutz ing e r, 1989; L u ijk et al., 1992). W a tana be and Tatsukawa (1987) observe d the formation of B D F s from the photoly s is of decabromobipheny l ether. A pprox imately 20% of the decabromobipheny l ether
was converted to B D F s in samp les that were irradiated with ultraviolet lig ht for 16 hr.
Thoma and Hutz ing e r (1989) observed the formation of B D F s during combustion

ex periments with poly buty l ene- terephthalate poly m er s containing 9 to 11% decabromodipheny l
ether. Max imum formation of B D F s occurre d at 400 to 600°C, with a B D F y i eld of 16%. Althoug h the authors did not provide specifi c quantitative results fo r similar ex periments
conducted with octabrom odipheny l ether and 1,2-bi s(tri-bromophenox y ) etha ne, they did report
that B DDs and B D F s were formed.
L u ijk et al. (1992) studied the formati on of B DDs/B DF s during the compounding and

ex trusion of decabromodipheny l ether into hig h -impact poly s ty rene poly m er at 275°C. Heptaand octa-B DF were formed during repeated ex trus i on cy cl es, and t h e y i el d of BDFs i n creased as
a function of the number of ex trusion cy cles

. HpB D F increased from 1.5 to 9 ppm (in the poly m er matrix ), and OB DF increased from 4.5 to 45 ppm after four ex trusion cy cles.
I n sufficient data are available at this time from which to de rive annual B DD/B D F

e mission e s tima te s f o r

this sour c e

.

5.7. CARBON REACT IVATION F URNACES Granular activated carbon (GAC) is an adsorbent that is widely used to remove org a nic pollutants from wastewater and to treat finished drinking water at wa te r tr e a tme nt pla n ts. Activated carbon is manufactured from the py roly tic treatment of nut shells and coal (B uonicore,

5-39

### 1992a). The properties of GAC ma ke it ideal for adsorbing and controlling vaporous org a nic and
i norg a ni c chem i cal s ent r ai ned i n combustion plasmas as well as soluble org a nic contaminants in industrial effluents and drinking water. The hig h ratio of surface area to particle weig ht (600:1,600 m 2 

### /g )
, c o mbine d with the e x tr e m e l y sma ll por e dia m e t e r of the pa r tic le s ( 15 to 25

ang s troms), increases the adsorption charact eristics (B uonicore, 1992a). GAC eventually
be c o me s sa tur a te d, a nd the a d sor p tion pr ope r tie s sig n if ic a n tly de g r ade. W h en sat u rat i on occurs, GAC usually must be discarded and repl aced, whi c h si g n i f i cant l y i n creases t h e cost s of pol l u t i o n control.
The introduction of carbon reactivation furn ace technolog y in the mid-1980s created a method involving the thermal trea tment of used GAC to thermo ly tically desorb the sy nthetic compounds and restore the adsorption properties for reuse (L y k ins et al., 1987). L a rg e-scale

reg e neration operations, such as those used in i ndustrial water tr eatment operations, ty pically use multiple-hearth furnaces. F o r smaller-scale operati ons, such as those used in municipal water

t r eat m e nt operat i ons, fl ui di z e d-bed and i n frare d furnaces are used. Em i ssi ons are t ypi cal l y controlled by afterburne rs followed by water sc rubbers (U.S. EPA, 1997a). The used GAC can contain compounds that are precursors to the formation of
CDDs/CDF s during the thermal treatment process. A study by EPA (U.S. EPA, 1987a) measured precursor compounds in spent GAC that was used as a feed material to a carbon

react i v at i on furnace t e st ed duri n g t h e Nat i onal Di ox i n S t udy

. The t o t a l chl o robenz ene cont ent of the GAC rang ed from 150 to 6,630 ppb. Trichlor obenz ene was the most prevalent species

pr e s e n t, with sma lle r qua ntitie s of di- a nd te tr a

- c h lor obe nze n e s de te c t e d. Tota l ha log e na te d

org a nics were measured to be about 150 ppm.
EP A has st ack-t est e d t w o GAC react i v at i on furnaces for t h e em i ssi on of di ox i n (U.S

. EPA, 1987a; L y kins et al., 1987). One facility wa s an industrial carbon r eactivation plant, and the second facility was used to restore GAC at a municipal drinking wa ter plant. EPA (U.S. EPA, 1997a) reported results of ot her testing performed at a count y water facility in California during 1990. The industrial carbon reactivation plant pro cessed 36,000 kg /day of spent GAC used in
the treatment of industrial wastew ater effluents. This facility was chosen for testing because it was considered to be represen tative of other facilities in the source categ ory (U.S. EPA, 1987a). Spent carbon was reactivated in a multiple-hearth furnace, cooled in a water quench, and shipped back to primary chemical manufact uring facilities for reuse. The furnace was fired by natural g a s and consisted of seven hear t h s arrang ed vert i cal l y i n seri es. The heart h t e m p erat ures rang ed from 480 to 1,000°C. Air pollutant emissions were c ontrolled by an afterburner, a sodium spray cooler, and an F F

. Temperatures in the af terburner were about 930° C. The estimated I

- TEQ DF 

### emission factor (treating nondetect values as z e ro) was 0.76 ng TEQ DF 

### -W HO 98 

### /kg (0.64 ng

5-40

### I

- TEQ DF 

### /kg ) carbon processed. The emission fact or for total CDDs/CDF s was 58.6 ng /kg

. B ecause analy s es were performed onl y for 2,3,7,8-TCDD; 2,3,7,8-TC DF; OCDD; and OCDF and the cong ener g r oups, equiva lent concentrations were a ssumed for all tox i c and nontox ic

cong eners in each of the penta, hex a , and hepta cong ener g r oups. The second GAC reactivation fac ility tested by EPA consisted of a fluidiz e d-bed furnace located at a municipal drinking water treatment plant (L y k ins et al., 1987). The furnace was
divided into three sections: a combustion cham ber, a reactivation sec tion, and a dry e r section. The combustion chamber was fired by natural g a s and consisted of a stoi c h iome tr ic a lly ba la nc e d
stream of fuel and ox y g en. Combustion temp eratures were about 1,038°C. Gases from the
reactivation section and combus tion chamber were directed th roug h an acid g a s scrubber and hig h -temperature afterburne r prior to discharg e from a stack. Althoug h measurable
concentrations of diox in-like compounds were de tected in the stack e missions, measurements of
the individual CDD/CDF cong eners were not perfo rmed; therefore, it was not possible to derive TEQ e mission f a c t or s f o r

this f a c ility

. With the a f te r bur ne r ope r a ting

, no CDD c ong e n e r s be low HpC DD were det ect ed i n t h e st ack em i ssi ons. Concentrations of HpCDDs and OCDD rang ed from 0.001 to 0.05 ppt/volume basis (ppt/v) and 0.006 to 0.28 ppt/v, respectively

. All CDF

cong ener g r oups were detected in the stack emissi ons even with the after burner operating

. Total
CDF s emitted from the stack averag ed 0.023 ppt/v. EPA (U.S. EPA, 1997a) reported a TEQ emission factor of 1.73 ng I

- TEQ DF 

### /kg of carbon processed for the reactivation unit at a county wa ter facility in Californi a in 1990. The emission
f

a c t or f

o r

tota l CDDs/CDF s wa s r e por te d to be 47 ng /kg ( i .e ., simila r to the tota l CDD/CDF emission factor of 58.6 ng /kg at the industrial GAC facility ). B e cause cong ener-specific results were not reported, it was not possi bl e t o cal cul a t e t h e TEQ DF 

### -W HO 98 

### emission factor. The report
al so di d not provi de t h e confi g urat i on and t ype of furnace t e st ed; however, i t di d st at e t h at t h e emissions from the furnace were controlle d by an afterburner and a scrubber.
The industrial GAC reaction furnace test da ta indicate that an averag e of 0.64 ng
I

- TEQ DF 

### /kg of GAC may be released. The I

- TEQ DF 

### e mission r a te f o r

the r e a c tiva tion unit a t the
county water treatment facility was 1.73 ng I

- TEQ DF 

### /kg carbon. L o w confidence rating s are
g i ven t o t h ese em i ssi on fact ors because onl y t w o GAC react i v at i on furnaces were st ack t e st ed, and not all cong eners were analy z ed at the industrial GAC facility

. The mass of GAC that is reactivated a nnually in carbon reactivation furnaces is not
known. However, a roug h estimate, to which a lo w confidence rating is assig n ed, is the mass of
vi rg i n GAC shi pped each y ear by GAC m a nufact urers. Accordi n g t o t h e U.S

. Depart m e nt of Commerce (U.S. DOC, 1990c), 48,000 me tric tons of GAC were sh ipped in 1987. EPA reported that in 1990, water and wastewat er treatment operations cons umed 65,000 metric tons of GAC

5-41

### (U.S. EPA, 1995b, 1997a). The 1990 activity level was used in this document as a surrog a te for the 1995 and 2000 activity levels. Apply i ng the averag e TEQ emission factor of 1.2 ng (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) per kg
of reactivated carbon for the two tested facilitie s to the estimates of pot ential GAC reactivation volumes y i elds annual rel ease estimates of 0.06 g (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) in 1987 and
0.08 g (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) in 1995 and 2000 (assuming that the activity level for 1990 is representative of the 1995 and 2000 ac tivity levels). These emissi on estimates are assig n ed a low confidence rating because both the activity and emission factor estimate s had low confidence

r a ting s

.

5.8. K RAF T BLACK LIQUOR RECOVERY BOILERS Kraft black liquor recovery bo ilers are associated with the production of pulp in the making of paper using the Kraft pr ocess. I n this process, wood chips are cooked in larg e vertical
vessel s cal l e d di g e st ers at el evat ed t e m p erat ures and pressures in an a queous solution of sodium hy drox ide and sodium sulfide. W ood is br oken down into two phases: a soluble phase containing primarily lig nin, and an insoluble phase containing th e pulp. The spent liquor (called black liquor) from the dig e ster c ontains sodium sulfate and sodi um sulfide, which the industry recovers for reuse in the Kraft process.
I n the recovery of black liquor chemicals, weak black liquor is first concentrated in multiple-effect evaporators to about 65% solids. The concentrated black liquor also contains 0.5 to 4% chlorides by weig ht, which are recove red throug h combustion. The concentrated black liquor is spray e d into a Kraft black liquor recove ry furnace equipped with a heat recovery boiler.
The bul k of t h e i norg a ni c m o l t e n sm el t t h at form s i n t h e bot t o m of t h e furnace cont ai ns sodi um carbonate and sodium sulfide in a ratio of a bout 3:1. The combustion g a s is usually passed throug h an ESP that collects PM prior to being ve nted out the stack. The PM can be processed to further recover and recy cle sodium sulfate (Someshwar and Pinkerton, 1992).
I n 1987, EPA stack-tested three Kraft black li quor recovery boilers for the emission of
diox in in conjunction with the National Diox in Study (U.S. EPA, 1987a). The three sites tested by EPA were judg ed to be ty pical of Kraft bl ack liquor recovery boilers at that time. During

pr e t e s t sur v e y s, two f a c ilitie s we r e judg e d to ha ve a v e r a g e pote n tia l f o r

CDD/CDF e missions a n d one was judg ed to have hig h pot ential, based on the amount of chlorine found in the feed to these
units. Dr y

- bottom ESPs c ontr o lle d e missions f r o m two of the boile r s ; a we t- bottom ESP

c ontr o lle d e missions f r o m the thir d. The r e su lts of these tests included cong ener g r oup concentrations but lacked m easurement results for specific cong eners other than 2,3,7,8-TCDD and 2,3,7,8-TCDF

.

5-42

### NCASI (1995) provided cong ene r-specific emission test resu lts for six additional boilers tested during 1990 to 1993. Three boilers were of the direct contact ty pe, and three were
noncontact ty pe. All were equi pped with ESPs. The averag e cong ener and cong ener g r oup

e mission f a c t or s a r e pr e s e n te d in Ta ble 5- 13 f o r

the thr e e f a c ilitie s r e por te d by EPA ( U .S. EPA, 1987a) and the six facilities repor ted by NCASI (1995). F i g u re 5-8 presents the averag e
cong ener and cong ener g r oup pr ofiles based on the te st results presented by NCASI (1995).
The a v e r a g e TEQ e mission f a c t or , ba se d on the da ta f

o r

the six NCASI f

a c ilitie s with complete cong ener data, was 0.028 ng TEQ DF 

### -W HO 98 

### /kg (0.029 ng I

- TEQ DF 

### /kg ) of black liquor

­ solids, assuming nondetect valu es were z e ro, and 0.078 ng TEQ DF 

### -W HO 98 

### /kg (0.068 ng I TEQ DF 

### /kg ) , assuming nondetect values were present at one-half the DL

. This value is assumed to apply to all three reference y ears (1987, 1995, a nd 2000). The results for the three facilities
report e d by EP A were not used i n t h e deri vat i on of t h e TEQ em i ssi on fact or because cong enerspecific measurements for most 2,3,7,8-substituted cong eners were not made in the study (U.S.
EP A, 1987a). A medium confidence rating is a ssig n ed to those emission factors because they
were derived from the stack testin g of six Kraft black liquor recove ry boilers that were judg ed to be fairly representative of technolog ies used at Kraft pulp mills in the United States. A 1995 survey of the industry indicated that 215 black liquor recove ry boilers were in

ope r a tion a t U.S. pulp a nd pa pe r mills. All but one of the s e boile r s use d ESPs f o r

c ontr o l of particulate emissions; the one unique facility used dual scrubbe rs. I n addition, ESPs were reported to have been the predo m i n ant m eans of part i c ul at e cont ro l at recovery boi l e rs for t h e past 20 y ears (letter dated Oc tober 8, 1998, from W

. Gillespie, National Council of the Paper
I ndustry for Air and Stream I m provement , I n c., to G. Schweer, Versar, I n c.). The amounts of black liquor solids burned in Kr aft black liquor recovery boilers in the United States during 1987 and 1995 were 69.8 million metric tons and 80.8 million metric tons, respectively (American Paper I n stitute, 1992; American F o rest and Paper Association, 1997). These activity level estimates are assig n ed a hig h confidence rating because they are based on comprehensive industry survey data. Combinin g the emission factors de rived above with the activity level estimates for 1987 and 1995 y i elds estimated annual emissions from this source of

approx imately 2 g (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) in 1987 and 2.3 g (TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### ) i n 1995. These emission estimates are assig n ed a me dium confidence rating because the emission factor have a medium confidence rating

. F o r 2000, NCASI provided estimates of activity levels for Kraft recovery furnaces and
Kraft lime kilns and CDD/CDF releases, includi ng emissions from 11 Kraft recovery furnaces
and four Kraft lime kiln s (Gillespie, 2002). The activity leve ls were reporte d to be 90.7 million

5-43

### Table 5-13. CDD/CDF m e an em ission f a ctors (ng/kg f eed) f o r black liquor recovery b o i l ers

Congener U

. S

. E P A (1987a) (3 fa cilities) NCAS I (1995) (6 fa cilities)

Non d e tect s e t to

zero Non d e tect s e t to 1⁄2 detectio n lim it Non d e tect s e t to

zero Non d e tect s e t to 1⁄2 detectio n lim it
2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 0 NR NR NR NR NR 4.24 0.04 NR NR NR NR NR 4.24 0 0 0.001 0.003 0.006 0.108 1.033 0.016 0.016 0.018 0.015 0.019 0.135 1.054
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 0.04 NR NR NR NR NR NR NR NR 0.35 0.06 NR NR NR NR NR NR NR NR 0.35 0.04 0.03 0.033 0.007 0.012 0.005 0.01 0.024 0 0.113 0.049 0.036 0.037 0.022 0.021 0.016 0.021 0.035 0.014 0.13

T o tal T C DD T o tal P e CDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal P e CDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF 0.21 0.27 0.8 2.05 4.24 0.95 0.64 1.16 1.05 0.35 0.36 0.35 1.02 2.05 4.24 1 0.77 1.2 1.05 0.35 0.106 0.013 0.104 0.252 1.033 1.27 0.37 0.102 0.024 0.113 0.123 0.059 0.122 0.279 1.054 1.275 0.376 0.109 0.038 0.13

T o tal I- T E Q DF T o tal T E Q DF -W H O 98 0.10 a 0.10 a 0.15 a 0.16 a 0.029 0.028 0.065 0.072

T o t a l C D D / C D F 11.72 12.39 3.39 3.57

a Es t i m at e bas e d on t h e m eas u r ed dat a f o r 2,3,7,8- T C D D ; 2,3,7,8- T C D F ; O C D D ; an d O C D F an d con g e n e r g r ou p

em is s i on s (i.e., f o r th e pen t a- , h e x a

- , an d h e pta- C DD an d C D Fs , it w a s as s u m e d th at th e m eas u r ed em is s i on f actor

w i t h i n a c o nge ne r gr o u p w a s t h e sum o f e q ua l e m i ssi o n fa c t o r s fo r a l l c o nge ne r s i n t h a t gr o u p , i n c l ud i ng no n­ 2
, 3
, 7
, 8

- su b s titu ted co n g e n e rs).

NR = No t rep o r ted



### metric tons for Kraft recovery furnaces and 13 million metric tons for Kraft lime kilns. These activity level estimates are assig n ed a hig h confidence rating because they are based on comprehensive industry survey data. Emi ssion factors were take n from “NCASI Handbook of Chemical Specific I n formation for SARA Section 313 F o rm R Re porting

. ” The factors provided

5-44R a t i o ( m e a n co ng e n e r g r ou p e m i s si on f a ct or / t o t a l C D D / C D F e m i s s i o n f a c t o r )

0 a 0. 1 0.2 0. 3 0. 4 0. 5

TC D D

Pe C D D

Hx C D D

Hp C D D

OC D D

TC D F

Pe C D F

Hx C D F

Hp C D F

OC D F



### F i gu re 5-8. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om Kraf t b l ack l i q u o r recovery b o i l ers ( nondetect set equal to z e ro ).

S o u r ce: N C A S I (1995).



### 5-45

### in this handbook were compiled from valid test data supplied to NC ASI by a variety of sources, including NCASI member companies who had perfo rmed the tests in response to a reg u latory

prog ram

. They are assi g n ed a hi g h confi d ence rat i n g because t h ey are based on a com p rehensi v e
survey of stack emissions. C ong ener-speci fi c C DD/ C D F TEQ emission factors were provided for both source categ ories (Table 5-14). Using t h e cong ener-speci fi c em i ssi on fact ors and t h e activity levels pr ovided above, NCASI estimated CDD/CDF TEQ DF 

### -W HO 98 

### em i ssi ons for each

cong ener (Table 5-14) and repor ted total emissions of 0.75 g TEQ DF 

### -W HO 98 

### /y r and 6.9e



### ! 5 g TEQ DF 

### -W HO 98 

### /y r for Kraft recovery furnaces and Kraf t lime kilns, respectively

. This 2000 emissions estimate has a hig h confidence rating because both th e emission factor and activity
l e vel are rat e d as hi g h confi d ence.

5.9. OTHER IDENTIF I ED SOURCES
S e veral m a nufact uri n g processes are i d en tified as potential sources of CDD/CDF formation because the processes use chlorine-containing compone nts or involve application of hig h temperatures. However, no te sting of e missions f r o m the s e processes has been performed in
the Unite d Sta t e s , a nd only minima l e mission r a te information has been reported for these processes in other countries. Therefore, these sources are rated as Categ o ry E sources, meaning their emissions cannot be quantified.
B u rn i n g of can d l es. Schwind et al. (1995) analy z ed the wicks and wax e s of uncolored candles as well as the fumes of burning candles for CDDs/CDF s, total chlorophenol, and total
chlorobenz ene content. The results, presented in Table 5-15, show that beeswax contained the hig h est levels of CDDs/CDF s and total chlorophenols. I n contra st, the concentration of total
chl o robenz enes i n st eari n wax was hi g h er t h an t h at in paraffin or beeswax by a factor of 2 to 3. The concentrations of the three analy t e g r oups were sig n ificantly lower in the wicks than in the

wa x e s. Emissions of CDDs/CDF s f r o m a ll thr e e ty pes of candles were very low during burning

. I n fact, comparison of the emission factor with the or ig ina l CDD/CDF c onc e n tr a tions in the wa x indicates a net destruction of th e CDDs/CDF s or ig ina lly pr e s e n t in the wa x

. I n f o r m a tion on the

a c tivity le ve l is la c k ing

, the r e f or e , no e s tima te of e nvir onme n ta l r e le a s e c a n be ma de a t this time

. G l ass m a nufac t u r i ng. Annual emissions of less than 1 g I

- TEQ DF 

### /y

r have been estimated for g l ass manufacturing facilities in the Netherlands (B remmer et al., 1994) and the United King dom (Douben et al., 1995). Glass is ma nufactured by heating a mix ture of sand and, depending on the ty pe of g l a ss, lime, sodium carbonate, dolomite , clay , or feldspar to a temperature of 1,400 to 1,650°C. I n addition, vari ous coloring and clarify i ng ag ents may be
added. Chlorine enters the process as a conta minant (NaCl) in sodium carbonate (B remmer et al. 1994). However, the emission factors used by B r emmer et al. and Douben et al. were not reported. Umweltbundesa mt (1996) reported relatively low emission factor s (approx imately
0.002 and 0.007 ng I

- TEQ DF 

### /kg ) f o r

two g l a ss ma nuf a c t ur ing f a c ilitie s in Ge r m a n y

.

5-46

### Table 5-14. CDD/CDF TEQ em ission f a ctor s and em ission estim a tes f r om K r af t recovery f u rn aces an d Kraf t l i m e k i l n s

C o ngener Kraf t recovery f u rnaces Kraf t lime kilns TEQ DF 

### -WHO 98



### (n g/lb BL S ) E m issions (ng/yr) TEQ DF 

### -WHO 98 

### (n g/lb C a O) E m issions (ng/yr)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD 1,2,3,4,6,7,8,9- OCDD 0.00e+00 0.00e+00 0.00e+00 2.00e



### ! 04 5.00e



### ! 04 4.90e



### ! 04 1.42e



### ! 04 0.00e+00 0.00e+00 0.00e+00 3.33e+07 8.31e+07 8.15e+07 2.36e+07 0.00e+00 0.00e+00 0.00e+00 1.00e–04 0.00e+00 2.80e



### ! 04 2.56e



### ! 04 0.00e+00 0.00e+00 0.00e+00 2.60e+03 0.00e+00 7.27e+03 6.65e+03
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF 1,2,3,4,6,7,8,9- OCDF 5.00e



### ! 04 1.00e



### ! 04 1.50e



### ! 03 4.00e



### ! 04 2.00e



### ! 04 0.00e+00 4.00e



### ! 04 6.00e



### ! 05 0.00e+00 2.60e



### ! 05 8.31e+07 1.66e+07 2.49e+08 6.65e+07 3.33e+07 0.00e+00 6.65e+07 9.98e+06 0.00e+00 4.32e+06 8.00e



### ! 04 1.00e



### ! 04 0.00e+00 9.00e



### ! 04 2.00e



### ! 04 0.00e+00 0.00e+00 0.00e+00 0.00e+00 0.00e+00 2.08e+04 2.60e+03 0.00e+00 2.34e+04 5.20e+03 0.00e+00 0.00e+00 0.00e+00 0.00e+00 0.00e+00
B L S = B l ack liq u o r so lid s CaO = Calciu m o x id e



### Table 5-15. CDD/CDF concentrations in candle m a terials and em issions

Wax material Candl e component Concentration E mission f a ctor

CDD/ CDF (ng I-TEQ DF 

### /k g) Tot a l chl o rophenol s ( 

### : g/kg) Tot a l chlorobenz enes ( 

### : g/kg) CDD/ CDF (ng I-TEQ DF 

### /k g burnt w a x )

P a raffin Wax 0.59 14.8 130 0.015 Stearin Wax 1.62 32.3 330 0.027 B eesw a x Wax 10.99 256 120 0.004

P a raffin Wick 0.18 1.23 0.67 NR Stearin Wick 0.12 0.94 0.34 NR B eesw a x Wick 0.08 0.74 0.35 NR

S o u r ce: S c h w i n d et al . (1995).



### 5-47

### Lim e kilns. Annual emissions from lime kilns in B e lg ium and the United King dom have been reported by W e vers and De F r e (1995) a nd Douben et al. (1995), respectively

. However, the emission factors used to g e nerate thos e estimates were not pr ovided. Umweltbundesamt (1996) reported low emissi ons (0.016 to 0.028 ng I

- TEQ DF 

### /kg ) dur ing te sts a t two lime kilns in Germany

. Ceram i cs an d ru b b er m a n u f actu rers. Douben et al. (1995) estimated annual emissions
from ceramic manufacturers and rubber manufacturers in the United King dom. L e x e n et al. (1993) had previously detected hig h concentra tions of CDDs/CDF s in emissions from a ceramic manufacturer in Sweden that occasionally g l az ed ceramics by volatiliz ation of sodium chloride in
a coal-fired oven. L e x e n et al. (1993) also detected hig h pg /L levels of I

- TEQ DF 

### in the scrubber
water from the vulcaniz ation process at a Swedish rubber manufacturer.

5-48

### 6. COMBUSTION SOURCES OF CDDs /CDF s: MINIMALLY CONTROLLED AND UNCONTROLLED COMB USTION SOURCES

This chapter discusses combustion sources of CDDs/CDF s that have some (in the case of combustion of landfill g a s) or no post-combusti on pollution control equipment for conventional pollutant emissions.

6.1. COMBUSTION OF LANDF ILL G A S
6.1.1. Em issions Data Althoug h no data could be locat ed on levels in untreated la ndfill g a s, several studies have

r e por te d de te c ting CDDs/CDF s in the e missions r e sulting f r o m the c o mbustion of la ndf ill g a s. Only one study of CDD/CDF e missions f r o m a la ndf ill f l a r e ha s be e n r e por te d f o r

a

U.S. la ndf ill (CARB
, 1990c). The TEQ DF 

### -W HO 98 

### and I

- TEQ DF 

### e mission f a c t or c a l c u la te d f r o m the r e sults of this study is approx imately 2.4 ng TEQ/m 3 

### la ndf ill g a s c o mbuste d. The c ong e n e r

- spe c i f i c r e sults of this study are presented in Table 6-1. F i g u re 6-1 presents the CDD/CDF cong ener emission profile based on these emission f actors. B r emmer et al. (1994) reported a lower emission factor,
0.4 ng I

- TEQ DF 

### /m 3 

### , f r o m the inc i ne r a tion of untr e a t e d la ndf ill g a s in a f

l a r e a t a f

a c ility loc a t e d in

t h e Net h erl a nds. No cong ener-speci fi c em i ssion factors were provided. The averag e TEQ
emission factor for the CARB and B r emmer et al. studies is 1.4 ng I

- TEQ DF 

### /m 3 

### la ndf ill g a s combusted. Umweltbundesamt (1996) reported even lower TEQ emi ssion factors for landfill g a s burned in eng i nes or boiler muffler s rather than in a flare. The reported results for 30 eng i nes and mufflers tested in Germany rang ed from 0.001 to 0.28 ng I

- TEQ DF 

### /m 3 

### , with most va lue s below 0.1 ng I

- TEQ DF 

### /m 3



### . However, B r emmer et al. (1994) reported an emission factor of 0.5 ng
I

- TEQ DF 

### /m 3 

### f r o m a la ndf ill g a s- f i r e d e n g i ne in the Ne the r la nds.

6.1.2. Activity Level Inf orm ation
I n 1996 EPA promulg a ted emission standards and g uidelines to control emissions of landfill g a s from ex isting and futu re landfills under the Clean Air Act (F ederal Reg i ster, 1996b).
Those r e g u la tions r e quir e the la r g e st la ndf ills in the Unite d Sta t e s ( on the ba sis of de sig n capacity ) to periodically measure and determine their annual emissions of landfill g a s. L a ndfills
that emit more than 50 metric tons of nonmethane org a nic compounds (NMOC) annually must

c o lle c t la ndf ill g a s a nd r e duc e its NMOC c onte n t by 98% we ig ht thr oug h the use of a

c ontr o l
device.

6-1

### Table 6-1. CDD/CDF em ission f actors f or a landf ill f l are

Con g en er/ con g en er grou p M e an fac ilit y e m ission fac t or a 

### (ng/m 3 

### gas com busted) 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0.02 0.09 0.07 0.07 0.26 0.76 4.41 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 14.07 0.39 1.14 1.46 0.42 0.11 0.68 1.22 0.07 0.64 Total 2,3,7,8-CDD Total 2,3,7,8-CDF Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 5.68 20.20

2.39 2.43

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF NR NR NR NR NR NR NR NR NR NR

Tota l CDD/CDF N R

a A s s u m e s h eat con t en t of 1.86e+07 J/ m 3 f o r lan d f ill g a s (Federal R e g i s t er, 1996a).

NR = No t rep o r ted

S o u rce: C A R B (1990c).



### 6-2Ratio (congener emission factor/total 2378-CDD/CDF emission factor)

0 0 .1 0.2 0 .3 0.4 0 .5



### F igur e 6- 1. Conge n e r pr ofile for landfill flar e air e m issions.

S o u rce: C A R B (1990c).



### 6.1.2.1. Activity Levels for 1987 an d 1995 EPA estimated that when the 1996 reg ulations were implemented, the controls would
reduce annual NMOC emissions from ex isting landf ills by 77,600 metric tons. The cost analy s is supporting this rulemaking base d control device costs on open flares because flares are

a pplic a b le to a ll the r e g u la te d f a c ilitie s. Assuming tha t the ma ss r e duc tion would be a c h ie ve d by the use of flares, the corres ponding volume of landfill g a s burne d would be approx imately 14
billion m 3 

### /y r. The calculation was based on an assu me d de f a ult NMOC c onc e n tr a tion in la ndf ill

g a s of 1,532 ppmv and a conve rsion factor of 3.545 mg /m 3 

### NMOC per 1 ppmv NMOC (F ederal Reg i ster, 1993b).

6-3 0.6

### Of the approx imately 312 landfills that were affected by the promulg a tion of the emission standards and g uidelines in 1996, EPA estimated that more than 100 had some form of collection or control sy stem (or both) in place in 1991 (Federal Reg i ster, 1991c). Thus, a roug h

approx imation of the volum e of landfill g a s combusted in 1995 was 4.7 billion m 3 

### / y r (or 33% of
the f u tur e e x pe c t e d 14 billion m 3 

### /y r r e duc tion)

. This e stima te is simila r to the 2 to 4 billion m 3 

### landfill g a s estimated by the Energ y I nformati on Administration (EI A , 1994) as collected and consumed for energ y recovery purposes in 1992.
EI A (1992) estimated that between 0.9 and 1.8 billion m 3 

### of la ndf ill g a s we r e c o lle c t e d and burned in 1990 for energ y recovery purposes. B ecause there were no specific data available for 1987, EPA assumed that the mean of this rang e, 1.35 billion m 3 

### , would serve as an

approx imate estimate of the volume of landfill g a s combusted in 1987.

6.1.2.2. Activity Level for 2000 According to the EPA 2001 inventory of g r eenhouse g a s emissions , approx imately 7.7
billion m 3 

### of landfill g a s were com busted in 2000 throug h 477 landf ill flares (averag e of 16.5
million m 3 

### of landfill g a s per flare). As of 2003, ther e were more than 1,000 landfill flares in the United States (e-mails date d F e bruary 28, 2003, and March 7, 2003, from B

. Guz z one, U.S. EPA, to K. Riley , Versar). Assuming that the amount of landfill g a s combusted throug h the 477
landfill flares inventoried is representative of the landfill g a s combusted throug h these 1,000+
f l a r e s, a ppr ox ima te ly 16 billion m 3 

### of la ndf ill g a s we r e c o mbuste d in the Unite d Sta t e s thr oug h
flares in 2000.

6.1.3. Em ission Estim a tes
The limite d e mission f a c t or da ta tha t a r e a v a ila ble we r e judg e d ina d e qua te f o r

de ve loping

na tiona l e mission e stima te s tha t c ould be inc l ude d in the na tiona l inve ntor y

. Howe ve r , a preliminary estimate of the poten tial annual TEQ releases from la ndfills can be obtained using
the e stima te d volume of c o mbuste d g a s a nd the a v a ila ble e mission f a c t or s. Combining the estimates of landfill g a s volume th at was combusted (1.35 billion m 3 

### in 1987, 4.7 billion m 3 

### in 1995, and 16 billion m 3 

### in 2000) with the emission factor of 1.4 ng I

- TEQ DF 

### /m 3 

### of flarecombusted g a s y i elds annual emi ssion estimates of 1.9, 6.6, and 22 g I

- TEQ DF 

### /m 3 

### for 1987, 1995, and 2000, respectively

. These estimates should be reg a rded as preliminary indications of possible emissions from this source; further testin g is ne e d e d to c onf ir m the tr ue ma g n itude of
those emissions.

6-4

### 6.2. ACCIDENTAL F I RES Accidental fires in building s and vehicles are uncontrolled combustion processes that, because of poor combustion conditions, ty pica lly result in relatively hig h emissions of incomplete combustion products (B remmer et al., 1994), which can include CDDs and CDF s

. Poly viny l c h lor i de ( P VC) building ma te r i a l s a nd f u r n ishing s, c h lor opa r a f f i n- c onta i ning te x tile s and paints, and other chlorina ted org a nic compound-containing materials appear to be the primary sources of the chlorine (Rotard, 1993). Althoug h the results of several studies have
dem onst r at ed t h e presence of C DD/ C DF concent r ations in soot deposits and residual ash from
such fi res, few di rect m easurem ent s of C DDs/ C DF s in the fumes or smoke of fires have been reported. The results of some of those studies are described below, a nd an evaluation of the

a v a ila ble da ta f

o llows.

6.2.1. Soot and Ash Studies Christmann et al. (1989a) analy z ed the soot formed during combustion and py roly sis of

pur e PVC a nd PVC c a b le she a t hing s in simple la bor a t or y e x pe r ime nts de sig n e d to mimic the
conditions of fires. F or the combustion ex perime nts, 2 g of a PVC sample we r e inc i ne r a te d with a laboratory g a s burner. The combustion products were collected on the inner walls of a cooled

g a s funnel placed above the sample. For the py ro ly sis ex periments, about 50 mg of the sample were placed in a quartz tube and heated to about 950°C for 10 min in either an air atmosphere or a nitrog en atmosphere. The combustion ex per iments y i elded CDD/CDF c oncentrations in soot of 110 μg I

- TEQ DF 

### /kg for a low-molecular-weig ht PVC, 450 μg I

- TEQ DF 

### / k g for a hi g h

molecular-weig ht PVC, and 270 μg I

- TEQ DF 

### /kg f o r

PVC c a b le

. The py r o ly sis e x pe r ime nts in the air atmosphere y i elded lower CDD/CDF concentrations in soot: 24.4 μg I

- TEQ DF 

### / k g for a l o wmolecular-weig ht PVC, 18.7 μg I

- TEQ DF 

### /kg for a hig h-molecular-weig ht PVC, and up to 41 μg I

TEQ DF 

### / k g for P VC cabl e

.

I n g e neral, more CDF s than CDDs were fo rmed. The lower-chlorinated CDF cong eners

we r e domina n t in the c o mbustion e x pe r ime nts; however, the HpCDF and OCDF cong eners were domina n t in the py r o ly sis e x pe r ime nts. No CDDs/CDF s we r e de te c t e d in py r o ly sis e x pe r ime nts under a nitrog en atmosphere. Also, no CDDs /CDFs were detected when chlorine-free poly e thy l e n e sa mple s we r e subje c t e d to th e same combustion and py roly sis conditions. Deutsch and Goldfarb (1988) reported finding CDD/CDF c oncentrations rang ing from
0.04 to 6.6 μg /kg in soot samples collected after a 1986 fire in a State University of New York
lecture hall. The fire consumed or melted pl astic furnishing s and cleaning products containing chlorine, wood, and paper.
I n a study that analy z ed 200 ash and soot sa mples from sites of accidental fires in which PVC was involved (F uncke et al., 1988, as repor ted in B r emmer et al., 1994; Rotard, 1993),

6-5

### CDDs/CDF s were detected in more than 90% of the sa mple s a t c onc e n tr a tions in the ng I

TEQ DF 

### /kg to μg I

- TEQ DF 

### /kg rang e. F i res involving the combustion of materials containing relatively larg e amounts of PVC and other chlorina ted org a nic substances resulted in the hig h est levels of CDDs/CDF s, with concentr ations rang ing from 0.2 to 110 μg I

- TEQ DF 

### /kg residue. Thiesen et al. (1989) analy z ed residues from surfaces of P V C-containing materials that
were part i a l l y burned duri n g acci dent al fi res at si t e s i n Germ any t h at m a nufact ured or st ored plastics. CDD/CDF concentrations in residues were repor ted as 0.5 μg I

- TEQ DF 

### / k g for soft P V C
, 4.6 μg I

- TEQ DF 

### /kg for PVC fibers, and 28.3 μg I

- TEQ DF 

### /kg for a hard PVC. The ratio of total
CDF s to total CDDs in the three samples rang ed from 4:1 to 7:1. The dominant 2,3,7,8­
substituted CDF and CDD cong eners in all three samples were 1,2,3,4,6,7,8-HpCDF and 1,2,3,4,6,7,8-HpCDD.
I n an accidental fire at a S w edish carpet factory in 1987, 200 metric tons of P V C and 500
metric tons of PVC-c ontaining carpet were burned. Mark lund et al. (1989) analy z ed snow samples up to 1,500 m downwind from the fire site and found CDD/CDF concentrations in the top 2 cm rang ing from 0.32 μg I

- TEQ DF 

### /m 2 

### at 10 m from the site to 0.01 μg I

- TEQ DF 

### /m 2 

### at 1,500

m. B ecause of an atmospheric inversion and very lig ht wind at the time of the fire, the smoke from the fire remained close to the g r ound. The soot deposited onto the s now was thus assumed to be representative of the soot g e nerat e d and rel eased from t h e fi re. W i pe samples of soot from interior posts of the plant that were 5 and 20 m from the fire contained Eadon TEQ concentrations of 0.18 and 0.05 μg /m 2 

### , r e spe c tive l y

. On the ba sis of the se de position

me a sur e m e n ts, the inve stig a t or s e stima te d tota l CDD/CDF e missions f r o m the f i r e to be le ss tha n 3 mg I

- TEQ DF 

### . Carroll (1996) estimated a soot-associated C DD/CDF emission factor for the Swedish carpet factory fire (i.e., not including volatile emissions) of 28 to 138 ng I

- TEQ DF 

### /kg PVC burned using the f o llowing a ssumptions: the PVC c a r pe t ba c k ing wa s one

- h a l f the we ig ht of the c a r p e t , the carpet backing contained 30% by weig ht PVC resin, and 20 to 100% of the PVC and PVC carpet backing present in the warehouse actually burned. Using the resu lts of wipe samples collected at downwind distances of up to 6,300 m, Carroll (1996) also estimated a similar sootassociated emission factor (48 to 240 ng I

- TEQ DF 

### /kg of PVC burned) for a fire at a plastics

r e c y c ling f a c ility in L e ng e r ic h, Ge r m a n y

. F i edler et al. (1993) presented a case study of CDD/CDF contamin ation and associated
remedial actions taken at a kinde rg art e n i n Germ any fol l o wi ng a fi re that destroy e d parts of the roof, windows, and furnishing s. Soot collect ed from the building contained CDDs/CDF s at a concentration of 45 μg I

- TEQ DF 

### /kg (15 μg I

- TEQ DF 

### /m 2 

### ). The study authors attributed the
CDDs/CDF s detected to the co mbustion of plastic and wooden toy s , floors, and furnishing s; howe v e r , no inf o r m a tion wa s pr ovide d on the qua ntitie s of those ma te r i a l s.

6-6

### F i edler and L i ndert (1998) pres ented results of soot sampling following a serious fire at the airport in Düsseldorf, Germany

. Poly sty r ene sheets and PVC-coated cables were involved in the fire, tog e ther with P C B

- containing condenser s (bulbs). S u rface wipe samples contained up to
0.33 μg I

- TEQ DF 

### /m 2



### . Concentrations in soot rang ed from 7 to 130 μg I

- TEQ DF 

### /kg

. Concentrations of poly brominated dibenz o- p -diox i ns and dibenz ofurans were detected in soot at concentrations as hig h as 0.9 mg /kg soot.
W i chmann et al. (1993, 1995) measured the C DD/CDF content of ash and debris and deposited surface residues that resulted from ex pe rimental test burns of two cars (a 1974 Ford Taurus [ o ld car] and a 1988 Renault Espace [ n ew car ] ) , one subway car, and one railway coach in a tunnel in Germany

. On the basis of measur ements obtained from the sampled ash and debris and from soot collectors placed at reg u lar inte rvals up to 420 m downwind of the burn site, the
total estimated amount of CDDs/CDF s in the ash/debris and tunnel surface residues from each
vehicle burn ex periment was 0.044 mg I

- TEQ DF 

### for the 1974 model car, 0.052 mg I

- TEQ DF 

### for the 1988 model car, 2.6 mg I

- TEQ DF 

### for the subway car, and 10.3 mg I

- TEQ DF 

### for t h e rai l w ay coach. For each vehicle burn ex periment, the mass of TEQ in tunnel surface residue ex ceeded
the mass in ash and debris: 73 to 89% were accounted for by the tunnel surface residues and 11

t o 27% by ash and debri s

. The averag e C DD/ C D F cont ent of t h e ash and debri s from each

ex perimental burn was: 0.14 μg I

- TEQ DF 

### /kg for the new car, 0.3 μg I

- TEQ DF 

### / k g for t h e ol d car,
3.1 μg I

- TEQ DF 

### /kg for the subway car, and 5.1 μg I

- TEQ DF 

### /kg f o r

the r a ilwa y c o a c h.

6.2.2. F u m e and Sm oke Studies Merk et al. (1995) collected fume and smoke g e nerated during the burning of 400 kg of wood and 40 kg of PVC in a building (4,500 m 3 

### volume) over a 45-min period. The sampling device consisted of dual g l ass fibe r filters to collect particles g r eater than 0.5 μm followed by a poly u r e tha n e f o a m f ilte r to c o lle c t va por

- pha se CDDs/CDF s. The pa r tic ula t e pha se ( p a r tic le s
g r eater than 0.5 μm diameter) and the g a s phase showed the same cong ener pattern: decreasing concentration with increasing deg r ee of chlori nation, thus indicating no preferential sorption of hig h er-chlorinated cong eners to smoke particulates. However, the CDDs/CDF s found in the g a s phase (about 5 ng I

- TEQ DF 

### /m 3 

### ) accounted for more than 90% of the detected CDDs/CDF s. The authors also reported that the soot deposited from this fire onto a 1 m 2 

### aluminum sheet resulted in surface contamination of 0.05 μ g I

- TEQ DF 

### /m 2



### . Althoug h it was stated in Merk et al. (1995) that the building was “closed,” subsequent
communication with one of the coauthors (telephone conversati on on September 29, 1998,
be twe e n Ka r l

- W e r ne r Sc hr a mm, GSF

- I n stitute of Ec olog ic a l Che mistr y , a nd Gr e g Sc hwe e r , Versar, I n c.) clarified that a “g as cleaning ” sy stem was in operation. B ecause a ventilation

sy stem was in operation, there was likely some loss of vapor-phase CDDs/CDF s from the hall;

6-7

### therefore, the deposits (from particulate depos ition and vapor-phase c ondensation) on the test aluminum plate may not have r e f l e c t e d tota l CDD/CDF f o r m a tion dur ing the f i r e

. Dy ke and Coleman (1995) repor ted a fourfold increase in CDD/CDF TEQ concentrations in the ambient air during “bonfire nig h t” (an a nnual event held on Novemb er 5 during which it is
customary to set off fireworks and have bonfires) in Ox ford, Eng l and. Air concentrations before and after bonfire nig h t rang ed from 0.15 to 0.17 pg I

- TEQ DF 

### /m 3



### . The air concentration during bonfire nig ht was 0.65 pg I

- TEQ DF 

### /m 3



### . The domina n t c ong e n e r s in a ll sa mple s we r e the he pta

and octa-CDDs. The study was not desig n ed to co llect data that would enabl e cal cul a t i on of an

e mission r a te or to dif f

e r e ntia te the r e la tive impor ta nc e of the va r i ous ma te r i a l s c o mbuste d. However, the results do indicate that open burni ng of materials likely to be combusted in
acci dent al fi res (wi t h t h e ex cept i on of fi reworks) resul t s i n t h e rel ease of C DDs and C DFs.

6.2.3. Data Evaluation
6.2.3.1. Struc tural Fire s 6.2.3.1.1. Em issions data

. Only limite d e missions da ta f

o r

str u c t ur a l f i r e s we r e loc a t e d. Most
of the studies obtained involved situations (field and laboratory ) where relatively hig h loading s of PVC or plastics were combus ted. The effects of different mix e s of c o mbuste d ma te r i a l s,

ox y g en supplies, building config urations, and durations of burn, for ex ample, that are likely to
occur or be found in accidental fi res cannot be accounted for by th e factors that can be derived
from these studies. Also, most of the studies addressed only soot or ash residues and did not address potential vola tile emissions of CDDs/CDF s, which, according to Merk et al. (1995), may represent 90% of the CDDs/CDF s g e nerated during the burning of PVC.
Two reports (Carroll, 1996; Thomas and Spiro, 1995) attempted to quantify CDD/CDF emissions from U.S. structural fires, and L orenz et al. (1996) estimated emissions from structural
fi res i n Germ any

. Carroll (1996) estimated the tota l CDD/CDF content of soot and ash g e nerated from the 358,000 residential fires in the United States in 1993 (as reported in U. S. DOC, 1995b). Detailed

e stima te s we r e de ve lope d of the PVC c onte n t of ite ms in ty pic a l home s, inc l uding plumbing

, wiring , siding and windows, wallpaper, bli nds and shades, and upholstery

. The ty pical
percentag e of PVC burned in hous ehold fires was assumed to be 9.5%. Ex trapolating to all 358,000 one- to two-family unit fires y i elded an annual mass of 2,470 metr ic tons PVC burned. Carroll then developed TEQ emi ssion factors from the results of Thiesen et al. (1989) and Marklund et al. (1989). The estimated CDD/ CDF content rang ed from 0.47 to 22.8 g I

- TEQ DF 

### , with 0.07 to 8.6 g I

- TEQ DF 

### in soot and 0.4 to 14.2 g I

- TEQ DF 

### in ash. A soot emission factor (i.e.,

g r ams of soot produced per g r am of PVC co mbusted) was derived from the investig ator’s assumptions reg a rding the surface area of the soot collection funnel used by Christmann et al.

6-8

### (1989b) and the soot deposition rate on that funnel. These I

- TEQ DF 

### emission factors were then applied to the estimated 2,470 metr ic tons of PVC bur ned annually in one- to two-family unit
residential fires to obtain estima tes of the annual mass of TEQ that would be found in the soot
and ash of residential fires (0.48 to 22.8 g I

- TEQ DF 

### /y r). The averag e emission per fire is thus 1.3 to 64 μg I

- TEQ DF 

### . Thomas and Spiro (1995) estimated that 20 g I

- TEQ DF 

### may be released annually to air
f r o m str u c t ur a l f i r e s. This e stima te a ssume s a n e mission f a c t or of 4 ng I

- TEQ DF 

### /kg ma te r ia l combusted (i.e., the emission rate for “poor ly ” controlled wood combustion), a material combustion factor of 6,800 kg per fire, and 688,000 structural fires per y ear. The averag e emission per fire is thus 29 μg I

- TEQ DF 

### . L orenz et al. (1996) estimate d annual g e neration of CDDs/C DF s in Germany using data
on the number of residential and industrial/commerc ial structural fires coupled with data on
CDD/CDF content in soot and ash residues rema ining after fires. The potential annual I

- TEQ DF 

### g e neration was estimate d to be 78 to 212 g

. Using the emissions data estimated by Carroll (1996) and Thom as and Spiro (1995) provi des an averag e em i ssi on factor of 32 μg I

- TEQ/fire.

6.2.3.1.2. A c t i v i t y l evel i n form at i o n . I n 1987, there were appr ox imately 2,330,000 fires in the Unites States, of which approx imately 745,600 (32%) were struct ural fires (F EMA, 1997). I n 1995, approx imately 574,000 structural fires were reported in th e United States. Of these, 426,000 were reported to be in residential structures, incl uding 320,000 in one- to two-family units, 94,000 in apartments, and 12,000 in other reside ntial setting s

. The ty pes of structures for the remaining 148,000 fires were public assembly , 15,000; edu cational, 9,000; institutional, 9,000; stores and offices, 29,000; sp ecial structures, 29,000; storag e, 39,000; and industry , utility

, and defense, 18,000. The latter tw o categ ories may be underreported, as some incidents were not recorded because they were handled by private fire brig ades or fix e d suppression sy stems (U.S

. DOC, 1997). F o r 2000, the National F i re Data Center estimated that approx imately 1,708,000 fires occurred in the United States, of which approx imately 512,400 (30%) we re structural fires (F EMA, 2001).

6.2.3.1.3. Em ission estim ates

. The limite d da ta a v a ila ble on str u c t ur a l f i r e s we r e judg e d
ina d e qua te f o r

de ve loping na tiona l e mission e stima te s. This c onc lusion wa s a l so r e a c he d f o r national emission invent ories developed for the Netherla nds (B remmer et al., 1994) and the United King dom (U.K. Department of the Environment, 1995). However, preliminary estimates
were cal cul a t e d by com b i n i n g t h e averag e em i ssi on factor of 32 μg I

- TEQ/fire and the number of structural fires in the Unites States (745,600 in 1987; 426,000 in 1995; and 512,400 in 2000),

6-9

### y i elding an annual release of 24 g I

- TEQ DF 

### in 1987, 14 g I

- TEQ DF 

### in 1995, and 16 g I

- TEQ DF 

### in
2000. Confidence in these estimated emissions is very low because of the numerous assumptions employ ed in their derivation. I f the conclusion by Merk et al. (1995) is assumed to be correct,
that 90% of the CDDs/CDF s formed in fires are in the g a seous phase rather than particulate phase, and it is also assumed that the estimates by Carroll ( 1996) and Thomas and Spiro (1995) did not totally account for volatile emissions, then the total CDD/CDF emissions estimated by Carroll and Thomas and Spiro may be underestimates. F u rther testing is needed to confirm the
true mag n itude of these releases.

6.2.3.2. V e h i cl e F i res As with str u c t ur a l f i r e s, the limite d da ta a v a ila ble on ve hic l e f i r e s we r e judg e d ina d e qua te
f

o r

de ve loping na tiona l e mission e stima te s tha t c ould be inc l ude d in the na tiona l inve ntor y

. Howe ve r , a pr e limina r y e stima te of the r a ng e of pote n tia l CDD/CDF e missions tha t ma y r e sult from vehicle fires can be calculated using th e results reported by W i chmann et al. (1993, 1995) for controlled vehicle fires in a tunnel (0.044 mg I

- TEQ DF 

### for an old car to 2.6 mg I

- TEQ DF 

### for a subway car). Althoug h W i chmann et al. did not measure volatile C DDs/CDF s (which were reported by Merk et al., 1995, to account for the majority of CDDs/CDFs formed during a fire), the study was conducted in a tunne l, and it is likely that a sig nificant fraction of the volatile
CDDs/CDFs sorbed to tunnel and collector surfaces and were thus measured as surface residues. The number of vehicle fires reported in the United States wa s approx imately 561,530 in 1987 (F EMA, 1997), 406,000 in 1995 (U.S. DOC, 1997), and 341,600 in 2000 (F EMA, 2001).
I f

it is assumed that 99% of those fires involve d cars and trucks (the a pprox imate percentag e of
all U.S. motor vehicles that are in-service cars and trucks; U.S. DOC, 1995b) and that the applicable emission rate is 0.044 mg I

- TEQ DF 

### per incident, then the annual TEQ formation was
24.4 g I

- TEQ DF 

### for 1987, 17.7 g I

- TEQ DF 

### for 1995, and 14.9 g I

- TEQ DF 

### for 2000. The emission factor of 2.6 mg I

- TEQ DF 

### /f

ir e is a ssume d to be a pplic a b le to the r e ma ining 1% of ve hic l e f i r e s, thus y i elding emissions of 14.6 g I

- TEQ DF 

### /y r for 1987, 10.6 g I

- TEQ DF 

### /y r for 1995, and 8.9 g I

TEQ DF 

### /y

r for 2000. Total TEQ annual emissi ons for 1987, 1995, and 2000 were roug hly estimated to have been 39, 28.3, and 23.8 g I

- TEQ DF 

### /y

r, respectively

. These estimates should be

r e g a r d e d a s pr e limina r y indic a tions of possible e missions f r o m this sour c e c a t e g or y ; f u r t he r
te sting is ne e d e d to c onf ir m the tr ue ma g n itude of the se e missions.

6-10

### 6.3. LANDF ILL F IRES
6.3.1. Em issions Data
I n the late 1980s, two serious fires occurred in landfills near Stockholm, Sweden. The
fi rst fi re was i n a l a rg e pi l e of refuse-deri v ed fu el. Using measurements of chlorobenz enes in the air emissions, it was estimated that 50 to 100 kg of chlorobenz enes were released. CDD/CDF

e missions we r e e stima te d to be se ve r a l te ns of g r a m s, on the a ssumption tha t the r a tio of
CDDs/CDF s to c h lor obe nze n e s in la ndf ill f i r e e missions is simila r to the r a tio obse r ve d in sta c k

g a ses of municipal waste combusto rs. To measure releases in connection with the second fire, which occurred at a larg e conven tional landfill, birch leaves were collected from trees close to the fire and at distances up to 2 km downwind of the fire, as well as from nearby areas not affected by smoke from the fire. The disc harg e of CDDs/CDF s necessary to cause the

c onc e n tr a tions me a sur e d on the le a v e s wa s e stima te d to be se ve r a l te ns of g r a m s ( P e r sson a n d
B e rg ström, 1991).
I n response to these incidents, Persson a nd B e rg ström (1991) also measured CDD/CDF
emissions from ex perimental fires desig ned to simulate surface landfill fires and deep landfill
fires. The ex periments used 9-month-old domestic waste. Th e tests showed no sig nificant
di fference i n C DD/ C DF cont ent of t h e fi re g a ses produced by t h e si m u l a t e d surface and t h at of

t h e deep fi res. The averag e C DD/ C DF em i ssi on rate was reported to be 1 μg Nordic TEQ/kg
waste burned.
Persson and B e rg ström (1991) and B e rg st röm and B j örner ( 1992) estimated annual
CDD/CDF Nor d ic TEQ e missions in Swe d e n f r o m la ndf ill f i r e s to be 35 g

. The e stima te wa s based on the emission rate of 1 μg Nordic TEQ/kg waste burned, an assumed averag e density of landfill waste of 700 kg /m 3 

### , an assumed waste burn of 150 m 3 

### for each surface landfill fire (167 fires in Sweden per y ear), a nd an assumed waste burn of 500 m 3 

### for each deep landfill fire (50 fires in Sweden per y ear). The estimates of waste burn mass for each ty pe of fire were the

averag e values obtained from a survey of 62 su rface fires and 25 deep fires. The estimated
numbe r of f

i r e s pe r y e a r wa s ba se d on the r e sults of a

sur v e y of a ll Swe d ish munic i pa litie s f o r fires reported during 1988 and 1989. I n 1991, Swed en had an estimated 400 municipal landfills (Persson and B e rg ström, 1991). Ruokojärvi et al. (1995) meas ured ambient air concentra tions of CDDs/CDF s in the vicinity of real and ex periment al landfill fires in F i nland. Th e most abundant tox i c cong eners were the hepta- and octa-CDDs a nd the penta-, hepta-, and octa-C DF s. The hig hest contributors to the measured TEQ were 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF

. I n F i nland, annual
CDD/CDF e missions f r o m la ndf ill f i r e s a r e e stima te d to be 50 to 70 g Nor d ic TEQ ( A ittola

, 1993, as reported in Ruokojärvi et al., 1995).

6-11

### 6.3.2. Activity Level Inf orm at ion and Em ission Estim a tes Althoug h no U.S. monitoring studies are ava ilable, an emission factor similar to the
S w edi s h em i ssi on fact or woul d be ex pect ed for t h e Uni t e d S t at es because t h e cont ent of
munic i pa l wa ste in the Unite d Sta t e s a nd Swe d e n a r e e x pe c t e d to be simila r

. B e c a use no da ta

c ould be loc a t e d on c h a r a c t e r iza tion of la ndf ill f i r e s in the Unite d Sta t e s ( i .e ., numbe r , ty pe , ma ss of waste involved), the limited data available were judg ed inade quate for developing national

e mission e stima te s tha t c ould be inc l ude d in the na tiona l inve ntor y

. Howe ve r , a pr e limina r y

e stima te of the pote n tia l ma g n itude of TEQ e missions a ssoc i a t e d with la ndf ill f i r e s in the Unite d States can be obtained by assu ming a direct correlation of emi ssions to population siz e for the United States and Sweden or by assuming a dir ect correl a t i on bet ween e missions and the number of landfills in each country

. B o th the United States and Sweden are indus trializ ed countries. Althoug h the per capita
waste g e neration rate in the United States is nearly 1.5 times that of Sweden, the composition of municipal waste and the fraction of municipal waste disposed of in landfills in the two countries are nearly identical (U.S. EPA, 1996d). Th e population of Sweden was 8,825,417 in 1995 (U.S. DOC, 1995b) and 8,873,052 in 2000 (U.S. DOC, 2002). B a sed on these population estimates
and the estimated annual Nordic TEQ emission factor of 35 g
, the per capita landfill fire–associated Nordic TEQ emi ssion factor was 4 μg TEQ per person per y ear for both 1995 and
2000. B ecause cong ener-specific results were not provided in P e rsson and B e rg ström (1991) or
B e rg ström and B j örner (1992), it was not possible to derive emission factors in units of TEQ DF 

### WH O 98 

### or I

- TEQ DF 

### . Apply i ng this factor to the U.S. population of 263,814,000 in 1995 (U.S. DOC, 1995b) and 281,421,906 in 2000 (U.S. DOC, 2003) results in an estimated annual emission of 1,050 g TEQ for 1995 and 1,126 g TEQ for 2000. These estimates should be

r e g a r d e d a s pr e limina r y indic a tions of possible e missions f r o m this sour c e c a t e g or y ; f u r t he r
te sting is ne e d e d to c onf ir m the tr ue ma g n itude of the se e missions.

6.4. F O REST AND BRUSH F IRES
6.4.1. Em issions Data
B ecause CDDs/CDFs have been detected both in the soot from residential wood burning (B umb et al., 1980; Nestrick and L a mparski, 1982, 1983; B acher et al., 1992) and in the flue

g a ses from residential wood burni ng (Schatowitz et al., 1993; Vi ckelsoe et al., 1993; L a unhardt and Thoma, 2000; Environment Ca nada, 2000), it is reasonable to assume that wood burned in forest and brush fires may also be a source of CDDs/CDF s (Section 4.2 c ontains details on these studies). Only one study (Tashiro et al., 1990) could be found that reported direct measurements of
C DDs/ C DFs i n em i ssi ons from forest fi res. Thi s study reported detecti on of tota l CDDs/CDF s in

6-12

### air at levels rang ing from about 15 to 400 pg /m 3



### . The samples were taken from fix e d collectors located 10 m above the g r ound and from aircraft fly i ng throug h the smoke. B ackg r ound samples

c o lle c t e d be f o r e a nd a f te r the te sts indic a t e d ne g lig ible le ve ls in the a tmosphe r e

. The se r e sults were presented in a preliminary report; however, no firm conclusi ons were drawn about whether
forest fires are a CDD/CDF sour ce. The final report on this st udy , Clement and Tashiro (1991),
showed total CDD/CDF levels in the smoke of about 20 pg /m 3



### . The authors concluded that
CDDs/CDF s a r e e mitte d dur ing f o r e st f i r e s but r e c o g n ize d tha t some por tion of the se e missions could represent resuspension from residues de posited on leaves rather than newly formed
C DDs/C DFs. Althoug h not desig ned to directly assess whether CDDs/CDF s are formed during brush fires, B u ckland et al. (1994) measured CDD/CDF levels in soil samples from both burnt and unburnt areas in national parks in New Z ealand 6 weeks after larg e-scale brush fires. F our surface soi l cores (2 cm dept h) were col l ect ed and com posi t e d from each of t h ree burnt and t h ree unburnt areas. Survey results indicated that brush fires did not have a major impact on
CDD/CDF le ve ls in soil. The I

- TEQ DF 

### content in the soil sample composites was 3, 8.7, and 10

ng /kg for the three unburnt areas and 2.2, 3.1, and 36.8 ng /kg for the three burnt areas. Total
CDD/CDF content rang ed from 1,050 to 7,700 ng /k g in the unburnt area soil samples and from 1,310 to 27,800 ng /kg in the burnt area soil sample s. OCDD accounted for 94 to 97% of total
CDD/CDF c onte n t in a ll sa mple s. Simila r l y , a sur v e y of c ontr o lle d str a w- f i e l d bur ning in the Unite d King dom ( W a l sh e t a l

., 1994) indicated that the stra w burning did not increase the CDD/CDF burden in the soil; however, a chang e in cong ener distribution was observed. Soils from thr ee fi el ds were sam p l e d
imme dia t e l y be f o r e a nd a f te r bur ning , a l ong with a sh f r o m the f i r e

. The me a n I

- TEQ DF 

### concentrations in the preburn soil, postburn soil, and ash were 1.79, 1.72, and 1.81 ng /kg

, respectively

. Concentrations of 2,3,7,8-TCDF we re lower in the postburn soils than in the preburn soils. Conversely

, concen trations of OCDD were hig h er in the postburn soils, indicating possible formation of OCDD dur ing the combustion process.
Van Oostdam and W a rd ( 1995) reported finding no de tectable levels of 2,3,7,8­
substitute d CDDs/CDF s in thr e e soil sa mple s a nd f our a sh sa mple s f o llowing a f

o r e st f i r e in
B r itish Columbia

. The de te c tion limits ( D L s)
, on a c ong e n e r

- spe c i f i c ba sis ( unwe i g h te d f o r TEQ), rang ed from 1 to 2 ng /kg

. Nondetect valu es were also reported for ashes at a slash and
burn site: the soil contained about 0.05 ng I

- TEQ DF 

### /kg

, whereas backg r ound soil contained about
0.02 ng I

- TEQ DF 

### /kg

. The concentrations presented by Clemen t and Tashiro (1991) cannot accurately be
converted to an emission factor because the corresponding rates of combustion g a s production

6-13

### and wood consumption are not known. As a result, the following four alternative approaches
were considered for devel oping an emission factor. Soot-based approach. This a ppr oa c h a ssume s tha t the le ve ls of CDDs/CDF s in c h imne y
soot are represent a t i v e of t h e C DDs/ C DFs i n emissions. The CDD/CDF emission factor is calculated as the product of the CDD/CDF concen tration in soot and the total particulate
emission factor. This calculati on involves first assuming that th e CDD/CDF levels measured in chimney soot by B acher et al. (1992) (720 ng I

- TEQ DF 

### / k g ) are represent a t i v e of t h e C DD/ C DF concentrations of partic les emitted during forest fires. Second, the tota l particulate g e neration
factor must be estimated. Using primarily data for head fires, W a rd et al. (1976) estimated the national averag e particulate e mission factor for wildfires as 150 lb/ton biomass dry weig ht.
W a rd et al. (1993) estimated the national averag e particulate emission factor for prescribed burning to be 50 lb/ton biomass dry weig ht. Co mbining the tota l pa r tic ula t e g e ne r a tion r a te s with the I

- TEQ DF 

### le ve l in soot r e sults in e mission f a c t or e stima te s of 54 ng of I

- TEQ DF 

### and 18 ng
of I

- TEQ DF 

### /kg of biomass burned in w ildfires and prescribed burns, respectively

. These estimated factors are likely to be overestimates because the leve ls of CDDs/CDF s measured in chimney soot by B acher et al. (1992) may represent the accumulation and enrichment of
CDDs/CDF s me a sur e d in c h imne y soot ove r time , le a d ing to muc h hig h e r a ssume d le ve ls tha n the a c t ua l le ve ls on e mitte d pa r tic le s. Carbon m onoxide (CO) approach. CO is a g e neral indicator of the efficiency of combustion, and the emission factors of many e mission products can be correlated with the CO
emission factor. Data from Scha towitz et al. (1993) for emi ssions during natural wood burning in open stoves sug g e st an emission factor of 10 μg I

- TEQ DF 

### /kg CO. Combining this f a c t or with the CO emission factor during forest fires (roug hly 0.1 kg CO/kg of biomass [ W ard et al., 1993] )

y i elds an emission factor of 1,000 ng I

- TEQ DF 

### /kg biomass. This factor is hig her than the sootbased factor discussed above, which is itself considered to be an overestima te. I n addition, althoug h the formation kinetics of CDDs/C DF s during combustion are not well understood,
CDD/CDF emissions have not been shown to c o r r e la te we ll with CO e missions f r o m othe r combustion sources. Wood stove approach. This approach assumes that th e emission factor for residential wood burning (using natural wood a nd open door, i.e., uncontro lled draft) applies to forest fires. As discussed in Section 4.2.1, this approach su g g e sts an emission factor of about 0.5 ng I TEQ/kg wood combusted. This value appears more reasonable than the factors sug g e sted by the

soot and C O approaches because i t i s base d on di rect m easurem ent of C DDs/ C DFs from
combustion of wood rather than on indirect techni ques. However, forest fire conditions differ sig nificantly from combustion conditions in wood st oves. F o r ex ample, fo rest fire combustion

6-14 ­

### does not occur in an enclosed chamber, and the bi omass consumed in forest fires is usually g r een and includes underbrush, leaves, and g r ass. F orest f i re sim u lation approach. This approach quan tif ie s CDD/CDF e missions
thr oug h the c o mbustion of f

o r e st bioma ss in a c ontr o lle d- bur n f a c ility

. Using this a ppr oa c h

, Gullet and Touati (2003) estimated CDD/CDF emissions throug h the testing of three biomass

sam p l e s col l ect ed from t h e Oreg on coast near S eal R o ck and from four bi om ass sam p l e s collected from the North Carolina Piedmont reg i on, approx imately 200 km from the Atlantic

coast. The samples g e nerally consisted of equal por tions of live shoots (needles cut from tree
br a n c h e s) a nd ne e d le litte r g a the r e d f r o m the f o r e st f l oor

. The Or e g on sa mple s we r e c o mpose d of pine needles ( Pinus contorta and Pinus monticola ) and hemlock needles ( Tyuga heterophylla );
the Nor t h Ca r o lina sa mple s we r e c o m posed entirely of lobolly pine ( Pinus taeda ). The combustion of these seven samp les, piled approx imately 10 cm hig h, took place on top of an open, flat combustion platform. C DD/ C DF em i ssi ons were m easured usi n g a Graseby P S

- 1 sampler and EPA’s ambient TO-9 method. As shown in Table 6-2, the overall averag e tota l TEQ e mission f a c t or f

o r

the se ve n samples was 19.9 ng TEQ DF 

### -W HO 98 

### /kg (18.6 ng I

- TEQ DF 

### ), assuming nondetects were z e ro. Se pa r a te ly , the a v e r a g e tota l TEQ e mission f a c t or s f o r

the thr e e Or e g on sa mple s a nd the f our North Carolina samples were 15 ng and 25 ng TEQ DF 

### -W HO 98 

### /kg , respectively

. Even thoug h the

a ve r a g e TEQ e mission f a c t or s f or

the Or e g on a nd Nor t h Ca r olina r uns we r e simila r , CDF

c ong e n e r s we r e domina n t in the Or e g on sa mple s, whereas C DD cong eners were dom i n ant i n t h e North Carolina samples. F i g ure 6-2 shows th e cong ener profile for the Oreg on and North
Ca r o lina sa mple s c o mbine d

. To test an alternative CDD/CDF sampling method, CDD/CDF emissions from one of the Oreg on sam p l e s were al so m easured usi n g a “Nom ad” (a prototy p e portable sampler desig n ed for mobile, in-field sampling )

. The results fro m both sampling methods showed very similar
CDD/CDF TEQ va lue s, tota l va lu es, and ratio values. An a dditiona l Or e g on sa mple wa s a l so combusted to test influences of fuel config uration on emissions. I n this ex periment, the biomass was pl aced i n a m e t a l barrel wi t h ai r hol es cut i n t o t h e bot t o m

. The resul t s showed t h e hi g h est

tota l TEQ e mission va lue c a l c u la te d in this study ( 47 ng TEQ DF 

### -W HO 98 

### /kg ) ; howe v e r , this va lue
is simila r to the ne x t hig h e st tota l TEQ va lue ( 46 ng TEQ DF 

### -W HO 98 

### /kg )

. Because t h e wax y cut i c l e l a y e r on pi ne needl e s has been dem onst r at ed t o absorb lipophilic compounds from the atmosphere, Gullet a nd Touati (2003) also ex tracted a raw, asrecei ved Oreg on bi om ass sam p l e t o det e rm i n e whet her t h e observed em i ssi ons were due t o simple va por iza tion of e x isting CDDs/CDF s or the f o r m a tion of ne w CDDs/CDF s in the combustion process. The CDD/CDF concentr ation in the sample measured 1.3 ng TEQ DF 

### WH O 98 

### /kg

, whic h is a ppr ox ima te ly 20 time s lowe r tha n the Or e g on CDD/CDF e mission

6-15

### T a b l e 6-2. CDD/CDF m e an em ission f a ctors (n g/k g ) f o r f o rest f i res a



### Con g en er Non d e tect set to zero Non d e tect set to 1⁄2 d e tecti o n lim it 2,3,7,8-TCDD 1.15 1.28 1,2,3,7,8-PeCDD 3.83 3.83 1,2,3,4,7,8-Hx CDD 5.68 5.68 1,2,3,6,7,8-Hx CDD 10.70 10.70 1,2,3,7,8,9-Hx CDD 17.34 17.34 1,2,3,4,6,7,8-HpCDD 166.27 166.27

OCDD 663.67 663.67 2,3,7,8-TCDF 6.98 6.98 1,2,3,7,8-PeCDF 6.34 6.35 2,3,4,7,8-PeCDF 10.09 10.11 1,2,3,4,7,8-Hx CDF 16.72 16.74 1,2,3,6,7,8-Hx CDF 7.14 7.16 1,2,3,7,8,9-Hx CDF 1.11 1.20 2,3,4,6,7,8-Hx CDF 9.81 9.85 1,2,3,4,6,7,8-HpCDF 25.39 25.39 1,2,3,4,7,8,9-HpCDF 3.06 3.12

OCDF 10.27 10.32
Total CDD/CDF 965.55 965.99 Total TEQ DF 

### -W HO 98 

### 19.90 20.06

Total I

- TEQ DF 

### 18.60 18.75

a V a l u es w e re deri v e d f rom a t o t a l of s e v e n bi om as s s a m p l e s f rom O reg on an d N o rt h C a rol i n a.

S o u rce: G u l l e t an d T o u a t i (2003).



### concentrations (averag e , 25 ng TEQ DF 

### -W HO 98 

### /kg ; rang e, 14 to 46 ng TEQ DF 

### -W HO 98 

### /kg )

. The
CDD/CDF isome r pa tte r n s of the e x tr a c t e d bioma ss sa mple s a nd the e mission sa mple s we r e simila r

. The r e f or e , this pr e limina r y e v ide n c e sug g e sts CDD/CDF e missions a r e not due sole ly to vaporiz ation of cutic le-bound CDDs/CDF s but are formed anew during forest fires.
Additiona lly , the ne w CDDs/CDF s f o r m e d ma y be a d sor b e d to the wa x y c u tic le la y e r in suc h a

m a nner t h at t h e i s om er pat t e rn refl ect s t h e am bi ent C DD/ C DF concent r at i ons.

6-168F Ra t i o ( c o n g e n e r e m i s s i o n f a c t o r / 2 3 7 8

- CDD/ CDF e m i s s i o n f a c t o r )

0. 000 0. 100 0. 200 0. 300 0. 400 0. 500 0. 600 0. 700 0. 80 0

2, 3, 7, 8,

- T C D D
1, 2, 3, 7, 8- P e C D D
1, 2, 3, 4, 7, 8- H x C D D
1, 2, 3, 6, 7, 8- H x C D D
1, 2, 3, 7, 8, 9- H x C D D
1, 2, 3, 4, 6, 7, 8- H p C D D
1, 2, 3, 4, 6, 7, 8, 9- O C D D
2, 3, 7, 8- TC D F
1, 2, 3, 7, 8- P e C D F
2, 3, 4, 7, 8- H x C D F
1, 2, 3, 4, 7, 8- P e C D F
1, 2, 3, 6, 7, 8- H x C D F
1, 2, 3, 7, 8, 9- H x C D F
2, 3, 4, 6, 7, 8- H x C D F
1, 2, 3, 4, 6, 7, 8- H p C D F
1, 2, 3, 4, 7, 8, 9- H p C D F
1, 2, 3, 4, 6, 7, 8, 9- O C D F



### F i gu re 6-2. Con g en er p r of i l e f o r f o res t f i re sim u lation approach em issions.

S o u rce: G u l l e t an d T o u a t i (2003).



### Many fact ors m a y affect forest fi re C DD/ C DF emissions, such as the ty pe of fire (crown vs. understory and duff), ty pes of species combus ted, and location of the fire (near coastal vs. inland). Additionally , combustion conditions such as wind speed and fuel moisture content may
also result in variations in emissions. These va r i a b le s, the r e f or e , y i e l d unc e r ta intie s in the
cal cul a t i on of a represent a t i v e em i ssi on fact or t h roug h forest fire simulations. However, the emission factor of 19.9 ng TEQ DF 

### -W HO 98 

### /kg (18.6 ng I

- TEQ DF 

### ) calculated throug h this approach appears to be more reasonable than the fact ors sug g e sted by the soot, CO, and wood stove approaches because t h e forest fi re si m u l a t i on approach di rect l y m easures C DD/ C D F em i ssi ons from forest biomass combusted in an open pile

. Additionally , the fo rest biomass samples
consisted of both live shoots a nd needle litter of representative species from two distinct
loc a tions.

6-17

### 6.4.2. Activity Level Inf orm ation
6.4.2.1. Approach for Reference Y e ar 2000 (Office of Air Quality Planning and Standards [OA QPS ]) As part of the 2000 National Emissions I nve ntory , OAQPS develope d activity levels of wildfires and prescribed burning on a county

- le vel basis for reference y ear 2000. The number of acres burned by wildfires and prescribed burni ng was obtained from the U.S. F orest Service (USF S) and four U.S. De partment of I n terior ag encies: B u reau of L a nd Manag e ment, National
P a rk S e rvi ce, U.S

. Fi sh and W i l d l i f e S e rvi ce, and B u reau of I ndian Affairs (B I A ). USF S provided data for federal, state, and private lands. All data we re provided on a state level ex cept
for the B I A wildfire data and the USF S pres cribed burning data, wh ich were provided on a

r e g i ona l le ve l. Prior to allocating the forest fire activity to the county leve l, the B I A and USF S reg i onal
da ta we r e f i r st a lloc a t e d to the sta t e le ve l. The B I A da ta we r e a lloc a te d using the numbe r of
acres of t r i b al l a nd i n each st at e. The US FS dat a were al l o cat ed usi n g fact ors devel oped from
landcover data in the B i og enic Emissions L a ndcover Database ( B EL D2) within EPA’ s B i og e nic
Em i ssi ons I nvent ory S y st em ; however, t h e BEL D 2 dat a for C a l i f orni a were repl aced wi t h dat a from the 1996 National Tox i cs I nventory because US FS ’s Reg i on 5 contains both Hawaii and
California.
For each of t h e forest fi re cat eg ori e s, t h e act i v i t y from al l t h e ag enci es were t h en t o t a l e d by state and allocated to the county level usin g state-to-county land cove r factors developed from
B E L D 2. These B E L D 2 factors were based on the acr eag e of rural forest, brush, and g r ass in each
county

. This procedure was used for all states ex cept Alaska and Hawaii, for which B EL D 2 does
not contain land cover data. F o r Alaska and Hawaii, state-to-c ounty factors were derived from
data contained in the allocati on factor file used for the 1996 National Emissions I nventory

. Using this approach, OAQPS estimated that approx imately 8,357,958 acres were burned by wildfires in 2000 and approx imately 1,261,607 acres were burned by prescribed fires in 2000. To obtain the amount of biomass consumed by wildfires and prescribed burning , the acres of forest burned were combined with reg i on-specific fuel loading factors, as shown in Table 6-3. Nationally , approx ima tely 228 million tons of biomass were consumed by wildfires and 15.8
million metric tons of biom ass were consumed by prescribed burning in 2000.

6.4.2.2. Approach for Reference Y e ars 1987 and 1995 According to the Council on Environmental Quality ’s 25th annual report (CEQ, 1997), 5
million acres of forest were lost to wildfi res in 1987 and 7 million acres were lost in 1995. Estimates of the acreag e consumed annually during prescribed burns are not readily available for

6-18

### T a b l e 6-3. F o rest f i re f u el l oad i n g f a ctors (ton s / a cre)

R e gion Wildfir e s P r e s c r i be d bur ning
Alaska 6 12.6
California 18 14.2

I ntermountain 8 6.3
North Central 11 8.7
Northern 60 47.3
Pacific Northwest 6 0 47.3 Rocky Mountain 30 23.7
Southern 9 7.1
Southwestern 10 7.9

S o u rce: U

. S

. EPA (2002b).



### 1995 and 1997. An estimated 5.1 million acres of biomass were burned in 1989 during prescribed burns (W ard et al., 1993). This valu e was assumed to be a ppropriate for use for reference y ears 1987 and 1995. To obtain the amount of biomass consumed by wildfires and prescribed burning , the acres
of forest burned were combined with biomass consumption rates of 9.43 metric tons/acre in areas consumed by wildfires (W ard et al., 1976) a nd 7.44 metric tons/acre in areas consumed in prescribed burns. F o r 1987 and 1995, approx imately 38 million tons were consumed by

pr e sc r ibe d bur ns. Appr ox ima te ly 47 million me tr ic tons of bioma ss we r e c onsume d by wild f i r e s in 1987 and approx imately 66 million metric tons of biom ass were consumed in 1995.

6.4.3. Em ission Estim a tes Combining the emission factor developed usin g the forest fire simulation approach (19.9

ng TEQ DF 

### -W HO 98 

### /kg biomass [ 18.6 ng I

- TEQ DF 

### /kg biomass] ) with the amount of biomass consumed annually in wildfires and prescribed fires (total of 85 million metric tons in 1987, 104 million metric tons in 1995, a nd 244 million metric tons in 2000) y i elds annual emission estimates of 1,700 g TEQ DF 

### -W HO 98 

### (1,581 g I

- TEQ DF 

### ) for 1987; 2,080 g TEQ DF 

### -W HO 98 

### (1,934 g
I

- TEQ DF 

### ) for 1995; and 4,880 g TEQ DF 

### -W HO 98 

### (4,538 g I

- TEQ DF 

### ) for 2000. F o r wildfires specifically , annual reference y ear emission estimates are 940 g TEQ DF 

### -W HO 98 

### (874.2 g I TEQ DF 

### ) for 1987; 1,320 g TEQ DF 

### -W HO 98 

### (1,228 g I

- TEQ DF 

### ) for 1995; and 4,560 g TEQ DF 

### WH O 98 

### (4,241 g I

- TEQ DF 

### ) for 2000. F o r prescribed fires sp ecifically , annual emission estimates

6-19 ­

### are 760 g TEQ DF 

### -W HO 98 

### (706.8 g I

- TEQ DF 

### ) for reference y ears 1987 and 1995 and 320 g TEQ DF 

### WH O 98 

### (297 g I

- TEQ DF 

### ) for reference y ear 2000. These estimates should be reg a rded as prelimin ary indications of po ssible emissions from
this sour c e ; f u r t he r te sting is ne e d e d to c onf ir m the tr ue ma g n itude of e missions. The a c tivity
l e vel for bot h forest fi res and biomass combustion is g i ven a lo w confi d ence rat i n g because t h ese

va lue s we r e e stima te d a nd ma y not be r e pr e se n ta tive

. The e mission f a c t or is hig h ly va r i a b le a n d dependent on ty pe of bi omass burned, therefore, it is judg ed to be clearly nonrepresentative.

6.5. BACK YARD BARREL BURNING
6.5.1. Em issions Data
I n many rural and nonurban areas of the United States, residences may dispose of household refuse throug h open backy a rd burning

. This practice usually consists of burning
refuse in a 208-L capacity steel drum. Holes ar e punched near the bottom of the drum to allow

c o mbustion a i r to e n te r

. The f i r e is ig nite d with a petroleum fuel, e.g ., kerosene. The low combustion temperatures and ox y g en-starved conditions associated with household refuse burning in these “burn barrels” results in poor and uncontrolled combus tion conditions. Under such conditions, products of inco mplete combustion are formed a nd visible smoke is emitted into

t h e ai r. The practice of open burning in burn barrels causes CDDs and CDF s to be formed and
released as tox i c air contaminants. I n 1997, EPA’s Control Technolog y Center, in cooperation with the New York State’s Department of Health and Department of Environmental Conservation, conducted an initial study that ex amined, char acterized, and qua ntified emissions from simulated open burning s of household waste materials in barrels (L emieux , 1997). The
represent a t i v e wast e was prepared on t h e basi s of the ty pical percentag e s of various waste materials disposed of by New Yo rk State residents; haz a rdous wa stes (e.g ., chemicals, paints, oils) were not included in the test waste. A variety of compounds, in cluding CDDs/CDF s, were

me a sur e d in the e missions f r o m two simula ted open burning s of this “baseline” waste. Combustion studies were subsequently perform ed by EPA to provide additional baseline

wa ste te sts a nd a n initia l indic a tion of the impa c t of limite d va r i a tion in wa ste c o mposition a n d
combustion conditions on CDD/CDF emissions fro m a simula te d dome stic ba c k y a r d ba r r e l bur n of 6.8 kg of unshredded househol d waste (Gullet et al., 1999, 2000a, b; L e mieux et al., 2000; email dated September 7, 2000, from P. L e mieux , U.S. EPA, to D. Cleverly , U.S. EPA). The
results of seven baselin e open burning waste tests were repor ted in these EPA studies. These

tests ex hibited variation in th e emissions of CDDs/CDF s, with a one to two order-of-mag nitude spread between the lowest and hig h est values for individual cong eners, cong ener g r oups, total
C DDs/ C DFs, and TEQ val u es. The averag e TEQ e mission factor for the se ven baseline tests was

6-20

### 72.8 ng I

- TEQ DF 

### /kg waste burned (setting nondetect va lues equal to zero) and 73.7 ng I

TEQ DF 

### /kg waste burned (setting nondetect values e qual to one-half the DL ). The corresponding TEQ DF 

### -W HO 98 

### values were 76.8 and 77.7 ng /kg

. Table 6-4 presents the averag e cong ener and

cong ener g r oup results for these tests.
I n a ddition to the ba se line te sts, the c o mbustion e x pe r ime nts inc l ude d te sting a t thr e e different PVC levels: 0, 1, and 7.5% by weig ht PVC. The averag e emissions were 14, 201, and 4,916 ng I

- TEQ DF 

### /kg waste burned, respectively

. Two te sts using wa ste impr e g n a t e d with inorg a nic chloride (CaCl 2 

### ) at a concentration of 7.5% by we ig ht (and no PVC) averag ed 734 ng I

TEQ DF 

### /kg

. Qualitative comparisons sug g e st that th e tests conducted with hig her chlorine, via
PV C or Ca Cl 2 

### , r e sulte d in substa ntia l inc r e a se s in TEQ e missions.
Other variations in baseline waste co mposition included conduc ting one test with compressed waste, one test with a double load of wa ste, and one test in wh ich some of the waste

pa pe r wa s we tte d to simula te hi g h -moisture burns. These tests resul t e d i n a hi g h er m ean TEQ emission factor (534 ng I

- TEQ DF 

### /kg ) than that of the baseline runs.
S e veral wast e com bust i on vari abl e s were eval uat e d, such as averag e t e m p erat ures at

pr e sc r ibe d ba r r e l he ig hts, le ng th of time te mpe r a t ur e s ( f a vor a b le te mpe r a t ur e r a ng e s) f o r CDD/CDF formation, and measurement of CO, CO 2 

### , O 2 

### , pa r tic ula t e ma tte r , a nd HCl. Sta tistic a l analy s es of the results indicated that CO emi ssions and temperature measured in the uppermost portion of the barrel were the best predictors of TEQ variation. However, the wide variability in test results (from less than 10 to more than 6,000 ng I

- TEQ DF 

### / k g ) al so i ndi cat es t h at a hi g h deg r ee of CDD/CDF emission variation can be ex pected due to factors tha t a r e not wholly r e la te d to waste composition or burning practi ce, such as waste orientation. A mean emission factor of the baseline tests (without PV C added) was deve loped from the data. This mean emission factor was
78.6 mg TEQ DF 

### - W HO/kg , a nd it wa s use d to e stima te r e le a se s f r o m ba r r e l bur ning

. The emission factor is g i ven a low confidence ra ting because it is possibly nonrepresentative of barrel-burning emissions.

6.5.2. Activity Level Inf orm ation
The amount of refuse that is combusted a nnually in the United States in residential backy a rd burn barrels is larg ely unknown. Althoug h no national statistics are available, a limited number of telephone survey s have attempted to measure the pr evalence of backy a rd barrel
bur ning in a f

e w g e og r a phic a l a r e a s. This limite d numbe r of sur v e y s, c o mbine d with c e n sus da ta on the rural and nonurban population of the United States, were us ed to estimate annual activity
le ve l in te r m s of the qua ntity of r e f u se c o mbuste d in bur n ba r r e ls pe r r e f e r e nc e y e a r

. The
f

o llowing is a summa r y of this e stima tion pr oc e dur e

.

6-21

### T a b l e 6-4. CDD/CDF average air em ission f a ctors (n g/k g w a ste b u r n e d ) f

r om b a rrel b u r n i n g of h o u s eh ol d w a ste a



### Con g en er/ con g en er grou p Non d e tect set to 1⁄2 d e tecti o n l i m i t Non d e tect set to zero 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 3.4 8.2 6.6 9.9 19.1 39.8 49.7 2.7 8.1 6.4 9.7 19 39.8 49.7 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 45.6 37.2 65.2 113.8

38.5 61.9

3 128.6

14.6 37.5 45.6 37.2 65.2 113.8

38.5 61.9

2.5 124.4

15 36.4 Total 2,3,7,8-CDD Total 2,3,7,8-CDF Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 136.7 545.9

73.7 77.7 135.4 540.5

72.8 76.8

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 413 281 221 105

43 1,880 1,021

492 169

32 413 281 221 105

43 1,880 1,021

492 169

30
Total CDD/CDF 4,657 4,655

a L i s t ed v alu es are th e arith m etic av erag es of s ev en tes t s f o r th e con g en ers an d th e av erag es of f

i v e tes t s f o r th e

c o nge ne r gr o up s

.

S o u rces : E- m a i l dat e d S e pt em ber 7, 2000, f rom P. L e m i eu x , U

. S

. EPA
, t o D

. C l ev erl y , U

. S

. EPA ; G u l l e t t et

al

. (1999, 2000, 2001).



### 6-22

### 6.5.2.1. S u m m a ry of B a rrel B u rn S u r veys A total of seven survey s of the prevalence of backy a rd combustion of domestic refuse in
bur n ba r r e ls we r e ide n tif ie d in the lite r a tur e

. F o r the most pa r t , the se sur v e y s we r e a n a tte mpt to estimate the barrel-burning activity in a specific state, county

, or reg i on in support of reg u latory
determinations on barrel bur ning

. I n g e neral, the results of the survey s showed a prevalence of barrel burning within the rural population to ra ng e from 12 to 40%, with a mean of 28%. The following is a review of the survey s. The Two Rive rs Re g i on Counc il of Public Offic i a l s (TRRCPO) a nd Pa tric k Eng i ne e r ing conducted a telephone survey in th e early 1990s of residents of fi ve central I llinois counties. They found that about 40% of the residents in a ty pical rural county burned household waste. The survey also indicated that , on averag e, those households that burned waste disposed of

a pprox ima te ly 63% of the i r house hold wa ste by burning it in ba rre ls (TRRCPO, 1994). Similar results were obtained in a survey conducted by Z e nith Research Group, I n c., (2000) for the W e stern L a ke Superior Sanitary District of Minnesota. This survey of 760 residents of selected portions of northwestern W i sconsin and nor the a ste r n Minne so ta addressed, in part, the use of burn barrels or other devices to burn household g a rbag e or other materials. Among all survey respondents, 27.5% said they used burn barrels or other devices to burn household g a rbag e or other materials. Environics Research Group conducted a house hold g a rbag e disposal and burning survey of 1,516 residents of Ontario, Cana da. All respondents resided in detached sing le-family homes. Approx imately 24% of all respondents reported burning their household refuse in burn barrels (Environics Research Group, 2001).
E.H. Pechan and Associates conducted a residential municipa l solid waste survey for the
Mid- Atla ntic /Nor the a st Visibility Union ( MANE- VU) sta t e s a nd tr ibe s ( P e c h a n a nd Assoc i a t e s, 2002). The MANE-VU entities include Connecticut, Delaware, the District of Columbia, Maine, Mary land, Massachusetts, New Hampshire, New J e rsey , New York, Pennsy l vania, the Penobscot
I ndian Nation, Rhode I s land, the St. Reg i s Moha wk Tribe, and Vermont. Household waste burning survey s were conducted by telephone for 72 residents of rural, suburban, and urban jurisdictions, as classified by the 1990 census. The residents were aske d to estimate the number of households in their jurisdiction that burned hous ehold waste or trash. I n g e neral, the survey estimated that 11.9% of the rural population burned refuse in backy a rd burn barrels.
The State of California Air Resources B o ar d (CARB ) undertook a study of the prevalence of backy a rd refuse burning in rural areas of 21 air manag e ment distri c t s in Ca lif or nia ( C ARB
, 2002). F r om this study , CARB estimated that approx imately 18% of the rural population in
California combusted their household refuse in backy a rd burn barrels.

6-23

### I n 1993, the St. L a wrence County Planning O ffice in Canton, NY, conducted a survey of open burning of domestic refuse (St. L a wr ence County
, 1993). F r om the survey , it was concluded that 48.2% of 9,926 households in rura l areas of the county burned household refuse
in burn barrels.
I n 1997, the State of Maine Department of C onservation F o restry B u reau survey ed rural

t o wn fi re wardens and st at e fi re rang ers re g a rding the prevalence of backy a rd burning of
household waste. I t was revealed throug h the survey that each day approx imately 19,147 kg of domestic refuse was being combus ted state wide in approx imately 8,510 burn barrels. I n relation to the total population, it was noted that one burn barrel ex isted for every 144 individuals.

6.5.2.2

. E s t i m at es of A c t i v i t y Level The following chart summariz e s the steps ta ken to estimate the quantity of household refuse combusted in backy a rd burn barrels in1987, 1995, and 2000.

Ste p Assumption 2000 1995 1987

1 U .S. population 281,400,000 260,600,000 242,300,000

2 P opulation in rural and nonurban areas 59,000,000 52,700,000 50,700,000

3 P ercent nonurban population burning household refuse 28 40 40

4 A djusted population burning household refuse in barrels 16,726,500 21,080,000 20,280,000
5 P er capita household refuse
g e neration rate (kg / y r ) 616 616 616

6 P ercent of household refuse
g e nerated burned at homes 63 63 63

7 A djusted per capita household refuse burned (kg / y r ) 388 388 388

8 Total refuse g e nerated by rural and nonurban population burning household refuse (kg / y r ) 6,491,220,120 8,180,726,400 7,870,262,400

F or steps 1 and 2, the U.S. Census B ureau St at i s t i cal Abst ract of t h e Uni t e d S t at es was used to determine population siz e

. F or step 3, the assumption of the pe rcent of rural population

6-24

### combusting refuse in burn barrels in 2000 was derived from the overall mean prevalence rate
from six survey s (CARB , 2002; Z e nith Res earch Group, 2001; Environics Research Group,
2001: Pe c ha n a nd Assoc i a t e s, 2004; St. L a wre nc e County , 1993; a nd TRRCPO, 1994). This produced a mean prevalence of 28%, which should re flect the impact of stat e bans or restrictions on the practice of open burning of refuse. The 1995 and 1987 population was estimated using
the surve y by TRRCPO (1994). This produc e d a pre va l e nc e of 40%, whic h should re fle c t the fact that the practice of open burni ng of refuse was not banned or re str i c t e d by the ma jor ity of the

st at es. The above mean prevalence rates were used in step 4 to calculate the number of people residing in rural areas assumed to have burned househol d refuse in burn barre ls in each reference

y ear (assumption in step 2 multiplied by the pe rcentag e in step 3). The annual per capita household refuse g e neration rate in step 5 is from Municipal Solid W aste Fact Book (2000). The fig ure of 616 kg /person/y r is the result of subtr acting out weig ht of y a rd waste from the per capita

g e neration rate. The assumption in step 6 is that 63% of the household refu se g e nerated in rural areas is burned in backy a rd burn barrels. This percentag e was derived from the survey conducted
in rura l c ountie s of I llinois by TRRCPO (1994). These activity levels are adopted and assig n ed a confidence rating of low because they are derived from limited survey s that are possibly nonrep resentative of the nati onal activity level.

6.5.2.3. Alte rnativ e Approac h to Estim ating Ac tiv ity Le v e l
The actual amount of refuse combusted in burn barrels in the United States is unknown
and must be estimated. OAQPS de veloped activity leve ls of residential MSW combusted in backy a rd barrels for reference y ear 2000. The activ ity levels were deter mined by first estimating the amount of waste g e nerated for each county in the United S t ates. The amount of waste

g e ne r a te d wa s e stima te d by using a na tiona l a v e r a g e pe r c a p ita wa ste g e ne r a tion f a c t or , whic h is
1.5 kg /person/day

. This value was calculate d using population data from the 2000 census and 2000 waste g e neration data (U.S. EPA, 2002c). To better reflect the actual amount of household residential waste subject to being burned, noncombustib les (g lass and metals ) and y a rd waste

were ex cluded. This factor was then applied to the portion of th e county ’ s total population that is considered rural, since open burning is g e nerally not practiced in urban areas. Using da ta from TRRCPO (1994), it wa s e stima te d tha t for rura l popula tions, 25 to 32% of g e nerated MSW is burned. A median value of 28% was a ssumed for the nation, and this correction factor was applied to the total amount of waste g e nerate d. Controls (or burning bans) were accounted for by assuming that no burni ng takes place in counties where the urban population is at least 80% of the total population (i.e., urban plus rural). Z e ro emissions from open burning were attributed to these counties. This techni que produced an estimated annual

6-25

### activity level of 7.79 billion kg of residential household waste co mbusted in burn barrels in 2000. This estimate is approx imate ly 16.5% g r eater than the estimate used in this report.

6.5.3. Em ission Estim a tes
CDD/CDF emissions from burn barrels for reference y ears 1987, 1995, and 2000 were calculated by multiply ing the es timated annual total we ig ht of household refuse combusted in burn barrels (see Section 6.5.2.2) by the diox in e mission factor. The emission factor was 76.8 ng TEQ DF 

### -W HO 98 

### /kg (72.8 ng I

- TEQ DF 

### /kg ) waste burned. Annual nationwide TEQ emissions for 1987, 1995, and 2000 were calculated using the following equation:

E TE Q 

### = EF TE Q 

### H AL
where:
E TEQ 

### = Annual TEQ DF 

### emissions (g /y r)
EF TEQ 

### = TEQ DF 

### emission factor (76.8 ng TEQ DF 

### -W HO 98 

### /kg waste burned)
AL = Annual activity level (7,870,262,400 kg in 1987; 8,180,726,400 kg in 1995; and 6,491,220,120 kg in 2000).

Using this equation, estimated nationwide TEQ DF 

### emissions were 604 g TEQ DF 

### -W HO 98 

### (573 g I

- TEQ DF 

### ) in 1987, 628 g TEQ DF 

### -W HO 98 

### (595 g I

- TEQ DF 

### ) in 1995, and 498.53 g TEQ DF 

### WH O 98 

### (472.56 g I

- TEQ DF 

### ) in 2000. A low confidence rating is g i ven to both the emission factor

a nd the e stima te of a c tivity le ve l, the r e f or e , the c onf ide n c e r a ting is low f o r

the e stima te of TEQ emissions from backy a rd ba rrel burning of refuse.

6.5.4. Com p osition of Ash f r om Barrel Bu rn in g Ash samples were collected from open barrel burning (L emie ux , 1997) and analy z ed for
CDDs/CDF s a nd PCB s. Ash sa mple s f r o m the e x pe r ime nts we r e c o mbine d, r e sulting in two composite samples, one for recy clers and one for nonrecy clers. The results for PCB s depict only the data for specific PCB cong eners. The rema ining PCB data reported in L e mieux (1997) could not be related to a particular cong ener. The resul t s are pr esented in Tables 6-5 and 6-6.

6.6. RESIDENTIAL YARD WASTE BURNING
6.6.1. Em issions Data
I t is reasonable to assume that residen tial y a rd waste burning may be a source of
CDDs/CDF s, as they have been de tected in forest and brush fire s. No direct measurements of
CDD/CDF e missions f r o m r e side ntia l y a r d wa ste burning have been performed; however, Gullet

6-26

### T a b l e 6-5. CDD/ CDF an al ysi s f o r com p osi t e ash sam p l e s f r om b a rrel bur ning ( n g/kg ash)

Con g en er/ con g en er group Average

con cen trati o n i n

com p osi t e ash sam p l e I-T E Q DF 

### TEQ DF 

### -WH O 98 

### Avid recycl er Non

recycl er Avid recycl er Non

recycl er Avid recycl er Non

recycl er 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 31 230 270 420 300 4,000 9,600 9 53 44 74 56 630 690 31 115

27 42 30 40

9.6 9 26.5

4.4 7.4 5.6 6.3 0.69 31 230

27 42 30 40

0.96 9 53

4.4 7.4 5.6 6.3 0.069 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 830 1,000 2,500 2,300 2,100 2,900

810 12,000

1,400 8,200 220 270 690 480 490 670 150 2,100

170 560 83 50 1,250

230 210 290

81 120

14

8.2 22 13.5 345

48 49 67 15 21

1.7 0.56 83 50 1,250

230 210 290

81 120

14

0.82 22 13.5 345

48 67 15 21

1.7 0.056

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD 2,500 4,100 5,600 7,600 9,600 490 740 1,300 1,300

690 -

-

-

-

- -

-

-

-

- -

-

-

-

- -

-

-

-

- Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 25,000 21,000 19,000 17,000

8,200 8,200 6,600 4,600 2,900

560 -

-

-

-

- -

-

-

-

- -

-

-

-

- -

-

-

-

- Tota l CDD Tota l CDF 29,400 90,200 4,520 22,860 -

- -

- -

- -

- Total CDD/CDF 119,600 27,380

- - - -

S o u rce: L e m i eu x (1997).



### 6-27

### T a b l e 6-6. P C B an al ysi s f o r com p osi t e ash sam p l e s f r om b a rrel b u r n i n g (ng/kg ash)

Com p ou n d Avi d recycl er Non recycl er 2-Chlorobipheny l < 2,500 4,900 2,3' -Dichlorobipheny l 3,700 4,700 2,2' ,6-Trichlorobipheny l < 500 5,600 2,2' ,5-Trichlorobipheny l 32,000 6,300 2,3' ,5-Trichlorobipheny l 800 800 2,3' ,4-Trichlorobipheny l < 500 700 2,4' ,5-Trichlorobipheny l 1,500 900 2,4,4' -Trichlorobipheny l < 500 500 2,2' ,4,6' -Tetrachlorobipheny l < 500 1,500 2,2' ,3,6' -Tetrachlorobipheny l 5,300 1,300 2,2' ,5,5' -Tetrachlorobipheny l 3,100 1,800 2,2' ,3,5' -Tetrachlorobipheny l 2,600 1,200 2,2' ,4,4' ,5-Pentachlorobipheny l 3,400 1,300 2,2' ,3,3' ,5-Pentachlorobipheny l 400 <500 2,2' ,3,4,5,5' -Hex achlorobipheny l 1,200 <500

S o u rce: L e m i eu x (1997).



### and Touati (2003) measured an averag e CDD/CDF emission factor of 20 ng TEQ DF 

### -W HO 98 

### /kg during forest fire simulations where bioma ss sa mple s f r o m Or e g on a nd Nor t h Ca r o lina we r e burned on an open platform (see Section 6.4). Therefore, the emission factor of 20 ng TEQ DF 

### WH O 98 

### /kg developed by Gullet and T ouati (2003) was used for resi dential y a rd waste burning

.

6.6.2. Activity Level Inf orm ation Pechan and Associates (2002) estimated that approx imately 233 lb of y a rd waste per household per y ear (based on a four-person house hold) were burned in 2000. This is similar to the estimate of 106 to 319 lb y a rd waste per household per y ear (based on a four-person household) that Pechan calculate d using the results of a household y a rd waste burning survey

. Pechan’s telephone survey was completed by 181 ru ral, suburban, and urban jurisdictions of the
MANE-VU entities. The results indicated that approx imately 28% of the population in rural
areas burned household y a rd waste and that hous eholds typically conduc ted two to three burns

6-28

### per y ear. Additionally , as indicated by informa tion provided by three respondents, 1 to 3 cubic

y a r d s of y a r d wa ste wa s ty pic a lly bur ne d a t a time

. As part of the 2000 National Emissions I nve ntory , OAQPS determin ed on a county

- level basis the amount of y a rd waste burned in 2000. The activity level estima tes were based on the assumption that y a rd waste was g e nerated at a rate of 0.54 lb/person/day in 2000, which in turn was derived using population da ta for 2000 and the assumption that 27.7 million tons of y a rd
waste were g e nerated in 2000 (U.S . EPA, 2002c). Of the total am ount of y a rd waste g e nerated, the composition was assumed to be 25% leaves, 25% brush, and 50% g r ass by weig ht (U.S. EPA, 2001b). B ecause open burning of g r ass clipping s is not ty pically practiced by homeowners, only 50% of the y a rd waste g e nera ted was assumed to be burnable. Add itionally , OAQP S assumed that burning primarily occurs in rural areas (i.e ., the per capita y a rd waste g e neration factor was applied to only the rural population in each county ) and that only 28% of the total y a rd waste

g e nerated was actually burned (see Section 6.5). The amount of y a rd waste assumed to be g e ne rated in each county was then adjusted for variation in veg e tation using B E L D 2. F or counties with 10 to 50% forested land, the amount of

y a rd waste g e nerated was reduced to 50% and fo r counties with less than 10% forested land, to

z e ro (i.e., no y a rd waste was g e nerated). Adjus tments for variation in veg e tation were not made

t o count i e s where t h e percent a g e of forest ed acr es was g r eater than or equal to 50%. B e fore calculating the percentag e of forested acres pe r county , the acreag e of ag ricultural lands was subtracted from the acreag e of forested lands to better account for the native veg e tation that would likely be occurring in the residential y a rds of farming states. Controls (or burning bans) were accounted for by assuming that no burni ng took place in counties where the urban population ex ceeded 80% of the total population (i .e., urban plus rural). Using this method, OAQPS estimated that 255,000 me tric tons of leaf and 255,000 metr ic tons of brush (total of 510,000 metric tons of y a rd waste) were burned in 2000.

6.6.3. Em ission Estim a tes Using the emission factor of 20 ng TEQ DF 

### -W HO 98 

### /kg (18.6 ng I

- TEQ DF 

### /kg ) and the activity level of 510,000 me tric tons y a rd waste burned in 2000, CDD/CDF emissions from open burning of y a rd waste were 10.2 g TEQ DF 

### -W HO 98 

### (9.5 g I

- TEQ DF 

### ) in 2000. Assuming 772 and 754 million kg of y a rd waste were burned in 1987 and 1995, respectively , then 15.4 g TEQ DF 

### WH O 98 

### (14.4 g I

- TEQ DF 

### ) and 15.19 g TEQ DF 

### -W HO 98 

### (14 g I

- TEQ DF 

### ) were emitted in 1987 and 1995, respectively

. These numbers should be re g a rded as preliminary estimates of possible

e missions f r o m this sour c e ; f u r t he r te sting is ne e d e d to c onf ir m the tr ue ma g n itude of e missions
because both the emission factor a nd activity levels are judg ed to be clearly nonrepresentative of

t h e source cat eg ory

.

6-29

### 6.7. LAND-CLEARING DEBRIS BURNING
6.7.1. Em issions Data During the clearing of land for the constr uction of new building s (residential and nonresidential) and hig h way s , trees, shrubs, and brush are often torn out, collected in piles, and
burned. As with residential y a rd waste burning , it is assumed th at the burning of land-clearing
debri s m a y g e nerat e C DDs/ C DFs because em i ssi ons have been det ect ed from forest and brush
fi res. No di rect m easurem en ts of CDD/CDF emissions from th e burning of land-clearing debris have been performed, so the aver ag e emission factor of 20 ng TEQ DF 

### -W HO 98 

### /kg

, which was used
for bot h forest fi res and resi dent i a l y a rd wast e bur ning , is also used for burning of land clearing debris (see Sections 6.4 and 6.6).

6.7.2. Activity Level Inf orm ation
Ac tivity le ve ls a ssoc i a t e d with la nd- c l e a r ing debris were calculated by OAQPS on a county

- level basis using the numbe r of acres disturbed throug h re sidential, nonresidential, and roadway construction.

6.7.2.1. Re side ntial Construc tion
I n 2000, approx imately 330,551 acres were disturbed by resi dential construction. This number is based on county

- level housing permit data and reg i ona l housing start data obtained
f r o m the U.S. Ce nsus B u r e a u f o r

sing le

- f a mily units, two- f a mily units, a nd a p a r tme nt building s. The county permit data were firs t adjusted to equal reg i onal hous ing

- start data, and then the number of building s in each housing categ ory was estimated. The to tal number of acres disturbed by residential construction was then de termined by apply i ng the following conversion factors to the housing

- start data for each categ ory :

Unit ty pe Acres per building Sing le

- f a mily unit 1/4 Two- f a mily unit 1/3 Apartments 1/2

6.7.2.2. Nonre s ide n tial Construc tion
I n 2000, approx imately 336,224 acr es were disturbed by nonresidential construction.
Thi s num ber i s based on t h e nat i onal val u e of c onst r uct i on put i n pl ace, as report e d by t h e U.S

. Census B u reau. The national va lue wa s a lloc a t e d to c ountie s using construction employ ment
data from the B u reau of L a bor Statistics and Dun & B r adstreet. A conversion factor of 1.6 acres disturbed per $100,000 spent was applied to the county

- leve l estimates of the value of

6-30

### construction put in place to obtai n the acres disturbed by nonresid ential construction per county

. The conversion factor was deve loped using the Price and Cost I ndices for Construction by adjusting the 1992 value of 2 acres per $100,000 for 2000.

6.7.2.3. Roadway Construction
I n 2000, approx imately 190,367 acres were disturbed by ro adway construction. This
number is based on 1999 F e deral Hig hway Administration state ex penditure data for capital
outla y within the f o llowing six r o a d c l a ssif i c a tions: inte r sta te ( u r b a n a nd r u r a l) , othe r a r te r i a l (urban and rural), and collectors (urban and rural)

. The ex penditure data were converted to miles
of road constructed based on da ta f

r o m the Nor t h Ca r o lina De pa r tme nt of Tr a n spor ta tion ( N CDOT)

. Ac c o r d ing to NCDOT, a ppr ox ima te ly $4 million pe r mile is spe n t f o r

f

r e e w a y a n d interstate projects, and appr ox imately $1.9 million per mile is sp ent for arterial and collector projects. The number of miles was then conve rted to acres disturbed using the following
conversion factors for each ro ad classification categ ory :

Road ty pe Ac r e s pe r mile I n terstate, urban 15.2 I n terstate, rural 15.2 Other arterial, urban 15.2 Other arterial, rural 12.7 Collectors, urban 9.8 Collectors, rural 7.9

F o r 1995, state ex penditure for capital outlay wa s assumed to be 74% of total funding

. This percentag e was derive d using 2000 data (U.S. DOT, 2002). F or 1987, 74% of the total capital outlay of the averag e of 1985 and 1989 wa s used (capital outlay s for 1985 and 1989 are reported in U.S. DOT, 2002). Therefor e, approx imately 83,110 and 123,140 acres were disturbed as the result of roadway construction in 1987 and 1995, respectively

.

6.7.2.4. Fuel Loading Factors To obtain the amount of biomass consumed by the burning of land-clearing debris, the total acreag e of land disturbed in each county by residential, nonres idential, and roadway construction was distributed according to veg e tation ty pe (hardwood, so ftwood, and g r ass) and
the n c o mbine d with ve g e ta tion- spe c i f i c f u e l loa d i n g fact ors. The percen tag e of veg e tation ty pe within each county was determined using B EL D 2. The averag e loading factors used for each fuel ty pe were 99 tons/acre for hardwood, 57 t ons/acre for softwood, and 4.5 tons/acre for g r ass.

6-31

### Using this method, OAQPS estimated that 28.4 million metric tons of biomass were burned throug h land clearing ac tivities in 2000. EPA developed a national averag e biomass loading factor of 33 metric t ons burned per acre in 2000. Using this loading factor combined with total acreag e disturbed, EPA estimated th at approx imately 27.7 a nd 26.4 million metric tons of biomass were burned by land cl earing in 1987 and 1995, respectively

.

6.7.3. Em ission Estim a tes Using the emission factor of 20 ng TEQ DF 

### -W HO 98 

### /kg (18.6 ng I

- TEQ DF 

### /kg ) and the activity level estimates in Section 6.7.2.4, CDD/CDF emissions from land clearing burning were 568 g TEQ DF 

### -W HO 98 

### (528 g I

- TEQ DF 

### ) in 2000, 528 g TEQ DF 

### -W HO 98 

### (491 g I

- TEQ DF 

### ) in 1995, and 553 g TEQ DF 

### -W HO 98 

### (515 g I

- TEQ DF 

### ) in 1987. These should be reg a rded as preliminary estimates of possible emissions from this s ource because the emission factor is clearly nonrepresentative; further testing is needed to confirm the true ma g nitude of emissions.

6.8. UNCONTROLLED COMBUSTION OF P O LYCHLORINATED BIP H ENYLS
The acci dent al com bust i on of P C B-cont ai ni ng el ect ri cal equi pm ent or i n t e nt i onal
combustion of PCB s in incinerators and bo ilers not approved for PCB burning (40 CF R 761)

m a y produce C DDs/ C DFs. At el evat ed t e m p erat ur es, such as i n t r ansform e r fi res, P C Bs can underg o reactions to form CDFs and other by -p roducts. More than 30 accidental fires and

ex plosions involving PCB transf ormers and capacitors in the Un ited States and Scandinavia that
involved the combustion of PCB s and the g e ne ration of CDDs/CDF s have been documented (Hutz i ng er and F i edler, 1991a; O’Keefe and S mith, 1989; W illiams et al., 1985). F or ex ample, analy s es of soot samples from a B i ng hamton, NY, office building fire detected 20 μg /g total CDDs (0.6 to 2.8 μg /g 2,3,7,8-TCDD) and 765 to 2,160 μg /g total CDF s (12 to 270 μg /g 2,3,7,8­
TCDF ). At that site, the fire involved a mix ture containing PCB s (65%) and chlorobenz ene (35%). L a boratory analy s es of soot samples fro m a PCB tr a n sf or me r f

i r e tha t oc c u r r e d in Re ims,
F r ance, indicated total CDD and CDF levels in the rang e of 4 to 58,000 ng /g and 45 to 81,000

ng /g , r e spe c tive l y

. Using a bench-scale thermal de struction sy stem, Erickson et al. (1984) determined the optimum conditions for CDF formation to be a temperature of 675°C, an ex cess ox y g en concentration of 8%, and a resi dence time of 0.8 sec (or long er). Combusting mineral oil and silicone oil containing 5, 50, and 500 ppm of Ar oclor 1254 at these conditions y i elded PCB to
CDF conversion efficiencies as hi g h as 4%. Up to 3% conversion efficiency was observed when an Askarel (70% Aroclor 1260) was combusted under the same conditions.

6-32

### The use of PCB s in new transformers in the United States is banned, and their use in

ex isting transformers and capacitors is being phased out under reg u lations promulg a ted under the
Tox i c Substances Control Act.
Because of t h e acci dent al nat u re of t h ese i n ci dent s, t h e vari at i on i n durat i on and i n t e nsi t y of el evat ed t e m p erat ures, t h e vari at i on i n CDD/CDF content of re sidues, and uncertainty

reg a rding the amount of PCB s still in service in electrical equipment, EP A judg ed the available
da ta ina d e qua te f o r

de ve loping a n y qua ntif ia ble e mission e stima te s. Howe ve r , Thoma s a n d Spiro (1995) conservatively estima ted that about 15 g of TEQ ma y be g e nerated annually from
fires in commercial and residential building s each y ear. Th is estimate is based on the following

a ssumptions: ( a ) the I

- TEQ DF 

### emission rate is 20 μg /kg of PCB burned, (b) 74,000 metric tons of
PCB a r e still in use in va r i ous e l e c t r i c a l e quipme n t, a nd ( c ) 1% of the in- u se PCB s a r e bur ne d during the course of st ructural fires annually

.

6.9. VOLCANOES To date, no studies demonstrating the form ation of CDDs/CDF s by volcanoes have been published. Given the available information fro m the studies discussed below, volcanoes do not appear to be sources of CDD/ C DF rel ease t o t h e envi ronm ent

. Gribble (1994) summariz e d some of the ex isting information on the formation of chlorinated compounds by natural sources, includi ng volcanoes. Gribble reported that several studies had demonstrated the presence of chlo rofluorocarbons and simple halog e nated aliphatic compounds (one and two carbon chain leng th) in volcan ic g a ses. I n additi on, several chlorinated monoaromatic compounds as well as three PeCB c ong eners were detected in the ash from the 1980 eruption of Mount St. Helens. Gribble hy pothesiz e d that the formation of these PCB compounds was the result of rapid, incomplete, hig h -temperature com bustion of chloridecontaining plant material in the eruption z one. However, no inform ation was presented to
i ndi cat e t h e form at i on of CDDs/CDF s by volcanoes.
L a mparski et al. (1990) analy z ed g r oundfall ash samples collected at various distances and locations from Mount St. Helens following the eruption in 1980. The finding s of this study indicate that volcanic particulat e emissions were free of detect able PCB s and nearly free of detectable CDDs (0.8 ng /k g HpCDD detected) upon ex iting the volcano and remained so throug hout their period of deposition in the blas t z one. However, upon transport throug h the

at m o sphere, m easurabl e and i n creas ing levels of CDDs and PCB s were detected in deposited ash as it passed from rural to urban environments. The authors hy pot hesiz e d that CDDs and PCB s in

t h e at m o sphere becam e associ at ed wi t h t h e vol cani c ash part i c ul at es t h roug h g a s-phase sorpt i o n or particulate ag g l omeration.

6-33

### Takiz a wa et al. (1994) investig ated the C DD/CDF content of volcanic dust fall from two

a c tive volc a noe s in J a pa n ( Mt. F u g e nda ke a nd Sa kur a jima )

. The study wa s not de sig n e d to determine whether the CDDs/CDF s observed were formed by the volcanoes or were scaveng e d
f r o m the a tmosphe r e by the f a lling dust a nd a sh. The dust f a ll wa s c o lle c t e d f o r

one

- m onth periods during J uly and Octobe r 1992; two samples of the volcanic ash were collected in 1992. The results of the sample analy s es for 2,3,7,8-s ubstituted CDDs and CDF s , presented in Table 6-7, show that no 2,3,7,8-substituted cong eners with less than seven chlo rines were detected; however, the authors reported that non-2,3,7,8-subs tituted cong eners in the lower-chlorinated

cong ener g r oups were detected.

T ab l e 6-7. CDDs/CDF s in d u s t f all an d ash e s f r om volcan oes

2,3,7,8-substituted

con g en er grou p Dust fall ( m g/km 2 

### /m onth) a 

### Volcanic ash (ng/kg) b



### July 1992 Oct. 1992 Ash no. 1 A sh no. 2

TCDD Pe CD D Hx C DD HpC D D OC DD TCDF Pe CD F Hx C DF HpC D F OC DF <0.5 <0.5 <0.5

9.2 14

<0.5 <0.5 <0.5

1.9 4.2 <0.5 <0.5 <0.5

5.2 11 <0.5 <0.5 <0.5

2.8 1.8 <0.1 <0.1 <0.1

2.5 1.7 <0.1 <0.1 <0.1

1.2 <0.5 <0.1 <0.1 <0.1

1.8 2.2 <0.1 <0.1 <0.1

1.2 <0.5

a Du s t f

all m eas u r ed f r om th e activ e v o lcan o Fu g en d ak e. b Volcan ic as h m eas u r ed f r om th e activ e v o lcan o Sak u r aj im a.

S o u r ce: T a k i zaw a et al . (1994).



### 6.10. F I REWORK S
I n or de r to pr oduc e va r i ous e f f

e c t s a nd illumina tions, mode r n f i r e wor k s c onta i n bla c k powder and substances such as chlorine-based ox idiz ers, flame-coloring copper salts, and pulveriz e d poly viny l chloride, which are known to be involved in diox in-forming processes. During deflag ration of py rotechnics, core temp eratures reach as hig h as 2,500°C, which would most likely inhibit the formation of org a nic pollu tants. However, CDDs /CDF s ma y be g e ne r a te d in the areas adjacent to the combustion z one, wh ere temperatures are lo wer and dwell times are long er. Therefore, CDDs/CDF s may be g e nerate d during the cooling period of the deflag ration

6-34

### products because the temperatures of the smoke and ash are within the possible temperature

rang e of diox in formation (F leischer et al., 1999). During a celebration in Ox ford, Eng l and, that was accompanied by fireworks and bonfires, Dy ke and Coleman (1995) reported a fourfold increase in C DD/CDF TEQ concentrations in the ambient air (see Section 6.2.2). F l eischer et al. (1999) conducted an ex periment to measure the

a i r e missions r e sulting spe c i f i c a lly f

r o m the f o llowing se ve n ty pe s of f

i r e wor k s: f i r e c r a c k e r , cone fountain, jumping jack, whistler, sparkling rocket, roman candle, and four-color fountain. The paper cart r i d g e s and charg e s were separat e d from each fi rework and defl ag rat e d separat e l y i n
a st eel cham ber. C DD/ C DF concent r at i ons were measured both in air samples and in paper and

a sh sa mple s. The r e sults indic a t e d tha t diox ins we r e not pr e se n t in sig n if ic a n t qua ntitie s in the air samples collected. Therefore, F l eisher et al. suspected that the increased backg r ound
concentrations of CDDs/CDF s de tected by Dy ke and Coleman ( 1995) were due mainly to the
bonfires and not the fireworks. However, concentrations of Hp CDD and OCDD/OCDF were present i n t h e paper and ash col l ect ed aft e r t h e fi reworks were det ona ted at concentrations

rang ing from less than the DL (10 ng /kg ) to 1,200 ng /kg

. Table 6-8 depicts the results of
F l eischer’s tests.

Table 6-8. Residue of HpCDD/HpCDF and OC D D /OC D F ( n g/kg) in pape r cartri d g es an d ch arges of sel ect p y rotech n i c p r od u c ts

P r oduc t P a p er Cartri d g es Ch arge Hp CDD OCDD OCDF Hp CDD OCDD OCDF

F i recracker 16 322 79 <10 535 26

Cone fountain 111 384 22 <10 < 10 <10

J u mping J ack <10 3 3 2 4 < 10 28 <10

W histler 22 353 121 <10 35 1200
Sparkling rocket 30 129 12 <10 1 3 < 10

Roman candle < 10 426 39 <10 < 10 22

F our-color fountain < 10 18 <10 < 10 <10 < 10

S o u r ce: F l ei s c h e r et al . (1999).



### Given the lack of information on the poten t i a l for C DD/ C D F em i ssi ons from fi reworks,
emissions cannot be quantified.

6-35

### 6.11. OP EN BURNING AND OP EN DETONATION OF ENERG ETIC MATERIALS Open burning and open detonati on (OB / OD) practices are routinely used to destroy surplus or unserviceable energ e tic materi als. Mitchell and S ug g s (1998) conducted a study to determine

e mission f a c t or s f r om OB /OD. Air sa mple s we r e col l ect ed for C DD/ C DF anal y s i s duri n g four
burns and after three detonations

. The results of the study i ndicated that emission levels of
CDDs/CDF s as a result of disposal of ener g e tic materials by OB /OD were nondetectable.

6-36

### 7. METAL SMELTING AND REF I NING SOURCES OF CDDs/CDF s

7.1. P R IMARY NONF ERROUS METAL SMELTING /REF INING
L ittle information has been published on the potential for the formation and
environmental release of CDDs/CDF s from pr imary nonferrous meta l smelting facilities.
CDD/CDF r e le a se s f r o m the se f a c ilitie s we r e f i r st r e por te d in the wa ste w a t e r of a

ma g n e sium refining facility and in the recei ving water sediments downstream of a nickel refining facility in Norway (Oehme et al., 1989). This study re sulted in the evaluation of the potential for
CDD/CDF releases from primary nonf errous metal smeltin g operations in the United States. Air

e missions f r o m se ve r a l U.S. sme lting ope r a tion f a c ilitie s ha ve be e n sa mple d. The f i nding s of

t h ese st udi es are revi ewed i n t h e fol l o wi ng sect i ons.

7.1.1. P r im ary Copper Sm elting and Ref i ning Environmental Risk Sciences (1995) prepar ed an analy s is for the National Mining Association on the potential for CDD/CDF emi ssions from operations in the primary copper smelting industry

. The analy s is included revi ewing the process che mistry and technolog y of primary copper smelting

, iden tify i ng operating conditions, a nd comparing process stream compositions from seven of the eig ht U.S. prima ry

copper smelters that are members of the National Mining Association. The analy s is also included stack testing for CDDs/CDF s at two
facilities. The stack testing involved the principa l off-g as streams for copper smelters: the main

st ack st ream , t h e pl ant t a i l g a s st ack st ream , and vent fume ex haust (Secor I n te r n a tiona l, I n c

. , 1995b). The two facilities that we re tested (Phelps Dodg e Mini ng Co. in Play as, NM, and Cy prus Miami Mining Co. in Clay pool, AZ ) were selected as representative of the industry because of their similarity to other facilities in term s of process chemis try , process stream composition, and process stream temperatures. CDDs/CDF s were not detected in the air

e missions f r o m e ithe r f

a c ility

. The results of the analy s is indicate that althoug h there is some potential for CDD/CDF formation in this industry ’ s operations, several f actors lessen the probability , including the following : (a) most of the energ y used to melt copper is derived from ox id ation of copper sulfide

ore m i n eral s (C uFeS 2 

### ) rather than carbon (fossil fuels), (b) low concentrations of org a nic carbon
and chl o ri de are present i n raw m a t e ri al s a nd reag ents, (c) hig h concentrations of SO 2 

### are present
i n process g a ses (6 t o 40% by vol um e), (d) hi g h t e m p erat ures are m a i n t a i n ed i n t h e furnaces and converters (1,100 to 1,500°C), and (e ) copper (I I ) chloride is a pparently absent in process
emissions. Althoug h CDDs/CDF s have not been detect ed in U.S. facilities, CDD/CDF emissions have been measured in the stack of a prima ry

copper smelter in Ca nada. I n 2001, emission

7-1

### m easurem ent s for vari ous persi s t e nt , bi o accum u l a t i v e, and t o x i c subst a nces, i n cl udi ng CDDs/CDF s, were collected in Canada as a voluntary initiative under the Great L a kes B i national
Tox i cs Strateg y (Cianc iarelli, 2001). One of the facilities tested was the F a lconbridg e Kidd Metallurg ical plant in Timmins, Ontario, a c opper smelting plant. Emission summaries are provided in Table 7-1 as TEQ concentrations corr ect ed for 11% ox y g en for t h e averag e of t h ree

runs. The total concentrations for th e three runs were 3.8, 1.7, and 0.7 pg TEQ/m 3



### . Annual
CDD/CDF emission rates were estimated to be 0.002 g I

- TEQ/y r. I n 2002, Environment Canada beg a n developing a g e neric diox in/furan emissions testing protocol for use by the base metals smelting sector (Charles E. Napier Company , L t d., 2002).
Se ve r a l ba se me ta ls sme lting a nd r e f i ning c o mple x e s we r e ide n tif ie d, a nd a summa r y of r e a d ily available published information on diox in/furan e missions f r o m the ba se me ta ls sme lte r
pr oc e sse s wa s c o mpile d. A summa r y of this inf o r m a tion is pr ovide d in Ta ble 7- 2. F our f

a c ilitie s were identified as primary coppe r smelters and had CDD/CDF e mission concentrations rang ing from less than 1 to 559 pg I

- TEQ/dscm.

T a b l e 7-1. CDD/CDF em ission con cen tration s (p g T E Q/m 3 

### @ 11% oxygen) f or p r i m ary cop p er sm el ters

C o nge n e r / c o nge n e r gr oup R un 1 R un 2 R un 3 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0 0 0 0.1 0.1 0.1 0 0 0 0 0 0 0.1 0 0 0.1 0 0 0 0 0 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.7 0.1 2.2 0 0.1 0.3 0 0.1 0 0 0.2 0 0.9 0.2 0.1 0.2 0 0.1 0 0 0.1 0 0 0.1 0 0.1 0 0 0 0

TOTAL 3.8 1.8 0.4

Sou r ce: C i an ciarelli (2001).



### 7-2

### T a b l e 7-2. CDD/CDF em ission s d a ta f r om p r im ary an d secon d a ry cop p e r

an d secon d a ry l e ad sm el ters

C o m p an y, l o cati on Proces s u n i ts E m is s i on control tech n o l ogy CDD/CDF em issio n concentration ( p g I- TEQ/dsc m )

Prim ary copper s m elters
N o r d d e ut sc he A ffi ne r i e , Germ an y Ou to k u m p u f lash sm eltin g f u rn ace W a s t e h eat boiler, ESP < 20

P e irce- Sm ith con v e rter ESP N A

F a l c on bri d g e , S u dbu ry , O n t a ri o (n i c k e l an d copper) Ro astin g Electric sm eltin g P eirce- Sm ith con v erters C y cl on e/ ES P 559

Noran d a, Horn e s m elter, Noran d a, Qu ebec Noran d a reactor N o r a nd a c o nt i nuo us c o nve r t e r ES P < 1

Noran d a, Gas p e s m elter, Mu rd o ck v ille, Qu eb ec R e v e rberatory f u rn ace ESP N A

P eirce- Sm ith con v erter 82 Secondary copper s m elters
N o r d d e ut sc he A ffi ne r i e , Germ an y P eirce- Sm ith con v erter FF <500

H ut t e nw e r ke K a y s e r , Germ an y B l as t f u rn ace P o s t

- c om bu s tion , w a s t e h eat boiler, FF <500

P eirce- Sm ith con v erters Hearth f u rn ace (f or tin /lead) F F <100

R e v e rberatory an ode f u rn ace W a s t e h eat boiler, FF

M a nsfe l d e r K up f e r und M e ssing, Ge r m a n y B l as t f u rn ace P o s t

- c om bu s tion , w a s t e h eat boiler, cooler, FF, FF

w ith lim e/co k e in j ectio n <500

U nkno w n c o m p a ny , Germ an y S h af t f

u rn ace Pos t

- c om bu s t i o n , dry
qu en ch w ith s econ d ary

o ff-ga s , F F <100

U nkno w n c o m p a ny , Germ an y R o t a ry f u rn ace F F <100–1,000

U nkno w n c o m p a ny , Germ an y R o t a ry f u rn ace G a s cool i n g , F F <100

U nkno w n c o m p a ny , Germ an y R o tary f u rn ace Gas coolin g , FF, activ ated carbon ized lig n ite ads o rben t box es <100

ESP = Electro static p r ecip itato r FF = Fab r ic f ilter NA = No t av ailab l e

S o u r ce: C h arl e s E. N a pi er C o m p an y , L t d. (2002).



### 7-3

### I n 1995, eig ht primary smelters were in ope ration in the United States, one of which closed at the end of that y ear (Edelste in, 1995). Total refine ry production was 1.60 million metric tons in 1995, including 0.36 million metric tons from scra p material (Edelstein, 1995),
and 1.13 million metric tons in 1987 (USGS, 1997a). I n 2000, four primary smelters of copper were in operation in the United States, pr oducing 1.61 million metric t ons of copper (USGS, 2002).
CDD/CDF emission estimates fo r primary copper smelters were developed using the

sta c k te st da ta f

r o m the two te ste d f a c ilitie s in the Unite d Sta t e s. Conse r va tive l y a ssuming tha t all nondetect values were presen t at one-half the detection limit, Environmental Risk Sciences,
I n c. (1995) calculated the annual TEQ emi ssion to air to be less than 0.5 g I

- TEQ DF 

### in 1995 for the seven facilities (out of a to tal of eig ht) belong ing to th e National Mining Association. Assuming that 1987 feed and processing material s were similar, 1987 rel eases can be estimated at less than 0.5 g I

- TEQ DF 

### as well. B ecause the number of facilities was reduced in 2000, the
national emissions estimate wa s reduced proportionally to 0.29 g I

- TEQ. The activity level

e stima te s a r e a ssig n e d a hig h c onf ide n c e r a ting a nd the e mission f a c t or e stima te s a me dium

r a ting ; the r e f or e , the e mission e stima te s a r e a ssig n e d a me dium c onf ide n c e r a ting

. The a c tivity levels are based on comprehensive survey s. Th e em i ssi on fact ors are reasonabl y represent a t i v e of emissions from the source categ ory

.

7.1.2. P r im ary Magnesium Sm elting and Ref i ning Oehme et al. (1989) reported that the producti on of mag nesium can lead to the formation
of CDDs and CDF s

. They estimated that 500 g of I

- TEQ DF 

### were released to the environment in

wast ewat er and 6 g I

- TEQ DF 

### were released to air annually from a mag nesium production facility
in Nor w a y ; CDF s pr e domina t e d, with a CDF

- to- C DD c onc e n tr a tion r a tio of 10:1. At the time of sampling , the mag nesium production process i nvolved formation of mag nesium ox ide (Mg O )
f r o m c a l c i na te d dolomite f o llowe d by a

ste p in whic h ma g n e sium c h lor i de ( Mg C l 2 

### ) was produced by heating Mg O/coke pellets in a shaft furnace in a pure chlorine atmosphere to about 700 to
800°C. The Mg Cl 2 

### wa s the n e l e c t r o ly ze d to f o r m me ta llic ma g n e sium a nd c h lor i de

. The
chl o ri de ex cess from t h e Mg C l 2 

### process and the chloride fo rm ed duri n g el ect rol y si s were collected by water scrubbers a nd directly discharg ed to the environment. The discharg ed wastewater contained 200 to 500 ppm of suspended partic ulate matter. All but trace quantities of
the hex a throug h octa cong eners we re associ at ed wi t h t h e part i c ul at es; up t o 10% of t h e t e t r a and
penta cong eners were pres e n t in the wa te r pha se

. A study by the firm operating the facility (Musdalslien et al., 1998) indicated that
installation of a water tr eatment sy stem had reduced annual e missions to water to less than 1 g Nordic TEQ, and emissions to air had been reduced to less than 2 g Nordic TEQ. This study also

7-4

### pr e se n te d r e sults de monstr a ting tha t the c a r bon- r e duc ing a g e n t use d in the Mg Cl 2 

### production step
and t h e operat i n g condi t i ons of t h e shaft furnace g r eat l y affect ed t h e form at i on of C DDs/ C DFs.
Gases from the furnace were measured nine time s over sampling periods of 6 to 8 hr. The
cal cul a t e d em i ssi on fact or t o ai r (i.e., before any air pollution control device [ A PCD] controls)

rang ed from 468 to 3,860 ng Nordic TEQ per kg of Mg Cl 2 

### produced. The APCD controls
consisted of three water scrubbe rs, a wet electrostatic precipita tor (ESP), and an incinerator.
F r om 1950 to 2000, the United States was th e world’s larg est producer of metallic

mag n esium (Kramer, 1995). I n 1995, three ma g nesium production fac ilities were operating in

t h e Uni t e d S t at es. As i n t h e Norweg i a n pl ant , an el ect rol y t i c process (el ect rol y si s of Mg C l 2 

### ) was used at the plants in Tex a s (capacity of 65,000 metric tons/y r) and Utah (capacity of 40,000

me tr ic tons/y r ) to r e c ove r me ta llic ma g n e s ium f r o m Mg Cl 2 

### . Howe ve r , the se two f a c ilitie s reportedly used seawater and la ke brines as the source of ma g n esium, and the procedures to obtain and purify Mg Cl 2 

### did not involve chlorinating furn aces and carboniz e d pellets (L ockwood et al., 1981). A thermic process was used to r ecover mag n esium from dolo mite at the facility in
W a shing t on (capacity of 40,000 metric tons/y r) (Kra mer, 1995). I n thermic processes, Mg O, a component of calcinated dolomite, is reacted with a metal such as silic on (usually alloy e d with iron) to produce metallic mag n es ium. I n 2000, the Mag nesium Co rporation of America facility

ne a r Rowle y , UT, wa s the only ope r a tiona l ma g n e sium sme lting f a c ility in the Unite d Sta t e s. Monitoring of wastewater discharg es from U.S. mag nesium production facilities for
CDD/CDF content has not been reported. W a stew ater discharg es of CDDs/CDF s reported for the Norweg ian facility (Oehme et al., 1989), di scussed in the previous parag r aphs, are not adequate to support development of wastewater emission factor s for U.S. facilities because of possible differences in the pro cesses used to manufacture Mg Cl 2 

### and pollution control equipment. Monitoring of air emissions for CDD/CDF c ontent has been reported for the Mag n esium
Cor por a tion of Ame r ic a f

a c ility ne a r Rowle y , UT ( W e ste r n Envir onme n ta l Se r v ic e s a nd Te sting

, I n c., 2000). The averag e emission rates (for three tests) reported for the melt reactor stack and the cathode stack were 0.31 mg I

- TEQ DF 

### /hr and 0.16 mg I

- TEQ DF 

### /hr

, r e spe c tive l y

. Emissions da ta we r e judg e d ina d e qua te f o r

de ve loping na tiona l e mission e stima te s f o r 1987 that could be included in the national inventory

. The confid ence in the deg r ee to which the

one te ste d f a c ility r e pr e se n ts e missions f r o m the othe r two U.S. f a c ilitie s is low. Howe ve r , a n estimate of the potential TEQ annual emissions for 1995 fro m U.S. primary mag nesium production facilities can be made by assuming that the averag e total emission factor for the Utah facility measured in May 2000 (0.47 mg I

- TEQ DF 

### /hr ) is r e pr e se n ta tive of the othe r two f a c ilitie s for mag nesium production. Specifically , if it is a ssumed that this facility operated for 24 hr/day for 365 day s in 1995, then the annual rel ease in 1995 would have been 4.1 g I

- TEQ DF 

### . I f it is

7-5

### further assumed that this facility operated at 98% of its rated capacity of 40,000 metric tons/y r, then the production-based emissi on factor would be 105 ng I

- TEQ DF 

### /kg of mag nesium produced. Apply i ng this emission factor to 98% of the industry ’ s production capacity in 1995 (142,000 metric tons) y i elds a preliminary a nnual emissions estimate of 14.6 g I

- TEQ DF 

### in 1995.
I n 2000, the Mag nesium Corporation of Ameri ca facility near Rowley , UT, was the only

mag nesium smelting facility opera ting in the United States. Pr oduction of primary mag n esium at this facility was 41,000 me tric tons in 2000. Using the emission factor of 105 ng I

- TEQ DF 

### /kg of

mag nesium produced, the nationa l estimate for diox in releases in 2000 due to primary

mag nesium smelting is 4.3 g I

- TEQ/yr. The emi ssion factor has a hig h confidence rating because
it wa s de ve lope d using da ta f

r o m this f a c ility ; the r e f or e , the e missions e stima te is a ssig n e d a hig h
confi d ence l e vel

.

7.1.3. P r im ary Nickel Sm elting and Ref i ning Oehme et al. (1989) reported that certain pr imary nickel refining processes g e nerate CDDs and CDF s , primarily CDF s

. Althoug h the current low-temperature process used at a
Nor w e g ia n f a c ility wa s e stima te d to r e sult in r e le a se s to wa te r of only 1 g I

- TEQ DF 

### /y

r, a hig htemperature (800°C) process to c onvert nickel chloride to nickel ox ide that had been used for 17 y r a t the f a c ility is be lie ve d to ha ve r e sulte d in sig n if ic a n t r e le a se s in e a r lie r y e a r s, ba se d on
the pa r t s- pe r

- b illion le ve ls of CDF s de te c t e d in a qua tic se dime nts downstr e a m of the f a c ility

. According to Kuck (1995), the only nickel mining and smelting complex in the United States (located in Oreg on) had a capacity of 16,000 metric tons/y r. The facility had been on standby since Aug ust 1993 and had no production in 1994. The facility re started operations in April 1995 and produced 8,290 metric tons of nick el that y ear. I n 1998, the smelter closed because of low nickel prices (US G S
, 2002). M onitoring for discharg es of CDDs/CDFs at this
f

a c ility ha s not be e n r e por te d. Emissions of CDDs/CDF s we r e r e por te d f o r

a

Nor w e g ia n f a c ility in the late 1980s, as discussed above (Oehme et al., 1989). The emissions information contained in the Norweg ian study is not adequate to s upport development of emi ssion factors for the U.S. facility for 1987 and 1995. B ecause the facility closed in 1998, emission estimates for 2000 for

pr ima r y nic k e l sme lting a r e ze r o

.

7.1.4. P r im ary Alum inum Sm elting and Ref i ning No sampling of air emissions for the presen ce of CDDs/CDF s has been reported for this industry

. L e x e n et al. (1993) reported that sa mples of filter powder and sludg e from a lag oon at the only primary aluminum production plant in Sweden showed no or little CDDs/CDF s. B ecause the primary smelting pr ocess does not use chlorine, th ere is widespread belief that

7-6

### diox in e missions f r o m pr ima r y a l uminum sme lting f a c ilitie s do not e x ist; the r e f or e , no sa mpling
has been done.
I n the pr ima r y a l uminum sme lting pr oc e ss, ba ux ite or e , a hy dr a t e d ox ide of a l uminum consisting of 30 to 56% alumina (Al 2 

### O 3 

### ), is refined into alumina by the B a y e r process. The alumina is then shipped to a primary aluminum smelter for electroly tic reduction to aluminum. Electroly tic reduction of alumina occurs in sha l l o w rect ang u l a r cel l s , or pot s, whi c h are st eel
shells lined with carbon. Carbon electrodes (p etroleum coke mix ed with a pitch binder)

ex tending into the pot serve as the anodes, a nd the carbon lining serves as the cathode. Three
ty pes of pots are used: prebaked anode cell, horiz ontal stud Soderberg anode cell, and vertical stud Soderberg anode cell. Most of the alu minum produced in the United States is produced using the pr e b a k e d c e lls. Molte n c r y o lite ( N a 3 

### AlF 6 

### ) functions as both the electroly t e and the
solvent for the aluminum. Aluminum is de posited on the cathode as molten metal (U.S. EPA, 1998a).
P r i o r t o cast i n g , t h e m o l t e n al um i num m a y be bat c h t r eat ed i n reverberat ory furnaces (such as those used in secondary aluminum smelting ) to remove ox ides, g a seous impurities, and

a c tive me ta ls suc h a s sodium a nd ma g n e sium. On e process consists of adding a flux of chloride and fluoride salts and then bubbling chlorine g a s throug h the molten mix ture (U.S. EPA, 1998a).
U.S. production of primary aluminum was 3.343 million metric tons in 1987 and 3.375
million metric tons in 1995. I n 1995, 13 compan ies operated 22 primary aluminum reduction plants (USGS, 1997b, c). I n 2000, 12 companie s operated 23 primary aluminum reduction plants, and primary aluminum smelters produ ced 3.7 million metric tons of aluminum (USGS, 2002). B ecause emission factors have not been de veloped for this sector, there are no emission

e s tima te s f o r

this c a t e g or y

.

7.1.5. P r im ary Titanium Sm elting and Ref i ning
I t has been sug g e sted that carbochlorination processes used in th is industry may be a
source of CDDs/CDF s (B ramley ,1998; ERG, 1998)

. As discussed below, CDDs/CDF s have
been measured in titanium diox ide production sludg es. A brief summary of the processes used in this industry is presented in the following parag r aphs.
I n pr ima r y tita nium sme lting

, tita nium ox ide or e s a nd c onc e n tr a t e s a r e c h lor i na te d in
fluidiz e d-bed reactors in the presence of coke at 925 to 1,010°C to form titanium tetrachloride (Ti C l 4 

### ). The TiCl 4 

### is separated from other chlori des by double distillation. The TiCl 4 

### is the n either ox idiz ed at 985°C to form pig m ent-g r ad e titanium diox ide or reduced using sodium or

mag nesium to form titanium spong e (i.e., metallic titanium) (Knittel, 1983)

. Titanium ing o t is produced by melting titanium spong e or scrap or a combination of both using electron beam,

7-7

### plasma, and vacuum arc methods. Scrap curre ntly supplies about 50% of ing ot feedstock (Gambog i, 1996). Titanium spong e is produced at two facilities in the United States, one in Albany , OR, and the other in Henderson, NV. I n 1995, the U.S. production volume of titanium spong e was withheld to avoid disclosi ng proprietary data; domestic spong e capacity was 29,500 metric tons/yr. I n 1987, U.S. production of titanium spong e was 17,849 metric tons.
More than 90% of titanium diox ide is pr oduced using the process described above.
Titanium diox ide pig m ent is used in paints , plastics, and paper products. I n 1995, titanium
diox ide was produced at nine facilities in th e United States. Production volumes in 1987 and 1995 were 821,000 and 1.8 million metric tons, respectively (Gambog i, 1996; USGS, 1997d). I n 2000, four companies at eig ht facilities in se ven states produced 1.44 million metric tons of
titanium diox ide (USGS, 2002).
Titanium diox ide production creates a sl udg e waste, and CDDs/CDF s have been measured in these sludg es (U.S . EPA, 2001c). F or the most part, these sludg es have been disposed of in either on-site or off-site RCRA Subtitle D solid wast e disposal facilities. However, g i ven the potential for leaching of the heavy metals from the sludg e in the Subtitle D landfill, EPA has listed this wast e as haz a rdous waste under Sub title C. These sludg es are now

c onside r e d a ha za rdous wa ste unde r RCRA a nd must be dispose d of in pe rmitte d la ndfills (U.S. EPA, 2001c). Therefore, they are not consider ed to cause environmental releases under the
definition in this document and ar e not included in the inventory

.

7.2. SECONDARY NONF ERROUS METAL SMELTING Secondary smelters prima rily eng a g e in the recovery of nonferrous metals and alloy s from new and used scrap and dross. Th e principal metals of this industry , both in terms of volume and value of product shipments, are aluminum, copper, lead, z i nc, and precious metals (U.S. DOC, 1990a). Scrap metal and metal wastes may contain org a nic im purities such as plastics, paints,
and solvents. Secondary smeltin g and refining processes for some metals (e.g ., aluminum, copper, and mag n esium) use chemicals such as sodium chloride, potassi um chloride, and other

sa lts. The c o mbustion of the se impur itie s a nd c h lor i ne sa lts in the pr e se n c e of va r i ous ty pe s of

me ta l dur ing r e c l a m a tion pr oc e sse s c a n r e sult in the f o r m a tion of CDDs/CDF s, a s e v ide n c e d by
their detection in the stack emi ssions of secondary aluminum, c opper, and lead smelters (Aittola et al., 1992; U.S. EPA, 1987a, 1997a).

7.2.1. Secondary Alum inum Sm elters Secondary aluminum smelters reclaim aluminum from sc rap using two processes: precleaning and smelting

. B oth pro cesses may produce CDD/CDF emissions.

7-8

### Precleaning processes involve sorting and cleanin g scrap to prepare it for smelting

. Cleaning processes that may produce CDD/CDF emissions use heat to separate aluminum from
contaminants and other m e t a l s

. These t echni ques are “roast i n g ” and “sweat i n g

. ” R o ast i n g uses rotary dry e rs with a temperature hig h enoug h to vaporiz e org a nic contaminants but not hig h

enoug h to melt aluminum. An ex ample of roastin g is the delacquering and processing of used beverag e cans. Sweating involve s heating aluminum-containing scrap metal to a temperature above the melting point of aluminum but below th e melting temperature of other metals such as
i r on and brass. The m e l t e d al um i num t r i c kl es down and accum u l a t e s i n t h e bot t o m of t h e sweat furnace and is periodically removed (U.S . EP A, 1997a).
Aft e r precl eani n g , t h e t r eat ed al um i num scrap is smelted and refined. This usually takes place in a reverberatory furnace. Once smelted, flux is added to remove impurities. The melt is
de ma g g e d to r e duc e the ma g n e sium c onte n t of the mo lten aluminum by adding chlorine g a s. The

m o l t e n al um i num i s t h en t r ansferred t o a hol di ng furnace and al l o y e d t o fi nal speci fi cat i ons (U.S

. EPA, 1997a).
CDD/CDF emissions to air ha ve been measured at seve n U.S. secondary aluminum operations. F i ve fac ilities were tested in 1995 and 1996 and two facilitie s were tested in 1992.
F our of the 1995 tests were c onducted by EPA in conjunction w ith The Aluminum Association,
I n c ., to ide n tif y

e mission r a te s f r o m f a c ilitie s with pote n tia lly ma x imum- a c h ie va ble

- c ontr o ltechnolog y

- g r ade operations and AP CD equipment. The fourth te st was performed by EPA (U.S. EPA, 1995c). Results from two facilities tested by the Califor nia Air Resources B o ard (CARB ) in 1992 were presented in two confidential reports. The first facility tested in 1995 was a t op-charg e melt furnace (Advanced Technolog y S y stems, I nc., 1995). During testing , the charg e material to the furnace was specially formulated to contain no oil, paint, coating s , rubber, or plastics other than inci dental amounts. The TEQ emission factor from such a clean charg e , 0.27 ng TEQ DF 

### -W HO 98 

### /kg (0.26 ng I

- TEQ DF 

### / k g ) charg e material, would be ex pected to represen t the low end of the normal industry rang e. The second facility operated a sweat furnace to preclean the scrap and a reverberatory furnace to smelt the precleaned al uminum (U.S . EP A, 1995c). S t ack emissions were controlled by an afterburner operated at 788°C. The TEQ emission factor for this facility was 3.37 ng TEQ DF 

### -W HO 98 

### /kg (3.22 ng I

- TEQ DF 

### /kg ) aluminum produced.
The thir d f a c ility e m ploy e d a c r ushe r / r o a sting dr y e r a s a pr e c l e a ning ste p f o llowe d by a reverberatory furnace (Galson Corporation, 1995)

. The emissions from the two units were vented separately

. The ex haust from the crushe r/dry e r was treated with an afterburner and a fabric filter (F F )

. The ex haust from the furnace passed throug h an F F with lime injection. B oth
stack ex hausts were tested, and the co mbined TEQ emission factor was 13.55 ng TEQ DF 

### WH O 98 

### /kg (12.95 ng I

- TEQ DF 

### /kg ) a l uminum pr oduc e d. B e c a use the a c tivity le ve l of the f a c ility

7-9

### at the time of sampling was treated as confiden tial business information, the calculated emission factor was based on the reporte d ty pical production rates of th e two operations: 26,000 lb/hr for the crusher/dry e r and 6,700 lb/hr for the furnace.
The f our th f a c ility ope r a te d a sc r a p r o a sting dr y e r f

o llowe d by a

side we ll r e ve r b e r a t or y furnace (W eston,1996). The emissions from the two un its were vented sepa rately

. Ex haust from
the dr y e r pa sse d thr oug h a n a f te r bur ne r a nd a lime

- c oa te d F F

. The e x ha ust f r o m the f u r n a c e
pa sse d thr oug h a lime

- c oa te d F F

. B o th sta c k e x ha usts we r e te ste d, a nd the c o mbine d TEQ emission factor was 8.52 ng TEQ DF 

### -W HO 98 

### /kg (7.93 ng I

- TEQ DF 

### /kg ) of charg e material. The two facilities tested by CARB in 1992, which were reported in two confidential reports (CARB , 1992a, b, as reported in U.S. EPA, 1997a) had TEQ emission factors of 55.68 and 23.44 ng TEQ DF 

### -W HO 98 

### /kg (52.21 and 21.67 ng I

- TEQ DF 

### /kg ) of scrap aluminum consumed. One facility was equipped with a venturi scrubber; the other was assumed to be uncontrolled (U.S. EPA, 1997a). The seventh facility was tested in 1995 by Commonwealth Aluminum Corp. (1995). The test involved sampling air emissi ons from a delaquering kiln. Th e facility was equipped with an
F F a s the pr ima r y APCD.
The CDD/CDF cong ener and cong ener g r oup emission factors derived from these stack tests were used to represent emissions fro m secondary aluminum facilities operating in 2000, 1995, and 1987. Table 7-3 shows the TEQ emissi on factors for facilitie s operating in 2000, and
Table 7-4 shows those for 1995 and 1987. The 2000 emission factors do not include the results from the two facilities tested by CARB (1992a, b) because it wa s assumed that all facilities operating in 2000 were equi pped with APCDs on all ve nts and stacks. The averag e cong ener and

cong ener g r oup profiles are presented in F i g u re 7-1. The averag e of the TEQ emission factors
measured at the five tested facilities re presentative of the y ear 2000 is 5.17 ng TEQ DF 

### -W HO 98 

### /kg (4.90 ng I

- TEQ DF 

### / k g ) of scrap feed. A l o w confi d ence rat i n g i s assi g n ed t o t h e averag e em i ssi on factor for 2000 because it is based on the results of testing at only five facilities, and they may not be r e pr e se n ta tive of a ll f a c ilitie s ope r a ting in the Unite d Sta t e s in tha t y e a r

. The emission factors for f acilities operating in 1995 and 1987 do include the results from the two facilities tested by CARB in 1992. The av erag e of the TEQ emission factor measured at
the seven tested facilities representative of the y ears 1995 and 1987 is 15.0 ng TEQ DF 

### -W HO 98 

### /kg (14.05 ng I

- TEQ DF 

### / k g ) of scrap feed. A l o w confi d ence rat i n g i s assi g n ed t o t h e averag e emission factor for 1995 and 1987 because it is ba sed on the results of testing at only seven f

a c ilitie s, a nd tha t ma y not be r e pr e se n ta tive of a ll f a c ilitie s ope r a ting in the Unite d Sta t e s in

t hose reference y ears.

7-10

### T a b l e 7-3. CDD/CDF em ission f a ctors (ng/kg scrap f eed) 

### f o r secon d a ry alum inum sm e lt e r s f o r 2000

C ongener Mean f a cility emission f a ctor Overall

mean emission

fa c t o r a b c d e

2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND (0.01) 0.02 0.05 0.13 0.15 0.51 0.42 0.13 0.39 0.24 0.86 1.26 7.67 14.97 0.51 1.19 1.35 1.52 2.51 2.6 1.01 0.40 1.19 0.72 0.94 1.62 3.49 NR 0.01 0.02 0.02 0.03 0.05 0.10 NR 0.21 0.56 0.48 0.70 1.12 2.87 5.47

2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.44 0.06 0.17 0.32 0.11 0.02 0.3 0.07 0.03 0.3 0.74 1.51 2.44 2.44 2.69 1.02 3.82 11.39

5.5 30.4 14.20 10.47 11.06 21.84

7.1 0.47 7.09 14.61

1.21 3.15 10.46 12.52

6.98 8.14 2.74 0.14 4.30 3.18 0.45 1.23 0.07 0.08 0.12 0.16 0.06 0.01 0.08 0.17 0.04 0.06 5.18 4.93 4.15 6.58 2.54 0.33 3.12 5.88 1.45 7.03

Total I

- T E Q DF f 

### 0.26 3.22 12.95 8.09 0.14 4.93

Total TE Q DF 

### -W H O 98 f 

### 0.27 3.37 13.55 8.68 0.15 5.20

a S o u r ce: A d v a n ced T ech n o l o g y S y s t em s , In c. (1995).

b S o u rce: U

. S

. EPA (1995c).

c S o u rce: G a l s on C o rporat i o n (1995).

d S o u rce: Wes t on (1996).

e S o u r ce: C o m m o n w eal t h A l u m i n u m C o rp. (1995).

f T E Q calcu lation s as s u m e n o n d etect v alu es w ere zero.

NR = No t rep o r ted ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)



### F or comparison purposes, the European Commission uses 22 ng I

- TEQ DF 

### /kg sc r a p al um i num as t h e t y pi cal em i ssi on factor for the European Diox in I nventory (Quab and F e rmann, 1997). Umweltbundesamt (1996) reported stack testing results for 25 aluminum smelters and foundries in Germany

. This study provided suffici ent data to enable cal culation of TEQ emission
factors for 11 of the tested facilities. The cal culated emission factors rang ed from 0.01 to 167 ng

7-11

### T a b l e 7-4. CDD/CDF em ission f a ctors (n g/k g scrap f eed ) f o r secon d ary alum inum sm elters f o r 1995 and 1987

C ongener Mean f a cility emission f a ctor Overall

mean emission

fa c t o r a b c d e f f

2,3,7,8- T C DD ND (0.01) 0.13 0.51 0.40 0.01 1.97 0.85 0.54 1,2,3,7,8- PeCDD 0.02 0.39 1.19 1.19 0.02 7.1 3.64 1.94 1,2,3,4,7,8- HxCDD 0.05 0.24 1.35 0.72 0.02 4.26 2.82 1.35 1,2,3,6,7,8- HxCDD 0.13 0.86 1.52 0.94 0.03 5.3 4.12 1.84 1,2,3,7,8,9- HxCDD 0.15 1.26 2.51 1.62 0.05 5.3 2.02 1.84 1,2,3,4,6,7,8- HpCDD 0.51 7.67 2.6 3.49 0.10 28.9 19.3 8.94 OCDD 0.42 14.97 1.01 NR NR 33.2 24.3 14.78

2,3,7,8- T C DF 0.44 0.74 14.20 10.46 0.07 23.2 4.84 7.71 1,2,3,7,8- PeCDF 0.06 1.51 10.47 12.52 0.08 33.8 1.18 8.52 2,3,4,7,8- PeCDF 0.17 2.44 11.06 6.98 0.12 48 23.3 13.15 1,2,3,4,7,8- HxCDF 0.32 2.44 21.84 8.14 0.16 46.1 17.6 13.80 1,2,3,6,7,8- HxCDF 0.11 2.69 7.1 2.74 0.06 46.1 16.9 10.81 1,2,3,7,8,9- HxCDF 0.02 1.02 0.47 0.14 0.01 22 1.35 3.57 2,3,4,6,7,8- HxCDF 0.3 3.82 7.09 4.30 0.08 39 16 10.08 1,2,3,4,6,7,8- HpCDF 0.07 11.39 14.61 3.18 0.17 122 42.6 27.71 1,2,3,4,7,8,9- HpCDF 0.03 5.5 1.21 0.45 0.04 27.1 6.2 5.79 OCDF 0.3 30.4 3.15 1.23 0.06 60.5 29.5 17.88

Total I

- T E Q DF g 

### 0.26 3.22 12.95 8.09 0.14 52.21 21.68 14.08

Total TE Q DF 

### -W H O 98 g 

### 0.27 3.37 13.55 8.68 0.15 55.68 23.45 15.02

a S o u r ce: A d v a n ced T ech n o l o g y S y s t em s , In c. (1995).

b S o u rce: U

. S

. EPA (1995c).

c S o u rce: G a l s on C o rporat i o n (1995).

d S o u rce: Wes t on (1996).

e S o u r ce: C o m m o n w eal t h A l u m i n u m C o rp. (1995).

f S o u rce: C A R B (1992a, b), as report e d i n U

. S

. EPA (1997a).

g T E Q calcu lation s as s u m e n o n d etects w ere zero.

NR = No t rep o r ted ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)



### I

- TEQ DF 

### /kg of scrap feed. Thr ee facilities had emission fact ors ex ceeding 100 ng I

- TEQ DF 

### /kg

,

a nd two f a c ilitie s ha d e mission f a c t or s of le ss tha n 1 ng I

- TEQ DF 

### /kg

. The mean emission factor
f

o r

the 11 f a c ilitie s wa s 42 ng I

- TEQ DF 

### /kg

. Approx imately 727,000 metr ic tons of scrap aluminum were consumed by 67 secondary
aluminum smelters in the United States in 1987 (U.S. DOC, 1995c). I n 1995, consumption of

7-12

### F i gu re 7-1. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om

secon d a ry al u m i n u m sm el ters.

S o u rces : U

. S

. EPA (1995c); G a l s on C o rporat i o n (1995).



### scrap aluminum by the 76 facilities that compos ed the secondary aluminum smelting industry had nearly doubled, to 1.3 million me tric tons (USGS, 1997e; The Aluminum Association, I nc., 1997). I n 2000, secondary aluminum smelters consumed 1.6 million metr ic tons of scrap aluminum (USGS, 2002). A hig h confidence ra ting is assig ned to these production estimates

7-13

### because they are based on g overnment survey data. Apply i ng the 15.0 ng TEQ DF 

### -W HO 98 

### /kg (14.05 ng I

- TEQ DF 

### /kg ) emission factor to the metric t ons of scrap aluminum processed in 1987 and 1995 y i elds estimated a nnual emissions of 10.9 g TEQ DF 

### -W HO 98 

### (10.21 g I

- TEQ) in 1987 and 19.5 TEQ DF 

### -W HO 98 

### (18.27 g I

- TEQ DF 

### ) in reference y ear 1995. Apply i ng the emission factor of 5.17 ng TEQ DF 

### -W HO 98 

### /kg (4.9 ng I

- TEQ DF 

### /kg ) to the me tr ic tons of scrap aluminum processed in 2000 y i elds estimated a nnual emissions of 8.27 g TEQ DF 

### -W HO 98 

### (7.84 g I

- TEQ) in reference

y ear 2000. These emission estimates are assig n ed a low confidence rating because the rating

g i ven to the emission factor was low.
I t should be noted that a sig nificant amount of scrap aluminum is also consumed by other

seg m ents of the aluminum industry

. However, this scrap is g e nerally from metal manufacturing processes, including metal and alloy production (e.g ., boring s , turn ing s , and dross), rather than old scrap that results from recy c ling of consumer products (e.g ., can s, radiators, auto shredders).
I n 1995, integ r ated aluminum companies consum ed 1.4 million metric tons of scrap aluminum, and independent mill fabricators consumed 0.68 million metric tons (USGS, 1997e).

7.2.2. Secondary Copper Sm elters Secondary copper smelting is pa rt of the scrap copper, br ass, and bronze reprocessing industry

. B r ass is an alloy of copper and z i nc; bronz e is an a lloy of copper and tin. F acilities in this industry fall into three g e neral classifi cations: secondary smelting , ing ot making , and

r e me lting

. Simila r pr oc e ssing e quipme n t ma y be use d a t a ll thr e e ty pe s of f

a c ilitie s, so the disting uishing features are not imme diately apparent (U.S. EPA, 1994b). The feature that disting u ishes secondary smelters from ing ot makers and remelters is the

ex tent to which py rometallurg i cal purification is performed. A ty pical charg e at a secondary smelter may contain from 30 to 98% copper. The secondary sm elter upg rades the material by

r e duc ing the qua ntity of impur itie s a nd a lloy i ng ma te r i a l s, the r e b y inc r e a sing the r e la tive concentration of copper. This deg r ee of purification and separation of the alloy constituents does not occur at ing o t makers and remelters. F eed material to a seconda ry copper smelter is a
mix ture of copper-bearing scrap such as tubing , valves, motors, winding s, wire, radiators, turning s , mill scrap, printed circ uit boards, telephone switching g ear, and ammunition casing s

. Nonscrap i t e m s such as bl ast furnace sl ag s and drosses from i n g o t m a kers or rem e l t e rs m a y represent a portion of the charg e

. Secondary sm elter operators use a va riety of processes to

se pa r a te the a lloy c onstitue n ts. Some pur if y

the sc r a p in the r e duc tive a tmosphe r e of a

bla st furnace and then purify the charg e in the ox idiz in g atmosphere of a convert er; others perform all purification by ox idation in top- blown rotary converters or in reverberatory furnaces (U.S . EP A, 1994b).

7-14

### I n g o t maker operators ble nd and melt scrap copper, br ass, and bronz e of various compositions to produce a specification brass or br onz e ing o t. W h en necessary , they add ing o ts of other metals (e.g ., z i nc or tin) to adjust the metallurg y of the final product. The feed materials for ing ot makers contain relatively hig h amounts of copper. Ex amples of feed materials include copper tubing , valves, brass and bronz e casting s , ammunition shell casing s , and automobile
radiators. “F ire-refined” a node copper or cathode copper may al so be charg e d. I t ems such as motors, telephone switchboa rd scrap, circuit board scrap, and purchased slag s are not used by ing o t makers. The reductive step (melting in a reducing atmosphere, as in a blast furnace) that some secondary smelters employ is not used by ing ot makers. I ng ot makers do, however, use some of the other ty pes of furnaces used by s econdary smelters, including direct-fired converters, reverberatory furnaces, and electric induction furnaces (U.S . EP A, 1994b). Remelting facilities do not conduct substantial purif ication of the incoming feeds. These facilities ty pically melt the charg e and then cast or ex trude a product. The feeds to a remelter are

g e nerally alloy material of approx imately the desired com position of the product (U.S. EPA, 1994b).

7.2.2.1. Em issions Data
Stack emissions of CDDs/CDF s from a seconda ry copper smelter were measured by EPA during 1984 and 1985 as part of the National Diox in Tier 4 Study (U.S. EPA, 1987a). The
f

a c ility c hose n f o r

te sting wa s e stima te d to ha ve a hig h pote n tia l f o r

CDD/CDF e missions
because of the abundance of chlo rinated plastics in the feed. This facility ceased operations in
1986. The facility was chosen for testing by EPA because the process technolog y and APCD equi pm ent i n pl ace were consi d ered t y pi cal for t h e source cat eg ory

. During operations, copper and ir on-bearing scrap were fed in batches to a cupola blast furnace, which produced a mix ture of slag and black copper. Approx imately 4 to 5 tons of

m e t a l

- beari n g scrap were fed t o t h e furnace per charg e , wi t h m a t e ri al s t ypi cal l y bei n g charg e d 10 to 12 times per hour. Coke fueled the furnace a nd represented approx imate ly 14% (by weig ht) of
the total feed. During the stack tests, the feed consisted of electronic telephone scra p and other plastic scrap, brass a nd copper shot, iron-bearing copper sc rap, precious metals, copper-bearing residues, refinery by -products , converter furnace slag , anode furnace slag , and metallic floorcleaning material. The telephone scrap made up 22% (by weig ht) of the feed and was the only scrap component that containe d plastic materials. Ox y g en -enriched combustion air for combustion of the coke was blown throug h tuy e res ( noz z l es) at t h e bot t o m of t h e furnace. At t h e
t op of t h e bl ast furnace were four nat u ral g a s-fi red aft e rburners t o ai d i n com p l e t i n g com bust i o n of the ex haust g a ses. Particul ate emissions were controlled by F F s , and the flue g a s was then
disc ha r g e d into a c o mmon sta c k. The e stima te d e mission f a c t or s de r i ve d f o r

this site a r e

7-15

### presented in Table 7-5. The emission factors are ba se d on the tota l we ig ht of scrap fed to the
furnace. B a sed on the measured cong ener and cong ener g r oup emission factors, the TEQ emission factor is 779 ng I

- TEQ DF 

### /kg (810 ng TEQ DF



### WH O 98 

### /kg ) of sc r a p me ta l sme lte d. F i g u r e 7-2a presents the cong ener g r oup pr ofile based on thes e emission factors.
I n 1992, stack testing of the blast furnace e missions of a secondary smelter located in Philadelphia, PA (F ranklin Sm elting and Refining Co.), was conducted by Applied Geotechnical
& Environmental Services Corpor ation (AGES, 1992). L i ke the facility tested by EPA during 1984 and 1985, this facility proce ssed low-purity copper-bearing scrap, telephone switch g ear, and slag s, as well as hig h e r-copper-content materials (U.S. EP A, 1994b). The facility used a blast (cupola-ty pe) furnace coupled with a pair of rotary converters to produce blister copper.
The bl ast furnace used coke as bot h t h e fuel a nd t h e ag ent t o m a i n t a i n a reduci n g at m o sphere. The black copper-slag mix ture from the blast furn ace was charg e d to the rotary converters for further refining with the aid of ox y g en, sand, and oak log s (AGES, 1992; U.S. EPA, 1994b). The
AP C D equi pm ent i n st al l e d on t h e bl ast furnace i n cl uded an aft e rburner, a cool i n g t o wer, and an
F F

. Dur i ng te sting

, the a f te r burner was reported to be ope r a ting e r r a tic a lly and was particularly low during one of the two sampling episodes. St ack g a s flow was also low during both sampling episodes because one or more F F compartments were inoperable (AGES, 1992). The estimated
emission factors derived for this site from the AGES results are presented in Table 7-5. The

em i ssi on fact ors were based on t h e t o t a l wei g ht of scrap fed t o t h e bl ast furnace. The TEQ emission factor was 16,618 ng I

- TEQ DF 

### /kg (16,917 ng TEQ DF 

### -W HO 98 

### /kg ) of scrap. F i g u re 7-2b presents the cong ener and cong ener g r oup profiles based on th ese emission factors.
I n 1991, stack testing of the rotary furnace stack emissions of a secondary smelter (Chemetco, I n c.) located in Alton, I L , was c onducted by Sverdrup Corp. (1991). The Chemetco facility used four tap-down rota ry

(i.e., ox idiz ing ) furnaces. F u rnace-processed g a s emissions were controlled by a primary que ncher and a venturi scrubber. The feed was relatively hig h

purity copper scrap containing min imal, if any , plastics. The same manufacturing process and APCD equipment were in place in 1987 and 1995 (U.S. EPA, 1994b). B ecause this facility operated under ox idiz ing rather than reducing conditions and pr ocessed relatively hig h-purity
scrap, t h e pot ent i a l for C DD/ C DF form at i on and rel ease was ex pect ed t o be dram at i cal l y different from that of the two tested facilitie s reported above. The es timated emission factors
derived for this site from the results of Sverdr up Corp. (1991) are presented in Table 7-5. The

em i ssi on fact ors were based on t h e t o t a l wei g ht of scrap feed g o i n g t o t h e furnace. The TEQ emission factor was 3.60 ng I

- TEQ DF 

### /kg (3.66 ng TEQ DF 

### -W HO 98 

### /kg ) of scrap.

7-16

### T a b l e 7-5. CDD/CDF m e an em ission f a ctors (ng/kg scrap f eed) 

### f o r secon d a ry cop p er sm el ters

C o ngener/
congener group EP A Ti e r 4 f a cility a,b 

### F r ankl i n sm el t i ng f a cility c 

### C h emetco smelting f a cility d


### 2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 127 NR NR NR NR NR 1,350 227 846 1,476 1,746 2,132 17,065 55,668 ND (0.05) 0.21 0.39 0.70 1.26 8.95 22.45
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2,720 NR NR NR NR NR NR NR NR 2,520 4,457 9,455 5,773 70,742 20,524

5,362 12,082 37,251

7,570 82,192 2.11 1.47 2.63 7.30 2.15 4.06 0.27 11.48

2.74 21.61

Total I

- T E Q DF e 

### 779 f 

### 16,618 3.59

Total TE Q DF 

### -W H O 98 e 

### 810 f 

### 16,917 3.66

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 736 970 1,260 2,080 1,350 13,720

8,640 4,240 3,420 2,520 14,503 30,248 55,765 38,994 55,668 108,546

71,136 164,834

66,253 82,192 3.05 5.19 9.62 16.71 22.45 46.42 27.99 27.96 23.38 21.61

T otal CDD/CDF 38,936 688,139 204.38

a N o n o n d et ect v a l u es w e re report e d f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , or an y con g e n e r g rou p i n t h e t h ree t e s t ru n s

. b S o u rce: U

. S

. EPA (1987a).

c S o u rce: A G ES (1992).

d S o u rce: S v erdru p C o rp. (1991).

e T E Q calcu lation s as s u m e n o n d etect v alu es w ere zero. f Es t i m at ed u s i n g t h e m eas u red dat a f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , O C D D
, an d O C D F an d con g e n e r g rou p

em is s i on s (i.e., f o r th e pen t a- , h ex a- , an d h epta- C DDs an d C D Fs , it w as as s u m ed th at th e m eas u r ed em is s i on f actor

w i t hi n a c o nge ne r gr o up w a s t he sum o f e q ua l e m i ssi o n fa c t o r s fo r a l l c o nge ne r s i n t ha t gr o up , i nc l ud i ng no n- 2
, 3
, 7
, 8

- su b s titu ted co n g e n e rs).

NR = No t rep o r ted ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)



### 7-17

### F i gure 7-2a. Congener group prof ile f or air em issions f r om a secondary cop p er sm el ter.

S o u rce: U

. S

. EPA (1987d).



### Only limited data on emissions from secondary copper sme lters are reported in the European Diox in I nventory (L UA, 1997). TEQ emission factors reported for German shaft furnaces/converters and reverberatory furnaces rang e from 5.6 to 110 ng I

- TEQ DF 

### /kg and from
0.005 to 1.56 ng I

- TEQ DF 

### /kg , respectively

. Emission factors reported for two sm e lte r a nd c a sting
furnaces in S w eden in which relatively clean scrap is used as input are 0.024 and 0.04 ng I TEQ DF 

### /kg

. A sme lte r in Austr i a is r e por te d to have a TEQ emission factor of 4 ng I

- TEQ DF 

### /kg

. The minimum, ty pical, and max imu m default emission factors sel ected in L UA (1997) are 5, 50, and 400 ng I

- TEQ DF 

### /kg

, r e spe c tive l y

. I n the 2002 Environment Canada report on CDD/CDF emissions from the base metals smelting sector (Charles E. Napier Company

, L t d., 2002), three secondary copper smelters were identified (see Table 7-2). CDD/CDF emission c oncentrations were reported as rang ing from less than 100 to less than 500 pg I

- TEQ/dscm.

7-18 ­

### F i gu re 7-2b

. Con g en er an d con g en er grou p p r of i l e s f o r a cl osed secon d a ry cop p er sm el ter.

S o u rce: A G ES (1992).



### 7-19

### 7.2.2.2. A c t i v i t y Level In form at i o n I n 1987, four secondary copper smelters were in operation: F r anklin Smelting and Refining Co. (Philadelphia, PA ), Chemetco, I n c. (Alton, I L ), Southwire Co. (Carrollton, GA), and a facility located in Gaston, SC, that wa s owned by American Telephone and Teleg r aph (AT& T) until 1990, when it was purchased by Southwire Co. I n 1987, estimated smelter capacities were 13,600 metric tons for the F r anklin facility , 120,000 metric tons for the Chemetco facility , 48,000 metric tons for the S outhwire facility , and 85,000 metric tons for the
AT& T facility (telephone c onversation on Aug ust 17, 1999, between D. Edelstein, U.S. Geolog ical Survey , and G. Schweer, Versar, I n c. ). I n 1995, only three of these four facilities were still in operation. The S outhwire facility in Gaston was closed in J a nuary 1995. The
F r anklin facility ceased operations in Aug ust 1997. Estimated smelter capacities in 1995 were 16,000 metric tons for the F r anklin facility , 135,000 metric tons for the Chemetco facility , and 92,000 metric tons for the Southwire Georg i a facility (Edelstein, 1999). I n May 2000, the Southwire Co. closed its Georg i a facility and ceased operations (Edelstein, 2000). I n November 2001, Chemetco closed its facility and ceased operations (Edelstein, 2001). According to Edelstein (2001), smelters a nd refineries consumed 255,000 metric tons of purchased copper-based scrap in 2000 and 196,000 metric tons in 2001. Assuming Chemetco was the sole smelter facility operating in 2001, and that it opera ted for 10 of 12 months in 2001, its estimated annual consumption of copper-based scrap would be 235,000 metric tons per y ear. Assuming Chemetco’s annual consumption rate did not chang e from 2000 to 2001, the estimated consumption of copper-based scrap for the Southwire Co. in 2000 was 20,000 metric tons.

7.2.2.3. Em ission Estim ates Althoug h little research has been done to de fine the CDD/CDF formation mechanisms in secondary copper smelting operations, two g e neral obs ervations have been ma de (B uekens et al., 1997). F i rst, the presence of chlorinated plastics in copper scraps used as feed for smelters is
believed to increase CDD/CDF formation. Second, the reducing or py roly tic conditions in blast
furnaces can l ead t o hi g h C DD/ C DF concent r at i ons i n t h e furnace process g a ses. As not ed i n Section 7.2.2.1, two of the U.S. facilities that ha ve been tested (U.S. EPA, 1987a; AGES, 1992) had the following characteristics: both pro cessed low-purity copper-b earing scrap containing sig nificant quantities of plastics and telephone switch g ears, and both used blast furnaces. The
APCD e quipme n t a t both f a c ilitie s c onsiste d of a n a f te r bur ne r , a c ooling towe r ( F r a nklin f a c ility only ) , and an F F (U.S. EPA, 1994b). The other test ed U.S. facility used ox idizing rather than reducing conditions and proce ssed relatively hig h-purity scrap (Sverdrup Corp., 1991).

7-20

### Annual TEQ emissions for 1987, 1995, and 2000 we re derived as the sum of the TEQ emissions for each secondary copper facility in operation during the reference y ears. The following discussion summariz e s the procedure used to estimate annual TEQ air emissions.
The F r anklin Smelting f acility operated in 1987 and 1995 but not in 2000. The TEQ emission factor measured at this facility in 1992 is assumed to be re presentative of the TEQ
emission factors in 1987 and 1995. Combinin g this emission factor (16,618 ng I

- TEQ DF 

### /kg [ 16,917 ng TEQ DF 

### -W HO 98 

### /kg ] of sc r a p f e e d ) with the e stima te d sme lte r c a p a c itie s ( d a t a a r e not available on the amount of sc rap processed) for this f acility in 1987 (13,600,000 kg ) and 1995 (16,000,000 kg ) y i elds TEQ emission estimates of 226 g I

- TEQ DF 

### (230 g TEQ DF 

### -W HO 98 

### ) in 1987 and 266 g I

- TEQ DF 

### (271 g TEQ DF 

### -W HO 98 

### ) in 1995. This facility ceased operations in 1997. The Chemetco facility operated in 1987, 1995, and 2000. Similarly , for purposes of this

r e por t, the TEQ e mission f a c t or f

o r

the Che m e t c o f a c ility is c onside r e d to be r e pr e se n ta tive of the TEQ emission factor for this facility for 1987, 1995, and 2000. Combining this emission factor (3.60 ng I

- TEQ DF 

### /kg [ 3.66 ng TEQ DF 

### -W HO 98 

### /kg ] of sc r a p f e e d ) with the e stima te d sme lte r capacities of 120,000,000 kg in 1987 and 135,000,000 kg in 1995 y i elds TEQ estimates of 0.43 g
I

- TEQ DF 

### (0.44 g TEQ DF 

### -W HO 98 

### ) in 1987 and 0.49 g I

- TEQ DF 

### (0.49 g TEQ DF 

### -W HO 98 

### ) in 1995. Combining the same emission factor with th e scrap consumption for this facility in 2000 (235,000,000 kg ) y i elds a TEQ estimate of 0.85 g I

- TEQ DF 

### (0.86 g TEQ DF 

### -W HO 98 

### ) for 2000. The facility in Gaston, SC, was in opera tion during 1987 but ceased operations in 1995. Prior to 1990, when this facility was owned by AT & T, the plant processed a g r eat deal of hig h plastics-content scrap (such as w hole telephones). This scrap was fed to a py roly sis unit prior to entering the blast furnace. I n addition to a bl ast furnace, the facility also had an ox idiz ing reverberatory furnace for processing hig h er-purity scrap. The facility ha d separate F F s for the blast furnace, the converters, and the reverb eratory furnace (U.S . EP A, 1994b). B e cause this facility processed low- purity , hig h-plastics-c ontent scrap in 1987, and presumably processed

m u ch of t h i s i n t h e reduci n g at m o sphere of a py rol y si s uni t and bl ast furnace, t h e averag e of t h e TEQ emission factors for the Tier 4 EPA-test ed facility (U.S. EPA, 1987a) and the F r anklin facility (8,700 ng I

- TEQ DF 

### /kg [ 8,860 ng TEQ DF 

### -W HO 98 

### /kg ] ) wa s use d to e stima te pote n tia l emissions in 1987 of 740 g I

- TEQ DF 

### (753 g TEQ DF 

### -W HO 98 

### ) ( a ssuming a n a c tivity le ve l of 85,000,000 kg ). This activity level is the estima ted capacity of the fa cility ; data were not
available on the amount of scrap processed. The Southwire facility had both a blast fu rnace and a reverberatory furnace. I n 1992,

approx imately 50% of incoming scrap was processed in each furnace (U.S . EP A, 1994b). Unlike
the F r anklin, Chemetco, and Gaston secondary copper smelters, the S outhwire facility stopped processing plastic-coate d scrap in the 1970s. I n addition, th is facility had a more complex APCD

sy st em , whi c h m a y have reduced t h e form at i on and rel ease of C DDs/ C DFs. The bl ast furnace­ ­

7-21

### processed g a ses passed throug h an afterburner (871°C), U- tube coolers, and an evaporative spray

sy stem before entering the F F at a temperatur e of 107 to 191°C. F o r these reasons, EPA has
determined that the ex isting emissions data fo r secondary smelters ca nnot reliably be used to

g e nerate a quantitative estima te of potential emissions during 1987, 1995, or 2000 for this
f

a c ility

. Total secondary copper smelte r emissions for 1987 are the sum of the F r anklin smelting facility emissions (271 g TEQ DF 

### -W HO 98 

### [ 266 g I

- TEQ DF 

### ] ) , the Chemetco smelter facility (0.44 g TEQ DF 

### -W HO 98 

### [ 0.43 g I

- TEQ DF 

### ] ) and the Gaston, SC, facility (753 g TEQ DF 

### -W HO 98 

### [ 740 g I

TEQ DF 

### ] )

. Total secondary copper sme lter emissions for 1987 are 983.44 g TEQ DF 

### -W HO 98 

### (966.43 g I

- TEQ DF 

### ). Total secondary copper smelte r emissions for 1995 are the sum of the F r anklin smelting facility emissions (271 g TEQ DF 

### -W HO 98 

### [ 266 g I

- TEQ DF 

### ]) a nd the Che me tc o sme lte r f

a c ility (0.49 g TEQ DF 

### -W HO 98 

### [ 0.49 g TEQ DF 

### -W HO 98 

### ] ) . Total secondary coppe r smelter emissions for 1995 are 271.49 g TEQ DF 

### -W HO 98 

### (266.49 I

- TEQ DF 

### ). The Chemetco smelter provides the TEQ e missions estimate for the y ear 2000. Total secondary copper smelter e missions for 2000 are 0.86 g TEQ DF 

### -W HO 98 

### (0.85 g I

- TEQ DF 

### ). A hig h confidence rating is assig n ed to the production and c onsumption estimates
because t h ey are based on g overnm e nt survey dat a

. A l o w confi d ence rat i n g i s assi g n ed t o t h e TEQ emission estimates because th ey are based on limited measuremen ts made at three smelters,
one of which was not in operation in 1987 or 1995.
I t should be noted that a sig nificant amount of scrap copper is consumed by other

seg m ents of the copper industry

. I n 1995 and 2000, brass mills and wire-rod mills consumed 886,000 and 1,070,000 metric tons of copper-based scrap, resp ectively ; foundries and
iscellaneous manufacturers c onsumed 71,500 and 96,200 metric tons, respectively (USGS, 1997e; Edelstein, 2001). As noted above, however , these facilities g e nera lly do not conduct any sig n if ic a n t pur if ic a tion of the sc r a p. Ra the r , the sc r a p c onsume d is a l r e a d y of a lloy qua lity , a n d processes employ ed ty pically i nvolve only melting , casting , and ex truding

. Thus, the potential
for formation of CDDs/CDF s is ex pected to be much less than the potential during secondary

sme lting ope r a tions.

7.2.3. Secondary Lead Sm elters The secondary lead smelting industry produ ces elemental lead throug h the chemical reduction of lead compounds in a hig h-tempe rature furnace (1,200 to 1,260°C). Smelting is perform ed i n reverberat ory , bl ast , rot a ry , or el ect ri c furnaces. Bl ast and reverberat ory furnaces are the most common ty pes of smelting furnaces used by the 23 facilities that make up the current secondary lead smelting industry in the United States. Of the 45 furnaces at these 23

7-22

### facilities, 15 are reve rberatory furnaces, 24 are blast furnaces, 5 are rotary furnaces, and 1 is an
el ect ri c furnace. The el ect ri c furnace and 11 of t h e 24 bl ast furnaces are co-l ocat ed wi t h
reverberat ory furnaces, and m o st share a com m on ex haust and em i ssi ons cont rol sy st em (U.S

. EPA, 1994c). Furnace charg e m a t e ri al s consi s t of l ead-bear i n g raw m a t e ri al s, l ead-beari n g sl ag and drosses, fl ux i n g ag ent s (bl a st and rot a ry furnaces onl y ) , and coke. S c rap m o t o r vehi cl e l ead-aci d batteries represent about 90% of the lead-bearing ra w materials at a ty pical lead smelter. F l ux ing

ag ents consist of iron, silica sand, and limestone or soda ash. Coke is used as fuel in blast
furnaces and as a reduci n g ag ent i n reverberat or y and rot a ry furnaces. Org a ni c em i ssi ons from
co-located blast and reverberator y

furnaces are more similar to th e emissions of a reverberatory
furnace than to those of a blast furnace (U.S . EP A, 1994c).
I n 1987, the lead smelting industry cons isted of 24 facilitie s producing 0.72 million metric tons of lead (U.S. EPA, 1994c). I n 1995, there were 23 companies producing 0.97 million metric tons (USGS, 1997e), and in 2000 there were 27 secondary lead smelters in operation in the United States producing 1.02 million metric tons (USGS, 2002)

. I n 1995, the total annual production capacity of the 23 companies that ma de up the U.S. lead smelting industry was 1.36
million metric tons. B l ast furnaces not co-located with reverberatory furnaces accounted for 21% of capacity (0.28 million metric tons ). Reverberatory furnaces and blast and electri c furnaces colocated with reverberatory fu rnaces accounted for 74% of capac ity (1.01 million metric tons). Rotary furnaces accounted for the remaining 5% of capacity (0.07 million metric tons) (U.S. EPA, 1994c). Actual production volume statistics by furnace ty pe were not available. However, if it is
assumed that the total actual production volume of the industr y reflects the production capacity breakdown by furnace ty pe, then the estimated act ual production volumes of blast furnaces (not
co-l ocat ed), reverberat ory and co-l ocat ed bl ast / e l ect ri c and reverberat ory furnaces, and rot a ry furnaces were 0.15, 0.53, and 0.04 million metric t ons, respectively , in 1987; 0.2, 0.72, and 0.05 million metric tons, respectively , in 1995; a nd 0.29, 1, and 0.07 million metric tons, respectively

, in 2000. A report commissioned by Envi ronment Canada (Charles E. Napier Company , L t d., 2000) reviewed published literatu re and other information on the diox in/furan formation mechanisms; diox in/furan emissions; emissi on control technolog y , including cost; and
diox in/furan published emission standards pertinent to steel production processes of plants
in Ca na da

. The r e por t inc l ude d f our f

a c ilitie s ide n tif ie d a s pr ima r y le a d sme lte r s. CDD/CDF

emission concentrations were reported to rang e from less than 100 to less than 1,000 pg I TEQ/dsc m.

7-23

### CDD/CDF emission factors were estimated for secondary lead smelters using the results of emission tests performed by EP A at three sm elters (a blast furnace [ U .S . EP A, 1995d] , a colocated blast/reverberatory furnace [ U .S . EP A, 1992c]
, and a rotary kiln furnace [ U .S . EP A, 1995e] )

. The air pollution control sy stems at the three tested facilities c onsisted of both F F s and
scrubbers. Cong ener-specific measurements were made at both AP CD ex it points at each facility

. Table 7-6 presents the cong ener and cong ener g r oup emission factors for the F F and the
scrubber for each site. Fig u re 7-3 presents th e corresponding profiles for the FF emissions from
the tested blast furnace and reve rberatory furnace. F o r the f acilities in operation in 1995, all 23 smelters employ ed F F s , with only 9 employ ing scrubber technolog y

. F acilities with scrubbers accounted for 14% of the blast furnace (not co-located) production capacity , 52% of the reverberatory and co-located furnace production capacity , and 57% of the rotary furnace production capacity

. TEQ emission factors (ng TEQ/kg lead produced when nondetect values

are set equal t o z e ro) from t h e report e d dat a for each of t h e t h ree furnace confi g urat i ons, presented as a rang e reflecting the pr esence or absence of a scrubber, are

• B last furnace: 0.64 to 8.81 ng TEQ DF 

### -W HO 98 

### /kg (0.63 to 8.31 ng I

- TEQ DF 

### /kg )

• R everberatory /co-located furnace: 0.05 to 0.42 ng TEQ DF 

### -W HO 98 

### /kg (0.05 to 0.41 ng I

- TEQ DF 

### /kg )

• R otary furnace: 0.24 to 0.66 ng TEQ DF 

### -W HO 98 

### /kg (0.24 to 0.66 ng I

- TEQ DF 

### /kg )

I f

these rang es of emission rates are assume d to be representative of those at nontested
facilities with the same basic fu rnace config uration, with and wit hout scrubbers, then combining
these emission rates with the estimated production volumes derive d above and the percentag e of each config uration ty pe that have scrubbers y i elds the estimated ai r emissions shown in Table 7-7 for reference y ears 1987, 1995, and 2000.
A m e di um confi d ence rat i n g i s assi g n ed t o t h e em i ssi on fact ors because st ack t e st dat a were available for 3 of the 27 sme lte r s ope r a ting in the Unite d States (of which only 16 were in operation as of December 1993), and the stack test data used represent the three major furnace

c onf ig ur a tions. The a c tivity le ve l e stima te ha s be e n a ssig n e d a me dium c onf ide n c e r a ting because, althoug h it is based on a U.S. Depa rtment of Commerce es timate of total U.S. production, no production data were available on a furnace ty pe or furnace config uration basis.
The r e f or e , a me dium c onf ide n c e r a ting is a ssig n e d to the e mission e stima te s.

7-24

### T a b l e 7-6. CDD/CDF em ission f a ctors (n g/k g lead p r od u ced ) f o r secon d a ry l e ad sm el ters a

Congener/congener grou p Blas t fu rn ace b B l as t/reverberatory fu rn ace c Ro ta ry k iln d

Be for e

s crubber/ FF After

s crubber/ FF Be for e

s crubber/ FF After

s crubber/ FF Be for e

s crubber/ FF After

s crubber/ FF
2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 2.11 0.99 0.43 0.99 1.55 2.06 1.4 0.25 0.03 0 0.03 0.03 0.08 0.39 0 0 0 0 0 0.1 0.57 0 0 0 0 0 0.06 0.55 0.1 0.01 0 0 0 0 0.24 0.24 0 0 0 0 0.22 2.41
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 8.73 3.88 6.65 5.83 1.67 0.11 2.06 2.34 0.63 1.39 0.93 0.43 0.36 0.37 0.11 0 0.11 0.19 0.06 0.18 1.46 0.24 0.31 0.63 0.19 0 0.15 0.48 0 0.29 0.49 0.02 0 0 0 0 0 0 0 0 0.40 0.14 0.14 0.11 0.02 0.04 0 0.03 0 0 1.2 0.4 0.46 0.27 0.1 0.13 0 0.13 0 0

T o t a l 2,3,7,8- C D D T o t a l 2,3,7,8- C D F T o tal I- T E Q DF (n on detect s e t to zero) T o tal T E Q DF -W H O 98 (n on detect s e t to zero) 9.53 33.29

8.31

8.81 0.81 2.74 0.63

0.64 0.67 3.75 0.42

0.42 0.61 0.51 0.05

0.05 0.35 0.88 0.24

0.24 2.87 2.69 0.67

0.66

T o tal T C DD T o tal P e CDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal P e CDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF 74.33 39.29 20.05

4.2 1.39 145.71

69.59 19.73

4.74 1.39 7.39 1.73 0.81 9.72 0.18 17.34

3.45 1.02 0.11 0.18 0.97 0.15 0.14 0.09 0.57 8.21 3.07 1.14 0.72 0.29 1.58 0.16 0.02 0.09 0.55 4.71 0.36 0.19 0.01 0.00 3.4 0.29 0.1 0.01 0.24 10.82

1.69 0.15 0.05 0 7.9 0.27 0.23 0.29 2.41 28.57

5.04 0.73 0.14 0

T o tal CDD/CDF

(n on detect s e t to zero) 380.42 41.93 15.35 7.67 16.75 45.58

a Ex cept w h ere n o ted, em is s i on f actors w e re calcu lated as s u m i n g n o n d etect v a lu es w e re zero. b S o u rce: U

. S

. EPA (1995d).

c S o u rce: U

. S

. EPA (1992c).

d S o u rce: U

. S

. EPA (1995e).

FF = Fab r ic f ilter



### 7-25

### F i gu re 7-3. Con g en er an d con g en er grou p p r of i l e s f o r ai r em i ssi on s f r om

secon d a ry l e ad sm el ters. Profiles are for emissions from fabric filters; nondetect

va lue s se t e qua l to ze r o

.

S o u rces : U

. S

. EPA (1992c, 1995d, e).



### 7-26

### Table 7- 7. Est im a t e d annual TEQ e m issions ( g TEQ ) a



### Conf i g urat i o n Ref . year 1987 Ref . year 1995 Ref . year 2000

TEQ DF 

### ­ WHO 98 

### I

- TEQ DF 

### TEQ DF 

### ­ WHO 98 

### I

- TEQ DF 

### TEQ DF 

### ­ WHO 98 

### I

- TEQ DF



### Blast furnaces w / scrubbers 0.013 0.013 0.018 0.018 0.026 0.026

B l ast furnaces w / o scrubbers 1.136 1.072 1.515 1.429 2.197 2.073

R ev erberatory furnaces w/scrubbers 0.014 0.014 0.019 0.019 0.026 0.026

R ev erberatory furnaces w / o scrubbers 0.106 0.104 0.145 0.142 0.202 0.197

R o tary furnaces w/scrubbers 0.015 0.015 0.019 0.019 0.026 0.026

R o tary furnaces w / o scrubbers 0.004 0.004 0.005 0.005 0.007 0.007

T O T A L 1.288 1.222 1.721 1.632 2.484 2.355

a C a lcu l ated u s in g em is s i on f actors bas e d on n o n d etect v alu es s et equ al to zero.



### 7.3. P R IMARY F E RROUS M ETAL SMELTING /REF INING
I r on is manufactured from its ores (mag netic py rites, mag netite, hematite, and carbonates
of i r on) i n a bl ast furnace, and t h e i r on obt ai ned from t h i s process i s furt her refi ned i n st eel pl ant s to make steel. The primary production of iron and steel invol ves two operations identified by European researchers as potential emission sour ces of CDDs/CDF s: iron ore sinter production and coke production. Each of th ese potential sources is discussed in the following subsections.

7.3.1. Sinter P r oduction At some iron manufacturing f acilities, iron ores and waste iron-bearing materials underg o sintering to convert the materials to usable feed for the blast fu rnace. I n the sintering process, i r on ore fi nes and wast e m a t e ri al s are m i x ed wi t h coke fi nes, and t h e m i x t u re i s pl aced on a g r at e that is then heated to a temperature of 1,000 to 1,400°C. The heat g e nerated during combustion
sinte r s the sma ll pa r tic le s. I r on- be a r ing dusts a nd sl ag s from processes i n t h e st eel pl ant are t h e ty pes of iron-bearing waste mate rials used as a feed mix for the sintering plant (Knepper, 1981; Capes, 1983; U.S. EPA, 1995b).

7-27

### Several European investig ator s have reported that iron ore si nt eri n g pl ant s are m a j o r sources of airborne emissions of CDDs/C DF s (Rappe, 1992a; L e x e n et al., 1993; L a hl, 1993, 1994). L a hl reported that the prac tice of recy cling dusts and scra ps from other processes in the steel plant for use in the sintering plant introdu ces traces of chlorine and org a nic compounds that

g e nerate the CDDs/CDF s found in these plants. Org a nic compounds that are potential precurs ors to CDD/CDF form ation come primarily from oil, which is found in mill scale, as well as from some blast furnace sludg es that are used as part of the sinter feed mix ture. Most U.S. plants limit the amount of oil because it increases emissions of volatile org a nic co mpounds and may create a fire haz a rd. I n addition, plants with
F F s must limit the oil content because the oil tends to blind the F F s

. Ty pical oil content of the feed at U.S. sintering plants rang es from 0.1 to 0.75% (Calcag ni et al., 1998).
Sinte r ing pla n ts in Swe d e n ha ve be e n r e por te d to e mit up to 3 ng I

- TEQ DF 

### /Nm 3 

### stack g a s, or 2 to 4 g I

- TEQ DF 

### /y

r (Rappe, 1992a; L e x e n et al., 1993). B r emmer et al. (1994) reported the

r e sults of sta c k te sting a t thr e e ir on or e sinte r ing pla n ts in the Ne the r la nds. One f a c ility e quippe d with wet scrubbers (W Ss) had an emission factor of 1.8 ng I

- TEQ DF 

### /dscm (at 11% ox y g en). The

other two facilities, both equippe d with cy clones, had emissi on factors of 6.3 and 9.6 ng I TEQ DF 

### /dscm (at 7% ox y g en). L a hl (1993, 1994) repor ted stack emissions for sintering plants in
Ge r m a n y ( a f t e r pa ssa g e thr oug h me c h a n ic a l f ilte r s a nd ESPs) r a ng ing f r o m 3 to 10 ng I

TEQ DF 

### /Nm 3



### . A compilation of emission measurements by the German F e deral Environmental Ag ency indicated stack e mission concentrations rang ing from 1.2 to 60.6 ng I

- TEQ DF 

### /m 3 

### (at 7%

ox y g en); the majority of emi ssions in 1996 were around 3 ng I

- TEQ DF 

### /m 3 

### (Umweltbundesamt, 1996). The report commissioned by Environment Ca nada in 2000 to review steel production processes in Canadian plants (Charles E. Na pier Company , L t d., 2000) included information on

e missions f r o m ir on sinte r ing

. F o r ir on sinte r ing

, the CDD/CDF e missions f r o m one f a c ility , the
Stelco Hilton W orks sintering plant, were a ssumed to be representative of the 1998 sinter production. The averag e emission rate was 19.9 ng I

- TEQ/day

. Apply i ng a production rate of 1,143 metric tons/day y i elds a mass emissi on factor of 17.4 ng I

- TEQ/kg of sinter.
EPA conducted tests at two of the nine U.S. sintering plants operating in 1997 in order to quantify emissions of CDDs/CDF s (Calcag ni et al., 1998). I n choos ing representative plants for

te sting

, EPA c onside r e d a va r i e t y of issue s, inc l uding the ty pe s a nd qua ntitie s of f

e e d ma te r i a l s, the ty pes of emission controls, and t h e oi l cont ent of t h e si nt er fee d. EPA decided to test a plant
with an F F and a plant with a venturi (or wet) scrubber. F F s and W S s are the principal APCDs used to control emissions from the sintering pl ant windbox

. F our plants used an F F and five plants used a W S

. The ty pes of feed materials and oi l cont ent at t h e t w o sel ect ed pl ant s were

7-28

### determined to be representative of other plants in the industry

. Sampling was performed over 3 day s (4 hr/ d ay ) at each pl ant

. The averag e CDD/CDF TEQ concentrations m easured in the stack emissions were 0.19

ng I

- TEQ DF 

### /Nm 3 

### and 0.81 ng I

- TEQ DF 

### /Nm 3 

### for t h e W S and t h e FF, respect i v el y

. The corresponding TEQ emission factors are 0.62 ng TEQ DF 

### -W HO 98 

### /kg (0.55 ng I

- TEQ DF 

### /kg ) sinter and 4.61 ng TEQ DF 

### -W HO 98 

### /kg (4.14 ng I

- TEQ DF 

### /kg ) sinter, respectively

, for W S s and F F s. These em i ssi on fact ors are assi g n ed a hi g h rat i n g because t h ey are based on EP A t e st i n g at t w o facilities considered by EPA to be representative of both cu rrent and 1995 standard industry
pract i ces. Cong e n e r

- spe c i f i c e mission f a c t or s f o r

the se two f a c ilitie s a r e pr e se n te d in Ta ble 7- 8.
F i g u re 7-4 presents the cong ener profiles for these facilities. Althoug h concentrations were hig h er from the F F than from the W S , both concen tr a tions we r e low r e la tive to wha t ha d be e n

r e por te d f r o m te sting a t Ge r m a n, Dutch, Swedish, and Canadian sint e r ing pla n ts. This dispa r ity

may be due to differences in the operation or APCDs of U.S. si nt eri n g pl ant s and t h e t e st ed European plants. Most of the U.S. integ r ated iron and steel pl ants, including those with sintering plants,
ha ve e limina t e d the pur c h a se a nd use of c h lor i na te d or g a nic s in the i r f

a c ilitie s, a nd the i r r o lling mill oils (lubricants and hy draulic fluids) do not contain chlorinated compounds. I n addition,

rout i n e anal y s es of wast e m a t e ri al s g o i n g t o t h e si nt eri n g pl ant have not det ect ed any chl o ri nat e d
solve n ts.
F i nally , none of the U.S. plants use an E SP to control emissions from the sinter windbox (Calcag ni et al., 1998).
I n 1996 (data were not readily available fo r 1995), 11 sintering plants were operating in the United States, with a total annual produc tion capacity of about 17.6 million metric tons (Metal Producing , 1996). Since the 1980s, the siz e of this industry has decreased dramatically

. I n 1982, 33 facilities were in ope ration, with a combined tota l capacity of 48.3 million metric tons (U.S. EPA, 1982a). The nine U.S. si ntering plants operating in 1995 had a combined capacity of 15.6 million metric tons (Calcag ni et al., 1998). I n 1987, sinter consumption by iron and steel plants was 14.5 million metric tons (AI S I , 1990); in 1995, consumption was 12.4 million metric tons (F enton, 1996) , or approx imately 70% of production capacity , assuming that production capacity in 1995 was the same as in 1996. These activity leve l estimates are assig n ed a confidence rating of medium.
B a sed on the production capabilities shown in Table 7-9, 59% of 1998 sinter production

c a p a c ity wa s a t f a c ilitie s with WSs a nd 41% wa s a t f a c ilitie s with F F s. I f it is a ssume d tha t the se proportions of APCD-to-producti on capacity ex isted in 1995 and that actual production in 1995 was equal to sinter consumption at iron and steel plants (12.4 milli on metric tons), then estimated

7-29

### T a b l e 7-8. CDD/CDF em ission f a ctors (n g/k g sin t er) f o r sin t erin g p l an ts

C o ngener/congener
group Wet scrubber F abri c f i l t er

Nondet ect set to z ero N o n d e tect set to 1⁄2 d e tection limit Nondet ect set to z ero Nondet ect set t o 1⁄2 d e tection limit
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.049 0.138 0.03 0.612 0.288 0.696 0.496 0.049 0.138 0.03 0.612 0.288 0.696 0.496 0.406 0.937 0.135 1.469 0.609 0.698 0.695 0.406 0.937 0.135 1.469 0.609 0.698 0.695
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.602 0.343 0.349 0.421 0.164 0.011 0.142 0.247 0.036 0.103 0.602 0.343 0.349 0.421 0.164 0.014 0.142 0.247 0.036 0.103 10.232 3.518 3.228 1.382 0.495 0.029 0.285 0.316 0 0.05 10.232 3.518 3.228 1.382 0.495 0.057 0.285 0.316 0.115 0.192

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### 2.309 2.418 0.55 0.62 2.309 2.421 0.55 0.62 4.949 19.820

4.14 4.61 4.949 19.82

4.14 4.61

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F NR NR NR NR 0.496 NR NR NR NR 0.103 NR NR NR NR 0.496 NR NR NR NR 0.103 NR NR NR NR 0.695

NR NR NR NR 0.050 NR NR NR NR 0.695 NR NR NR NR 0.192

T otal 2,3,7,8 CDD/CDF a 

### 4.73 4.73 24.77 24.77

a T h e listed v a lu es f o r to tal CDD/CDF in clu d e o n ly th e 1 7 to x i c co n g e n e rs.

S o u r ce: C a l cag n i et al . (1998).



### 7-30

### F i gu re 7-4. Con g en er p r of i l e s f o r ai r em issions f r om U.S. iron ore sintering plants.

S o u r ce: C a l cag n i et al . (1998).



### TEQ emissions from W S -equi pped facilities were 4.5 g TEQ DF 

### -W HO 98 

### (4 g I

- TEQ DF 

### ) and
emissions from F F

- equippe d facilities were 23.4 g TEQ DF 

### -W HO 98 

### (21 g I

- TEQ DF 

### ), for a t o t a l of
27.9 g TEQ DF 

### -W HO 98 

### (25.1 g I

- TEQ DF 

### )

. The se e mission e stima te s a r e a ssig n e d a n ove r a ll

me dium c onf ide n c e r a ting on the ba sis of the me dium r a ting f o r

the a c tivity le ve l e stima te s. I f

these same assumptions are applied to the 1987 sinter consumption rate of 14.5 million metric tons, then estimate d TEQ emissions from W S -equi pped facilities were 5.3 g TEQ DF 

### WH O 98 

### (4.7 g I

- TEQ DF 

### ) and emissions from F F

- equi pped facilities were 27.4 g TEQ DF 

### -W HO 98 

### (24.6 g I

- TEQ DF 

### ), for a total of 32.7 g TEQ DF 

### -W HO 98 

### (29.3 g I

- TEQ DF 

### ). These em i ssi on estimates are less certain than the estimates for 1995 because of uncertainties concerning actual
AP CDs in place in 1987 and the content of wast e feed (i.e., oil content and presence of

7-31

### T a b l e 7-9. O p erati n g p a ram e ters f o r U.S

. i r on ore si n t eri n g p l an ts

Company L ocation 1998 capacity (1,000 metric ton s/yr) C u rrent air pol l u t i on cont rol devi ce
AK Steel Middletown, OH 907 Wet scrubber

A K Steel a 

### Ashland, K Y 816 a 

### NA

Bethlehem Steel Burns Har bor, I N 2,676 Wet scrubber

Bethlehem Steel Sparrows Point, MD 3,856 Wet scrubber

G e nev a Steel Prov o, U T 816 Fabric filter

I n land Steel East C h icag o, I N 1,089 Fabric filter

LT V Steel East Chicag o, I N 1,270 Wet scrubber

U

. S. Steel G ary , I N 3,992 Fabric filter

Weirton Steel a 

### Weirton, WV 1,179 a 

### NA Wheeling

- Pittsburg h Steel East Steubenv ille, WV 519 Wet scrubber

WC I Steel Warren, O H 477 Fabric filter

T O T A L 17,597 b

a N o t i n operat i o n du ri n g 1998 (C al cag n i et al ., 1998).

b W h en th e A s h l an d, KY, an d W eirton

, W V , f acilities ar e ex clu d ed, total 1998 capacity w a s 15,600,000 m e tric ton s

.

NA = No t av ailab l e

S o u rces : Met a l Produ ci n g (1991, 1996); C a l cag n i et al . (1998).



### c h lor i na te d or g a nic s in the oil) a t tha t time

. Conse que ntly , a low c onf ide n c e r a ting is a ssig n e d to
the e mission f a c t or a nd the e missions e stima te

. I n 2000, a total of 10,600 million metr ic tons of sinter were consumed in blast furnaces (Fenton, 2001). This activity le vel has a hig h confidence ra ting because it is based on a comprehensive survey

. Assuming the same pr oportions for facilities w ith WSs and facilities
with F F s as in 1995 and 1987, then estimated TEQ emissions from W S -equipped facilities were
3.9 g TEQ DF 

### -W HO 98 

### (3.4 g I

- TEQ DF 

### ) and emissions from F F

- e quipped facilities were 23.7 g TEQ DF 

### -W HO 98 

### (21.3 g I

- TEQ DF 

### ), for a total of 27.6 TEQ DF 

### -W HO 98 

### (24.4 g I

- TEQ DF 

### ) for 2000.
This e missions e stima te is a ssig n e d a hig h c onf ide n c e r a ting on the ba sis of the hig h r a ting s
g i ven to the activity le vel and emission factor for reference y ear 2000.

7.3.2. Coke P r oduction Coke is the principal fuel used in the ma nufacture of iron and steel. I t is the solid

c a r bona c e ous ma te r i a l pr oduc e d by the de str u c tive distilla tion of c o a l in hig h

- t e m pe r a tur e ove ns.

7-32

### No te sting of CDD/CDF e missions f r o m U.S. c oke f a c ilitie s ha s be e n r e por te d. Howe ve r , a t a facility in the Netherlands, B r e mmer et al. (1994) measured a CDD/CDF emission rate to air during the water quenching of hot coke of 0.23 ng I

- TEQ DF 

### /kg of coal consumed. B r emmer et al.
estimated minimal CDD/CDF ai r emissions (0.002 ng I

- TEQ DF 

### / k g of coal ) for fl ue g a ses
g e nerated during the charg i ng a nd empty i ng of the coke ovens. The report commissioned by Environment Ca nada in 2000 to review steel production processes in Canadian plants (Charles E. Napier Company

, L t d., 2000) also provided information
on emissions from coke ovens. Mean emission fact ors (ng I

- TEQ/kg ) of the four Canadian coke oven facilities (as indicated in Table 7- 10) were 0.3 ng I

- TEQ/kg coke produced. Althoug h there are no testing data on which to base an estimate of CDD/CDF emissions in the United States, a preliminary estimate of potential TEQ annual e missions from U.S. coke plants can be made by combining the estimate d consumption values of 33.5 million metric tons in 1987, 29.9 million metric tons in 1995, and 26.2 million metric tons in 2000 (EI A , 2002) with the emission factor reported by B r emmer et al. (1994) for a Dutch coke plant (0.23 ng I

TEQ DF 

### /kg of coal consumed). These calculations y i eld annual emissions of 7.7, 6.9, and 6.03 g I

TEQ DF 

### for 1987, 1995, and 2000, respectively

. Th ese estimates should be reg a rded as

pr e limina r y indic a tions of possible e missions f r o m this sour c e c a t e g or y ; f u r t he r te sting is ne e d e d

to c onf ir m the tr ue ma g n itude of the se e missions.

7.4. SECONDARY F E RROUS METAL SMELTING /REF INING
El ect ri c arc furnaces i n Europe have been report e d t o be sources of C DD/ C D F em i ssi ons; no testing has been reported at U.S. facilities. Electric arc fu rnaces are used to produce carbon and steel alloy s , primarily from scrap material, using a batch pr ocess. The input material is
ty pically 100% scrap. Scrap, a lloy i ng ag ents, and flux ing materials are loaded into the

cy lindrical, refractory

- lined furn ace, and then carbon electrodes are lowered into the mix

. The current of the opposite-polarity elect rodes g e nerates heat throug h th e scrap. Processing time of a batch rang es from about 1.5 to 5 hr to produce carbon steel and from 5 to 10 hr to produce alloy steel (U.S. EPA, 1995b).
The me lting of sc r a p f e r

r ous ma te r i a l c onta mina t e d with me ta lwor king f l uids a nd pla stic s that contain chlorine provides the conditions c onducive to formation of CDDs/CDF s. Ty sklind et al. (1989) studied the formati on and release of CDDs/CDF s at a pilot 10-ton electric furnace in
Sweden. Scrap ferrous metal feedstocks containing vary ing amounts of chlorinated compounds (PVC plastics, cutting oils, or calcium chlori de) were charg e d into the furnace under different operating conditions (continuous fee d, batch feed into the open furn ace, or batch feed throug h the furnace lid). During continuous charg i ng ope rations, the hig hest emissions, 1.5 ng Nordic

7-33

### Table 7-10. CDD/CDF em issi on estim ates f or Canadi an coke oven f acilities, blast fur n ac e fac ilit ie s, and e le c t r ic ar c fur n ac e s

Co m p a n y / fa cility L o c a t io n Plan t capacity (1,000 n e t t o nnes/y r ) E s tim a ted pro duct io n (1,000 n e t

t o nnes) E s tim a ted CDD/CDF

e m issio ns ( g I- TEQ) E s tim a ted CDD/CDF

e m issio n

factor (n g I

TEQ/k g )

Co k e o v e n fa cilities

A l g o m a S t eel In c. S a u l t S t e. Mari e, O n t a ri o 1 ,021 979 0.29 0.296

Do f a sco In c. Ham ilto n , On tario 1 ,6 5 6 1
, 5 8 8 0

. 4 8 0

. 3 0 2

S t el co In c., L a k e Eri e S t eel N a n t i c ok e, O n t a ri o 563 540 0.16 0.296

Stelco In c., Hilto n W o rk s H am ilto n , On tario 1 ,0 3 5 9 9 3 0

. 3 0 0

. 3 0 2

T O T A L 4 ,275 4,100 1.23

B l a s t furna ce fa cilities

A l g o m a Steel In c. Sau lt Ste. Marie, On tario 2 ,270 2,177 <0.01 N A

Do f a sco In c. Ham ilto n , On tario 2 ,7 2 5 2
, 6 1 3 <0 .0 1 N A

Stelco In c., L a k e Erie Steel Nan ticok e, On tario 1 ,680 1,611 <0.01 N A

Stelco In c., Hilto n W o rk s H am ilto n , On tario 2 ,7 2 0 2
, 6 0 8 <0 .0 1 N A

T O T A L 9 ,395 9,009 <0.01

E l ectric arc furnaces

A l t a S t eel L t d. Edm o n t on , A l bert a 295 256 0.67 2.62

A t l a s S p eci al t y S t eel s W el l a n d , O n t a ri o 218 189 0.49 2.59

A t l a s S t ai n l es s S t eel s T racy , Q u ebec 118 103 0.27 2.62

C o

- S t eel L a s c o W h i t b y , O n t a ri o 907 788 0.79 1.00

Do f a sco In c. Ham ilto n , On tario 1 ,2 2 5 1
, 0 6 5 0

. 5 0 0

. 4 6 9

G e rdau MR M S t eel In c. C a m b ri dg e, O n t a ri o 290 252 0.66 2.62

G e rdan MR M S t eel In c. S e l k i rk

, Man i t oba 281 244 0.63 2.58

IPS C O In c. R e g i n a , S a s k at ch ew an 907 788 1.13 1.43

Is pat S i dbec In c. C o n t recoeu r, Q u ebec 1,633 1,419 3.69 2.60

Iv an co Ro llin g Mills In c. L ’ Orig in al, On tario 4 0 8 3 5 5 0

. 9 2 2

. 5 9
Slater Steels, Ham ilto n Specialty B a r Div

. Ham ilto n , On tario 3 6 3 3 1 5 0

. 8 2 2

. 6 0

Stelco- M cMas ter L t èe C o n t recoeu r, Qu ebec 499 434 1.13 2.60

S y dn ey C o rp. S y d n e y , N o v a S c ot i a 454 395 0.40 1.01

T O T A L 7,598 6,603 12.10
NA = No t av ailab l e

S o u r ce: C h arl e s E. N a pi er C o m p an y , L t d. (2000).



### 7-34

### TEQ/dry Nm 3 

### (after an F F ) , were observed with a feed stoc k c onsisting of sc r a p me ta l with PVC plastics (1.3 g chlorine/kg feedstock). This e mission rate equates to 7.7 ng Nordic TEQ/kg of
feedstock. The hig hest emissions during batch charg i ng a l so oc c u r r e d whe n the sc r a p me ta l with PVC plastic was combusted (0.3 ng Nordic TEQ/dry Nm 3 

### [ 1.7 ng Nordic TEQ/kg ] feedstock). Much lower emissions (0.1 ng Nordic TEQ/dry Nm 3 

### [ 0.6 ng Nordic TEQ/kg ] feedstock) were observed when scrap metal with cutting oils that contained chlorinated additives (0.4 g chlorine/kg feedstock) was me lted. Althoug h these cutting o il-related emissions were not sig n if ic a n tly dif f

e r e nt f r o m the e missions obse r ve d f r o m the me lting of no- c h lor i ne sc r a p me ta l, relatively hig h levels of CDDs /CDF s (110 ng Nordic TEQ/dry Nm 3 

### ) were detected in flue g a ses
pr ior to the F F

. The cong ener profiles of raw flue g a s samples (prior to the APCD) showed that CDF s

r a the r tha n CDDs we r e pr e domina n t in a ll thr e e feedstock ty pes. The c ong ener profile from the test burn with PVC-containing f eedstock showed a hig h er chlorina ted cong ener content than was
observed with the other feedstocks. Eduljee and Dy ke (1996) used a rang e of 0.7 to 10 ng I

- TEQ DF 

### /kg of scrap feed to

e stima te na tiona l e missions f o r

the Unite d King dom. This r a ng e wa s a ssume d to be representative of no-chlorine a nd hig h -chlorine operations. Howe ver, the study authors provided little information on the supporting emission test studies (i.e., tested facility operational

m a t e ri al s, feed rat e s, cong ener-speci fi c em i ssi on rat e s). Umweltbundesamt (1996) re ported stack testing results fo r a variety of electric arc
furnaces i n Germ any

. S u ffi ci ent dat a were provi ded i n t h e report t o enabl e cal cul a t i on of TEQ
emission factors for six of the tested facilities. Tw o facilities had emissi on factors ex ceeding 1

ng I

- TEQ DF 

### /kg of scrap processed, and two facilities had e mission factors of less than 0.1 ng I TEQ DF 

### /kg of scrap. The mean emission factor was 1.15 ng I

- TEQ DF 

### /kg of scrap. The TEQ

c onc e n tr a tions in the sta c k g a se s a t the se f a c ilitie s ( c or r e c t e d to 7% ox y g e n ) r a ng e d f r o m le ss than 0.1 to 1.3 ng I

- TEQ DF 

### /m 3



### . The report commissioned by Environment Ca nada in 2000 to review steel production processes at Canadian plants (Charles E. Napier Company

, L t d., 2000) included information on

em i ssi ons from i r on si nt eri n g and provi ded i n form at i on on em i ssi ons from el ect ri c arc furnaces,
which were estimated on the basi s of plant capacity and estima ted production. Mean emission factors (ng I

- TEQ/kg ) of the 13 Canadian elect ric arc furnace f acilities (as indicated in Table 7-10) were 2.1 ng I

- TEQ DF 

### /kg steel produced.
I n March 2000, Environment Ca nada reported on source tes ting to determine CDD/CDF emissions from a facility in Ontario (Cianc iarelli, 2000). Samplin g was conducted on the

ex haust st ack of t h e el ect ri c arc furnace of Dofa sco I n c., and bot h concen t r at i ons and em i ssi on ­

7-35

### rates were provided (see Table 7- 11). Total CDD/CDF concentra tions were reported to be 51.15

pg TEQ/m 3 

### , and the total emission rate was reported to be 0.47 ng TEQ/kg steel produced. I n Aug ust 2000, the Emissions Research and M easurement Division of Environment Canada conducted source testing to dete rmine CDDs/CDF s from the elect ric arc furnace of another facility , Gerdau Courtice Steel I n c. (Cianciarelli, 2001). These re sults (presented in Table 7-11) are being used to support the Canadian diox in/furan inventory for electric arc furnaces. The total
CDD/CDF concentrations were reported to be 125.5 pg TEQ/m 3 

### , a nd the tota l e mission r a te wa s reported to be 1.1 ng TEQ/kg steel produced.
I n 1987, electric arc furnaces accounted for 38.1% of U.S

. steel production, or 30.8 billion kg of raw steel produced (Peters, 1988)

. I n 1995, electric arc furnaces accounted for 40.4% of U.S. steel production, or 38.4 of the to tal 95.2 million metric tons of raw steel produced (Fenton, 1996). I n 2000, electric arc furnaces accounted for 46.2% of U.S . steel production, or
49 of the 106 million metric tons of raw steel produced (USGS, 2002).
No t e st i n g of C DD/ C DF em i ssi ons from U.S

. el ect ri c arc furnaces on whi c h t o base an

e stima te of na tiona l e missions ha s be e n r e por te d. A pr e limina r y e stima te of pote n tia l TEQ
annual emissions from U.S . elect ric arc furnaces can be made by combining the production estimate of steel and an averag e emission factor of 1.21 ng I

- TEQ DF 

### /kg steel derived from the data reported in Umwelt bundesamt (1996) and the three Environm ent Canada reports (Charles E. Napier Company , L t d., 2000; Cianciarelli, 2000, 2001). This calculation y i elds an annual emissions estimate of 37.3 g I

- TEQ DF 

### in 1987, 46.5 g I

- TEQ DF 

### in 1995, and 59.3 g I

- TEQ DF 

### in
2000. These estimates should be reg a rded as pre liminary indications of possible emissions from

t h i s source cat eg ory ; furt her t e st i n g i s needed t o c onf ir m the tr ue ma g n it ude of these emissions.

7.5. F E RROUS F O UNDRIES
F e rrous foundries produce hig h -streng t h iron and steel casting s used in industrial machinery

, pipes, and heavy transportation equipm ent. I r on and steel casting s are solid solutions of iron, carbon, and various alloy i ng materials. Casting s are pr oduced by injecting or pouring
molten metal into cavities of a mo ld made of sand, metal, or cer amic material. Metallic raw materials are pig iron, iron and steel scrap, foundry returns, a nd metal turning s (U.S. EPA, 1995b, 1997a). The melting process takes place primarily in cupola (or blas t) furnaces and to a lesser

ex tent in electric arc furnaces. About 70% of all iron casting s are produced using cupolas, althoug h steel foundries rely almost ex clusively on electric arc furnaces or induction furnaces for melting

. The cupola is ty pically a vertical, cy lindr ical steel shell with either a refractory

- lined or

a

wa te r

- c oole d inne r wa ll. Cha r g e s a r e loa d e d a t the top of the unit; the ir on is me lte d a s it f l ows

7-36

### Table 7-11. CDD/CDF em i ssion concentrations and rates f or Canadian el ectri c arc f u rn aces

Congener M ea n fa cility co ncentra t io n ( p g TEQ/m 3 ) M ea n fa cility em issio n ra te ( n g TEQ/t o nne st e e l )

Run 1 Run 2 R un 3 A v g . Run 1 R un 2 R un 3 A v g . Do f a sc o Inc

. 2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 0 1.96 0 0 0.25 0.11 0.04 1.99 4.09 0 0.33 0 0 0.01 0 6.44 0 1.13 0.63 0.05 0 0.66 4.16 0 0.49 0.29 0.05 0.02 0 20.5

0 0 2.7 1.2 0.4 17.2 35.3

0 2.8 0 0 0 0 60.5

0 10.6

5.9 0.5 0 5.7 38.8

0 4.5 2.9 0.6 0.1
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 9.96 0.48 5.88 1.12 0.51 0 0 0.11 0 0.01 37.11 1.23 14.9

2.23 0.81 0.52 0 0.05 0 0 29.45 1.60 22.98

3.86 2.02 1.43 0 0.16 0 0 25.51 1.1 14.59

2.4 1.11 0.65 0 0.11 0 0 104.2 5 61.6 11.7

5.3 0 0 1.1 0 0.1 320.9 10.6 128.8

19.3

7 4.5 0 0.4 0 0 276.5 15 215.7

36.3 19 13.4

0 1.5 0 0 233.9 10.2 135.4

22.4 10.4

6 0 1 0 0

T O T A L 20.43 63.27 69.75 51.14 213.8 546.8 654.9 471.9

G erdau Courtice Steel I n c. 2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 6.3 8.3 0.6 1 0.8 0.2 0 2.7 4.7 0.4 0.7 0.5 0.1 0 2.6 3.1 0.2 0.4 0.3 0.1 0 3.9 5.4 0.4 0.7 0.5 0.1 0 57 75

5 9 8 1 0 21 37

3 6 4 1 0 22 27

2 3 3 1 0 33.3 46.3

3.3 6 5 1 0
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 65 5.5 95.5 12.5

6.9 5.8 0.5 0.7 0.1 0 29.4 2.9 46.2

7.9 4.6 4.3 0.5 0.5 0.1 0 18 1.7 26

4.3 2.4 1.7 0.2 0.2 0 0 37.5 3.4 55.9

8.2 4.6 3.9 0.4 0.5 0.1 0 588 50 864 113

62 52

5 6 1 0 232 23 364

63 36 34

4 4 1 0 154 15 222

37 20 14

2 2 0 0 324.7 29.3 483.3

71 39.3 33.3

3.7 4 0.7 0

T O T A L 209.7 105.5 61.2 125.5 1 ,896 833 524 1,084.2

Sou r ce: C i an ciarelli (2000).



### 7-37

### down the cupola and is removed at the bottom. Electric induction furnaces are batch-ty pe furnaces in which the charg e is melted by a fluctuating electromag n e tic charg e produced by electrical coils surrounding the unit (U.S. EPA, 1995b, 1997a).
I r on and steel foundries, par ticularly those using elect ric arc furnaces, are hig h ly
de pe nde nt on ir on a nd ste e l sc r a p. Of the e stima te d 72 million me tr ic tons of ir on a nd ste e l sc r a p consumed by the iron and steel industry in 1995, 25% (18 million metric tons) were used by
ferrous foundries. The other 75% were used by primary ferrous me tal smelters (principally those using electric arc furn aces) (USGS, 1997f). I n 2000, 20% ( 12.4 million metric tons) were used by ferrous foundries; the remain ing 80% were used by primary ferrous smelters (USGS, 2000).
I n 2000, there were approx imate ly 1,100 ferrous foundries in the United States producing
1.3 million metric tons of steel cas ting s and 10 metric tons of ir on casting s

. Thus, foundries face

t h e sam e pot ent i a l for C DD/ C D F em i ssi ons as do el ect ri c arc furnaces because of t h ei r use of scrap that contains chlorinated solvents, plastic s, and cutting oils (see Section 7.4) The potential
for formation and release of CDDs/CDF s during the casting process is not known.
I n 1993, emissions testing wa s conducted at a U.S. ferrous foundry (CARB
, 1993, as reported in U.S. EPA, 1997a). The tested f acility consisted of a ba tch-operated, coke-fired cupola furnace charg e d with pig iron, scrap ir on, scrap steel, coke, a nd limestone. Emission control devices operating during th e te sting we r e a n oil- f i r e d afterburner and an F F

. The

cong ener and cong ener g r oup emi ssion factors derived from the te sting are presented in Table
7-12. The calculated TEQ emission factor for this set of tests is 0.42 ng TEQ DF 

### -W HO 98 

### (0.37 ng
I

- TEQ DF 

### / k g ) of m e t a l charg e d t o t h e furnace. Umweltbundesamt (1996) repor ted stack testing results for a variety of ferrous foundries
i n Germ any

. S u ffi ci ent dat a were provided to enable calcula tion of TEQ emission factors for eig h t of the tested facilities. Three fac ilities had emission factors ex ceeding 1 ng I

- TEQ DF 

### /kg of metal charg e , and four facilities had emission fact ors less than 0.1 ng I

- TEQ DF 

### /kg of me ta l charg e

. The em i ssi on fact ors span m o re t h an four orders of mag n it ude. The mean emission factor was 1.26 ng I

- TEQ DF 

### /kg of me ta l f e e d

. I n 1997, EPA conducted testing for emissions of diox ins at two ferrous foundries (U.S. EPA, 1999c, f). One study was conducted on th e cupola’s W S ; the second study was performed on the cupola’s F F

. A summary of the results is presented in Table 7-13. The emission factor developed from these tests is 2.05 ng I

- TEQ/kg of metal processed.
B ecause of the wide rang e of emissions for the tested German foundries reported in Umweltbundesamt (1996), the confiden ce in the deg r ee to which the three tested U.S. facilities represent the mean emission factor for the appr ox imately 1,100 U.S. foundrie s is considered very
low. The r e f or e , the limite d da ta a v a ila ble we r e judg e d ina d e qua te f o r

de ve loping na tiona l

e mission e stima te s tha t c ould be inc l ude d in the na tiona l inve ntor y

. Howe ve r , a pr e limina r y

7-38

### Table 7-12. CDD/CDF em ission f actors f or a U.S. f errous f oundry

C o ngener/congener group Mean f a cility emission f a ctor (ng/kg scrap f eed)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.033 0.086 NR 0.051 NR 0.093 NR
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.52 0.305 0.35 0.19 0.17 NR 0.101 0.193 NR 0.059

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### (for reported cong eners) Total TE Q DF 

### -W H O 98 

### 0.263 1.888 0.372 0.415

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 3.96 1.76 0.55 0.19 NR 25.8 850 1.74 0.24 0.06

T otal CDD/CDF (not including OCDD) 884.3
NR = No t rep o r ted

S o u rce: C A R B (1993), as report e d i n U

. S

. EPA (1997a).



### estimate of potential TEQ annua l emissions from U.S. ferrous foundries can be made by combining the mean emission factor (1.23 ng I

- TEQ DF 

### /kg of me ta l f e e d ) de r i ve d f r o m the da ta reported in Umweltbunde samt (1996), CARB (1993) , and U.S. EPA (1997a) with an estimated activity level for U.S. foundries.

7-39

### Table 7-13. Conge n e r - spe c i f i c pr of ile f o r f e r r ous f o undr ie s

C ongener Mean emission f a ctor (2 f a cilities) (ng I-TEQ/kg)

N o ndetect set to z ero N o ndetect set to 1⁄2 detection limit
2,3,7,8- T C DD 1,2,3,7,8- PeCD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.11 0.15 0.012 0.023 0.028 0.0033 0.16 0.11 0.15 0.012 0.023 0.028 0.0033 0.16
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.084 1.08 0.21 0.1 0.0079 0.075 0.0082 0.0014 0.00009 0.00007 0.084 1.08 0.21 0.1 0.0079 0.075 0.0082 0.0014 0.00009 0.00007

T o tal I

- T EQ 2.05 2.05

S o u rces : U

. S

. EPA (1999c, f )



### .

I n 1987, U.S. shipments from ferrous foundrie s were 9.19 million metric tons, of which about 90% were iron casting s and 10% were steel casting s (Houck, 1991). I n 1995, U.S. shipments from the approx imately 1,000 U.S. fe rrous foundries were 13.9 million metric tons, of
which about 90% were iron castin g s and 10% were steel casting s (F enton, 1996). I n 2000, U.S. shipments from the approx imate 1,100 U.S. ferr ous foundries were 11.3 million metric tons, of
which about 89% were iron castin g s and 11% were steel casting s (USGS, 2001). Using the mean
emission factors and these ac tivity levels y i elds annual emission estimates of 11.3 g I

- TEQ DF 

### , 17.1 g I

- TEQ DF 

### , and 13.9 g I

- TEQ DF 

### for 1987, 1995, and 2000, respectively

. These estimates should be reg a rded as preliminary indications of possible emissions from this source categ ory ; f u r t he r te sting is ne e d e d to c onf ir m the tr ue ma g n itude of the se e missions.

7.6. SCRAPELECTRIC WIRE RECOVERY The objective of wire recovery is to recla im the metal (copper, lea d, silver, and g old) in
the e l e c t r i c wir e by r e moving the insula ting ma te r i a l

. The r e c ove r y f

a c ility the n se lls the
reclaimed metal to a sec ondary metal smelter. W i re insulation commonly consists of a variety of

7-40

### pla stic s, a spha lt- impr e g n a t e d f a br ic s, or burlap. Chlorinated org a ni cs are used t o preserve t h e cable casing in below-g r ound cables. The combus tion of chlorinated org a nic compounds in the cable insulation, cataly z ed by the presence of wire metals such as copper and iron, can lead to the
formation of CDDs and CDF s (Van W ijnen et al., 1992). Althoug h, in the past, scrap electric wire was commonly recovered using thermal

pr oc e ssing to bur n of f the insula ting ma te r i a l

, current recovery operati ons typically no long er involve thermal treatment, accordin g to industry and trade association representatives. I n stead, scrap electric wire is m echanically chopped into fi ne particles. The insu lating material is then removed by mix ing , followed by settling of the heavier metal (telephone conversations between
T. L e ig hton, Versar, I nc., and R. Garino, I nstitu te of Scrap Recy cling I ndustries, March 2, 1993,
and T. L e ig hton and J . Sullivan, Tr iple F

. Dy namics, March 8, 1993).
EPA measured diox in-like compounds emitted to the air from a scrap wire reclamation incinerator during its 1986 National Diox in Study of combustion sources (U.S. EPA, 1987a).
EPA determined that the tested facility was ty pical of this indus trial source categ ory at that time.
I n sula te d wir e a nd othe r me ta l- be a r ing sc r a p ma te r i a l we r e f e d to the inc i ne r a tor on a ste e l pa lle t.
The i n ci nerat o r operat e d i n a bat c h m ode, wi t h t h e com bust i on cy cl es for each bat c h of scrap feed lasting between 1 and 3 hr. Natural g a s was used to incine rate the material. Althoug h most of the wire had a tar-based insulation, PVC-coat ed wire was also fed to the incinerator. Temperatures during combustion in the primary chamber furnace were about 570°C. The tested facility was equipped with a hi g h -temperature, natural g a s-fi red afterburner (980 to 1090°C). Emission factors estimated for this facility ar e presented in Table 7-14. The estimated TEQ emission factor (based only on 2,3,7,8-TCDD, 2,3,7,8-TCDF , OCDD, and OCDF ) is 15.8 ng TEQ DF 

### -W HO 98 

### (16.9 ng I

- TEQ DF 

### /kg ) of scrap feed. F i g u re 7- 5 presents a cong ener g r oup profile
based on these emission factors.
B r emmer et al. (1994) reported emission factors for three fac ilities in the Netherlands that subsequently ceased operations. Emission rate s at a facility burning underg round cables and cables containing PVC rang ed from 3.7 ng I

- TEQ DF 

### /kg to 14 ng I

- TEQ DF 

### /kg

. The e mission r a te s at a second facility rang ed from 21 ng I

- TEQ DF 

### /kg of scrap (when burning copper core coated with g r easy paper) to 2,280 ng I

- TEQ DF 

### /kg of sc r a p ( w he n bur ning le a d c a b le )

. The thir d f a c ility

, which burned motors, was re ported to have an emi ssion rate of 3,300 ng I

- TEQ DF 

### /kg of scrap.
On t h e basi s of t h ese m easurem ent s , Brem m e r et al. used emission rates of 40 ng I

- TEQ DF 

### /kg of scrap and 3,300 ng I

- TEQ DF 

### /kg of sc r a p f o r

e stima ting na tiona l e missions in the Ne the r la nds f o r f

a c ilitie s bur ning wir e s a nd c a b le s a nd those bur ning motor s, r e spe c tive l y

. Althoug h limited emissions testing has been conducted at one U.S. facility , the activity level for this industry sector in reference y ears 1987, 1995, and 2000 is unknown; therefore, an

7-41

### Table 7-14. CDD/CDF em ission f a ct ors f o r a scrap w i re incinerator

C o n g en er/con g en er grou p Mean f a cility emission f a ctor a 

### (ng/kg scrap f eed)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.374 NR NR NR NR NR 1,000
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2.67 NR NR NR NR NR NR NR NR 807

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### NR NR 16.9 b 

### 15.8

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 1,000 4.42 13.7 71.1 347 107

97.4 203 623 807

T otal CDD/CDF 3,274

a N o n o n d et ect v a l u es w e re report e d f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , or an y con g e n e r g rou p i n t h e t h ree t e s t ru n s

. b Es t i m at ed on t h e bas i s of t h e m eas u red dat a f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , O C D D
, an d O C D F an d con g e n e r g r ou p em is s i on s (i.e., f o r th e pen t a- , h e x a

- , an d h e pta- C DDs an d C D Fs , it w a s as s u m e d th at th e m eas u r ed

em is s i on f actor w ith in a con g e n e r g r ou p w a s th e s u m of equ a l em is s i on f actors f o r all con g e n e rs in th at g r ou p, in clu d in g n o n

- 2
, 3
, 7
, 8

- su b s titu ted co n g e n e rs).

NR = No t rep o r ted

S o u rce: U

. S

. EPA (1987a).



### 7-42

### F i gure 7-5. Congener group prof ile f o r ai r em i ssi on s f r om a scrap w i re i n ci n erator.

S o u rce: U

. S

. EPA (1987a).



### estimate of national emissions cannot be made. I t is uncer tain how many fac ilities in the United States still combust scrap wire. Trade associa tion and industry representatives state that U.S.

sc r a p wir e r e c ove r y f

a c ilitie s now bur n only minima l qua ntitie s of sc r a p wir e

. Howe ve r , a n inve ntor y of CDD/CDF sour c e s in the Sa n F r a n c i sc o B a y a r e a note d tha t two f a c ilitie s the r ma lly
treated electric motors to recove r electrical windi ng s (B AAQMD, 1996).
I n a ddition to r e le a se s f r o m r e g u la te d r e c ove r y f

a c ilitie s, CDD/CDF r e le a se s f r o m sma llsc a l e bur ning of wir e a t unr e g ula t e d f a c ilitie s a nd ope n a i r site s ha ve oc c u r r e d; howe v e r , the current mag n itude of these ty pes of activity in the United States is not known. Harnly et al. (1995) analy z ed soil/ash mix tures from three cl osed metal recovery facilities and from three closed sites using open burning fo r copper recovery near a Californi a desert town. The g e ometric

me a n s of the tota l CDD/CDF c onc e n tr a tions a t the f a c ility site s a nd the ope n bur ning site s we r e 86,000 and 48,500 ng /kg

, respectively

. The g e omet ric mean TEQ concentrations were 2,900 and 1,300 ng I

- TEQ DF 

### /kg , respectively

. A sig nificantly hi g h er g e ometric mean concentration (19,000

ng I

- TEQ DF 

### /kg ) was found in fly ash located at two of the facility sites. The cong ener-specific

7-43

### and cong ener g r oup results from this study are pres ented in Table 7-15. The results show that the
f

our domina n t c ong e n e r s in the soil sa mple s a t both the f a c ility a nd the ope n bur ning site s we r e OCDF , 1,2,3,4,6,7,8-HpCDF , 1,2,3,4,7,8-Hx CDF , and 2,3,7,8-TC DF

. A slig htly different profile was observed in the fly ash samples, with 1,2,3,7,8-PeCDF a nd 1,2,3,4,7,8,9-HpCDF replacing OCDD and 2,3,7,8-TCDF as the dominant cong eners.

Table 7-15. CDD/CDF concentrations in f l y ash and ash/soil at m e tal recovery sites

Congener/congener grou p M e ta l reco v ery fa cilities O pen burn sites

F l y a s h ( 2 sit e s) Ash/so il ( 3 sit e s) Ash/so il ( 3 sit e s)

G e om etric

me a n ( 

### : g/ k g) Rela tiv e percent of total CDD/CDF G e om etric

me a n ( 

### : g/ k g) Rela tiv e percent of total CDD/CDF G e om etric

me a n ( 

### : g/ k g) Rela tiv e percent of total CDD/CDF
2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD a 400 1,200 2,300 1,700 12,000 18,000 0.1 0.2 0.5 0.3 2.4 3.5 a 0.24 0.25 0.49 1.3 2.6 7.2 0.3 0.3 0.6 1.5 3.1 8.5 a 0.24 0.13 0.33 0.39 1.2 3.4 0.5 0.3 0.7 0.8 2.5 7

2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 15,000 35,000 10,000 46,000 12,000

5,000 5,000 71,000 25,000 100,000 2.9 6.9 2 9 2.4 1 1 13.9

4.9 19.6 6.4 2.9 1.4 5.9 1.8 0.92 1.6 12

3 14 7.5 3.4 1.6 6.9 2.1 1.1 1.9 14.1

3.5 16.5 1.7 0.58 0.66 2.7 0.76 0.66 0.49 4.3 0.71 6.6 3.5 1.2 1.4 5.6 1.6 1.4 1 8.9 1.5 13.6

T o tal T C DD T o tal P e CDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal P e CDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF a 2,000 4,000 24,000 18,000 23,000 110,000

88,000 110,000 100,000 a 0.4 0.8 4.7 3.5 4.5 21.6 17.3 21.6 19.6 a 1.4 2.7 4.1 7.2 14 12 12 17 14 a 1.6 3.2 4.8 8.5 16.5 14.1 14.1 20 16.5 a 2.8 0.98 2 3.4 5.6 7 7.6 7.4 6.6 a 5.8 2 4.1 7 11.5 14.4 15.7 15.3 13.6

T o tal I- T E Q DF T o tal CDD/CDF 16,968 479,000 3 84.4 1.3 48.4

a A n aly tical m e th o d u s ed h a d lo w sen s itiv ity f o r T C DDs; resu lts w e re n o t rep o r ted

.

S o u r ce: H a rn l y et al . (1995).



### 7-44

### Van W ijnen et al. (1992) reported similar results for soil samples collected from unpermitted incineration site s of former scrap wire and cars in the Netherlands. Total CDD/CDF concentrations in the soil rang ed from 60 to 98,000 ng /kg , with 9 of the 15 soil samples having levels above 1,000 ng /kg

. Chen et al. (1986) reported finding hig h levels of CDDs/CDF s in residues from open air burning of wire in Taiwan, and Huang et al. (1992) reported elevated levels in soil near wire scrap recovery operations in J a pan. B r emmer et al. (1994) estimated an emission rate to air of 500 ng I

- TEQ DF 

### /kg of sc r a p f o r

ille g a l, unr e g ula t e d bur ning of c a b le s in the
Ne the r la nds.

7.7. DRUM AND BARREL RE CLAMATION F URNACES
Hutz ing e r and F i edler (1991a) reported det ecting CDDs/CDF s in stack g a s emissions
f r o m dr um a nd ba r r e l r e c l a m a tion f a c ilitie s a t le ve ls r a ng ing f r o m 5 to 27 ng /m 3



### . EPA measured
diox in-like compounds in the stack g a s emissions of a drum and barrel reclamation furnace as part of the National Diox in Study (U.S. EPA, 1987a).
Drum and barrel reclamation facilities operate a burning fu rnace to thermally clean used
55- g a llon ste e l dr ums of r e sidue s a nd c o a ting s. The dr ums pr oc e sse d a t the se f a c ilitie s c o me from a variety of sources in the petroleum and ch emical industries. The thermally cleaned drums are then repaired, repain ted, relined, and sold for reuse. Th e drum-burning process subjects the used drums to an elevated temp erature in a tunnel furnace fired by aux iliary fuel for a sufficient
time so tha t the pa int, inte r i or lining s, a nd pr e v ious c onte n ts a r e bur ne d or disinte g r a te d. Use d drums are loaded onto a convey o r that moves at a fix e d speed. As the drums pass throug h the preheat and i g ni t i on z one of t h e furnace, resi dual c ont ent s of t h e drum s drai n i n t o t h e furnace ash
troug h. A drag convey o r moves these sludg es and ashes to a collection pit. The drums are aircool ed as t h ey ex i t t h e furnace. Ex haust g a ses from t h e burni ng furnace are t y pi cal l y drawn

t h roug h a breechi n g fan t o a hi g h -t em perat u re aft e rburner. The afterburner at the facility tested by EPA operated at an averag e of 827°C during testing and achieved a 95% re duction in CDD/CDF emissions (U.S. EPA, 1987a). Emission factors estimated for this facility are presented in Table 7-16. On the basis of the measured

cong ener and cong ener g r oup emissions, the aver ag e TEQ emission factor is estimated to be 17.5

ng TEQ DF 

### -W HO 98 

### /drum (16.5 ng I

- TEQ DF 

### /drum). The cong ener g r oup profile is presented in
F i g u re 7-6. Approx imately 2.8 to 6.4 million 55-g a llon drums are reclaime d by incineration annually in the United States (telephone conversation between C. D. Ruiz , Versar, I n c., and P. Rankin,
Association of Container Rec onditioners, December 21, 1992). Th is estimate is based on the assumption that 23 to 26 incinerators are in opera tion; each incinerator, on averag e, handles 500

7-45

### Tab l e 7-16. CDD/CDF em ission f a ctors f o r a d r u m an d b a rrel reclam ation fac ilit y

C o n g en er/con g en er grou p Mean f a cility emission f a ctor a 

### ( n g/ drum )
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 2.09 NR NR NR NR NR 37.5
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 36.5 NR NR NR NR NR NR NR NR 22.4

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF 

### Total TE Q DF 

### -W H O 98 

### NR NR 16.5 b 

### 17.5

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 50.29 29.2 32.2 53.4 37.5 623 253 122

82.2 22.4

T otal CDD/CDF 1,305.2

a N o n o n d et ect v a l u es w e re report e d f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , or an y con g e n e r g rou p i n t h e t h ree t e s t ru n s

. b Es t i m at ed on t h e bas i s of t h e m eas u red dat a f o r 2,3,7,8- T C D D
, 2,3,7,8- T C D F , O C D D
, an d O C D F an d con g e n e r g r ou p em is s i on s (i.e., f o r th e pen t a- , h e x a

- , an d h e pta- C DDs an d C D Fs , it w a s as s u m e d th at th e m eas u r ed

em is s i on f actor w ith in a con g e n e r g r ou p w a s th e s u m of equ a l em is s i on f actors f o r all con g e n e rs in th at g r ou p, in clu d in g n o n

- 2
, 3
, 7
, 8

- su b s titu ted co n g e n e rs).

NR = No t rep o r ted

S o u rce: U

. S

. EPA (1987a)



### .

7-46

### F i gure 7-6. Congener group prof ile f or ai r em i ssi on s f r om a d r u m i n ci n erator.

S o u rce: U

. S

. EPA (1987a).



### to 1,000 drums each day and, on averag e, each in cinerator operates 5 da y s/wk, with 14 downtime day s annually for maintenance ac tivities. The weig hts of 55-g a llon drums vary considerably ; however, on averag e, a drum weig hs 38 lb (or 17 kg ); therefore, an estimated 48 to 109 million kg of drums are incinerate d annually

. F or 1987 and 1995, EPA assumed that 4.6 million drums were burned each y ear (i.e., the midpoint of the rang e); apply i ng the e mission factors developed above, the estimated annua l emission is 0.08 g TEQ DF 

### -W HO 98 

### (0.08 g I

- TEQ DF 

### ).
The Reusable I ndustrial Packag ing Associ ation estimated that approx imately 35 million 55-g a llon barrels were reclaime d in 1997 (RI P A, 1997). Assuming the number of drums treated has remained constant throug h 2000, the estimate for 2000 would be 0.61 g TEQ DF 

### -W HO 98 

### (0.58

g I

- TEQ DF 

### ).
A low c onf ide n c e r a ting is a ssig n e d to the a c tivity le ve l e stima te s f o r

a ll r e f e r e nc e y e a r s because they are based on ex pert judg ment rather than a published reference. A low confidence

7-47

### rating is also assig ned to the emission factor because it was developed from stack tests conducted

at j u st one U.S

. drum and barrel furnace and t hus m a y not represent averag e em i ssi ons from

c u r r e nt ope r a tions in the Unite d Sta t e s. B a se d on the se r a ting s, the e mission e stima te s a r e assi g n ed a l o w confi d ence rat i n g

.

7.8. SOLID WASTE F R OM P R IMARY/SECONDARY IRON/STEEL
MIL L S /F OUNDRIE S Table 17 in Quab and F e rmann (1997) cont ains summary data on the ty pical annual

qua ntitie s a nd r a ng e s of TEQ ( N or we g i a n- TEQ [NTEQ] a nd I

- TEQ) f r om va r i ous solid r e sidua ls from the metallurg ical industries in Europe, but support information and specific cong eners were not discussed. The summary data for annual TEQ g e neration are pr esented below (in g r ams) for informational purposes only and are not included in the inventory of diox in releases presented in this report because they are disposed of in permanent landfills and are not considered an
envi ronm ent a l rel ease.

• G rey iron foundries, F F dust a nd scrubber sludg e: 0.817 NTEQ

• S teel mill coke oven door leakag e dust: 0.31 NTEQ

• S teel mill coke oven door leakag e dust: 0.04 I

- TEQ

• P ig iron tapping slag : 0.041 NTEQ

• B asic ox y g en furnace scrubber sludg e: 1.53 NTEQ (rang e, 0.3–7.81)

• Electric furnace FF dust: 3.1 I

- TEQ (rang e of 0.4–2.4)

• Electric furnace slag or FF dust: 19.2 NTEQ

7-48

### 8. CHE M ICAL MANUF ACT URING AND P R OCE S S I NG S O URCE S

8.1. BLEACHED CHEMICAL WOOD P U LP AND P A P E R MILLS
I n March 1988, EPA and the U.S. pulp and paper industry jointly released the results of a screening study that provided the first compre hensive data on the formation and discharg e of
CDDs/CDF s from pulp and paper mills (U.S. EPA, 1988d). This early screening study of five bleached kraft mills (the F i ve Mill Study ) c onfirmed that the pulp bleaching process was primarily responsible for the fo rmation of CDDs/CDF s. The study results showed that 2,3,7,8­
TC DD was present i n seven of ni ne bl eached pul ps , fi ve of fi ve wast ewat er t r eat m e nt sl udg es, and three of five treated wast ewater effluents. The study results also indicated that 2,3,7,8­ TCDD and 2,3,7,8-TCDF were the pr incipal CDDs/CDF s formed. To provide EPA with more complete data on the releas e of these compounds, EPA and the pulp and paper industry jo intly conducted a survey durin g 1988 of 104 pulp and paper mills
in the United States to measure levels of 2,3,7,8-TCDD and 2,3,7,8-TCDF in effluent, sludg e, and pulp. The survey study , commonly called the 104 Mill Study , was manag e d by the National Council of the Paper I ndustry for Air and Stream I m provement, I nc. (NCASI ), with oversig ht by EPA, and included all mills wher e chemically produced wood pulps were bleached with chlorine
or chlorine derivatives. The final study re port (U.S. EPA, 1990e) was released in J uly 1990. An initial phase of the 104 Mill Study involved the analy s is of bleached pulp (10 samples), wastewater sludg e (9 sa mples), and wastewater effluent ( 9 sa mple s) f r o m e i g h t kr a f t
mills and one sulfite mill for all 2,3,7,8-substituted CDDs/CDF s. Th ese analy s es were conducted
to test the conclusion drawn in the F i ve Mill Study that 2,3,7,8-TCDD and 2,3,7,8-TCDF were the principal CDDs/CDF s found in pulp, wastewat er sludg e, and wastewater effluent on a TEQ
basis. Althoug h at the time of the study there were no reference analy tical methods for many of the 2,3,7,8-substituted CDDs/CDF s, the data obtaine d were considered valid by EPA for the purposes intended because of the identification and quantification criteri a used, duplicate sample

r e sults, a nd limite d ma tr ix spike e x pe r ime nts. Ta ble 8- 1 pr e se n ts a summa r y of the r e sults
obt ai ned i n t e rm s of t h e m e di an concent r at i ons and t h e rang e of concent r at i ons observed for each
matrix (pulp, sludg e, and effluent ). F i g u res 8-1, 8-2, and 8-3 pr esent cong ener profi l e s for each

ma tr ix ( nor ma lize d to tota l CDD/CDF ) using the me dia n r e por te d c onc e n tr a tions.
Af te r e x a mina tion of the r a w, mill- spe c i f i c da ta , EPA c onc lude d tha t the c ong e n e r profiles were fairly consistent across matrices with in mills and that 2,3,7,8-TCDD and 2,3,7,8­
TCDF accounted for the majority of TEQ in th e samples (U.S. EPA, 1990e). Using the median
concentrations and trea ting nondetect values as either z e ro or one-half the detection limit (DL )
,

8-1Table 8-1.CDD/CDFconcentrations inpulp and paper mill bleached pulp,wastewater sludge, and wastewatereffluent (circa 1988)



### 8-2Congener/congenergroupBleachedpulpWastewater sludgeWastewater effluentMedian(ng/kg)Range(ng/kg)No.ofdetects(10samples)Median(ng/kg)Range(ng/kg)No.ofdetects(9samples)Median(pg/L)Range(pg/L)No.ofdetects(9samples)2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD6.4ND(0.3)ND(0.4)ND(0.5)ND(0.5)3.3460.4 to 124ND(0.1)to 1.4ND(0.2)to 0.4ND(0.2)to 1.6ND(0.2)to 0.52.3 to 8.428 to 81102121101063ND(2.5)ND(3.1)ND(3.2)ND(3.9)37698ND(6.3)to 180ND(1.4)to 28ND(1.5)to 40ND(1.7)to 95ND(1.7)to 8018 to 490263 to 1,780811119942ND(9.6)ND(12)ND(12)ND(12)1703,000ND(11)to 98ND(2.8)to ND(25)ND(6.6)to ND(12)ND(6.6)to ND(24)ND(6.6)to ND(23)77 to 2701,000 to 4,60080000992,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF18ND(0.7)ND(0.2)ND(0.3)ND(0.3)ND(0.3)ND(0.3)ND(0.6)ND(0.6)2.21.4 to 716ND(0.1)to 3.9ND(0.1)to 4.7ND(0.2)to ND(0.6)ND(0.1)to ND(0.4)ND(0.1)to ND(0.4)ND(0.2)to ND(0.4)ND(0.1)to 0.8ND(0.1)to ND(2.1)ND(2.8)to 4.3104300003082336.24.7ND(2.5)ND(1.4)ND(1.7)ND(1.7)6.6ND(1.6)2213 to 1150ND(1.2)to 22ND(0.9)to 38ND(0.9)to 31ND(0.9)to 33ND(0.9)toND(4)ND(0.9)to 34ND(3.6)to 70ND(1.2)to 10ND(54)to 1689662101718120ND(7.2)ND(6.3)ND(8.4)ND(7.1)ND(6.2)ND(8.2)ND(23)ND(22)19012 to 840ND(2.2)to 36ND(2.2)to 33ND(4.8)to ND(15)ND(4.8)to ND(15)ND(2.5)to ND(15)ND(4.8)to ND(15)ND(13)to 44ND(6.4)to ND(41)ND(180)to 2309220000308Total 2,3,7,8-CDDa,b55.77983,212Total 2,3,7,8-CDFa,b20.2272.5310Total I-TEQDF8.2890.1258.89(nondetect=0)b91.7266.57Total I-TEQDF8.56(nondetect=1⁄2DL)bTotal TEQDF-WHO988.2489.4756.02(nondetect=0)bTotal TEQDF-WHO988.5991.766.09(nondetect=1⁄2DL)bTotal CDD/CDFb75.91,070.53,522aCalculatedassumingnondetectvalueswerezero.bSum ofmedianvalues.DL=Detection limitND =Not detected(valuein parenthesis is thedetection limit)Source:U.S. EPA(1990e).2, 3,7

,8

- TC

D D

1,2

,3 ,7, 8- P eCD

D

1,2

,3 ,4,7

, 8- Hx

CD

D

1,2

,3 ,6, 7, 8- Hx

CD

D

1, 2,3

,7 ,8, 9- Hx

CD

D

1,2

,3 ,4, 6, 7,8

- Hp

C DD O CDD

2 ,3 ,7,8

-T C DF

1,2

,3 ,7, 8- P eCD

F

2,3

,4 ,7 ,8-

P eC

DF

1 ,2, 3,4

,7 ,8

- Hx

CDF

1 ,2 ,3,6

, 7,8

- Hx

CDF

1 ,2 ,3,7

,8,9

- Hx

CDF

2 , 3,4,6 , 7,8

- Hx

CDF

1,2,

3 ,4,6

,7,8-

H p CDF

1,2,

3,4,7 , 8,9-

Hp

CDF O CDF

2, 3,7

,8

- TC

D D

1,2

,3 ,7,8

- Pe

C D D
1,2,3

, 4,7,

8- Hx

CD

D

1 ,2,3

,6,7,

8 -H

x C D D
1,2,3

, 7,8,

9- Hx

C D D

1,2

, 3,4,

6 ,7,8

- H p CDD O CDD
2,3 , 7,8

- T CDF

1 ,2,3

,7,8-

P eCDF

2 ,3,4

, 7,8-

P e CDF

1 ,2 ,3,4

,7 ,8

- Hx

CDF

1 ,2, 3,6

,7 ,8

- Hx

CDF

1 ,2, 3,7

,8 ,9

- Hx

CDF

2 ,3 ,4,6

,7 ,8

- Hx

CDF

1,2

, 3,4

,6 ,7, 8- Hp

CDF

1,2

, 3,4

,7 ,8,9

- H p CDF O CDF 0. 00 % 10. 00 % 20. 00 % 30. 00 % 40. 00 % 50. 00 % 60. 00 % 70. 00 %Percent ofTotalCDDs andCDFs

Congener



### F i gure 8-1. 104 Mill Study f u ll congener an alysis results f or pulp (nondetects
eq u a l to zero).

S o u r ce: Medi an con cen t r at i o n s f r om U

. S

. EPA (1990e).

0% 10 % 20 % 30 % 40 % 50 % 60 % 70 %Percent ofTotalCDDs andCDFs

Congener 

### F i gure 8-2. 104 Mill Study f u ll cong ener analysis res ults f or sludge.

S o u r ce: Medi an con cen t r at i o n s f r om U

. S

. EPA (1990e).



### 8-32, 3,7

,8

- TC

D D 1,2,3

, 7,8-

P e CDD

1,2

,3 ,4 ,7, 8- Hx

CD

D

1,2,

3 ,6,7

, 8- Hx

CD

D

1, 2,3

,7 ,8, 9- Hx

CD

D

1, 2 ,3,4

, 6,7

,8

- Hp

CDD O CDD
2,3 , 7,8

- T CDF

1,2

,3 ,7, 8- P eCD

F 2,3,4 , 7,8-

P e CDF

1 ,2 ,3,4

, 7,8

- Hx

CDF

1 ,2,3

,6 ,7, 8 - Hx

C DF

1 , 2,3,7 , 8,9

- Hx

CDF

2 ,3, 4,6

,7 ,8

- Hx

CDF

1,2,

3,4,6 , 7,8-

Hp

CDF

1 ,2, 3 ,4,7

,8 ,9- H p CD

F O CDF 0% 10% 20% 30% 40% 50% 60% 70% 80% 90%

Congener



### F i gure 8-3. 104 Mill Study f u ll congen er analysis results f o r ef f

l uent.

S o u r ce: Medi an con cen t r at i o n s f r om U

. S

. EPA (1990e).



### EP A concluded that 2,3,7,8-TCDF accounted for 77.8 to 99.5% of the total TEQ DF 

### -W HO 98 

### (77.3
to 99% of the tota l I

- TEQ DF 

### ) in pulp, 70.4 to 96.5% of the TEQ DF 

### -W HO 98 

### (69.9 to 95.8% of the
I

- TEQ DF 

### ) in sludg e, and 75.0 to 96.4% of the TEQ DF 

### -W HO 98 

### (71.3 to 91.7% of the I

- TEQ DF 

### ) i n effluent.
NCASI r e por te d on a simila r f

u ll- c ong e n e r a n a l y sis study f

o r

sa mple s c o lle c t e d f r o m eig ht mills during the mid-1990s (letter dated F e bruary 10, 1997, from W

. Gillespie, National Council of the Paper I ndustry for Air and Stream I m provement, I nc., to G. Schweer, Versar,
I n c.). The resul t s of t h ese anal y s es are pres ented in Table 8-2. The frequency of detection of 2,3,7,8-TCDD and 2,3,7,8-TCDF was sig nificantly lo wer than in the 1988 study ; therefore, deriving meaning f ul summary statistics con cerning the relative importance of 2,3,7,8-TCDD and 2,3,7,8-TCDF to the total TEQ is difficult. W ith all nondetect values assumed to be z e ro, 2,3,7,8-TCDD and 2,3,7,8-TCDF accounted for 97% of the total effluent TEQ DF 

### -W HO 98 

### (91% of
the I

- TEQ DF 

### ), 53% of the total sludg e TEQ DF 

### -W HO 98 

### (46% of the I

- TEQ DF 

### ), and 87% of the total pulp TEQ DF 

### -W HO 98 

### (87% of the I

- TEQ DF 

### ). B ecause of the hig h frequency of nondetects when all
nondetect values are one-half the DL

, 2,3,7,8-TCDD and 2,3,7,8-TCDF accounted for only 13%
of

the tota l e f f l ue nt I

- TEQ DF 

### , 13% of the total sludg e I

- TEQ DF 

### , and 28% of the total pulp I TEQ DF 

### . ­

8-4Table 8-2.CDD/CDFconcentrations inpulp and paper mill bleached pulp,wastewater sludge, and wastewatereffluent (mid-1990s)



### 8-5Congener/congenergroupBleachedpulpWastewater sludgeWastewater effluentMeannondetect= 0(ng/kg)Median(ng/kg)Range(ng/kg)No.ofdetects/samplesMeannondetect= 0(ng/kg)Median(ng/kg)Range(ng/kg)No.ofdetects/samplesMeannondetect= 0(pg/L)Median(ng/kg)Range(pg/L)No.ofdetects/samples2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD0.3000002.4ND(1)ND(5)ND(5)ND(5)ND(5)ND(5)ND(10)ND(1) to5ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(10)to 151/180/180/180/180/180/183/160.800.52.31.641.4445ND(1)ND(5)ND(5)ND(5)ND(5)7150ND(1) to4ND(4)toND(52)ND(4) to7ND(4)to 18ND(4)to 14ND(4)to 33021 to 2,9004/120/121/132/132/139/1310/101.200003.299ND(11)ND(53)ND(53)ND(53)ND(53)ND(53)ND(110)ND(10)to 21ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)to 58ND(100)to 3701/180/180/180/180/181/186/142,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF10.300.40000000ND(1)ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(10)ND(1)to 170ND(3)toND(7)ND(3) to7ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(3)toND(7)ND(6)toND(14)7/180/181/180/180/180/180/180/180/180/186.200.50000.51.2003ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(5)ND(10)ND(1)to 31ND(4)toND(52)ND(4) to7ND(4)toND(52)ND(4)toND(52)ND(4)toND(52)ND(4) to6ND(4)to 10ND(4)toND(52)ND(9)to ND(100)9/120/131/130/130/130/131/132/130/130/132.3ND(11)ND(53)ND(53)ND(53)ND(53)ND(53)ND(53)ND(53)ND(53)ND(106)ND(10)to 23ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(50)toND(55)ND(104)to ND(110)2/180/180/180/180/180/180/180/180/180/18Total 2,3,7,8-CDDa2.7491.6103Total 2,3,7,8-CDFa10.78.42.3Total I-TEQDF1.5331.5(nondetect=0)a53.6Total I-TEQDF6.412.91.4(nondetect=1⁄2DL)a66.5Total TEQDF-WHO981.52.6(nondetect=0)aTotal TEQDF-WHO987.615.2(nondetect=1⁄2DL)aaSumofmeanvalues.DL=Detection limitND =Not detected(valuein parenthesis is thedetection limit)Source:Letter dated February10, 1997, fromW.Gillespie, National Council ofthePaper Industryfor Air and StreamImprovement, Inc., to G. Schweer, Versar, Inc.

### I n 1992, the pulp and paper industry conducte d its own NCASI

- coordinated survey of 2,3,7,8-TCDD and 2,3,7,8-TCDF emissions (NCASI , 1993)

. Ninety -four mills participated in the study , and NCASI assumed that the remainin g 10 (of 104) operated at the same levels as measured in the 1988 104 Mill Study

. All nondetect values were counted as one-half the DL

. I f
a DL was not reported, it was a ssumed to be 10 pg /L for effluent and 1 ng /kg for sludg e or bl eached pul p. The dat a used i n t h e report were provi ded by i ndi vi dual pul p and paper companies that had been requested by NCASI to g e nerate the data using the same protocols used in the 104 Mill Study

. I n 1993, as part of its efforts to develop revi sed effluent g u idelines and standards for the pulp, paper, and paperboard industry , EPA published the development document for the

g uidelines and standards being proposed for th is industry (U.S. EPA, 1993b). The development document presented estimates of the 2,3,7,8- TCDD and 2,3,7,8-TCDF annual discharg es in wastewater from the mills in this industry as of J a nuary 1, 1993. To estimate these discharg es, EPA used the most recent information about each mill from four databa ses (104 Mill Study , EPA
shor t- te r m monitor i ng studie s a t 13 mills, EPA long

- t e r m monitor i ng studie s a t e i g h t mills, a n d industry self-monitoring data submitted to EPA)

. The 104 Mill Study data were used for only those mills that did not report making any proce ss chang e s subsequent to the 104 Mill Study and did not submit any more recent effluent monitoring data. Gillespie (1994) and Gillespie (1995) reported the results of 1993 and 1994 updates, respectively , to the 1992 NCASI survey

. As in the 1992 survey , companies were requested to follow the same protocols for g e nerating data that were used in the 104 Mill Study

. Gillespie (1994, 1995) reported that fewer than 10% of mills had 2,3,7,8-TCDD and 2,3,7,8-TCDF
concentrations in effluent a bove the nominal DL s of 10 pg /L and 100 pg /L , respectively

. EPA
obtained similar results in its short- a nd long -term sampling for 18 mills; 2,3,7,8-TCDD was detected at four mills, and 2,3,7,8-TCDF was detected at nine mills (U.S. EPA, 1993b). Gillespie (1994) reporte d that wastewater sludg es at mo st mills (90%) contained less than 31 ng /kg of 2,3,7,8-TCDD and less than 100 ng /kg of 2,3,7,8-TCDF

. Gillesp ie (1995) reported that 90% of the mills had 2,3,7,8-TCDD and 2,3,7,8-TCDF concentrations in sludg e of less than 17 ng /kg and 76 ng /kg , respectively , in 1994. U.S. EPA (1993b) repor ted similar results but
found detectable levels of 2,3,7,8-TCDD and 2,3,7,8-TCDF in sludg es from 64% and 85%,

r e spe c tive l y , of the f a c ilitie s sa mple d. Gillespie (1994) reporte d that nearly 90% of the bleac hed pulps contained less than 2

ng /kg of 2,3,7,8-TCDD and less than 160 ng /kg of 2,3,7,8-TCDF

. Gillespie (1995) reported that 90% of the bleached pulps contained 1.5 ng /n g or less of 2,3,7,8-TCDD a nd 5.9 ng /kg or less of 2,3,7,8-TCDF

. The final levels in white paper products would co rrespond to levels in bleached pulp, so bleached paper products would also be ex pected to contain less than 2 ng /kg of 2,3,7,8­
TC DD.

8-6

### On April 15, 1998, EPA promulg a ted effluent limitation g uidelines and standards for certain seg m ents of the pulp, pa per, and paperboard industry (F ederal Reg i ster, 1998c). The industry seg m ents covered by th is rulemaking (i.e., the bleach ed paper-g rade kraft and soda subcateg ory and the paper-g rade sulfite subcateg ory ) are those seg m ents responsible for more than 90% of the bleached chemical pulp producti on in the United S t ates. For this rule, EP A updated the estimates of baseline loading s made in 1993 for the proposed rule by using more recent data collected by EP A, NCAS I (incl uding the 1994 NCAS I survey ), and individual facilities (U.S. EPA, 1997d). These revised estimates are presented in the last column in Table
8-3. EPA projects that, after full compliance w ith these rules, annual TEQ discharg es will be reduced to 5 g in effluent and 7 g in sludg e.

Table 8- 3. Sum m a r y of ble a c h e d c h e m ic al pulp and pape r m ill disc har g e s (g/yr) of 2,3,7,8-TCDD and 2,3,7,8-TCDF

Matrix C o ngener U.S. EP A 1988 a 

### NCASI 1992 b 

### U.S. EP A 1993 c 

### NCASI 1993 b 

### NCASI 1994 b 

### U.S. EP A 1995 d



### Effluent 2,3,7,8- T C DD 2,3,7,8- T C DF T E Q 201 1,550

356 22 99 32 71 341 105 19 76 27 14.6 49.0 19.5 16 120

28 Sludg e e 

### 2,3,7,8- T C DD 2,3,7,8- T C DF T E Q 210 1,320

343 33 118

45 - ­

- ­ 177 24 114

35 18.9 95.2 28.4 - ­

- ­ 50 Pulp 2,3,7,8- T C DD 2,3,7,8- T C DF T E Q 262 2,430

505 24 124

36 - ­

- ­ 149 22 106

33 16.2 78.8 24.1 - ­

- ­ 40

a Data f r om th e 104 Mill Stu d y (U.S. EP A , 1990e). T h e total dis c h a rg e rate of con g e n e r or T E Q (bas ed on ly on 2,3,7,8- T C DD an d 2,3,7,8- T C DF con cen tration s ) w a s s u m m e d acros s all 104 m ills

. b T h e t o t a l di s c h a rg e rat e of con g e n e r or T E Q (bas ed on l y on 2,3,7,8- T C D D an d 2,3,7,8- T C D F con cen t rat i o n s ) w a s

s u m m e d acros s all 104 m ills

. T h e daily dis c h a rg e rates reported in NC A S I (1993) an d Gilles p ie (1994, 1995) w e re

m

u ltiplied by a f actor of 350 day s /y r to obtain es tim ates of a nnua l d i sc ha r g e r a t e s. N C A S I 1992 s u rv ey (N C A S I, 1993), 1993 u pdate (Gilles p ie, 1994), an d 1994 u pdate (Gilles p ie, 1995).

c T h e di s c h a rg es i n ef f l u e n t an d s l u d g e w e re es t i m at ed i n U

. S

. EPA (1993b, 1997d) f o r Jan u a ry 1, 1993. T h e T EQ dis c h a rg e in pu lp w a s es tim ated by m u ltiply in g th e 1988 dis c h a rg e es tim ate by th e ratio of th e 1988 an d1993 ef

f l u e n t di s c h a rg e es t i m at es (i .e., t h e es t i m at e of t h e redu ct i o n i n 1988 di s c h a rg es ach i e v e d by pol l u t i o n prev en t i o n

m eas u res t a k e n by t h e i n du s t ry bet w een 1988 an d 1993).

d T h e di s c h a rg es i n ef f l u e n t an d s l u d g e w e re es t i m at ed i n U

. S

. EPA (1997d) f o r m i d- 1995. T h e T EQ di s c h a rg e i n pu lp w a s es tim ated by m u ltiply in g th e 1988 dis c h a rg e es tim ate by th e ratio of th e 1988 an d1995 ef f l u e n t dis c h a rg e

es t i m at es (i .e., t h e es t i m at e of t h e redu ct i o n i n 1988 di s c h a rg es ach i e v e d by pol l u t i o n prev en t i o n m eas u r es t a k e n by i n du s t ry bet w een 1988 an d 1995).

e A pprox i m at el y 20.5% of t h e s l u d g e g e n e rat e d i n 1990 w a s i n ci n e rat e d. T h e rem a i n i n g 79.5% w a s predom i n an t l y lan d f illed (5 6

. 5 % ) o r p l aced in su rf ace im p o u n d m e n t s (1 8

. 1 % ); 4

. 1 % w a s lan d

- a p p lied d i rectly o r as co m p o s t, an d 0.3% w a s di s t ri bu t e d or m a rk et ed (U .S . EPA
, 1993e).

NC A S I = Nation a l C o u n c il of th e P a per In du s t ry f o r A i r an d S t ream Im prov em en t, In c.

-- = N o i n fo r m a t i o n gi ve n



### 8-7

### 8.1.1. Estim a tes of National Em issions in 1987 and 1995 The U.S. annual discharg es of 2,3,7,8-TCDD and 2,3,7,8-TCDF are summariz e d in Table
8-3 for each of the six survey s discussed a bove. EPA release estima tes for 1988 (U.S. EPA, 1990e) and 1995 (U.S. EPA, 1997d) are believed to best represent e missions in reference y ears 1987 and 1995, respectively

. During the period between EPA’s 104 Mill Study and issuance of the development document (U.S. EPA, 1993b), the U.S. pulp and paper industry reduced releases
of

CDDs/CDF s, pr ima r ily by instituting nume r ous pr oc e ss c h a n g e s to r e duc e the f o r m a tion of CDDs/CDFs during the production of chemically bleached wood pulp. Details on the process chang e s implemented are provided in U.S. EP A (1993b) and Gillespie (1995). Much of the
reduction between 1988 and 1995 can be attributed to process chang e s for pollution prevention. The confidence rating s for these release estima tes are judg ed to be hig h because direct

me a sur e m e n ts we r e ma de a t vir t ua lly a ll f a c ilitie s, pr oviding a hig h le ve l of c onf ide n c e in both the production and the emission fact or estimates. The best estima tes of annual emissions in 1987 (i.e., the 1988 estimates presented in Table 8-3) are 356 g TEQ/y r for effluent and 343 g TEQ/y r for sludg e. The best estimate s of annual emissions in 1995 (i .e., the 1995 estimates presented in Table 8-3) are 28 g TEQ/y r for effluent and 50 g TEQ/y r for sludg e. The CDD/CDF content in bleached chemical wood pulp as a product is es timated to be approx ima tely 505 g TEQ and 40 g TEQ in 1987 and 1995, respectively

. Althoug h EPA provided an estimate of contaminant levels
of CDDs/CDF s in wood pulp, it is currently not known whether the diox in contamination in the product actually resulted in a release to the open and circulating environment.
I n 1990, the majority (75.5%) of the wastewat er sludg e g e nerated by these facilities was placed in landfills or in surface impoundments, with the remainder incine rated (20.5%), applied to land directly or as compost (4.1%), or di stributed as a commercia l product (less than 1%) (U.S. EPA, 1993e). Data on the disposition of wa stewater sludg es are av ailable only for y e ars 1988 throug h 1995. On the basis of these data, the best estimate of TEQ a pplied to land (i.e., not
incinerated or landfille d) is 14.1 g TEQ (4.1% of 343 g ) fo r 1987 and 2 g (4.1% of 50 g ) for
1995. These emission estimates are assig n ed a hig h level of confidence on the basis of the hig h

c onf ide n c e r a ting s g i ve n to both the a c tivity le ve l a nd the e mission f a c t or e stima te s.

8.1.2. Estim a tes of National Em issions in 2000
I n 2000, NCASI provided estimates of cong en er-specific CDD/CDF releases from the pulp and paper industry in effl uent, wastewater residuals, a nd pulp (Gillespie, 2002). Emission
factors were taken from “N CASI Handbook of Chemical Specific I nformation for SARA (Superfund Amendments and Reau thoriz ation Act) Section 313 F orm R Reporting .” Emission
f

a c t or s we r e c o mpile d f r o m va lid te st da ta supplie d to NCASI by a variet y of sources, including member companies that had performed the tests in response to a reg u latory prog ram. The mass

8-8

### throug hput parameter of total pulp production (31.9 million metr ic tons/y r) was provided by the
Ame r ic a n F o r e st a nd Pa pe r Assoc i a tion a nd inc l ude d da ta f

r o m 12 e l e m e n ta l c h lor i ne

- f r e e mills. The effluent flow from chemical pulp mills with aerated stabiliz ation basins (1,509 million

g a l/day ) and with activated sludg e treatment (660 million g a l/day ) was taken from the NCASI
da ta ba se a nd inc l ude d da ta f

r o m f i ve a e r a t e d sta b iliza tion ba sin mills a nd thr e e a c tiva t e d sludg e treatment mills. The primary waste treatment residuals fro m pulp mills (0.974 million dry metric tons/y r) and the combined, secondary , and dr edg e d waste treatment residuals from pulp mills (1.37 million dry metric tons/y r) we re also taken from the NCAS I database a nd included data from five mills for the primary residuals and da ta from three mills for the secondary residuals (Gillespie, 2002). Table 8-4 provides a breakdown of TEQ DF 

### -W HO 98 

### concentrations and emissions by

cong ener. Total TEQ DF



### WH O 98 

### concentrations were reported to be 0.49 pg /L , 1.76 ng /kg , and
0.02 pg /g for effluent, sludg e, and pulp, resp ectively

. CDD/CDF emission estimates were reported as 1.02 g TEQ DF



### WH O 98 

### /y r, 1.93 g TEQ DF



### WH O 98 

### /y r, and 0.582 g TEQ DF



### WH O 98 

### / y r for effluent, sludg e, and pulp, respectively

. F i fty

- one percent of the sludg e g e nerated in 2000 was sent to landfills or lag oons. I t is uncertain how much of the remaining 49% of the sludg e was applied to land. However, a
conservative estimate can be de veloped by apply i ng the 4.1% used to develop the 1987 and 1995
estimates. I n this case, 0.08 g TEQ DF



### WH O 98 

### /y r of sludg e is e stima te d to ha ve be e n a pplie d to
land in 2000. These estimates are assig n ed a hig h confidence rating because they are based on recent industry survey data; however, EP A is wo rking with NCAS I to develop a QA/QC protocol
to monitor the da ta be ing c o lle c t e d

.

8.2. MANUF ACTURE OF CHLORINE, CH LORINE DERIVATIVES, AND METAL CHL O RIDE S Testing of CDD/CDF emissions to air, land, or water from U.S. manufacturers of

c h lor i ne , c h lor i ne de r i va tive s, a nd me ta l c h lor i de s on whic h to ba se e stima te s of na tiona l emissions has not been reported. Sa mpling of g r a phite e l e c tr ode sludg es from European chlorine

ma nuf a c t ur e r s indic a t e s hig h le ve ls of CDF s. L imite d sa mpling of c h lor i ne de r i va tive s a nd me ta l chlorides in Europe indicates low-le vel contamination in some products.

8.2.1. Manuf acture of Chlorine Chlorine g a s is produced by electroly sis of brine electroly tic cells. Until the late 1970s, the primary ty pe of electroly tic process used in the chlor-alkali industry to produce chlorine consisted of the use of mercury ce lls containing g r aphite electrode s. As shown in Table 8-5, hig h
levels of CDF s have been found in several samples of g r aphite electrode sludg e from facilities in

8-9

### T a b l e 8-4. CDD/CDF T E Q con cen tration s an d em ission s f o r th e p a p er an d pulp indust r y by sour c e

C ongener Ef f l uent Waste treatmen t residuals not lagooned or lan d f illed (slu d g e) (49% n o t lan d f illed ) Pu lp TEQ

conc. a 

### (p g/L ) TEQ emissions

(ng/yr) TEQ

conc. a 

### (ng/kg) TEQ emissions

(ng/yr) TEQ

conc. a 

### ( p g/ g pul p) TEQ emissions

(ng/yr)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD 1,2,3,4,6,7,8,9- OCDD 0
0.00e+00
0.00e+00
1.30e



### ! 01
9.00e



### ! 02
7.00e



### ! 02
7.37e



### ! 02 0.00e+00
0.00e+00
0.00e+00
2.71e+08
1.88e+08
1.46e+08
1.54e+08 4.00e



### ! 01
5.00e



### ! 02
1.00e



### ! 02
8.00e



### ! 02
9.00e



### ! 02
1.82e



### ! 01
2.80e



### ! 01 4.63e+08
6.24e+07
1.25e+07
8.53e+07
9.05e+07
1.97e+08
2.81e+08 1.00e



### ! 02
0.00e+00
0.00e+00
0.00e+00
0.00e+00
3.00e



### ! 03
3.04e



### ! 03 2.90e+08
0.00e+00
0.00e+00
0.00e+00
0.00e+00
8.69e+07
8.80e+07 2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF 1,2,3,4,6,7,8,9- OCDF 1.00e



### ! 01
0.00e+00
0.00e+00
0.00e+00
0.00e+00
0.00e+00
0.00e+00
1.90e



### ! 02
5.00e



### ! 03
2.00e



### ! 03 2.08e+08
0.00e+00
0.00e+00
0.00e+00
0.00e+00
0.00e+00
0.00e+00
3.96e+07
1.04e+07
4.17e+06 4.00e



### ! 01
1.00e



### ! 02
1.00e



### ! 01
4.00e



### ! 02
1.00e



### ! 02
5.00e



### ! 02
0.00e+00
1.70e



### ! 02
0.00e+00
3.70e



### ! 03 4.66e+08
1.25e+07
1.25e+08
4.63e+07
1.25e+07
5.15e+07
0.00e+00
1.83e+07
0.00e+00
3.93e+06 1.00e



### ! 03
0.00e+00
0.00e+00
0.00e+00
0.00e+00
2.00e



### ! 03
0.00e+00
1.00e



### ! 03
0.00e+00
6.00e



### ! 05 2.90e+07
0.00e+00
0.00e+00
0.00e+00
0.00e+00 5.79e+07
0.00e+00
2.90e+07
0.00e+00
1.74e+06
TE Q DF 

### -W H O 98 

### 0.49 1.02e+09 1.76 0.02 5.83e+08
Residuals total
R esiduals not landfilled 1.93e+09
9.44e+08

a T E Q con cen tration s are in T E Q DF -W H O 98 .

Sou r ce: Gilles p ie (2002).



### Europe. The CDF s predominate in these sludg es, and the 2,3,7,8-substituted cong eners account for a larg e fraction of the respective cong en er totals (Rappe et al., 1990a, 1991; Rappe, 1993; Strandell et al., 1994). During the 1980s, titani um metal anodes were developed to replace

g r aphite electrodes (U.S. EPA, 1982b; Curlin and B ommaraju, 1991). Cu rrently , no U.S. facility is believed to use g r aphite el ectrodes in the production of chlo rine g a s (telephone conversation
between L . Phillips, Versar, I nc., and T. F i eldi ng , U.S. EPA, Office of W a ter, F e bruary 1993).

8-10

### T a b l e 8-5. CDD/CDF con cen tration s (μ g/k g ) in grap h i te electrod e slu d g e fr om c h lor ine pr oduc t ion

C o ngener/congener group S ludge 1 S l udge 2 S l udge 3 S l udge 4
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF ND (0.006) ND (0.007) ND (0.018) ND (0.012) ND (0.016) 0.095 0.92 26 25 12 32

7 1.3 0.87 9.1 8.1 31 ND (0.009) ND (0.009) ND (0.026) ND (0.016) ND (0.022) 0.21 2 56 55 25 71 16

2.8 1.9 19 19 76 ND (0.009) ND (0.009) ND (0.029) ND (0.019) ND (0.025) 0.25 2.2 57 56 24 73 15

2.6 2 19 20 71 ND ND (0.033) ND (0.49) ND (0.053) ND (1.2) 0.055 0.65 52 55 27 44 12

1.7 1.3 15 14 81

T o tal 2,3,7,8- CDD a 

### T o tal 2,3,7,8- CDF a 

### Total I

- T E Q DF a 

### Total TE Q DF 

### -W H O 98 a 

### 1.02 152.37

14.2 14.1 2.21 341.7

30.5 30.4 2.45 339.6

30.2 30.2 0.7 303

27.7 27.6

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F ND (0.006) ND (0.070) ND (0.046) 0.22 0.92 64 75 68 24 31 ND (0.009) ND (0.009) ND (0.064) 0.48 2 150 240 140

53 76 ND (0.009) ND (0.009) ND (0.074) 0.56 2.2 140 240 140

54 71 -­

-­

-­

-­ 0.65

-­

-­

-­

-­ 81

Total C D D / C D F a 

### 263.14 661.48 647.76

- ­

a C alcu l ated as s u m i n g n o n d etect v alu es w ere zero.

ND = No t d e tected (v alu e in p a ren t h e sis is th e rep o r ted d e tectio n lim it)

-- = N o i n fo r m a t i o n gi ve n

S o u rces : R a ppe et al . (1991); R a ppe (1993).



### Althoug h the orig in of the CDF s in g r aphite electrode sludg e is uncertain, chlorination of the cy clic aromatic hy drocarbons (such as dibenz ofuran) present in the coal tar used as a binding

ag ent in the g r aphite electrodes has been propos ed as the primary source (Strandell et al., 1994).

8-11

### F o r this reason, sludg es produced using metal el ectrodes were not ex pected to contain CDF s

. Howe ve r , r e sults of a n a n a l y sis of me ta l e l e c t r ode sludg e f r o m a f

a c ility in Swe d e n, a n a l y z e d a s part of the Swedish Diox in Survey , showed th at the sludg e contained hig h levels of CDF s (similar to those of the g r aphite sludg e) and primarily nondetectable levels of CDDs (Strandell et al., 1994). The sludg e showed the same ty pe of CDF cong ener pattern re ported by Rappe et al. (1991) and Rappe (1993). Stra ndell et al. sug g e sted that chlorination of poly a romatic hy drocarbons present in the rubber lining s of the electroly tic cell may have produced the CDF s found in the one sample analy z ed. Althoug h EPA does not reg ulate CDDs/CDF s specifically , it issued restrictions under
RCRA on the la nd disposa l of w a ste w a t e r a nd sludg e s g e ne r a te d by c h lor i ne ma nuf a c tur e r s tha t use the mercury cell process and the diaphrag m process (with g r a phite electrodes) (waste codes K071, K073, and K106) (40 CF R 268).
The Chlorine Che mistry Counc il (CCC), a tr a de a ssoc i a tion re pre s e nting ma nufa c t ure r s
t h at produce and/ or use chl o ri ne, sam p l e d t h e t r eat ed wast ewat er di scharg es t o surface wat e rs at

se ve n c h lor-a lka li fa c ilitie s in the U.S. (CCC, 2004)

. The re sults of this study a r e pre se nte d in
Table 8-6. The measurements are intended to re present wastewater discharg es in both 2000 and
1995. As indicated in Table 8-6, 1.79 g TEQ DF 

### -W HO 98 

### (1.81 g I

- TEQ) were released to water
from chlor-alkali facilities in 2000 and 1995. The emission estimates for 2000 and 1995 are
assi g n ed a hi g h confi d ence rat i n g , because t h ey were deri ved from t h e t e st i n g of chl o r-al k al i
f

a c ility tr e a t e d wa ste w a t e r

. The CCC re porte d on a i r e missions from two c hlor-a lka li produc tion fa c ilitie s in 2000 (CCC, 2004). Ta ble 8-7 summa rize s the CDD/CDF c ong e ne r-spe c i fic a nd TEQ a nnua l re le a se s to air from the Dow Chemical chlor-alkali facility in Midland, MI , and th e PPG I ndustries facility in Natrium, W V

. Total releases to air in 2000 were 0.08 g TEQ DF 

### -W HO 98 

### (0.08 g I

- TEQ). There are no data showing air releases from chlor-alkali facilities in 1995 and 1987. A hig h confidence rating is to assig n ed the estimate for 2000 because it is based on actual measurements
of

c h lor

- a lka li f a c ilitie s.

8.2.2. Manuf acture of Chlorine D erivatives and Metal Chlorides The limited sampling of chlorine-d erivative products indicates th at they contain very low, if any

, concentrations of CDDs /CDFs. Rappe et al. (1990b) anal y z ed a sample of chlorine bleach consisting of 4.4% sodium hy pochlorite. Most of the 2,3,7,8- substituted CDD/CDF cong eners were below the limits of detec tion (0.3 to 7 pg /L for all cong eners ex cept OCDD and OCDF

, which were 12 and 20 pg /L , respectively )

. No 2,3,7,8-substituted CDDs were detected. Tetra-, penta-, and hex a -CDF s were det ected at levels of 13 pg /L or lower. The TEQ content of the sample was 4.9 pg I

- TEQ DF 

### /L

. Hutz ing e r and F i edler (1991b) reported finding no CDDs/CDF s at

8-12

### Table 8- 6. R e le ase s of dioxin- like c o m p ounds in wast e w at e r disc har g e s fr om

c h lor

- alkali and m ixe d c h e m ic al m a nufac t u r ing fac ilit ie s to su rf ace w a ter i n ref eren ce years 2000 an d 1995

PPG

Con g en er Occi dent al Chem i c al Corporat i o n I ndus t r i e s

To ta l B a t t l e g r o und, TX Deer Pa r k , TX Delaw a re City , DE H a h n v ille , LA M o b ile , AL Mu s c l e S h oal s,

AL Natriu m , WV
2,3,7,8 T C D D 0.00 0.02 0. 00 0.00 0.00 0.00 0.00 0.02
1,2,3,7,8 P e CD D 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00
1,2,3,4,7,8 H x CD D 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00
1,2,3,6,7,8 H x CD D 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00
1,2,3,7,8,9 H x CD D 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00 0 .00
1,2,3,4,6,7,8 H p CD D 0 .00 0 .08 0 .00 0 .01 0 .00 0 .00 0 .22 0 .31

O C D D 0.48 21.50 4.09e

! 03 0.10 1.15e

! 03 1.13e

! 09 3.13 25.22
2,3,7,8 T C D F 0.00 0.63 1.02e

! 03 0.19 2.88e

! 04 3.94e

! 08 0.06 0.89
1,2,3,7,8 P e C D F 0 .00 1 .20 0 .00 0 .90 0 .00 1 .33e

! 07 0.06 2.16
2,3,4,7,8 P e C D F 0 .00 0 .21 0 .00 0 .85 0 .00 7 .99e

! 08 0.33 1.39
1,2,3,4,7,8 H x C D F 0 .00 2 .11 0 .00 2 .96 0 .00 1 .85e

! 07 0.11 5.18
1,2,3,6,7,8 H x C D F 0 .00 0 .38 0 .00 1 .18 0 .00 9 .76e

! 08 0.00 1.56
1,2,3,7,8,9 H x C D F 0 .00 2 .03e

! 03 0.00 0.63 0.00 2.29e

! 08 0.00 0.63
2,3,4,6,7,8 H x C D F 0 .00 0 .00 0 .00 0 .60 0 .00 3 .28e

! 08 0.00 0.60
1,2,3,4,6,7,8 H p C D F 0 .00 0 .59 2 .31e

! 03 4.47 6.49e

! 04 1.32e

! 07 0.15 5.22
1,2,3,4,7,8,9 H p C D F 0 .00 5 .66e

! 03 0.00 0.69 0.00 6.30e

! 08 0.00 0.69

O C D F 0.00 4.88 0.00 1.75 0.00 1.34e

! 07 0.66 7.29

T o ta l I

- T EQ 4.83e

! 04 0.53 1.29e

! 04 1.08 3.64e

! 05 8.65e

! 08 0.19 1.80

T o ta l T EQ DF -W HO 98 4.83e

! 05 0.51 1.26e

! 04 1.08 3.54e

! 05 8.63e

! 08 0.19 1.59

So ur c e : CCC ( 2004).



### a DL of 4 μg /kg in chlorine g a s or in sa mples of 10% sodium hy pochlorite, 13% sodium hy pochlorite, and 31 to 33% hy drochloric acid at a DL of 1 μg /kg

. Hutz ing e r and F i edler (1991b) reported the re sults of analy s es of samples of ferric

tr ic hlor ide ( F e C l 3 

### ), aluminum trichloride (AlCl 3 

### ), copper chloride (CuCl 2 

### ), cuprous chloride ( C uCl) , silic on te tr a c h lor i de ( S iCl 4 

### )
, a nd tita nium te tr a c h lor i de ( T iCl 4 

### ) for t h ei r HpC DF, OC DF, HpCDD, and OCDD content. The sample of F e Cl 3 

### contained HpCDF and OCDF in the low microg r ams per kilog r am rang e, but no HpCDD or OCDD was detected at a DL of 0.02 μg /kg

. One of the two sa mple s of AlCl 3 

### anal y z ed al so cont ai ned a l o w (μg / kg ) concentration of OCDF

. The sa mple s of CuCl 2 

### and CuCl contained concentrations of HpCDF

, OCDF , and OCDD of less than 1 μg /kg

. The results are presented in Table 8-8.

8-13

### Table 8- 7. C o nge n e r - spe c ific and TEQ annual r e le a se s t o air ( g /yr ) fr om

c h lor

- alkali and m ixe d c h e m ic al pr oduc t ion fac ilit ie s in 2000

C ongener Dow Che m i c al Co. Mi dl and, MI P P G Indust r i e s Natrium, WV
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD
OCDD 0.027
0.004
0.008
0.000
0.003
0.020
0.086 0.003
0.000
0.000
0.002
0.002
0.087
0.208 2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDD 1,2,3,4,7,8,9- HpCDD
OCDF 0.023
0.009
0.008
0.066
0.000
0.002
0.009
0.148
0.028
0.225 0.044
0.003
0.030
0.044
0.006
0.006
0.022
0.142
0.039
0.064
Total I

- T E Q DF 

### 0.047 0.034
Total TE Q DF 

### -W H O 98 

### 0.049 0.033

Sour c e : C h lor i ne C h e m is tr y C ounc il ( 2004)

.



### 8.3. MANUF ACTURE OF HALOG E NATED ORG ANIC CHEMICALS Several chemical production processes g e nerate CDDs /CDF s (Versar, I n c., 1985;
Hutz ing e r and F i edler, 1991b). CDDs/CDF s can be formed during the manufacture of chlorophenols, chlorobenz enes, and chlor obipheny ls (Versar, 1985; Ree et al., 1988). Consequently , disposal of industrial wastes from manufact uring facilities producing these compounds may result in the release of CDDs/C DF s to the environment. Also, the products themselves may contain these compounds, and thei r use or consumption ma y result in additional
rel eases t o t h e envi ronm ent

. CDD/CDF cong ener distribution patterns i ndicative of noncombustion sources have been observed in sediments in southwest Germany a nd t h e Net h erl a nds. Accordi n g t o R ee et al

. (1988), the cong ener patterns found sug g e st that wastes from the production of chlorinated

org a nic compounds may be importa nt historical sources of C DD/CDF contamination in these

8-14

### T a b l e 8-8. CDD/CDF con cen tration s (μ g/ k g ) i n m e tal ch l o ri d e s

C o ngener group F eC l 3 

### Al Cl 3 a 

### Al Cl 3 a 

### CuCl 2 

### CuCl Ti Cl 4 

### Si Cl 4 

### Total TC D D

-­ -­ -­ -­ -­ -­ -­ Total P e C D D

-­ -­ -­ -­ -­ -­ -­ Total H x C D D

-­ -­ -­ -­ -­ -­ -­ Total H p C D D ND ND ND 0.03 ND ND ND Total O C D D ND ND 0.1 0.60 0.03 ND ND

Total TC D F

-­ -­ -­ -­ -­ -­ -­ Total P e C D F

-­ -­ -­ -­ -­ -­ -­ Total H x C D F

-­ -­ -­ -­ -­ -­ -­ Total H p C D F 12 ND ND 0.10 0.08 ND ND Total O C D F 42 ND 34.0 0.50 0.20 ND ND

a Al C l 3 w a s tested tw ice.

ND = No t d e tected ; d e tectio n lim it o f 0

. 0 2 μg /k g

-- = N o i n fo r m a t i o n gi ve n

S o u rce: H u t z i n g e r an d F i edl e r (1991b).



### reg i ons. The production and use of many of th e chlorophenols, chlorophenox y herbicides, and
PCB products are now banned or st rictly reg ulated in most count ries. However, these products

may have been a source of the environmental c ontamination that occurred prior to the 1970s and

may continue to be a source of environmental releases unde r certain limited use and disposal conditions (Rappe, 1992b).

8.3.1. Chlorophenols Chlorophenols have been widely used for a vari ety of pesticidal applications. The hig herchlorinated phenols (tetrachlor ophenol and pentachlorophenol [ P CP] ) and their sodium salts have been used primarily for wood preservation. The lower-chlor inated phenols have been used primarily as chemical intermed iates in the manufacture of othe r pesticides. F o r ex ample, 2,4­ dichlorophenol is used to produce the herbicid es 2,4-dichlorophenox y acetic acid (2,4-D), 4-(2,4­ dichlorophenox y ) butanoic acid (2,4-DB ), 2-( 2,4-dichlorophenox y )-propanoic acid (2,4-DP), Nitrophen, Genite, and Z y tron a nd 2,4,5-trichlorophenol was used to produce hex achlorophene, 2,4,5-T, Silvex , Erbon, Ronnel, and Gardona (G ilman et al., 1988; Hutz ing e r and F i edler, 1991b). (Sections 8.3.7 and 8.3.8 contain informa tion on EPA actions to control CDD/CDF contamination of pestic ides, including PCP and its salts, and to obtain additional data on
CDD/CDF c onta mina ti on of pesticides.)

8-15

### The two major commercial methods used to produce chlorophenols are (1) electrophilic chlorination of molten phenol by chlorine g a s in the presence of cataly tic amounts of a metal

c h lor i de a nd or g a nic c h lor i na tion pr omote r s a nd sta b ilize r s, a nd ( 2 ) a l ka line hy dr oly sis of
chlorobenz enes under heat and pressure using a queous methanolic sodium hy drox ide. Other manufacturing methods include conve rsion of diaz onium salts of va rious chlorinated anilines and chlorination of phenolsulfonic acids and benz enesulfonic acids, followed by the removal of the sulfonic acid g r oup (Gilman et al., 1988; Hutz ing e r and F i edler, 1991b).
B ecause of the manufacturing processes employ ed, commercial chlorophenol products can contain appreciable amounts of impuritie s (Gilman et al., 1988). During the direct chlorination of phenol, CDDs/CDF s can form eith er by the condensation of tri-, tetra-, and pentachlorophenols or by the c ondensation of chlorophenols w ith hex achlorocy clohex a dienone (which forms from ex cessive chlorination of phenol). During alkaline hy droly s is of
chlorobenz enes, CDDs/CDF s can form throug h chlorophenate condens ation (Ree et al., 1988; Gilman et al., 1988; Hutz ing e r and F i edler, 1991b).
The limited information on CDD/CDF concentra tions in chlorophenols published in the 1970s and early 1980s was compiled by Versar, I n c. (1985) and Hutz ing e r and F i edler (1991b). The results of several major studi es cited by these reviewers (F ir estone et al., 1972; Rappe et al., 1978a, b) are presented in Table 8-9. Ty pically , CDDs/CDF s were not de tected in mono- and dichlorophenols but were re ported in tri- and tetr achlorophenols. More recent results of testing of 2,4-dichlorophenol, performed in response to the Tox i c Substances Control Act (TSCA)
diox in/furan test rule, showed no detectable concentrations of 2,3,7,8-s ubstituted tetra- throug h hepta-CDD/CDF s

. Other than a study by Hag e nmaier ( 1986), which reported finding 2,3,7,8-TCDD at a concentration of 0.3 μ g /kg in a sample of 2,3,4,5-tetrachlorophenol, no more recent data on
concentrations of CDDs and CDF s could be found in the lite rature for the mono- throug h tetrachlorophenols. Tables 8-10 and 8-11 present summaries of several studies that reported
CDD/CDF concentrations in PCP and in PCP-Na products , respectively

. Many of these studies do not report cong ener-specific concentrations , and many are based on products obtained from
non-U.S. sources.

8.3.1.1. Regulatory Actions for Chlorophenols Section 8.3.8 of this report desc ribes reg ulatory actions ta ken by EPA to control the manufacture and use of chlorophenol-based pestic ides. I n the mid-1980s, EPA’s Office of Solid
Wa ste (OSW) promulg a te d, unde r RCRA, la nd disposa l re stric tions on wa ste s (wa s te wa te rs a nd nonwastewaters) resulting from the manufacture of chlorophenols (40 CF R 268). Table 8-12
lists all wastes in which CDDs/CDF s are specifically reg u lated by EPA as haz a rdous

8-16Table 8-9.CDD/CDFconcentrations(mg/kg) inmono- throughtetrachlorophenols



### 8-17Congener/congenergroup2-CPa2,4-DCPa2,6-DCPa2,4,5-TrCP(Na salt)a2,4,5-TrCPa2,4,6-TrCPa2,4,6-TrCP(Na salt)b2,3,4,6-TeCPa2,3,4,6-TeCP(Na salt)bTotal TCDDND (0.02)ND (0.02)ND (0.02)ND(0.02) to14ND(0.02) to6.5ND(0.02) to49<0.02ND (0.02)0.7Total PeCDDND (0.02)ND (0.02)ND (0.02)ND (0.02)ND(0.02) to1.5ND (0.02)<0.03ND (0.02)5.2Total HxCDDND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)<0.03ND(0.02) to159.5Total HpCDDND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)<0.1ND(0.02) to5.15.6Total OCDDND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)<0.1ND(0.02) to0.170.7Total TCDF+NDNDNDND+1.5+0.5Total PeCDFNDNDNDNDND+17.5+10Total HxCDFNDNDNDNDND+36+70Total HpCDFNDNDNDNDNDND4.8+70Total OCDFNDNDNDNDNDND-­+10TOTAL-­-­-­-­-­-­-­-­-­aSource:Firestone et al. (1972); becauseofpoor recoveries, theauthorsstated that actual CDD/CDFlevelsmayhave beenconsiderablyhigher thanthosereported.bSources:Rappe etal. (1978a, b);commonScandinaviancommercialchlorophenols.ND = Not detected(valueinparenthesis is the detectionlimit, ifreported)+= Detectedbut not quantified-- =Noinformation givenTable 8-10.CDD/CDFconcentrations(historical andcurrent) (μg/kg) intechnical-grade pentachlorophenol(PCP) products



### 8-18Congener/congener group1973a1978b1979c1984d1985e1986e1987f1987g1985–88h1991i1988–99e1988–99jUnknownk2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­ND (10)ND (10)-­2,200100100,000610,000ND(0.05)ND (1)62,56544210,0001,475,000ND(0.05)ND (1)81,53228106,000930,000ND(0.03)1ND (1)8312878,000733,000ND (0.05)2ND (1)1,4805399,900790,000ND(0.05)ND (1)86001389,0002,723,000NDND-­-­-­-­1,100,000--------------ND(0.5)-­-­-­-­-­-­ND (10)ND (10)ND (10)8602036,400296,8102,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­130,000-­-­-­-­-­-­-­-­-­-­ND (10)-­-­-­-­-­-­-­-­130,000ND(0.5)ND (1)ND (1)4955ND (1)34,0004,100222,000ND(0.5)ND (1)ND (1)344ND (1)ND (1)29,0006,200233,000ND(0.1)0.51.5125ND (1)32ND (1)11,280637118,000ND (0.1)0.20.9163ND (1)146ND (1)19,940980137,000ND(0.5)ND (1)ND (1)672ND (1)ND (1)22,0003,400237,000NDNDND-­-­-­-­-­-­170,000---------------------­-­-­-­-­-­-­-­-­-­ND (10)ND (10)ND (10)200ND (20)ND (20)ND (20)2,00014019,940Total2,3,7,8-CDD1Total2,3,7,8-CDF1Total I-TEQDF1Total TEQDF-WHO981-­-­-­-­-­-­-­-­-­-­-­-­712,300130,0001,9701,687,615260,1594,4451,037,568268,2382,7351,689811,860130,0761,8531,088891,435158,2302,3211,4882,812,621262,4694,1731,5091,100,000170,000$1,270>127-­-­-­-­-­-­-­-­334,09022,280810525Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDFND(20)ND(30)5,50098,000220,0004025022,000150,000160,000-­-­-­-­-­9004,00032,000120,000130,000-­-­10,100296,0001,386,000-­1,4009,90088,00043,0001,304ND (10)ND (10)4,500135,000610,000ND (10)-­-­62,000130,0002,918NDND4,694283,0001,475,0006101,982125,000222,000NDND2,925134,000930,000ND31,407146,000233,0001.96.51,700154,000733,0000.81414,30074,000118,0000.415.23,300198,000790,0000.434313,900127,000137,000NDND912117,0002,723,000ND2001,48699,000237,000ND (10)ND (10)8,900130,0001,100,000ND (10)ND (10)14,00036,000170,000ND (1)ND(10)1,44055,560-­ND(10)ND(10)3,07036,530-­ND31,49048,430191,7004852013,65076,090136,310-­-­-­-­-­-­-­-­-­-­Total CDD/CDFl655,790286,9001,834,400941,5002,111,6921,447,3351,085,1501,269,5593,178,5981,458,900960,000468,241-­aSource:Buser and Bosshardt (1976); meanof10 samplesof“high” CDD/CDF-content PCPreceived fromSwisscommercial sourcesin1973.bSource:Rappe etal. (1978b);sampleofU.S.origin, “presumablyprepared byalkaline hydrolysisofhexachlorobenzene.”cSource:U.S.DepartmentofHealthand HumanServices(1989);compositeoftechnical-grade materialsproduced in1979 byMonsanto Industrial Chemical Co.(St.Louis,MO),ReichholdChemicals,Inc.(WhitePlains,NY),andVulcanMaterials Co.(Birmingham,AL).Table 8-10.CDD/CDFconcentrations(historical andcurrent) intechnical-grade pentachlorophenol (PCP)products(μg/kg)(continued)dSource:Cull et al. (1984); meanoffour“recent” productionbatchesfromeachoftwo manufacturersoftechnical PCPusingthree differentanalytical methods;ANOVAshowednostatisticallysignificant difference inCDD/CDF concentrationsbetweenthe eightsamples (samples obtainedintheUnited Kingdom).eSource:Letter dated February7, 1997, fromJohnWilkinson,PentachlorophenolTaskForce, toMatthewLorber, U.S.EPA;averageofmonthlybatch samplesfor the period January1987 toAugust1996.fSource:HagenmaierandBrunner(1987);sampleofWitophenP (DynamitNobel-Lotno. 7777) (obtained inGermany).gSource:HagenmaierandBrunner(1987);sampleofPCP produced byRhone Poulenc (obtained inGermany).hSource:Letter dated February7, 1997, fromJohnWilkinson,PentachlorophenolTaskForce, toMatthewLorber, U.S.EPA;samplesof“penta” manufactured in1985, 1986, and 1988.iSource:Harrad etal. (1991);PCP-based herbicide formulationfromthe NewYorkState DepartmentofEnvironmentalConservation.jSource:Letter dated March5, 1997, fromThomasMitchell,KMG-Bernuth,toMatthewLorber, U.S.EPA;average ofmonthlybatchsamplesfor the periodFebruary1987 to December 1996 (excludingthe followingmonths, forwhichdata were not available:February1993, January1992, December 1991,September 1991, December1988, and September 1988).kSource:Schecter etal. (1997);samplefoundstored ina barninVermont.lCalculated assumingnondetectswere zero.ND = Not detected(valueinparenthesis is the detectionlimit)-- =Noinformation given



### 8-19

### Table 8-11. Historical CDD/CDF concentrat ions (μg/kg) in pe ntachlorophenol-Na (P CP -Na)

Con g en er/ con g en er gr o u p 1969 a 1973 b 1973 c 1987 d 1987 e 1992 f 1980s g
2,3,7,8- T C D D 1,2,3,7,8- P e C D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD -­

-­

-­

-­

-­

-­ 3,600 -­

-­

-­

-­

-­

-­

-­ -­

-­

-­

-­

-­

-­

-­ 0.23 18.2 28.3 2,034

282 9,100 41,600 0.51 3.2 13.3 53 19 3,800 32,400 0.076 18.7 96 4,410

328 175,400 879,000 ND (1

. 4 ) 28.3 ND (6

. 1 ) 4,050 ND (1

. 4 ) 33,800 81,000 2,3,7,8- T C D F 1,2,3,7,8- P e C D F 2,3,4,7,8- P e C D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF -­

-­

-­

-­

-­

-­

-­

-­

-­

-­ -­

-­

-­

-­

-­

-­

-­

-­

-­

-­ -­

-­

-­

-­

-­

-­

-­

-­

-­

-­ 1.8 8.2 6.6 48 69 ND (1 ) 87 699 675 37,200 0.79 1.9 1.1 4.6 1.3 1.3 4.6 197 36 4,250 ND (1 ) ND (4 ) ND (4 ) 27.6 21.9

9.8 103 9,650 2,080 114,600 149 319 324 ND (2

. 8 )

225 480 N D ( 385) 6,190

154 36,000

T o ta l 2,3,7,8- C D D h

-­ -­ -­ 53,062.7 36,289 1,059,252.8 118,878.3 T o ta l 2,3,7,8- C D F h

-­ -­ -­ 38,794.6 4,498.6 126,492.3 43,841 T o ta l I-T EQ DF h

-­ -­ -­ 452 89.5 3,374 1,201 T o ta l T EQ DF -W HO 98 h

-­ -­ -­ 390 58.1 2,489 1,110

T o ta l T C DD T o ta l P e CDD T o ta l Hx CDD T o ta l HpCDD T o ta l OCDD T o ta l T C DF T o ta l P e CDF T o ta l Hx CDF T o ta l HpCDF T o ta l OCDF -­

-­ 17,000 9,600 3,600

-­

-­

-­

-­

-­ 140 40 140 1,600 4,000 ND (2 0 ) 60 1,400 4,300 4,300 50 ND (3 0 )

3,400 38,000 110,000 ND (2 0 ) 40 11,000 47,000 26,500 27 213 3,900 18,500 41,600 82 137 3,000 13,200 37,200 52 31 230 5,800 32,400 12 27 90 860 4,250 3.6 142.7 9,694 260,200 879,000 10.1 88.4 9,082.3 75,930 114,600 1.9 140 14,000 100,000

81,000

1,200 6,400 49,000 91,000 36,000

T o ta l CDD/CDF h 30,200 15,980 235,990 117,859 43,752 1,348,751 378,742

a S o u rce: F i res t on e et al . (1972); m ean of t w o s a m p l e s of PC P- N a obt ai n e d i n t h e U n i t e d S t at es bet w een 1967 an d 1969.

b S o u r ce: Bu s e r an d Bos s h ardt (1976); m ean of f

i v e s a m p les of “ l ow ” C DD/C D F

- con t en t P C P

- Na receiv e d f r om Sw iss co m m e rcial so u r ces.

c S o u r ce: Bu s e r an d Bos s h ardt (1976); s a m p le of “ h i g h ” C DD/C D F

- con t en t P C P

- Na receiv ed f r om a S w is s

com m ercial s o u r ce. d So ur c e : H a ge nm a i e r a n d B r unne r ( 1987); s a m p l e of D o w i ci de- G pu rch a s e d f rom F l u k a ; s a m p l e obt ai n e d i n Germ an y

.
e So ur c e : H a ge nm a i e r a n d B r unne r ( 1987); s a m p l e of Prev en t o l PN (Bay er A G ); s a m p l e obt ai n e d i n G e rm an y

. f S o u rce: S a n t l et al . (1994); 1992 s a m p l e of PC P- N a f rom Prol abo, F ran ce.
g Sou r ce: P a lm er et al. (1988); s a m p le of a P C P

- Na f o rm u l ation collected f r om a clos ed s aw m ill in C alif orn i a in th e l a t e 1980s

. h C alcu l ated as s u m i n g n o n d etect v alu es w ere zero.

ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)

-- = N o i n fo r m a t i o n gi ve n



### 8-20

### Table 8-12. Sum m ary of specif i c dioxin- containing w astes that m u st com p ly

w i th land disposal restrictions a



### EP A haz a rdous

wa s t e

num ber Wast e descri pt i on Land di sposal restriction ef

f ective date Regulated

wa s t e constituent
F020 Wastes (except w astew ater and spent carbon from HCl purification) from the production or

m anufacturing use (as a reactant, chem ical interm ediate, or com ponent in a form ulating process) of tri- or tetrachlorophenol or of interm ediates used to produce their pesticide deriv ativ es. (T his listing does not include wastes from the produc tion of hexachlorophene from hig h ly purified 2,4,5- trichlorophenol.) Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

F021 Wastes (except w astew ater and spent carbon from HCl purification) from the production or

m anufacturing use (as a reactant, chem ical interm ediate, or com ponent in a form ulating process) of pent achlorophenol or of interm ediates used to produce its deriv a tiv es. Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs
F022 Wastes (except w astew ater and spent carbon from HCl purification) from the m anufacturing use (as a reactant, chem ical interm ediate, or

com ponent in a form ulating process) of tetra-

, penta- , or hexachlorobenz enes under alk aline conditions. Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs
F023 Wastes (except w astew ater and spent carbon from HCl purification) from the production of

m aterials on equipm ent prev iously used for the production or m anufacturing use (as a reactant, chem ical interm ediate, or com ponent in a form ulating process) of tri- and tetrachlorophenols. (T his listing does not include wastes from equipm ent used only for the production or use of hexachlorophene from hig h ly purified 2,4,5- trichlorophenol.) Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

F026 Wastes (except w astew ater and spent carbon from HCl purification) from the production of

m aterials on equipm ent prev iously used for the

m anufacturing use (as a reactant, chem ical interm ediate, or com ponent in a form ulating process) of tetra- , penta- , or hexachlorobenz ene under alk aline conditions. Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs



### 8-21

### Table 8-12. Sum m ary of specif i c dioxin- containing w astes that m u st com p ly

w i th land disposal restrictions a 

### ( c ont i nue d)

EP A haz a rdous

wa s t e

num ber Wast e descri pt i on Land di sposal restriction ef

f ective date Regulated

wa s t e constituent
F027 Discarded unused form ul ations containing tri-

, tetra- , or pentachlorophe nol or discarded unused form ulations containing com pounds deriv ed from these chlorophenols. (T his listing does not include form ulations containing hexachlorophene sy nthesiz ed from prepurified 2,4,5- trichlorophenol as the sole com ponent.) Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

F 028 R esidues resulting from the incineration or therm a l treatm e nt of soil contam inated w ith EPA Haz a rdous Wastes No. F020–F023, F026, and F027 Nov e m b er 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs
F039 Leachate (liquids that hav e percolated throug h land- disposed w astes) resulting from the disposal of m o re than one restricted waste classified as haz ardous under Subpart D of 40 C F R 268. (Leachate resulting from the disposal of one or m o re of the following EPA haz a rdous wastes and no other haz ardous wastes retains its EPA haz a rdous waste num ber(s): F020, F021, F022, F026, F027, and/or F028.) Aug ust 8, 1990 (w astew a ter) May 8, 1992 (nonwastewater) T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

K 043 2,6- Dichlorophenol waste from the production of 2,4- D J une 8, 1989 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

K 099 Untreated wastewat er from the production of 2,4- D Aug u st 8, 1988 T C DDs Pe CDDs HxCDDs TC D F s PeCDFs HxCDFs

a For w as t ew ater, th e treatm en t s t an dard f o r all reg u l at ed w as t e con s titu en ts ex cept P eC D Fs is 0.063 μg /L ; th e

s t an dard f o r PeC D F s i s 0.035 μg / L

. F o r n o n w as t e w a t e r, t h e t r eat m e n t s t an dard f o r al l reg u l at ed w a s t e

con s titu en ts is 1 μg /k g

. T r eatm e n t s t an dards are bas e d on in cin e ration to 99.9999% des t ru ction an d rem o v a l ef f i cien cy

.

S o u rce: 40 C F R 268.



### 8-22

### constituents, including chlorophenol wastes (w aste codes F 020 and F 021). The reg u lations

pr ohibit the la nd disposa l of the se wa ste s until the y a r e tr e a t e d to a le ve l be low the r outine l y achievable DL s for the EPA haz a rdous waste num bers listed in Table 8-12 for each of the following cong ener g r oups: TCDDs, PeCDDs , Hx CDDs, TCDF s, PeCDF s , and Hx CDF s

. W a stes from PCP-based wood-pr eserving operations (waste codes K001 and F 032) are also

re g ula te d a s ha za rdous wa ste s unde r RCRA (40 CF R 261).
EPA’ s Of f i c e of Wa te r pr omulg a te d e f f l ue nt limita tions f o r

f

a c ilitie s tha t ma nuf a c t ur e chlorinated phenols and discharg e treated wastewater (40 CF R 414.70). These effluent
limita tions do not spe c i f i c a lly r e g u la te CDDs or CDF s. The e f f l ue nt limita tions f o r

the
individua lly r e g u la te d c h lor i na te d phe nols a r e le ss tha n or e qua l to 39 μg /L f

o r

f

a c ilitie s tha t use biolog ical end-of-pipe treatment. Di- and trichlorophenols are subj ect to reporting under the diox in /furan test rule, which is
discussed in Section 8.3.7 of this report. Since the effective date of that rule (J une 5, 1987), only the 2,4-dichlorophenol isomer has been commerc ially produced in (or imported to) the United States, and as noted in Table 8-9, no CDDs/CDF s were detected in the product. Testing is required for the other di- and tr ichlorophenols if manufacture or importation resumes. Similarly

, tetrachlorophenols were subject to reporting under the Diox in/F uran Pesticide Data Call-I n (DCI ) (discussed in Section 8.3.8 of this report). Si nce issuance of the DCI

, the reg i strants of tetrachlorophenol-containing pestic ide products have elected to no long er support the reg i stration of their products in the United States.
I n J a nuary 1987, EPA entered into a settleme nt ag reement with PCP manufacturers that set limits, effective in F e bruary 1989, on the allowed uses of PCP and its salts and the max imum
allowable concentrations of 2,3,7,8-TCDD and Hx CDDs. Sec tion 8.3.8 discusses the 1987 PCP

se ttle me nt a g r e e m e n t a nd inc l ude s e stima te s of c u r r e nt r e le a se s of CDDs/CDF s a ssoc i a t e d with
the use of PCP in the United States. Secti on 11.3.1 (Chapter 11) provide s an estimate of the
amount of CDDs/CDF s that may have entered the environment or that ar e contained in treated wood products as a result of pr ior use of PCP and PCP-Na. Since the late 1980s, U.S. commercial pr oduction of chlorophenol s has been limited to 2,4-dichlorophenol and PCP. As noted above, disposal of wastes g e nerated during the manufacture of chlorophenols is st rictly reg ulated, and thus rel eases to the environment are

ex pected to be neg lig ible. W ith reg a rd to rel eases associated with th e use of 2,4-dichlorophenol,
no CDDs/CDF s have been detected in 2,4-dichlorophenol. Releases associated with the use of PCP are presented in Sections 8.3.8 and 11.3.1.

8-23

### 8.3.2. Chlorobenzenes
Chlorobenz enes have been produced in th e United States since 1909. U.S. production operations were develope d primarily to provide chemical raw materials for the production of phenol, aniline, and various pestic ides based on the hig h er-chlorinated benz enes. B ecause of ( i nc r e me nta l ) c h a n g e s in the pr oc e sse s use d to ma nuf a c t ur e phe nol a nd a n iline a nd the pha se out of hig hly chlorinated pesticides such as DDT and hex achlorobenz ene, U.S. production of
chlorobenz enes in 1988 had decreased to 50% of the peak production level, in 1969.
Chlorobenz enes can be produced via thr ee methods: (1) electrophilic substitution of
benz ene (in liquid or vapor phase) with c h lor i ne g a s in the pr e se n c e of a

me ta l sa lt c a ta ly st, ( 2 )

ox idative chlorination of benz ene with HCl at 150 to 300°C in the presence of a metal salt cataly s t, and (3) dehy drohalog e nation of hex ach lorocy clohex a ne wastes at 200 to 240°C with a carbon cataly s t to produce trichlorobenz ene, which can be further chlorinated to produce hig h erchlorinated benz enes (Ree et al., 1988; Hu tz ing e r and F i edler, 1991b; B r y a nt, 1993).
All chlorobenz enes currently manufactured in the United States are produced by the

e l e c t r ophilic substitution pr oc e ss using liquid- pha se be nze n e ( i .e ., te mpe r a t ur e is a t or be low 80°C). F e Cl 3 

### is the most common cataly s t employ ed. Althoug h this method can be used to produce mono- throug h hex achlorobenz ene, the ex tent of chlorination is controlled to y i eld primarily monochlorobenz ene and dichlorobenz ene. The finished product is a mix ture of
chlorobenz enes, and refined produc ts must be obtained by distilla tion and cry s talliz ation (B ry ant, 1993).
CDDs/CDF s can be produced inadvertently dur ing the manufacture of chlorobenz enes by nucleophilic substitution and py roly sis mechanisms (Ree et al., 1988). Th e criteria required for production of CDDs/CDF s via nucle ophilic substitution are ox y g en as a nuclear substituent (i.e., presence of chlorophenols) a nd production or purification of the substance under alkaline
conditions. F ormation via py roly sis requires reaction temperatures above 150°C (Ree et al., 1988; Hutz ing e r and F i edler, 1991b). The li quid-phase electrophilic substitution process currently used in the United States does not meet e ither of these criteria. Althoug h Ree et al. and Hutzing e r a nd F i e d le r sta t e tha t the c r ite r i a f

o r

f

o r m a tion of CDDs/CDF s via nuc le ophilic
substitution ma y be pr e se n t in the c a t a l y st ne utr a liza tion a nd pur if ic a tion/distilla tion ste p s of the manufacturing process, Opatick (1995) states that the chlorobenz ene reaction product in U.S

. processes remains mildly acidic throug hout these steps.
Table 8-13 summariz e s the very limite d published information on CDD/CDF
contamination of chlorobenz en e products. The presence of CDDs/CDF s has been reported in tri-, penta-, and hex achlorobenz ene. No CDDs/CDF s have been reported in mono- or
dichlorobenz ene. Conflicting data ex ist concerni ng t h e presence of C DDs/ C DFs i n

8-24Table 8-13.CDD/CDFconcentrations (μg/kg) inchlorobenzenes



### 8-25Congener/congener groupMCBza1,2-DCBz(forsynthesis)a1,2,4-TrCBz(“pure”)bMixedTrCBz(47%)a1,2,4,5-TCBz(99%)aPeCBz(98%)aHCBz(97%)aHCBzbTotal TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDFND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)0.3ND (0.02)ND (0.02)ND (0.02)ND (0.02)ND (0.02)0.5ND (0.02)ND (0.02)ND (0.02)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)ND (0.1)0.0270.140.2590.2530.0810.7360.2720.0910.030.016ND (0.02)0.20.50.80.40.030.20.81.52.1ND (0.02)ND (0.02)0.020.020.050.02ND (0.02)ND (0.02)0.10.1ND (20)ND (20)ND (20)4706,700ND (20)ND (20)ND (20)4552,830-­-­-­-­50–212,000-­-­-­-­350–58,300Total CDD/CDFND0.8ND1.96.510,455400–270,3000.3aSource:Hutzinger and Fiedler (1991b);unpublished resultsoftestsperformed atthe UniversityofBayreuth, Germany,and byDr. H. Hagenmaier.bSource:Villanueva et al. (1974); range ofthree samplesofcommerciallyavailable HCBz.ND = Not detected(valueinparenthesis is the detectionlimit, ifreported)-- =Noinformation given

### trichlorobenz ene. One study (Villanueva et al ., 1974) detected no CDDs/CDF s in one sample of 1,2,4-TCB z at a DL of 0.1 μg /kg

. Hutz ing e r and F i edler (1991b) repor ted unpublished results of a study by Dr. Hans Hag e nmaier showing C DD/CDF cong ener g r oup concentrations rang ing from 0.02 to 0.074 μ g /kg in a sample of mix ed tr ichlorobenz ene. B ecause the TCB z ex amined by Hag e nmaier contained about 2% hex achlorocy clohex a ne, it is r easonable to assume that it was produced by dehy drohalog e nation of hex achlo rocy clohex a ne (a manufacturing process not

c u rr e ntly use d in the Unite d Sta t e s)

.

8.3.2.1. Re gulatory Ac tions f o r Chlorobe nze n e s EPA determined, as part of the F e de r a l I n se c tic ide

, F ung ic ide

, a nd Rode ntic ide Ac t (F I F RA) DCI (discussed in Section 8.3.8), that the 1,4-dichlorobenz ene manufacturing processes used in the United States are not likely to form CDDs/CDF s. Mono-, di-, and trichlorobenz ene are listed as potential precursor chemicals under th e TSCA diox in/furan test rule and are subject to reporting (see Section 8.3.7). I n addition, EP A issued a Sig n ifican t New Use Rule (SNUR)
under S ection 5(a)(2) of TS CA on Decem ber 1, 1993 (effective J a nuary 14, 1994) for pentachlorobenz ene and 1,2,4,5-tetrachlorobenz ene (F ed eral Reg i ster, 1993c). This rule requires that EPA be notified at least 90 day s before the manufacture, import, or pr ocessing of either of these compounds in amounts of 10,000 pounds or g r eater per y ear per facility for any use. All

reg i strations of pesticide produc ts containing hex achlorobenz ene were cancelled in the mid1980s (Carpenter et al., 1986).
OSW promulg a ted land dispos al restrictions on wastes (i .e., wast ewat ers and nonwastewaters) resulting from the manufacture of chlorobenz enes (40 CF R 268). Table 8-12
lists a ll solid wa ste s f o r

whic h EPA spe c i f i c a lly r e g u la te s CDDs a nd CDF s, inc l uding
chlorobenz ene wastes, as haz a rdous constituents. The reg ulations prohibit the land disposal of
the se wa ste s until the y a r e tr e a t e d to a le ve l be low the r outine l y a c h ie va ble DL s in the wa ste

ex tract listed in Table 8-12 for each of the following cong ener g r oups: TCDDs, P e CDDs,
Hx C DDs, TC DFs, P e C D Fs, and Hx C D Fs.
EPA’ s Of f i c e of Wa te r pr omulg a te d e f f l ue nt limita tions f o r

f

a c ilitie s tha t ma nuf a c t ur e chlorinated benz enes and discharg e treated wastewater (40 CF R 414.70). These effluent
limita tions do not spe c i f i c a lly a ddr e ss CDDs a nd CDF s. The f o llowing c h lor i na te d be nze n e s a r e
reg u lated: chlorobenz ene; 1,2-dichlorobenz ene; 1,3-dichlor obenz ene; 1,4-dichlorobenz ene; 1,2,4-trichlorobenz ene; and hex ach lorobenz ene. The effluent limitations for the individual

r e g u la te d c h lor i na te d be nze n e s a r e le ss tha n or e qua l to 77 μg /L f

o r

f

a c ilitie s tha t use biolog ic a l end-of-pipe treatment a nd less than or equal to 196 μg /L fo r facilities that do not use biolog ical

e nd- of

- p ipe tr e a tme nt.

8-26

### Since at least 1993, U.S. commercial producti on of chlorobenzenes has been limited to
monochlorobenz ene, 1,2-dichlorobenz ene, 1,4-dich lorobenz ene, and, to a much lesser ex tent, 1,2,4-trichlorobenz ene. As not ed above, CDD/CDF formation is not ex pected under the normal operating conditions of the processes currently used in the United States to produce these four
chemicals. No tetra-, penta-, or hex achlorinated benz enes are now intentionally produced or used in the United States (B ry ant, 1993). Thus, releases of CDDs/CDF s from the manufacture of
chlorobenz enes in 1995 were estima ted to be neg lig ible. B ecause the information available on
CDD/CDF content of mono- throug h pentachlor obenz ene is very limited and is based primarily on unpublished European data, and because info rmation on the chlorobenz ene manufacturing processes in place during 1987 is not readily ava ilable, no emission estima tes can be made for
1987.

8.3.3. Chlorobiphenyls
PCB s are manufactured by the direct batc h chlorination of molten bipheny l in the presence of a cataly s t, followed by separation and purification of the desired chlorinated bipheny l
fractions. During the manufacture of PCB s , th e inadvertent production of CDF s also occurs.
This section focuses on levels of CDD/CDF contamination that may have been present in PCB products.
CDF s have been shown to form when PC B

- containing transformers and capacitors underg o malfunctions or are subjected to fires that result in accidental combustion of the
dielectric fluid. The direct releases of diox in-like PCB s fro m sources is reviewed in Chapter 10. During the commercial production of PCB s , th ermal ox idative cy c liz ation under alkaline conditions resulted in the inadvertent production of CDF s in most of the commercial PCB
mix tures (B rown et al., 1988; ATSDR, 1993). B o wes et al. (1975a) firs t reported detection of
CDF s in Aroclor products; sa mples of unused Aroclors ma nufactured in 1969 and 1970 were
found to have CDF (TCDF throug h Hx CDF ) concen trations rang ing from 0.8 to 2 mg /kg

. B owes et al. used cong ener-speci fic analy tical methodolog y a nd detected 2,3,7,8-TCDF and 2,3,4,7,8­
PeCDF at concentrations rang ing from 0.11 to 0.33 mg /kg and 0.12 to 0.83 mg /kg , respectively

, in unused samples of Aroclo r 1254 and Aroclor 1260. The presence of CDDs in commercial
PCB mix tures, althoug h at much lower concentra tions than those of the CDF s , was reported by Hag e nmaier (1987) and Malisch (1994). Table 8-14 presents th e CDF and CDD cong ener g r oup concentrations reported by B o we s et al. (1975a) and those repor ted in subsequent y ears for
unused PCB s by Erickson (1986), ATSDR (1993) , Hag e nmaier (1987), and Malisch (1994).
S e veral researchers have re ported concentrations of sp eci fi c C DD/ C DF cong eners i n commercial PCB mix tures (B owes et al., 1975b; B r own et al., 1988; Hag e nmaier, 1987; Malisch, 1994). Table 8-15 presents the results of these f our studies. Only the Hag e nmaier and Malisch

8-27Table 8-14.Concentrations ofCDD/CDFcongener groups in unused commercial polychlorinated biphenyl (PCB)mixtures (mg/kg)



### 8-28Year ofCDD congener groupconcentrationsCDFcongener groupconcentrationsTotalTotalPCBmixturemanufactureTCDDPeCDDHxCDDHpCDDOCDDCDDTCDFPeCDFHxCDFHpCDFOCDFCDFSourceAroclor10161972-­-­-­-­-­-­NDNDND-­-­NDaAroclor1242-­-­-­-­-­-­-­0.070.030.003-­-­0.15b, cAroclor1242-­-­-­-­-­-­-­2.32.2ND-­-­4.5b, cAroclor1242-­-­-­-­-­-­-­0.250.70.81-­-­1.9bClophen A-30-­0.0007ND0.0010.0060.0310.0396.3772.4020.8050.1080.0169.708dClophen A-30-­NDNDND0.0050.0250.0300.7130.1370.0050.001ND0.855eAroclor12481969-­-­-­-­-­-­0.51.20.3-­-­22.2352bClophen A-40-­NDNDND0.0120.0300.0421.2890.7710.1440.020.011eKanechlor400-­-­-­-­-­-­-­-­-­-­-­-­b, cAroclor12541969-­-­-­-­-­-­0.10.21.4-­-­1.7aAroclor12541970-­-­-­-­-­-­0.20.40.9-­-­1.5aAroclor1254-­-­-­-­-­-­-­0.020.20.6-­-­0.8b, cAroclor1254-­-­-­-­-­-­-­0.050.10.02-­-­0.2bClophen A-50-­NDNDND0.0110.0270.0385.4022.1542.2140.4790.06910.318eAroclor1260Aroclor1260Aroclor1260Aroclor1260Clophen A-60Clophen A-60Clophen A-60Phenoclor DP-6-­1969-­-­-­-­-­-­-­-­-­-­0.0004ND-­-­-­-­-­-­0.002ND-­-­-­-­-­-­0.002ND-­-­-­-­-­-­0.0030.014-­-­-­-­-­-­0.0150.032-­-­-­-­-­-­0.0220.046-­-­0.30.10.80.215.78616.341.40.710.40.90.311.65521.1645101.10.50.50.34.4567.632.22.91.35-­-­-­1.5172.522-­-­-­-­-­-­0.6391.024-­-­3.812.20.834.05248.6818.613.6b, cab, cadeaaClophen T-64-­-­-­­­-­-­-­0.31.732.450.82-­5.4bProdelec3010-­-­-­­­-­-­-­1.080.350.07-­-­2baSource:Bowesetal. (1975a).bSource:Erickson (1986).cSource:ATSDR(1993).dSource:Malisch(1994).eSource:Hagenmaier(1987).ND = Not detected-- = NoinformationgivenTable8-15.2,3,7,8-Substituted congenerconcentrations in unusedpolychlorinated biphenyl (PCB) mixtures (μg/kg)



### 8-29CongenerCongener concentrationsinClophensCongener concentrationsinAroclorsA-30aA-30bA-40bA-50bA-60aA-60b1016c1242c1248d1254c1254c1254c1254d1260c1260c1260c2,3,7,8-TCDDNDNDNDNDNDND-­-­-­-­-­-­-­-­-­-­1,2,3,7,8-PeCDDNDNDNDND0.1ND-­-­-­-­-­-­-­-­-­-­1,2,3,4,7,8-HxCDDNDNDNDND0.2ND-­-­-­-­-­-­-­-­-­-­1,2,3,6,7,8-HxCDD0.8NDNDNDNDND-­-­-­-­-­-­-­-­-­-­1,2,3,7,8,9-HxCDDNDNDNDNDNDND-­-­-­-­-­-­-­-­-­-­1,2,3,4,6,7,8-HpCDD5.62.44.45.32.56.8-­-­-­-­-­-­-­-­-­-­OCDD31.124.730.326.914.932.3-­-­-­-­-­-­-­-­-­-­2,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF1,032.6135.8509.2301.465.3ND50.643.722.515.736.914.913.11.90.8ND0.10.6NDND250.252.7171.348.419.60.76.872.811.41,005.7155.2407.5647.5227.58.362.5205.572.269.22,287.7465.21,921.91,604.2157.642.8369.5480.6321.7639.23,077.21,750.82,917.02,324.1351.3194,08.31,126.13041,024.30.1-­1.75-­-­0.08-­-­-­-­40.1-­40.8-­-­0.26-­-­-­-­330-­830-­-­-­-­-­-­-­28-­110-­-­28.8-­-­-­-­20.9-­179-­-­28.7-­-­-­-­55.8-­105-­-­19.4-­-­-­-­110-­120-­-­-­-­-­-­-­63.5-­135-­-­5.1-­-­-­-­6.88-­58.2-­-­9.7-­-­-­-­29-­112-­-­10.7-­-­-­-­Total TCDD0.7NDNDND0.4ND-­-­-­-­-­-­-­-­-­-­Total PeCDDNDNDNDND2ND-­-­-­-­-­-­-­-­-­-­Total HxCDD1.2NDNDND1.8ND-­-­-­-­-­-­-­-­-­-­Total HpCDD5.65.411.611313.5-­-­-­-­-­-­-­-­-­-­Total OCDD31.124.730.326.914.932.3-­-­-­-­-­-­-­-­-­-­Total TCDF6,376.67131,289.45,402.315,785.716,340-­-­-­-­-­-­-­-­-­-­Total PeCDF2,402.4136.5770.82,153.711,654.621,164-­-­-­-­-­-­-­-­-­-­Total HxCDF804.85.1143.62,213.84,455.87,630.2-­-­-­-­-­-­-­-­-­-­Total HpCDF108.30.819.5478.81,5172,522.3-­-­-­-­-­-­-­-­-­-­Total OCDF15.7ND11.469.2639.21,024.3-­-­-­-­-­-­-­-­-­-­TotalCDD/CDFe9,746.4885.52,276.610,355.734,074.448,726.6-­-­-­-­-­-­-­-­-­-­Total I-TEQDFe407.211.3409.61,439.22,179-­-­-­-­-­-­-­-­-­-­Total TEQDF-WHO98e407.211.3409.51,4392,178-­-­-­-­-­-­-­-­-­-­aSource:Malisch(1994).bSource:Hagenmaier (1987).cSource:Brownetal. (1988).dSource:Bowes(1975b).eCalculated assumingnondetect valueswere zero.ND = Not detected-- =Noinformation given

### studies, however, reported the concentrations of all 2,3,7,8-substituted C DDs and CDF s

. I t is evident from the table that major variations are found in the levels of 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF in the Clophen mix tu res reported by Hag e nmai er and Malisch and the corresponding levels in the Aroclor mix tures reported by B o wes et al. and B r own et al.
B r own et al. (1988) compared the levels of 2,3,7,8-TCDF ; 2,3,4,7,8-PeCDF ; and 1,2,3,7,8,9-Hx CDF in used samples (from previously used capacitors and transformers) and unused samples of Aroclor 1016, 1242, 1254, and 1260. The concentration rang es reported for the used and unused Aroclors were similar, lead ing B r own et al. (1988) to conclude that CDF s are not formed during the normal use of PCB s in electrical equipment.

8.3.4. Ethylene Dichloride/Vin yl Chloride Monom er/P olyvi nyl Chloride Manuf acturing
I n t h e Uni t e d S t at es t h e m a nufact ure of P VC is an integ r ated manufacturing process. This means that most manufacturing fac ilities produce all the precursors and chemical intermediates necessary to manuf acture PVC as well as PVC resi ns and products. F o r ex ample, ethy lene dichloride (EDC) is used to produce viny l chloride monomer (VCM). VCM is then
converted to PVC resins. The resins ar e used to manufacture various PVC products. PVC resins are produced from the poly m eriz ation of VCM. VCM is ty pically produced by the thermal dehy drochlorina tion (commonly known as cracking ) of EDC. The cracking of EDC requires elevated pressure (20 to 30 atm) and temperature (450 to 650°C) and y i elds VCM
and HCl at about a 1:1 molar ratio. EDC is produced by two different methods: (1) direct chlorination of ethy lene with chlorine in the pr esence of a cat al y s t at a t e m p erat ure of 50 t o 60°C and pressure of 4 to 5 atm, a nd (2) ox y c hlorination, which involve s reaction of ethy lene with HCl
and ox y g en in the presence of a cataly s t at temp eratures g e nerally less than 325°C. The primary
source of HCl for the ox y c hlorination process is the HCl pr oduc e d f r o m the c r a c k ing of EDC to
form VCM. Most VCM manufacturing facilities are integ r ated with EDC production facilities (The Viny l I nstitute, 1998). Althoug h it has been g e nerally recog niz ed that CDDs/CDF s can be formed during the manufacture of EDC, VCM, and PVC, manufacturers and envir onmental public interest g r oups ha ve disa g r e e d a s to the qua ntity of CDDs/CDF s tha t a r e f o r m e d a nd r e le a se d to the e nvir onme n t in wastes and possibly in PVC products. A lthoug h EPA reg ulates emissions from EDC/VCM production facilities under the Clean W a ter Act (40 CF R 61), the Clean Air Act (40 CF R 414),

a nd RCRA (40 CF R 268, wa ste c ode s F 024, K019, a nd K020), CDDs/CDF s a r e not spe c i fic a lly

reg u lated pollutants; as a cons equence, monitoring data fo r C DDs/C DFs in emissions were

g e nerally lacking until the early 1990s. Greenpeace I n ternational initially determined that CDDs and CDF s can be formed during
the manufacture of PVC. I n 1993, it issued a re port on CDD/CDF emissions associated with the

8-30

### production of EDC/VCM (Greenpeace, 1993). Greenpeace estimated that 5 to 10 g I

- TEQ DF 

### were released to the environment (air, wa ter, and g r ound combined) annually for every 100,000

m e t r i c t ons of VC M produced. Thi s em i ssi on f act or was based on dat a g a t h ered by Greenpeace on four European plants. The Viny l I nstitute responded with a critique of the Greenpeace report (ChemRisk, 1993). Miller (1993) summariz e d the diffe ring views of the two parties. According

to Miller, European PVC manufacturers cla imed the emission factor was 0.01 to 0.5 g I TEQ DF 

### /100,000 metric tons of VCM, but althoug h Gr eenpeace and ChemRisk used basically the

sam e m oni t o ri ng i n form at i on t o devel op t h ei r em i ssi on fact ors, Greenpeace adj u st ed t h e emission factor to account for unquantified fug itive emissions a nd waste products that contain unspecified amounts of CDDs/CDF s. I n 1995, Greenpeace issued a second report (S tring e r et al., 1995) reiterating the

org a niz a tion’s concern that the g e neration and e mission of CDDs/CDF s ma y be sig n if ic a n t a n d

ur g i ng tha t f u r t he r wor k be initia te d to qua ntif y

a nd pr e v e n t e missions. Str i ng e r e t a l . pr e se n te d

t h e resul t s of anal y s es of t h ree sam p l e s of chlorinated wastes obtained from U.S. EDC/VCM manufacturing facilities. The thr ee wastes were characteriz ed acco rding to EPA haz a rdous waste
classification numbers as an F 024 waste (waste from the producti on of short-chain aliphatics by free radical-cataly z ed processes) , a K019 waste (heavy ends from the distillation of ethy lene from EDC production), and a probable K020 waste (heavy ends from distillation of viny l chloride in VCM manufacture). Table 8-16 presents the analy ti cal results reported by String er et al. This study acknowledg ed that because EDC/VCM pr oduction technolog ies and waste treatment and disposa l pr a c tic e s a r e ve r y site

- spe c i f i c , the limite d inf o r m a tion a v a ila ble on CDD/CDF

g e neration and emissions made it difficult to quantify am ounts of CDDs/CDF s g e nerated and

e mitte d.
I n response to the lack of definitive studi es, and at the recommendation of EPA, U.S. PVC manufacturers beg a n an ex tensive monitori ng prog ram, the Diox in Characteriz ation Prog ram (DCP). The objective of the DCP was to evaluate the ex tent and mag n itude of potential CDD/CDF releases to air, water, a nd land, as well as the potential for PVC product
contamination. Manufacturers pe rformed emissions and product te sting at severa l facilities that were representative of various manufacturing and process cont rol technolog ies. I n 1998, The Viny l I n stitute c o mple te d studie s of CDD/CDF r e le a se s in wa ste w a t e r , wa ste w a t e r tr e a tme nt plant solids, and stack g a ses, as well as studies of the CDD/CDF content of products (PVC resins and EDC sold as products) (The Viny l I nstitute, 1998).
I n Se pte m be r 2002, the CCC me t to re vie w diox in re le a se e stima te s for 2000 submitte d by va r i ous EDC/VCM ma nuf a c t ur ing f a c ilitie s. Se ve r a l c o mpa n ie s pr ovide d sta c k g a s e missions
and wast ewat er rel ease dat a as wel l as a di scussi on of how they g e nerated t h e rel e ase and t r ansfer

e stima te s re porte d in the Tox i c s Re le a se I nve ntory for 2000. I n Ma rc h 2004, the CCC me t a g a i n

8-31

### Table 8-16. Reported CDD/CDF concen trations (μg/kg) in w astes f r om polyvinyl c h lor ide ( P V C ) m a nufac t u r e

Congener/congener group F 024 w aste K 019 w aste K 020 w aste
2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 0.37 0.14 0.3 0.14 0.11 4.2 15 260 890 260 330 620 920 1,060 0.06 0.05 0.08 0.06 0.07 0.89 3
2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.91 9.5 1.6 110

24

9.5 3.1 250

51 390 680 975 1,050 10,100

9,760 21,800 930 13,400

1,340 43,500 0.44 1.8 0.58 11

2.4 1.3 0.89 38

6 650
Total 2,3,7,8-CDD Total 2,3,7,8-CDF Total I

- TEQ DF 

### Total TEQ DF 

### -W HO 98 

### 20.3 849.6

20 19.7 4,340 103,535 5,928 6,333 4.21 712.4 3.2 2.6

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF 3.1 3.6 1.3 5 15 15 65 300 450 390 1,230 3,540 3,950 1,270 1,060 20,600 45,300 63,700 16,600 43,500 1.9 1.7

a 

### 1.7 3 6 11 27 58 650

Total CDD/CDF 1,248 200,750 760.3

a Co n g e n e r g r o u p co n cen tratio n rep o r ted in so u r ce is n o t co n s isten t w ith rep o r ted co n g e n e r co n cen tratio n s

.

S o u r ce: S t ri n g e r et al . (1995).



### 8-32

### to discuss the results, to date, of its CDD/ CDF data validation study for P V C / EDC / VC M and

c h lor

- a lka li f a c ilitie s. The study ’ s g o a l wa s to pr ovide f a c ility

- spe c i f i c wa te r , a i r , a nd la nd
release estimates for 2000 and 2002. As of the date of this report, data validation studies were provide d for 17 of 20 fa c ilitie s in the CCC tha t we re c onside r e d c hlor-a lka li produc tion fa c ilitie s and PVC/EDC/VCM manufacturing plants.

8.3.4.1. Water Releases This section presents estimates of releas es of diox in-like compounds in wastewater discharg es to surface waters for 2000 and 1995 from the integ r ated EDC, VCM, and P V C

ma nuf a c t ur ing f a c ilitie s in the Unite d Sta t e s. Site

- spe c i f i c te sting of the wa ste w a t e r f

r o m facilities operated by Do w Chemical Co., Occidental Chemic al Corp., Georg i a Gulf Corp., PPG
I ndustries, and DuPont provide the basis for estimating annual releases of diox in-like compounds in 2000 (CCC, 2005, 2003a , b, c , d). I n tota l, the se te sts re pre se nt site -spe c i fic a na l y sis of 17 manufacturing facilities thr oug hout the United States. The site-s pecific releases of diox in-like compounds for these facilities are shown in Table 8-17. I n 2000, approx imately 23.08 g TEQ DF 

### WH O 98 

### (23.94 g I

- TEQ) were released from 17 ED C/VCM/PVC manufacturin g facilities in the
United States. These estimates are assig n ed a hi g h confidence rating because they were derived from the testing of individual manufacturing fac ilities and the activity leve l is known with a hig h deg r ee of certainty

. Estimating TEQ wastewater discharg es for 1995 from EDC/VCM/PVC integ r ated chemical manufacturing f acilities is problematic. A report by The Viny l I nstitute (1998) did not

r e pr e se n t a c o mpr e he nsive te sting of the wa ste w a t e r s f r o m a ll e x isting EDC/VCM/PVC manufacturing facilities in 1995. Th e report presented results for treated wastewater samples collected during April and May of 1995 at only 10 manufacturing sites (6 that manufactured only PVC, 3 that manufactured EDC and VCM, and 1 that manufactured EDC, VCM, and PVC). I n terms of production, the 10 site s represented only about 27% of the total estimated 1995 EDC/VCM/PVC production.
The r e pr e se n ta tive n e ss of the se site s to tota l EDC/VCM/PVC ma nuf a c t ur ing is questionable because the testing prog ram did not include some of th e hig her-emitting facilities
disc ove re d in 2000 (CCC, 2003a ). F or e x a m ple , the CCC re ports tha t provide d the ba sis for the
2000 re le a se e stima te s (CCC, 2005, 2003a , b, c

, d) indic a te d tha t the Dow fa c ility in F r e e m ont, TX, and the Occidental facility in I n g l eside, TX, released approx imately 3 g and 1.6 g TEQ DF 

### WH O 98 

### , r e spe c tive l y , a s wa ste w a t e r disc ha r g e s into sur f a c e wa te r s. The se two f a c ilitie s a r e about an order of mag n itude hig h er in wastewater releases than are the 10 facilities tested in 1995 (The Viny l I nstitute, 1998). I n an attempt to ove rcome this deficiency , it is assumed that the
wastewater releases from EDC/ VCM/PVC integ r ated chemical production facilitie s in 1995 were

8-33Table 8-17.Releases ofdioxin-like compounds (g/yr) in wastewater discharges fromEDC/VCM/PVC andintegratedchlorinechemical manufacturing facilitiesto surface water inreference years 2000 and1995



### 8-34CompanyFacility 2,3,7,8 T C D D 1,2,3,7,8 Pe C D D 1,2,3,4,7,8 H x C D D 1,2,3,6,7,8 H x C D D 1,2,3,7,8,9 H x C D D 1,2,3,4,6,7,8 H p C D D OCDD 2,3,7,8 T C D F 1,2,3,7,8 Pe C D F 2,3,4,7,8 Pe C D F 1,2,3,4,7,8 H x C D F 1,2,3,6,7,8 H x C D F 1,2,3,7,8,9 H x C D F 2,3,4,6,7,8 H x C D F 1,2,3,4,6,7,8 H p C D F 1,2,3,4,7,8,9 H p C D F OCDF I-TEQ TEQ DF -WHO 98DowaFreeport, TX0.000.000.570.000.3515.6174.612.633.571.6826.280.000.005.00125.7419.36297.946.486.14DowMidland, MI0.000.000.020.000.000.543.630.020.000.010.060.000.000.040.880.011.250.040.03DowPlaquemine, LA0.060.120.870.000.3318.72285.794.783.771.9721.420.000.983.14161.5711.81374.107.036.50DuPontbDeLisle,MS0.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.00DuPontEdgeMoor, DE0.000.000.000.000.000.000.100.000.000.000.080.000.000.000.140.1213.490.020.01DuPontJohnsonville, TN0.000.000.000.000.000.001.410.000.000.000.440.000.000.001.230.0011.030.070.06GeorgiaGulfcPlaquemine, LA0.000.000.000.000.000.030.120.010.010.020.020.010.010.010.110.020.410.020.02OccidentaldConvent, LA0.000.000.000.000.000.000.150.000.000.000.020.000.000.000.000.000.040.0020.002OccidentalDeerPark, TX0.000.000.000.000.000.081.190.000.000.000.040.030.030.010.690.265.850.030.02OccidentalIngleside,TX0.020.090.080.090.080.090.180.020.090.090.090.100.100.100.100.100.190.180.23OccidentalLaPorte,TX0.000.000.000.000.000.000.050.000.000.000.040.000.000.000.120.030.670.010.01OccidentalMobile, AL0.000.000.000.000.000.000.003e!040.000.000.000.000.000.006e!040.000.004e!054e!05OccidentalBattleground, TX0.000.000.000.000.000.000.480.000.000.000.000.000.000.000.000.000.005e!045e!05OccidentalDelawareCity, DE0.000.000.000.000.000.000.001e!030.000.000.000.000.000.002e!030.000.001e!041e!04OccidentalHahnville, LA0.000.000.000.000.000.010.100.190.900.852.961.180.630.604.470.691.751.081.08OccidentalMuscleShoals, AL0.000.000.000.000.000.001e!094e!081e!078e!082e!071e!072e!083e!081e!076e!081e!079e!089e!08PPGIndustriesLakeCharles,LA0.000.000.010.010.000.402.976.4714.3010.8312.293.963.231.574.412.6412.138.988.97TOTAL0.080.221.550.100.7735.49370.7814.1322.6415.4663.735.294.9810.47299.4735.03718.8523.9423.08Table 8-17.Releases ofdioxin-like compounds (g/yr) in wastewater discharges fromEDC/VCM/PVC andintegratedchlorinechemical manufacturing facilitiesto surface water inreference years 2000 and1995(continued)aDowChemical Company.bDuPont.cGeorgia GulfCorporation.dOccidental Chemical Corporation.Source:ChlorineChemistryCouncil(2004).EDC= EthylenedichloridePVC = Polyvinyl chlorideVCM = Vinyl chloridemonomer



### 8-35

### equal to wastewater discharg es in 2000. B a sed on this assumpti on, approx imately 23.08 g TEQ DF 

### -W HO 98 

### (23.94 g I

- TEQ) were released from 17 EDC/VCM/PVC manufac turing facilities in the United States in reference y ear 1995. Th ese estimates are assig n ed a low confidence rating because they may not be representative of wa stewater discharg es from facilities operating in 1995, althoug h the activity level is known with a hig h deg r ee of certainty and is assig n ed a hig h confidence rating

. The site-sp ecific releases of diox in-like compounds for facilities operating in
1995 are shown in Table 8-17.
A numbe r of EDC/VCM/PVC ma nuf a c t ur ing f a c ilitie s ha ve r e por te d sig n if ic a n t reductions in CDD/CDF wastewat er discharg es to surface wate r in 2002 from 2000 levels. For

ex ample, the Dow facility in F r eemont, TX, achieved a 47% reduction (from 6.4 g TEQ DF 

### WH O 98 

### in 2000 to 3.43 g TEQ DF 

### -W HO 98 

### in 2002) (CCC, 2003a ), the Dow f a c ility in Plaquemine, L A
, achieved a 69% reduction (from 6.86 g TEQ DF 

### -W HO 98 

### in 2000 to 2.16 g TEQ DF 

### -W HO 98 

### in 2002) (CCC, 2003a ), a nd the PPG I ndus trie s fa c ility in L a ke Cha r le s, L A
, achieved a 28% reduction (from 8.97 g TEQ DF 

### -W HO 98 

### in 2000 to 6.47 g TEQ DF 

### -W HO 98 

### in 2002) (CCC, 2003b).

8.3.4.2. Land Releases Only one EDC/VCM/PVC ma nuf a c t ur ing f a c ility ( t he Ge or g i a Gulf f

a c ility in Plaquemine, L A ) reported CDD/CDF releases to land from the land application of wastewater sludg e in 2000 (CCC, 2003c ). The c ong e ne r-spe c i fic a nd TEQ re le a s e s a r e pre s e nte d in Ta ble
8-18. Releases to land from EDC/VCM/PVC manufacturing in 2000 and 1995 were 1.36 g TEQ DF 

### -W HO 98 

### (1.45 g I

- TEQ DF 

### )
, a ssuming tha t the la nd a pplic a tion r a te s we r e the sa me in both

y ears. These emission estimates for 2000 are assig n ed a hig h confidence rating because the

r e le a se s to la nd we r e de te r mine d f r o m the a c t ua l me a sur e m e n ts ta ke n f r o m the sing le f a c ility tha t applies the wastewater sludg e to land. The emission estimates for 1995 are assig n ed a medium confidence rating because the estimates were ba sed on assuming that the CDD/CDF levels of

c onta mina tion in the wa ste w a t e r solids a nd the la nd a pplic a tion r a te s we r e the sa me in both reference y ears.

8.3.4.3. Air Re le ase s The Viny l I nstitute conducted a study of rel eases of EDC/VCM/PVC to air (The Viny l
I nstitute, 1998). B a sed on similar ities in desig n and service, thermal destruction units at
EDC/VCM and/or PVC manuf acturing units were subcateg oriz ed into three ty pes: ty pe A, vent

g a s incinerators at PVC-only resin plants; ty pe B , vent g a s thermal ox idiz ers at EDC/VCM plants; and ty pe C, liquid-only a nd liquid/vent g a s thermal ox idiz ers at EDC/VCM plants. Using

8-36

### Table 8-18. Congener-specif i c releases to lan d f r om an E DC/VCM/P VC int e gr at e d c h e m ic al m a nufac t u r ing fac ilit y a 

### in ref eren ce years 2000 and 1995

Congener Annual rel ease t o l and ( g/ yr)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD
OCDD 0.004
0.039
0.123
0.122
0.078
1.710
8.640 2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDD 1,2,3,4,7,8,9- HpCDD
OCDF 0.077
0.354
0.370
2.690
2.110
1.540
0.595
28.100

6.540
118.000
Total I

- T E Q DF 

### 1.450

Total TE Q DF 

### -W H O 98 

### 1.360

a G e o r gi a G u l f

, P l a q ue m i ne , LA

.

So ur c e : CCC ( 2004).

EDC = Eth y len e dich loride P V C = P o ly v i n y l ch lo rid e VCM = Vin y l ch lo rid e m o n o m e r



### an industry

- wide survey , The Viny l I nstitute iden tified 22 ty pe A units at 11 facilities, 23 ty pe B
units a t 10 f a c ilitie s, a nd 17 ty pe C units a t 10 f a c ilitie s. Te st da ta we r e g a the r e d f r o m 5 of the 22 ty pe A units (3 facilities repres enting 7% of total U.S. and Canadian EDC/VC M/PVC production in 1995), 14 of the 23 ty pe B units (8 facilities), and 13 of the 17 ty pe C units (7 facilities). The sampled type B and C units re presented 70% of total U.S. and Canadian EDC/VCM/PVC production in 1995.
Annual I

- TEQ DF 

### e mission e stima te s we r e g e ne r a te d by c o mbining e stima te d e missions
f r o m te ste d units ( b a se d on me a sur e d sta c k g a s r e sults a nd pla n t- spe c i f i c a c tivity da ta ) with a n

e stima te of e missions f r o m unte ste d units. The e missions f r o m the unte ste d units we r e e stima te d by multiply ing the a v e r a g e e mission f a c t or f

o r

the te ste d units in the c a t e g or y ( t he most like l y

8-37

### estimate) or the averag e emission factor of the tested units with the hig hest emissions in each class (the upper-bound estimate) by th e activity level for the untested units. I t is not possible to
cal cul a t e em i ssi on fact ors for TEQ DF 

### -W HO 98 

### using the da ta pr e se n te d in The Viny l I n stitute
report. The Viny l I nstitute estimates of most likely and upper-bound emissions during 1995 for

t h ese t h ree cat eg ori e s are as fol l o ws:

Most likely emissions Upper-bound emissions Ca te g o r y e stima te ( g I

- TEQ DF 

### /y r ) e stima te ( g I

- TEQ DF 

### /y r ) PVC-only incinerators 0.0014 0.0019 EDC/VCM liquid and liquid/vents 3.7 7.2 EDC/VCM vents for VCM only 6.9 21.6

The study a l so e stima te d e missions tha t ma y ha ve r e sulte d f r o m inc i ne r a tion of
EDC / VC M/ P V C wast es processed by off-si t e , t h i r d- part y processi ng

. Usi n g t h e em i ssi on fact ors f

o r

liquid a nd liquid/ve nts de ve lope d in its study , it wa s e stima te d tha t pote n tia l e missions to a i r from this source categ ory would be 0.65 g I

- TEQ DF 

### /y

r (most-likely estimate) and 2.3 g I

TEQ DF 

### /y

r (upper-bound estimate). Combining these third-party release estimates with those developed above y i elds a 1995 estimate of 11.2 g I

- TEQ DF 

### /y r

. D a ta va lida tion studie s by the CCC indic a t e tha t e i g h t ED C/V C M/PV C ma nuf a c t ur ing facilities released 5.51 g TEQ DF 

### -W HO 98 

### (5.56 g I

- TEQ DF 

### ) to a i r (CCC, 2004); more tha n 85% of
the r e le a se s oc c u r r e d a t two f a c ilitie s. Cong e n e r

- spe c i f i c a nd TEQ r e le a se e stima te s to a i r f

r o m EDC/VCM/PVC manufacturing fac ilities are shown in Table 8-19. The emission estimates for 1995 and 2000 are assig n ed a hig h confidence ra ting because they were based on emissions

te sting of on- site inc i ne rator and vent releases.

8.3.4.4. Transf e rs to Se c u re Landf ills
The CCC re porte d on the a m ount of CDDs/CDF s c onta i ne d in wa ste w a t e r tre a tme nt pla nt sludg e s use d to se c ure la ndfills in 2000 (CCC, 2004). The s e da ta we re de te rmine d on the ba sis
of

sa mpling wa ste w a t e r sludg e s a t 16 inte g r a t e d EDC/VCM/PVC ma nuf a c t ur ing f a c ilitie s. Ta ble
8-20 summariz e s the estimated CDD/CDF cong ene r-specific and TEQ am ounts (based on actual test data) transferred from speci fic facilities in 2000. I t should be noted that, because the wastes

we r e tr a n sf e r

r e d to se c u r e la ndf ills, this is not c onside r e d to ha ve be e n a n e nvir onme n ta l r e le a se ;
t h erefore, t h ese t r ansfers were not i n corporat ed i n t o t h e i nvent ory

.

8-38Table 8-19.Congener-specific and TEQ releases toair (g/yr) fromEDC/VCM/PVC integrated chemicalmanufacturing facilitiesin reference years 2000 and 1995CompanyFacility 2,3,7,8 T C D D 1,2,3,7,8 Pe C D D 1,2,3,4,7,8 H x C D D 1,2,3,6,7,8 H x C D D 1,2,3,7,8,9 H x C D D 1,2,3,4,6,7,8 H p C D D OCDD 2,3,7,8 T C D F 1,2,3,7,8 Pe C D F 2,3,4,7,8 Pe C D F 1,2,3,4,7,8 H x C D F 1,2,3,6,7,8 H x C D F 1,2,3,7,8,9 H x C D F 2,3,4,6,7,8 H x C D F 1,2,3,4,6,7,8 H p C D F 1,2,3,4,7,8,9 H p C D F OCDF I-TEQ TEQ **DF** -WHO **98**DowaFreeport, TX0.010.201.010.000.393.739.461.261.801.2811.980.000.342.5032.355.3466.923.083.11DowMidland, MI0.0260.0040.0080.0000.0030.020.0860.0230.0090.0080.0660.0000.0020.0090.1480.0280.2250.050.05DowPlaquemine, LA0.000.000.030.000.010.100.270.030.040.030.400.000.000.051.470.103.210.090.09DuPontbDeLisle,MS0.0000.0010.0000.0000.0000.0040.0110.0040.0040.0060.0070.0050.0020.0130.0280.0030.0420.0070.007DuPontEdgeMoor, DE0.0000.0010.0000.0000.0000.0030.0160.0010.0020.0020.0030.0020.0050.0030.0110.0180.2040.0040.004DuPontJohnsonville, TN0.0000.0010.0000.0000.0000.0030.0070.0050.0060.0080.0100.0080.0040.0230.0430.0030.0430.0110.011GeorgiaGulfcPlaquemine,LA0.000.000.000.000.000.020.120.090.070.030.170.070.040.010.320.031.010.070.07OccidentaldConvent, LA0.000.010.000.010.000.010.000.020.020.010.010.010.000.000.020.000.020.020.03OccidentalDeerPark, TX0.000.010.050.030.061.3713.540.060.120.141.380.580.550.0611.882.3252.830.580.53OccidentalIngleside,TX0.010.030.110.120.091.589.510.040.350.373.583.380.771.9425.715.1346.901.611.58OccidentalLaPorte,TX0.000.010.010.020.010.150.480.010.020.030.040.040.010.040.250.020.230.040.04TOTAL0.050.271.210.180.566.9933.491.542.451.9217.654.091.744.6472.2213.01171.645.565.51



### 8-39aDowChemical Company.bDuPont.cGeorgia GulfCorporation.dOccidental Chemical Corporation.Source:ChlorineChemistryCouncil(2004).EDC= EthylenedichloridePVC = Polyvinyl chlorideVCM = Vinyl chloridemonomerTable 8-20.Congener-specific and TEQtransfers to secure landfills (g/yr)**a**fromEDC/VCM/PVC integratedchemical production facilitiesin 2000



### 8-40CompanyFacility 2,3,7,8 T C D D 1,2,3,7,8 Pe C D D 1,2,3,4,7,8 H x C D D 1,2,3,6,7,8 H x C D D 1,2,3,7,8,9 H x C D D 1,2,3,4,6,7,8 H p C D D OCDD 2,3,7,8 T C D F 1,2,3,7,8 Pe C D F 2,3,4,7,8 Pe C D F 1,2,3,4,7,8 H x C D F 1,2,3,6,7,8 H x C D F 1,2,3,7,8,9 H x C D F 2,3,4,6,7,8 H x C D F 1,2,3,4,6,7,8 H p C D F 1,2,3,4,7,8,9 H p C D F OCDF TEQ **DF** -WHO **98**DowbFreeport, TX0.000.000.570.000.3515.6174.612.633.571.6826.280.000.005.00125.7419.36297.946.14DowMidland, MI0.000.000.020.000.000.543.630.020.000.010.060.000.000.040.880.011.250.03DowPlaquemine, LA0.060.120.870.000.3318.72285.794.783.771.9721.420.000.983.14161.5711.81374.106.50DuPontcDeLisle,MS0.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.00DuPontEdgeMoor, DE0.000.000.000.000.000.000.100.000.000.000.080.000.000.000.140.1213.490.01DuPontJohnsonville, TN0.000.000.000.000.000.001.410.000.000.000.440.000.000.001.230.0011.030.06GeorgiaGulfcPlaquemine,LA0.000.000.000.000.000.030.120.010.010.020.020.010.010.010.110.020.410.02OccidentaleConvent, LA0.000.000.000.000.000.000.150.000.000.000.020.000.000.000.000.000.040.002OccidentalDeerPark, TX0.000.000.000.000.000.081.190.000.000.000.040.030.030.010.690.265.850.02OccidentalIngleside,TX0.020.090.080.090.080.090.180.020.090.090.090.100.100.100.100.100.190.23OccidentalLaPorte,TX0.000.000.000.000.000.000.050.000.000.000.040.000.000.000.120.030.670.01OccidentalMobile, AL0.000.000.000.000.000.000.003e!040.000.000.000.000.000.006e!040.000.004e!05OccidentalBattleground, TX0.000.000.000.000.000.000.480.000.000.000.000.000.000.000.000.000.005e!05OccidentalDelawareCity, DE0.000.000.000.000.000.000.001e!030.000.000.000.000.000.002e!030.000.001e!04OccidentalHahnville, LA0.000.000.000.000.000.010.100.190.900.852.961.180.630.604.470.691.751.08OccidentalMuscleShoals, AL0.000.000.000.000.000.001e!094e!081e!078e!082e!071e!072e!083e!081e!076e!081e!079e!08TOTAL0.080.221.540.090.7635.09367.817.658.334.6251.441.321.758.90295.0632.40706.7214.11aNot considered to beenvironmental releases.EDC= EthylenedichloridebDowChemical Company.PVC = Polyvinyl chloridecDuPont.VCM = Vinyl chloridemonomerdGeorgia GulfCorporation.eOccidental Chemical Corporation.Source:CCC (2004).

### 8.3.4.5 Products The Viny l I nstitute (1998) presented results for 22 samples from 14 of the 24 U.S. and
Ca na dia n f a c ilitie s ma nuf a c t ur ing suspe n sion a nd ma ss PVC r e sins ( 13 pipe r e sins, 3 bottle resins, and 6 packag ing resins). The results for U.S. manufacturers are summariz e d in Table
8-21. The 14 sampled sites represented a pprox imately 74% of estimated 1995 U.S. and Canadian suspension and mass PVC resin production. CDDs/CDF s were detected in only one sample (0.043 ng I

- TEQ DF 

### /kg , assuming nondetects equal to z e ro). The overall mean TEQ concentrations were 0.002 ng I

- TEQ DF 

### /kg (assuming nondetects e qual to z e ro) and 0.7 ng
I

- TEQ DF 

### /kg (assuming nondetects equal to one-half the DL ). The DL s were 2 ng /kg or less for

a ll c ong e n e r s in a ll sa mple s e x c e p t f o r

OCDD and OCDF , which had DL s of 6 ng /kg or less. The same study also presented results fo r six samples from four of the seven U.S.
f

a c ilitie s ma nuf a c t ur ing dispe r sion PVC r e sins. CDDs/CDF s we r e de te c t e d in f i ve of the samples. The results are summariz e d in Table 8-21. I n terms of produc tion, the four sampled sites represent approx imately 61% of estimate d 1995 U.S. dispersion PVC resin production. The results rang ed from not detected to 0.008 ng I

- TEQ DF 

### /kg (overall mean = 0.001 ng I

- TEQ DF 

### /kg

, assuming nondetects equal to z e ro, and 0.4 ng I

- TEQ DF 

### /kg , assuming nondete cts equal to oneha lf the DL )

. The DL s we r e 2 ng /kg or le ss f o r

a ll c ong e n e r s in a ll sa mple s e x c e p t f o r

OCDD
and OCDF , which had DL s of 4 ng /kg or less.
Re sults we r e a l so pr e se n te d f o r

f

i ve sa mple s f r o m 5 of the 15 U.S. f a c ilitie s manufacturing EDC. The results are summariz e d in Table 8-21. I n terms of production, the five sampled sites represen ted approx imately 71% of the es timated EDC produced in the United
States in 1995. CDDs/CDF s were det ected in only one sample (0.03 ng I

- TEQ DF 

### /kg )

. The overall mean TEQ concentr ations were 0.006 ng I

- TEQ DF 

### /kg (nondetects equal to z e ro) and 0.21

ng I

- TEQ DF 

### /kg (nondetects equal to one-half the DL ). The DL s for all cong eners were 1 ng /kg or less. Using 1995 U.S. production data, 4.846 million metr ic tons of suspension and mass PVC,
0.367 million metric tons of disp ersion PVC resins, and 1.362 million metric tons of EDC were

pr oduc e d. B a se d on the a v e r a g e TEQ c onc e n tr a tion obse r ve d, The Viny l I n stitute e stima te d tha t
the tota l I

- TEQ DF 

### contents of suspension/mass PVC resins , dispersion PVC resi ns, and EDC were
0.01 g , 0.004 g
, and 0.008 g

, respectively (nondetect s equal to z e ro), and 3.39 g , 0.15 g , and 0.29

g , respectively (nondetects equal to one-half the DL ). Therefore, total I

- TEQ DF 

### pr e s e n t in PVC in
1995 was estimated to be between 0.02 g (nondetects equal to z e ro) and 3.83 g (nondetects equal

to one

- h a l f the DL )

. I t is not possible using the da ta pr e se n te d in The Viny l I n stitute r e por t to
cal cul a t e em i ssi on fact ors for TEQ DF 

### -W HO 98 

### . However, because neither 1,2,3,7,8-P e CDD nor
OCDD wa s de te c t e d in a ny sa mple , the TEQ DF 

### -W HO 98 

### e mission f a c t or s would be ve r y simila r to
the I

- TEQ DF 

### emission factors.

8-41Table 8-21.CDD/CDFconcentrations in products fromU.S. EDC/VCM/PVC manufacturers



### 8-42Congener/congener groupSuspension and mass PVC resinsDispersion PVC resinsEDC sold asproductdNo. detects/samplesaRangeb(ng/kg)No. ofdetects/samplesRangec(ng/kg)No. detects/samplesRangee(ng/kg)Min.Max.Min.Max.Min.Max.2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD0/220/220/220/220/221/220/22NDNDNDNDNDNDNDNDNDNDNDND0.64ND0/60/60/60/60/61/60/6NDNDNDNDNDNDNDNDNDNDNDND0.8ND0/50/50/50/50/50/50/5NDNDNDNDNDNDNDNDNDNDNDNDNDND2,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF0/220/220/220/220/220/221/220/220/220/22NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND0.37NDNDND0/60/60/60/60/60/60/60/60/62/6NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND0.380/50/50/50/50/50/50/51/51/51/5NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND1.10.411MeanI-TEQDF(nondetect= 0)MeanI-TEQDF(nondetect= 1⁄2DL)0.0020.70.0010.40.0010.21Total TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF0/220/220/221/220/220/220/221/220/220/22NDNDNDNDNDNDNDNDNDNDNDNDND0.64NDNDND0.37NDND1/61/65/61/60/60/61/60/60/62/6NDNDNDNDNDNDNDNDNDND0.240.320.971.3NDND0.3NDND0.380/50/50/50/50/50/50/50/51/51/5NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND2.0211Table 8-21.CDD/CDFconcentrations in productsfromU.S. EDC/VCM/PVC manufacturers (continued)aTwo ofthese 22 sampleswere duplicate samplesfromtwo sites.The resultswere averaged and treated asone sample for eachsite.bDetectionlimits (DLs) for individual samples were less than2ng/kg forallcongenersandcongenergroupsexceptOCDDandOCDF,which hadDLs less than6ng/kg.cDLs forindividualsamples wereless than2ng/kg forallcongenersandcongenergroupsexceptOCDDandOCDF,which hadDLs less than4ng/kg.d“Sales” EDCisdefined asEDCsold commerciallyfor non-VCM usesor exported fromthe United States.eDLs were less than1ng/kgfor all congeners inall samples.DL= DetectionlimitEDC= EthylenedichlorideND = Not detectedPVC = Polyvinyl chlorideVCM = Vinyl chloridemonomerSource: The Vinyl Institute (1998).



### 8-43

### Approx imately 6.55 million metric tons of PVC and 9.91 million metric tons of EDC were produced in North America in 2000 and a pprox imately 5.58 million metr ic tons of PVC and
7.83 million metric tons of EDC were produced in 1995 (C& EN, 2002). Approx imately 94% of PVC production and appr ox imately 17% of ED C production in 1995 occurred in the United
States. Of the PVC produced, 87% was for su spension and mass PVC pr oducts and 7% was for dispersion PVC resins. Assuming these product percentag e s remained the same for 2000, it is estimated that approx imately 5.69 million metric tons of suspension and mass PVC and 0.46 million metric tons of dispersi on PVC resins were produced a nd 1.69 million metric tons of EDC product were produced. Apply i ng the same averag e TEQ observed in The Viny l I n stitute samples from 1998, EPA estimated the total I

- TEQ DF 

### contents of suspension/mass PVC resins, dispersion PVC resins, and EDC produced in 2000 to be 0.01 g , 0.0004 g , and 0.01 g

, respectively (nondetects equal to z e ro) and 3.99 g

, 0.17 g
, and 0.36 g

, respectively (nondetects equal to one-half the DL ). Therefore, total I

- TEQ DF 

### present in PVC in 2000 was estimated to be between 0.02 g (nondetects equal to z e ro) and 4.52 g (nondetects equal to one-half the DL ).

8.3.5. Othe r Aliphatic Chlor i ne Com p ounds Aliphatic chlorine compounds are used as monomers in the production of plastics, as
sol v ent s and cl eani n g ag ent s , and as precursors for chem i c al sy nt hesi s (Hut z i ng er and
F i edler, 1991b). These compounds are produced in larg e quantities. I n 1992, 14.6 million metric tons of halog e nated hy drocar bons were produced in the United States (U.S. I TC, 1946–1994), with 1,2-dichloroethane and viny l chloride accounting for 82% of total production. Hig hly
chlorinated CDDs/CDF s (hex a- to octa-chlorinated cong eners) have been found in nanog radequality samples of 1,2-dichloro ethane (55 ng /kg of OCDF in one of five samples), tetrachloroethene (47 ng /kg of OCDD in one of four samples), epichl orohy drin (88 ng /kg of CDDs and 33 ng /kg of CDF s in one of three samples), and hex a chlo robutadiene (360 to 425

ng /kg of OCDF in two samples) obtained in Germ any from P r om ochem (H utz i ng er and F i edler, 1991b; Heindl and Hutz ing e r, 1987). No CDDs/CDF s were detected in two samples of ally l chloride, three samples of 1,1,1-tr ichloroethane, and four samp les of trichloroethy l ene (DL

rang ed from 5 to 20 ng /kg ) (Heindl and Hutz ing e r, 1987). B ecause no more recent or additional
data could be found in th e literature to confirm these values for products manufactured or used in
the Unite d Sta t e s, no na tiona l e stima te s of CDD/CDF e missions we r e ma de f o r

the inve ntor y

. EPA’ s Of f i c e of Wa te r pr omulg a te d e f f l ue nt limita tions f o r

f

a c ilitie s tha t ma nuf a c t ur e chlorinated aliphatic chlorine compounds and discharg e treat ed wastewater (40 CF R 414.70).
The se e f f l ue nt limita tions do not spe c i f i c a lly a ddr e ss CDDs/CDF s. Re g u la te d limits f o r chlorinated aliphatic compounds are 68 μg /L for 1,2-dichloroethane and 22 μg /L for

te tr a c h lor o e t hy le ne

. Simila r l y , OSW pr omulg a te d r e str i c tions on la nd disposa l of wa ste s

8-44

### g e nerated during the manufacture of many chlorinate d aliphatics (40 CF R 268); however, these restrictions do not specifi c a lly r e g u la te CDDs/CDF s.

8.3.6. Dyes, P i gm ents, and P r inting Inks
S e veral researchers have anal y z ed various dy es, pig m ents, and printing inks obtained in Canada and Germany for the presence of C DDs/CDF s (W illiams et al., 1992; Hutz ing e r and
F i edler, 1991b; Santl et al., 1994). The following subsections discuss the finding s of those
studies.

8.3.6.1. Dioxazine Dyes and Pigm ents
W illiams et al. (1992) analy z ed the CDD/CD F content in diox azine dy es and pig m ents available in Canada. As s hown in Table 8-22, OCDD and OC DF concentrations in the

nanog ram-per-kilog r am rang e and HpCDD, Hx CDD, and PeCDD concentrations in the microg r am-per-kilog r am rang e were found in Dir ect B l ue 106 dy e (three samples), Direct B l ue 108 dy e (one sample), and Violet 23 pig m ents (s ix samples). These diox az ine pig m ents are derived from chloranil, which has been found to contain hig h levels of CDDs/CDF s and has been

sug g e sted as the source of contamination am ong these dy es (Christmann et al., 1989b; W illiams et al., 1992; U.S . EP A, 1992d). I n May 1990, EP A r eceived test results showing that chloranil was heavily contaminated with diox ins; levels as hig h as 2,903 μg TEQ DF 

### -W HO 98 

### /kg (3,065 μg I

TEQ DF 

### /kg ) were measured in samples from f our importers (mean value of 1,388 μg TEQ DF 

### WH O 98 

### /kg [ 1,754 μg I

- TEQ DF 

### /kg ] ) (U.S. EPA, 1992d; Remmers et al., 1992). (See Section 8.3.6
for anal y t i cal resul t s .)
I n the early 1990s, EPA learned that I

- TEQ DF 

### levels in chloranil could be reduced by more than two orders of mag n itude (to less than 20 μg /kg ) th roug h manufacturing feedstock and process chang e s. EPA’s Office of Pollution Prev ention and Tox i cs subsequently beg a n efforts to complete an industry

- wide switch from the use of c ontaminated chloranil to low-diox in chloranil. Althoug h chloranil is not manufactured in the United States, sig nifican t quantities are imported. As of May 1992, EPA had neg o tiated ag reements with all chloranil importers and domestic dy e/pig m ent manufacturers known to EPA that used chloranil in their products to switch to lowdiox in chloranil. I n May 1993, when U.S. stocks of chloranil with hig h levels of CDDs/CDF s had been depleted, EPA proposed a SNUR under Section 5 of TSCA that would require industry
to notif y

EPA a t le a st 90 da y s pr ior to the ma nuf acture, import, or processing , for any use, of
chl o rani l cont ai ni ng C DDs/ C DFs at a concent r at i on g r eat er t h an 20 μ g I

- TEQ DF 

### / k g (Federal Reg i ster, 1993a; U.S. EPA, 1993d).

8-45Table 8-22.CDD/CDFconcentrations(μg/kg) in samples ofdioxazine dyes and pigments (Canada)



### 8-46Congener/congenergroupBlue 106Blue108Violet 232,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDDND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­ND (0.3)ND (0.3)-­1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDND (0.3)ND (0.3)31ND (0.3)ND (0.3)6ND (0.3)ND (0.3)9ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)9ND (0.3)ND (0.3)1ND (0.3)ND (0.3)16ND (0.3)ND (0.3)10ND (0.3)ND (0.3)2ND (0.3)ND (0.3)4OCDD41,95328,52318,066237,18080611,0227,9291,6271,4202,3,7,8-TCDFND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)1,2,3,7,8-PeCDFND (0.3)ND (0.3)ND (0.3)ND (0.3)0.5ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)2,3,4,7,8-PeCDFND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)1,2,3,4,7,8-HxCDF1222ND (0.3)7643931971,2,3,6,7,8-HxCDFa1,2,3,7,8,9-HxCDF-­-­-­-­-­-­-­-­-­-­2,3,4,6,7,8-HxCDFND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)1,2,3,4,6,7,8-HpCDF501014913101141121,2,3,4,7,8,9-HpCDF-­-­-­-­-­-­-­-­-­-­OCDF12,4631,4471,006119411253,7491,556147425Total2,3,7,8-CDD41,98428,52918,075237,18980711,0387,9391,6291,424Total2,3,7,8-CDF12,5251,4591,022201,030.51393,7991,591157444Total I-TEQDFb56.430.319.50.1161.418.912.72.72.7Total TEQDF-WHO98b7.453.42.30.18.70.65.64.21.11Total TCDDND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)Total PeCDDND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)Total HxCDDND (0.3)ND (0.3)ND (0.3)12127ND (0.3)ND (0.3)1Total HpCDD34812ND (0.3)305361126Total OCDD41,95328,52318,066237,18080611,0227,9291,6271,420Total TCDFND (0.3)0.3ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)0.4ND (0.3)Total PeCDFND (0.3)ND (0.3)ND (0.3)ND (0.3)0.5ND (0.3)ND (0.3)ND (0.3)ND (0.3)ND (0.3)Total HxCDF1222ND (0.3)765393197Total HpCDF7132261226142913221Total OCDF12,4631,4471,006119411253,7491,556147425Total CDD/CDFb54,53330,012.319,112478,274.595714,8829,5401,787.41,880Table 8-22.CDD/CDFconcentrations in samples ofdioxazine dyes and pigments (μg/kg) (Canada) (continued)aResultslisted for 1,2,3,4,7,8-HxCDFinclude concentrationsfor 1,2,3,6,7,8-HxCDF.bCalculationsassume nondetected valueswere equal to zero.ND = Not detected(valueinparenthesis is the detectionlimit)--= Not reportedSource:Williamset al. (1992).



### 8-47

### I n 1983, approx imately 36,500 kg of chloranil were imported (U.S. I TC, 1984). The U.S.
I n te r n a tiona l Tr a d e Commission ha s not publishe d qua ntita tive impor t da ta f

o r

c h lor a nil sinc e 1984. I f it is assumed that this import volume re flects actual usag e of chloranil in the United States during 1987 and that the CDD/CD F contamination le vel was 1,388 μg TEQ DF 

### -W HO 98 

### /kg (1,754 μg I

- TEQ DF 

### /kg ) , the n the ma x imum r e le a se to the e nvir onme n t via pr oc e ssing wa ste s a n d finished products was 50.6 g TEQ DF 

### -W HO 98 

### (64 g I

- TEQ DF 

### )

. I f it is a ssume d tha t the impor t volume in 1995 was also 36,500 kg but that th e imported chloranil contained 10 μg I

- TEQ DF 

### /kg

on averag e, then the total potential annual TEQ release associated with chloranil in 1995 was
50.6 g TEQ DF 

### -W HO 98 

### (64 g I

- TEQ DF 

### ).
I n 1986, EPA promulg a ted the I nventory Update Rule (I UR) that requires the partial updating of the TSCA Chemical I nventory database. Ev ery four y ears, chemical manufacturers

a nd impor te r s of c h e mic a l s liste d in the TSCA i nventory that produce at one plant site or import at production volume levels of 10,000 lb or more must report the rang e of chemical production or import. According to information entered in the TSCA database, 10,000 to 500,000 lb (4,540 to 227,000 kg ) of chloranil were imported in 1994 and 2000 (http://www.epa.g ov/opptintr/iur /iur02/search03.htm). Assuming th e imported chloranil containe d the same concentration of
diox in as the 1995 estimate (10 μg I

- TEQ DF 

### /kg ) , the total potential a nnual TEQ release associated with chloranil in 2000 was 0.05 to 2.27 g I

- TEQ DF 

### -W HO 98 

### (mean of 1.16 g I

- TEQ DF 

### ).

8.3.6.2. Ph t h al ocyan i n e Dyes and Printing Inks
Hutz ing e r and F i edler (1991b) found CDDs/CDF s (tetra-, penta-, and hex a -chlorinated

cong eners) i n t h e m i c rog r am -per-ki l o g r am rang e i n a sam p l e of a Ni -pht hal o cy ani n e dy e. No
CDDs/CDF s were detected (DL of 0.1 to 0.5 μg /k g ) in two samples of Cu-phthalocy anine dy es and in one Co-phthalocy anine dy e (Hutz i ng er and F i edler, 1991b). Santl et al. (1994) reported the results of analy s es of four printing inks obtained from a supplier in Germany

. Two of the inks are used for rotog r avure printing and two are used for offset printing

. The results of the anal y s es are presented in Table 8-23. The TEQ DF 

### -W HO 98 

### content of the inks rang ed from 17.7 to 87.2 ng /kg (15 to 88.6 ng /kg on an I

- TEQ DF 

### basis). Primarily non-2,3,7,8-substitute d cong eners were found. The iden tities of the dy es and pig m ents in these inks were not reported. Althoug h EPA provided an estimate of poten tial environmental re leases based on limited
information of contaminant le vels of CDDs/CDF s in the pr oduct, the estimate is still too uncertain to include in the quan titative inventory of sources. I t is currently not known whether
the diox in contamination in the product actually results in a rel ease to the open and circulating
environment.

8-48

### Table 8-23. CDD/CDF concentrations (n g/kg) in printing inks (G erm any)

C o ngener/congener group Rotogravure (2-color) Rotogravure (4-color) O ffs e t (4-color) O ffs e t (4-color)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND (1) 8 19 325 155 2,770 5,810 ND (1.5) ND ( 4 ) ND ( 5 ) 310 105 1,630 2,350 ND ( 2 ) 15 16 82 42 540 890 ND ( 2 ) 6 11 21 14 240 230
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 2.5 ND ( 2 ) ND ( 2 ) 4 ND ( 3 ) ND ( 3 ) ND ( 3 ) 40 ND ( 4 ) 129 14 ND ( 4 ) ND ( 4 ) 7 ND ( 5 ) ND ( 5 ) ND ( 5 ) 14 ND ( 7 ) ND ( 10) 7 ND ( 4 ) ND ( 4 ) 27 ND ( 5 ) ND ( 5 ) ND ( 5 ) 315

11 960 7 ND ( 3 ) ND ( 3 ) 35 ND ( 5 ) ND ( 5 ) ND ( 5 ) 42 ND ( 6 ) 165

T o tal 2,3,7,8- CDD T o tal 2,3,7,8- CDF Total I

- T E Q DF a 

### Total TE Q DF 

### -W H O 98 

### 9,087 175.5

88.6 87.2 4,395 35 62.4 60.3 1,585 1,320 35.4 41.2 522 249

15 18

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 4 58 2,679 5,630 5,810 5.5 13 29 64 129 ND ( 2 ) 145 2,485 3,460 2,350 28 ND ( 4 ) 45 14 ND ( 10) 77 35 660 1,100

890

90 340

95 566 960 38 25 246 445 230

35 110

94 63 165

T otal CDD/CDF 14,421.5 8,527 4,813 1,451

a C alcu l ation s as s u m e n o n d etect v alu es w ere zero.

ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)

S o u r ce: S a n t l et al . (1994).



### 8-49

### 8.3.7. TSCA Dioxin/F u ran Test Rule Citing evidence that halog e nated diox ins and fu rans may be formed as by -products during chemical manufacturing processe s (Versar, I n c., 1985), EPA issu ed a rule under Section 4 of
TS C A t h at requi res chem i cal m a nufact urers and importers to test for the presence of
CDDs/CDF s and brominated dibenz o- p -diox i ns (B DDs) and brominated dibenz ofurans (B DF s) in certain commercial org a nic chemicals (F ed eral Reg i ster, 1987a). The rule listed 12 manufactured or imported chemicals that re quired testing and 20 chemicals not currently manufactured or imported that would require testing if manuf acture or importation resumed.
These chemicals are listed in Table 8-24. The sp ecific diox in and furan cong eners that require

qua ntita tion a nd the ta r g e t limits of qua ntita tion ( L OQs) tha t a r e spe c i f i e d in the r u le a r e liste d in
Table 8-25. Under Section 8(a) of TSCA, the final rule also required that chemical
manufacturers submit data on ma nufacturing processes and reac tion conditions for chemicals produced using any of the 28 precursor chemical s listed in Table 8-26. The rule stated that subsequent to this data-g atheri ng effort, testing may be proposed for additional chemicals if any of the manufacturing conditions used favor ed the production of diox ins and furans. Twenty -three sampling and analy tical protocol s and test data for 10 of the 12 chemicals that required testing were sub mitted to EPA (U.S. EPA, 2003a, c). Manufacture or import of two substances (tetrabromobisphe nol-A-bis-2,3-dibromopropy letherand tetrabromobisphenol-Adiacry l ate) have stopped since the test rule was promulg a ted. (A ll data and reports in the EPA TSCA docket are available for pub lic review and inspection at EPA Headquarters in W a shing t on, DC .)
Tabl e 8-27 present s t h e resul t s of anal y t i cal t e st i n g for C DDs/ C DFs for t h e chem i cal s t h at have data available in the TS CA docket. F i ve of these 10 chem i cal s cont ai ned C DDs/ C DFs. Positive results were obtained for 2,3,5,6-tetrach loro-2,5-cy clohex a diene- 1,4-dione (chloranil), pentabromodipheny lox i de, oc tabromodipheny lox i de, decab romodipheny lox i de, and 1,2­ bis(tribromophenox y )-ethane. Table 8-28 presen ts the quantitative analy tical results for four
submitte d c h lor a nil sa mple s, a s we ll a s the r e sults of a n EPA a n a l y sis of a

sa mple of c a r ba zole violet, which is manufactured from chloranil. Althoug h testing conducted unde r this test rule for 2,4,6-tribromophenol indicated no halog e nated diox ins or furans above the L OQs, Thoma and Hutz ing e r (1989) reported detecting
B DDs and B D F s in a technical-g rade sample of this substance. Total TB DD, TB DF , and PeB D F were found at 84 μg /kg , 12 μg /kg , and 1 μg /kg , re spectively

. No hex a -, hepta-, or octa-B DF s were det ect ed. The i nvest i g at ors al so anal y z ed analy tical-g rade samples of two other brominated flame retardants, pentabromophe nol and tetrabromophthalic anhy dride; no B DDs or B D F s were detected (DL s not reported).

8-50

### Table 8-24. Chem icals requiring Toxi c Substances Control Act Section 4 t e st ing unde r t h e dioxin/fur a n r u le

CAS No. C he m i c a l nam e C u rrently manuf actured or imported as of June 5, 1987
79- 94- 7
118- 75- 2
118- 79- 6
120- 83- 2
1163- 19- 5
4162- 45- 2
21850- 44- 2
25327- 89- 3
32534- 81- 9
32536- 52- 0
37853- 59- 1
55205- 38- 4 T etrabrom obisphenol- A 2,3,5,6- T e trachloro- 2,5- cy clohexadiene- 1,4- dione 2,4,6- T r ibrom ophenol 2,4- Dichlorophenol
D ecabrom odipheny loxide
T etrabrom obisphenol- A

- b isethoxy late
T etrabrom obisphenol- A

- b is- 2,3- dibrom opropy lether a


### A lly l ether of tetrabrom obisphenol- A
P entabrom odipheny loxide
O ctabrom odipheny loxide 1,2- Bis(tribrom ophenoxy )- ethane
T etrabrom obis phenol- A

- d iacry l ate a


### Not manuf actured or imported as of June 5, 1987 b


### 79- 95- 8
87- 10- 5
87- 65- 0
95- 77- 2
95- 95- 4
99- 28- 5
120- 36- 5
320- 72- 9
488- 47- 1
576- 24- 9
583- 78- 8
608- 71- 9
615- 58- 7 933- 75- 5
1940- 42- 7
2577- 72- 2
3772- 94- 9
37853- 61- 5

-

- T etrachlorobisphenol- A 3,4' ,5- T r ibrom o salicy l anide 2,6- Dichlorophenol 3,4- Dichlorophenol 2,4,5- T r ichlorophenol 2,6- Dibrom o- 4- nitrophenol
2 [2,4- (Dichlorophe noxy )]- p ropanoic acid 3,5- Dichlorosalicy clic acid
T etrabrom ocatechol 2,3- Dichlorophenol 2,5- Dichlorophenol
P entabrom ophenol 2,4- Dibrom ophenol 2,3,6- T r ichlorophenol
4

- B rom o

- 2,5- dichlorophenol 3,5- Dibrom osalicy l anide
P entachloropheny l laurate
B ism ethy l ether of tetrabrom obisphenol- A
A lk y l am ine tetrachlorophenate
T etrabrom obisphenol- B

a N o l o n g e r m a n u f act u red i n or i m port e d i n t o t h e U n i t e d S t at es (m em oran du m dat e d May 4, 1993, f rom G o rdon Cash , U.S. EP A / OP P T S, to J o h n Sch a u m , U.S. EP A / ORD).

b A s o f A ugust 5
, 1995, n e i t h er m a n u f act u r e n o r i m port a t i o n of an y of t h es e ch em i cal s h a d res u m e d i n t h e U n i t e d St a t e s ( m e m o r a n d u m d a t e d A ugust 2
, 1995, f rom T

. S

. H o l d erm a n , U

. S

. EPA
, t o A

. A d e nuga , V e r s a r , I nc

. )

.



### 8-51

### Table 8-25. Congeners and lim its of quantitation (LOQs) f or w h ich quant it at ion is r e quir e d unde r t h e dioxin/fur a n t e st r u le and pe st ic ide D a t a Call- In

Chl o ri nat e d di ox i n s and f u rans B r ominated diox ins and f u rans LO Q (μg/kg) 2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD 2,3,7,8- T B DD 1,2,3,7,8- PeBDD 1,2,3,4,7,8- HxBDD 1,2,3,6,7,8- HxBDD 1,2,3,7,8,9- HxBDD 1,2,3,4,6,7,8- HpBDD 0.1
0.5
2.5
2.5
2.5
100 2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF 2,3,7,8- T B DF 1,2,3,7,8- PeBDF 2,3,4,7,8- PeBDF 1,2,3,4,7,8- HxBDF 1,2,3,6,7,8- HxBDF 1,2,3,7,8,9- HxBDF 2,3,4,6,7,8- HxBDF 1,2,3,4,6,7,8- HpBDF 1,2,3,4,7,8,9- HpBDF 1
5
5
2 5
2 5
2 5
2 5 1,000 1,000



### 8.3.8. Halogenated P e sticides and F I F RA P e sticides Data Call-In
I n the late 1970s and early 1980s, attention beg a n to focus on pesticides as potential

sour c e s of CDDs/CDF s in the e nvir onme nt. Up to tha t time , CDD/CDF le ve ls we r e not

reg u lated in end-use pesticide pr oducts. However, some of the ac tive ing r edients in pesticides, particularly chlorinated phe nols and their derivatives, were known or suspected to be
contaminated with CDDs/CDF s. During the 1980s and 1990s, EPA took several actions to investig ate and control CDD/CDF contamination of pe stic ide s. I n 1983, EPA cancelled the sale of Silvex a nd 2,4,5-T for all uses (F ederal Reg i ster, 1987a). Earlier, in 1979, EPA had ordered emerg e ncy suspension of the forestry , rig h ts-of-way

, and pasture uses of 2,4,5-T. Emerg e ncy suspensions of the forestry , rig h ts-of-way , pasture, home

a nd g a r d e n, c o mme r c ia l/or n a m e n ta l tur f

, a nd a qua tic we e d c ontr o l/ditc h bank uses of Silvex were also ordered (F ederal Reg i ster, 1979; Plimmer, 1980). The home and g a rden, commercial/ornamental turf, a nd aquatic weed control/ditch bank uses of 2,4,5-T had been suspended in 1970.

8-52

### Table 8-26. P recursor chem icals subj ect to reporting requirem ents under Toxic Subst a nc e s C o nt r o l A c t Se c t ion 8( a) a



### CAS No. C he m i c a l nam e
85- 22- 3 87- 61- 6 87- 84- 3 89- 61- 2 89- 64- 5 89- 69- 0 92- 04- 6 97- 74- 6 94- 81- 5 95- 50- 1 95- 56- 7 95- 57- 8 95- 88- 5 95- 94- 3 95- 50- 7 99- 30- 9 99- 54- 7 106- 46- 7 108- 70- 3 108- 86- 1 108- 90- 7 117- 18- 0 120- 82- 1 348- 51- 6 350- 30- 1 615- 67- 8 626- 39- 1 827- 94- 1 Pentabrom o ethy lbenz ene 1,2,3- T r ichlorobenz ene 1,2,3,4,5- Pentabrom o

- 6

- c hlorocy c lohexane 1,4- Dichloro- 2

- n itrobenz ene 4- Chloro- 2

- n itrophenol 2,4,5- T r ichloronitrobenz ene 2- Chloro- 4

- pheny lphenol 4- Chloro- o

- t oloxy acetic acid 4- (2- Methy l- 4- chlorophenoxy ) buty r ic acid

o- Dichlorobenz ene

o- Brom ophenol

o- Chlorophenol 4- C h lororesorcinol 1,2,4,5- T e trachlorobenz ene 5- C h loro- 2,4- dim ethoxy aniline 2,6- D i chloro- 4

- n itroaniline 1,2- Dichloro- 4

- n itrobenz ene p- Dichlorobenz ene 1,3,5- T r ichlorobenz ene Brom obenz ene Chlorobenz ene 1,2,4,5- T etrachloro- 3

- n itrobenz ene 1,2,4- T r ichlorobenz ene

o- Chlorofluorobenz ene 3- Chloro- 4

- f luoronitrobenz ene Chlorohy droquinone 1,3,5- T r ibrom obenz ene 2,6- D i brom o- 4- nitroaniline

a D i brom oben zen e (C A S N o . 106- 37- 6) w a s i d en t i f i e d i n t h e pream bl e t o 52 F R 21412 as on e of 29 precu rs or ch em icals; h o w e v e r, it w a s in ad v e rten tly o m itted f r o m th e reg u l ato r y tex t

. B ecau se th e reg u l ato r y tex t id en tif ied

on l y 28 ch em i cal s , 28 ch em i cal s appear i n 40 C F R 766.38 an d i n t h i s t a bl e.



### I n 1984, EPA issued a notice of intent to cancel reg i strations of pesticide products containing PCP (including its salts) for all wood preservative uses (F ederal Reg i ster, 1984). This notice specified modifications to the terms and conditions of product reg i strations that were required in order to avoid cancella tion of the products. I n response to this notice, several trade

a ssoc i a tions a nd r e g i str a nts r e que ste d a d ministr a tive he a r ing s to c h a lle ng e EPA’ s de te r mina tions.
Af te r c a r e f ully c onside r ing the c o mme nts a nd a lte r n a tive s sug g e ste d dur ing the pr e h e a r ing sta g e of the administrative proceeding s , EP A conclude d that certain chang e s to the 1984 notice were appropriate. These chang e s, finaliz ed in 1986 (F ederal Reg i ster, 1986), included the following :

8-53

### Table 8-27. Results of analytical te sting f o r dioxins and f u rans in the ch em i c al s tested to d a te u n d er S ecti o n 4 of th e d i oxi n / f u ran test ru l e

CAS No

. Chem i ca l na m e No . o f chem ical

com p anies th at subm it t e d da t a No . o f po sit i v e st udies Congeners detected (detection rang e in μg /k g )
79- 94- 7 T et rabrom obi s p h e n o l

- A 3 0 a 118- 75- 2 2 ,3,5,6- T et rach l o ro- 2 ,5­
cy cloh ex adien e

1,4- di on e (ch l oran i l ) 6 5 S ee T a bl e 8- 28

118- 79- 6 2 ,4,6- T ri brom oph en ol 1 0 a
120- 83- 2 2 ,4- D i c h l oroph en ol 1 0 a 1163- 19- 5 D ecabrom odiph en y l

ox i de 3 3 2,3,7,8- PeBD D (N D –0.1) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD D (N D –0.5) 1,2,3,7,8,9- H x BD D (N D –0.76) 1,2,3,7,8- PeBD F (N D –0.7) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD F (N D –0.8) 1,2,3,4,6,7,8- H p BD F (17–186)
25327- 89- 3 A l l y l et h e r of tetrab ro m o b i sp h e n o l- A 1 0 a

32536- 52- 0 O ct abrom odi ph en y l

ox i de 3 3 2,3,7,8- T B D D (N D –0.71) 1,2,3,7,8- PeBD D (N D –0.1) 2,3,7,8- T B D F (N D –12.6) 1,2,3,7,8- PeBD F (N D –6.3) 2,3,4,7,8- PeBD F (N D –83.1) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD F (N D –67.8) 1,2,3,7,8,9- H x BD F (N D –56.0) 1,2,3,4,6,7,8- H p BD F (N D –330)
378- 53- 59- 1 1,2- B i s (t ri brom oph en ox y )- e t h an e 1 1 2,3,7,8- T B D F (N D –0.04) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD F (N D –0.03) 1,2,3,4,6,7,8- H p BD F (N D –0.33)
32534- 81- 9 P en t a brom odi ph en y l

ox i de 3 3 1,2,3,7,8- PeBD D (N D –5.9) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD D (N D –6.8) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD D (N D –6.8) 1,2,3,7,8,9- H x BD D (N D –0.02) 2,3,7,8- T B D F (N D –3.1) 1,2,3,7,8- PeBD F (0.7–10.2) 2,3,4,7,8- PeBD F (0.1–2.9) 1,2,3,4,7,8/ 1,2,3, 6,7,8- H x BD F (15.6–61.2) 1,2,3,4,6,7,8- H p BD F (0.7–3.0)
4162- 45- 2 T et rabrom obi s p h e n o l

- A

bi s e t h ox y l at e 1 0 a

a No 2
, 3
, 7
, 8

- su b s titu ted d i o x in s an d f u ran s d e tected ab o v e th e test ru le targ et lim its o f q u an titatio n (see T a bl e 8- 20).

ND = No t d e tected

S o u r ce: H o l d erm a n an d C r am er (1995).



### 8-54

### Table 8-28. CDD/CDF concentrations (μ g/kg) in chloranil and carbazole violet sam p les analyzed pur suant t o t h e EP A dioxin/fur a n t e st r u le

C ongener Chl o r a ni l
Carbaz ole violet Importer 1 Importer 2 Importer 3 Importer 4
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND ( 1 ) ND ( 2 ) ND ( 3 ) ND ( 3 ) ND ( 1 ) 110 240,000 ND ( 1 ) ND ( 2 ) ND ( 10) 75 48 8,200 180,000 ND ( 2 ) ND ( 5 ) ND ( 5 ) ND ( 5 ) ND ( 5 ) 390 760,000 ND ( 2 ) ND ( 6 ) ND ( 3 ) 6 9 2,300 71,000 ND (0.8) ND (0.5) ND (1.2) ND (1.2) ND (1.2) 28 1,600
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF ND ( 1 ) ND ( 1 ) ND ( 1 ) 35 ND ( 5 ) 6 ND ( 5 ) 33 ND ( 15) 18,000 ND ( 2 ) ND ( 1 ) ND ( 1 ) ND (860) ND (860) ND (680) ND (680) 240,000 ND (100) 200,000 ND ( 1 ) ND ( 3 ) ND ( 3 ) ND ( 4 ) ND ( 4 ) ND ( 4 ) ND ( 4 ) 36 ND ( 15) 50,000 ND ( 2 ) ND ( 5 ) ND ( 5 ) 5,600 ND (600) ND (600) ND (600) 230,000 ND (400)

110,000 ND (1.6) ND (0.9) ND (0.9) ND ( 20) ND (20) ND ( 20) ND ( 20)

15,000 ND ( 20) 59,000

Total I

- T E Q DF a 

### 263 2,874 814 3,065 211

Total TE Q DF 

### -W H O 98 a 

### 31 2,532 85 2,903 156

a C alcu l ated as s u m i n g n o n d etect v alu es are zero.

ND = No t d e tected (v alu e in p a ren t h e sis is th e m i n i m u m d e tectio n lim it)

S o u r ce: R e m m e rs et al . (1992).



### (a) all wood preservative uses of PCP and its salts were classi fied as “restricted use” only by

c e r tif ie d a pplic a t or s, ( b ) spe c i f i c wor k e r pr ote c tion me a sur e s we r e r e quir e d, ( c ) limits we r e pl aced on t h e Hx C DD cont ent of P C P
, and (d) l a bel rest ri ct i ons for hom e and farm uses of P C P prohibited its application indoors and to wood intended for interior use (with a few ex ceptions)

a s we ll a s its a pplic a tion in a ma nne r tha t mig ht result in direct ex posure of domestic animals or
livestock or in the contamination of f ood, feed, or drinking and irrig a tion water. EPA subsequently amended its Notice on the w ood preservative uses to establish reliable and enforceable methods for implementin g certified limits for Hx CDD and 2,3,7,8-TCDD in

reg i stered wood preservative pe sticide products (F ederal Re g i ster, 1987b). L e vels of 2,3,7,8­
TCDD were not allowed to ex ceed 1 ppb in any product, and after February 2, 1989, any

m a nufact uri n g

- use P C P rel eased for shi p m e nt coul d not cont ai n Hx C DD l e vel s t h at ex ceeded an

8-55

### averag e of 2 ppm over a monthl y release or a batch level of 4 ppm (a g r adually phased-in requirement). On J a nuary 21, 1987, EPA prohibited the reg i stration of PCP and its salts for most nonwood uses (F ederal Reg i ster, 1987c). EP A deferred action on se veral uses (uses in pulp/paper mills, oil wells, and coo ling towers) pending receipt of additional ex posure, use, and ecolog i cal effects data. On J a nuary 8, 1993, EPA i ssued a press advisory stating that its special
review of these deferred nonwood us es was being terminated because all of these uses had been either voluntarily cancelled by the reg i st rant s or cancel l e d by EP A for fai l u re of t h e reg i st rant s t o
pay the required annual mainte nance fees (U.S. EPA, 1993e). PCP was one of the most widely used biocides in the Unite d Sta t e s pr ior to the r e g u la tor y actions to cancel and restrict certain of its wood and nonwood preservative uses. PCP was

reg i stered for use as a herbicide, defoliant, mossicide, and mushroom house biocide. I t also found use as a biocide in pulp-paper mills, oil wells , and cooling towers. These latter three uses
were terminated on or before 1993 (U.S. EPA, 1993e). However, the major use (g reater than 80% of consumption) of PCP was a nd continues to be wood preservation. The production of PCP for wood preserving be g a n on an ex perimental basis in the 1930s.
I n 1947, nearly 3,200 metric tons of PCP were reported to have been used in the United States by the commercial wood preserving industry

. Use in this industry steadily increased throug h the mid-1970s (American W ood Preservers I nstitu te, 1977). Althoug h domestic consumption volumes are not available for all y ears, it is es timated, on the basis of hi storical production/ex port data for PCP reported in Manns ville (1983), that 90 to 95% of production volume has ty pically been consumed domestically rather than ex por ted. A reasonable estimate of averag e annual domestic PCP consumption during the period of 1970 to 1995 is about 400,000 metric tons. This estimate assumes an averag e a nnual consumption rate of 20,000 me tric tons/y r during the 1970s, 15,000 metric tons/y r during the 1980s, a nd 10,000 metric tons/y r during the 1990s. Table 8-10 presents a compilation of pub lished data on the CDD/CDF content of technical-g rade PCP. The only samples that have been anal y z ed for al l di ox i n -l i k e C DDs/ C DFs
were manufactured in the mid to la te 1980s. F i g ure 8-4 presents th ese data in g r aphical form. I t is evident from the fig u res that the predo minant cong ener g r oups are OCDD, OCDF , HpCDF
, and HpCDD and the dominant 2,3,7,8-substitu ted cong eners are OCDD, 1,2,3,4,6,7,8-HpCDD,
and OCDF. W a ddell et al. (1995) tested analy tical-g rade P C P (fro m Aldrich Chemical Co.) for
CDD/CDF content and found the same cong ener profile; however, the CDD/CDF levels were three to four orders of mag n it ude lower. Table 8-11 presents a similar compilation of published
data on the CDD/CDF content of PCP-Na. The table shows th e same patterns of dominant

cong eners and cong ener g r oups reported for PCP.

8-562, 3,7

,8

- TC

D D

1,2

,3 ,7,8

- Pe

C D D
1,2,3

, 4,7,

8- Hx

CD

D

1 ,2,3

,6,7,

8 -H

x C D D
1,2,3

, 7,8,

9- Hx

C D D

1,2

, 3,4,

6 ,7,8

- H p CDD O CDD
2,3 , 7,8

- T CDF

1 ,2,3

,7,8-

P eCDF

2 ,3,4

, 7,8-

P e CDF

1 ,2 ,3,4

,7 ,8

- Hx

CDF

1 ,2, 3,6

,7 ,8

- Hx

CDF

1 ,2, 3,7

,8 ,9

- Hx

CDF

2 ,3 ,4,6

,7 ,8

- Hx

CDF

1,2

, 3,4

,6 ,7, 8- Hp

CDF

1,2

, 3,4

,7 ,8,9

- H p CDF O CDF 0% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 %Percent TotalCDDs andCDFs

Congener



### F i gu re 8-4. Con g en er p r of i l e f o r tech n i cal-grade P C P (dev eloped f r om data
in last colum n in Table 8-10).

Samples of technical-g rade PCP manufactured during the mid to late 1980s contained about 1.7 mg TEQ DF 

### -W HO 98 

### /kg (3 mg I

- TEQ/kg ) , based on the data presented in Table 8-10. No published reports could be located that present th e resul t s of any cong ener-speci fi c anal y s es of
PCP manufactured since the late 1980s. Howe ver, monthly measur ements of CDD/CDF

cong ener g r oup concentrations in technical PCP manufactured for use in the United States have been reported to EPA from 1987 to the pres ent (letter dated March 5, 1997, from Thomas Mitchell, KMG-B e rnuth, to Matthew L o rber, U. S. EPA; letter dated F e bruary 7, 1997, from J ohn
W ilkinson, Pentachlorophenol Task F orce, to Ma tthew L orber, U.S. EPA; U.S. EPA, 1999a). The averag e cong ener g r oup concentrations re ported to EPA for the y ears 1988 (i.e., one y ear after EPA reg ulations were imposed limiting Hx CDD and 2,3,7,8-TCDD concentrations in PCP) to 1999 are presented in Table 8-10. I n g e nera l, the averag e cong ener g r oup concentrations during the period of 1988 to 1999 are lower by factor s of 2 to 4 than those observed in the mid to late 1980s’ full cong ener analy s is samples. I f it is assumed that the tox i c CDD/CDF cong eners have also been reduced by similar factors, th en the TEQ content of PCP manufactured since 1988 is about 0.6 mg TEQ DF 

### -W HO 98 

### /kg ( 1 mg I

- TEQ/kg )

.

8-57

### An estimated 12,000 metric tons of PCP were used for wood preservation in the United States in 1987 (W HO, 1991). An estimated 8,400 metric tons were used in 1994 (American
W ood Preservers I nstitute, 1995); for purposes of this report, it is assumed that an identical
amount was used in 1995. I n 1999, approx imate ly 7,710 metric tons of PCP were produced annually in the United States (Council of Great L a kes I ndustries, 1999); for purposes of this report, it is assumed that an identical amount was produced in 2000. Assuming that 95% of the production volume was consumed domestically (M annsville, 1983), and th at all of the PCP produced in 2000 was used for wood preservation, approx imately 7,325 metric tons of PCP was used in the United States for wood preservati on. Combining these activ ity level estimates with the TEQ concentration estimates pres ented above indicates that 20,000 μg TEQ DF 

### -W HO 98 

### (36,000 μg I

- TEQ DF 

### ), 4,800 μg TEQ DF 

### -W HO 98 

### ( 8,400 μg I

- TEQ DF 

### ), and 4,175 μg TEQ DF 

### -W HO 98 

### (7,325 μg I

- TEQ DF 

### ) were incorporated into PCP-tr eated wood products in 1987, 1995, and 2000, respectively

. These amounts in PCP products are not considered an envi ronmental release and therefore are not included in the inventory

. As di scussed bel o w, t h ere i s som e evi d ence t h at releases could occur, but no consistent estimation approach could be found. Althoug h the estimates of the mass of TEQ in treated wood are fairly certain, no studies

a r e a v a ila ble tha t pr ovide me a sur e d CDD/CDF r e le a se r a te da ta f

r o m whic h a r e lia ble e stima te can be made of the amount of CDDs/CDF s that have or will volatiliz e or leach from treated
wood. S e veral recent field studies, discussed in the following parag r aphs, demonstrate that CDDs/CDFs do apparently leach into soil from P C P

- treated wood, but the studies do not provide

r e le a se r a te da ta

. No studie s we r e loc a t e d tha t pr ovide a n y me a sur e d CDD/CDF vola tiliza tion
rates from PCP-treated wood. Althoug h CDDs/CDF s have very low vapor pressures, they are not bound to, nor do they react with, the wood in any way that would preclude volatiliz ation.
Se ve r a l studie s, disc usse d be low, ha ve a tte mpte d to e stima te pote n tia l CDD/CDF vola tiliza tion

r e le a se s using c onse r va tive a ssumptions or mode ling a ppr oa c h e s, but the se e stima te s spa n ma ny orders of mag n itude. Gurprasad et al. (1995) analy z ed three PC P-treated utility poles and their surrounding
surface soi l s for pent a- t h roug h oct a -C DD cont ent

. Al l t h ree pol es showed si g n i f i cant l e vel s of
Hx CDD (0.29 to 0.47 mg /kg ) , HpCDD (4.69 to 6.63 mg /kg ) , and OCDD (27.9 to 42.1 mg /kg )
, but no P e C DD. S u rface soi l s col l ect ed 2 cm from t h e pol es al so had det ect abl e l e vel s of
Hx CDD, HpCDD, and OCDD; however, no cons istent pattern was found between the CDD

concent r at i ons i n t h e pol es and t hose i n t h e ad j acent soi l s

. The soi l concent r at i ons di d, however, show the same relative cong en er g r oup pattern observed in th e wood. CDD concentrations in soils obtained 20 cm from the poles were an orde r of mag n itude less than those measured at 2

cm. Soils 26 m from the poles showed nondetect va lues or values close to the DL of 0.01 to 0.02

mg /kg

.

8-58

### I n a study of the leaching of PCP from 31 utility poles, the Electric Power Research
I nstitute (EPRI , 1995) found patte rns of PCP distribution in soils surrounding poles similar to those found by Gurprasad et al. (1995) for CDDs. PCP concentrations decreased by as much as two orders of mag n itude between 7.5 cm from the poles and 20 cm from the poles, with an

averag e decrease of sl i g ht l y m o re t h an one or der of mag n itude over this distance. The EPRI study also found no obvious trend between PCP con centration in the wood (eig ht poles analy z ed)
and t h e ag e of t h e pol es (4 t o 11 y ears) or t h e P C P concent r at i on i n t h e surface soi l

. On t h e basi s of their results and those of the EPRI study , Gurp rasad et al. concluded th at CDDs probably leach
f r o m PCP- tr e a t e d utility pole s with the PCP/oil c a r r i e r a nd tr a v e l in the soil in a simila r ma nne r

. W a n (1995) and W a n and Van Oostdam (1995) measured CDD/CDF concentrations in
waters and sediments from ditc hes surrounding utility poles and railroad ties a nd demonstrated that chlorophenol-treated wood could serve as a source of CDD/CDF s to the aquatic
environment. Ten samples were collected at each of six utility pole sites and five railroad tie
site s 1 to 2 da y s a f te r ma jor r a inf a ll e v e n ts a nd the n we r e c o mposite d into one sa mple pe r site prior to analy s es. Total CDDs (mean value of 76.7 mg /kg ) and total CDF s (mean value of 18.7

mg /kg ) detected in chlorophenol/creosote-treat ed utility poles were about six to eig ht times

g r eater, respectively

, than the CDD and CDF con centrations detected in chlorophenol/creosotetr e a t e d r a ilr oa d tie s. Total CDDs found in water from railway ditc hes without utility poles (i.e., only treated railroad ties were present) we re approx imately 20 times hig her than the backg r ound level found
in farm ditch water. Total CDDs in railway ditches with utility poles were 4,300 times hig her than the backg r ound levels. W a ter from railway ditches without utility poles contained total
CDF levels 13 times hig her than backg r ound levels, whereas wate r in ditches adjacent to poles had levels 8,500 times hig her than backg r ound levels. Total CDDs in ditch sediments adjacent to and 4 m downstream of utility pol es were about 5,900 and 2,200 times hig h er, respectively

, than backg r ound levels; total CDF s for the same sites were about 8,100 and 1,700 times hig her, respectively , than backg r ound levels. Total CDDs found in ditch sediment s of railway and ditch sediments adjacent to utility poles were a bout 5 and 700 times hig her, respectively , than backg r ound levels, and total CD F s were about 9 and 1,800 times hig h er, respectively

, than backg r ound levels. B o th CDDs and CDF s were found in utility ditch se diments 4 m downstream of treated power poles, but at levels 200 and 400 times lower, respectively , than those found adjacent to poles, indicating that they were transported from point sources of contamination. The corresponding values for CDF s were 5,400 and 8,000 times hig her, respectively , in

concent r at i on. B r emmer et al. (1994) estimated an annual release of 15 to 125 g I

- TEQ DF 

### f

r o m PCPtreated wood in the Netherlands. The lower estimate was based on th ree basic assumptions:

8-59

### (1) the half-life of P C P in treated wood is 15 y ears (according to industrysources), (2) the halflife of CDDs/CDF s in treated wood is 10 times that of PCP (i.e., 150 y ears) because of the lower vapor pressures of CDDs/CDF s re la tive to PCP, a nd ( 3 ) the ty pic a l CDD/CDF c onc e n tr a tion in PCP has been 3,000 μg /kg

. The hig her estimate was based on an assume d half-life of PCP in wood of 15 y ears and the results of an indoor air study by Papke et al. (1989) conducted at several kinderg artens where PC P-treated wood had been used. Althoug h Papke et al. found no
clear correlation between indoor air concentrations of CDDs/CDF s and PCP across the rang e of
CDD/CDF concentrations observed in the 20-plus samples (2.6 to 427 pg CDD/CDF / m 3 

### ), t h ere did a ppe a r to be a positive c o r r e la tion a t the site s with mor e e l e v a t e d CDD/CDF c onc e n tr a tions.
B r emmer et al. (1994) reported the averag e ratio of PCP to I

- TEQ DF 

### air concentrations at these
elevated sites to be 1:5 × 10 -6 

### (or about the same ratio as the concentration of I

- TEQ DF 

### in technical PCP). The results of the Papke et al. (1989) study imply that CDDs/CDF s may be
released from PCP-treated wood at the same rate as is PCP rather than at a rate 10 times slower. Rappe (1995) used the emission factor approach developed by B r emmer et al. (1994) and an assumed U.S. usag e volume of PCP over the past 50 y ears (0.5 million metric tons) to estimate that as much as 10.5 kg I

- TEQ DF 

### could volatiliz e from PCP-treated wood in the United States annually

. Eitz er and H ites (1987) derived a dr amatically different estimate: 3 kg /y r of

tota l CDDs/CDF s ( o r 66 g I

- TEQ DF 

### per y ear, assum i n g an I

- TEQ DF 

### content in PCP of 3 mg /kg )

. Eitz er and Hites based their estimate on an assumption that 0.1% of the PCP produced annually

e n te r s the a tmosphe r e a nd tha t the CDD/CDF c onta mina n ts pr e se n t in the PCP ( a ssume d to be 130 mg /kg ) are released to the atmosphere at the same rate as the PCP (i.e., 0.1%). The basis for the first assumption by Eitz er and Hites is not clear because U.S

. EP A (1980), which was cited as the source of the 0.1% emission factor, does not a ppear to address volatiliz ation of PCP from inservice treated wood. The report does, however, estimate that most PCP in treated wood leaches relatively rapidly from the wood, presumably to land, within a period of 12 y e ars. Eduljee and Dy ke (1996) and Douben et al. (1995) estimated that 0.8 g I

- TEQ DF 

### is released to the air annually from PCP-treated wood in the United King dom. This estimate was
based on the assumed emission of 0.1% of the CDDs/CDF s presen t in PCP-treated wood during the first y ear of the service life of the wood th at was assumed by Eitz er and Hites (1987). No
emissions were assumed fo r subsequent y ears of use of the treated wood.
The California Air Resources B o ard (Chi nkin et al., 1987) g e nerated estimates of
CDD/CDF volatiliz ation releases at wood treatment facilities fro m bundles of treated wood that remain on site for 1 month prior to shipment. An “adapted” version of a model developed by McCord (1981) was used for es timating volatile releases from a constantly filling lag oon. The
mode l is pr ima r ily dr ive n by c h e mic a l

- spe c i f i c vapor pressures and air di ffusi vi t y coeffi ci ent s

. Chinkin et al. did not provide all model input pa rameter values used to g e nerate the emission
estimates. However, running the model with ty pical dimensions for treated poles y i elds an I

8-60

### TEQ DF 

### emission rate on the order of 6E-12 g / y r- pole, an ex tremely low number (170 billion poles would tog e the r e mit 1 g TEQ/y r )

. I n addition to cancelling some pesticide reg i strations and establis hing product standards, EPA’s Office of Pesticide Prog rams (OPP) issued two DCI s in 1987. Pesticide manufacturers are required to reg i ster their products with EPA in order to market them commercially in the
United States. Throug h the reg i stration process, mandated by F I F R A, EPA can require that the

m a nufact urer of each act i v e i n g r edi e nt g e nerat e a wi de vari et y of sci e nt i f i c dat a t h roug h several

me c h a n isms. The most c o mmon pr oc e ss is the f i ve -phase rereg i stration pr oc e ss, with whic h the manufacturers (i.e., reg i strants) of older pesticide products must comply

. I n most reg i stration activities, reg i strants must g e ne rate data under a series of st rict testing g uidelines, 40 CF R 158—Pesticide Assessment Guidelines (U.S. EPA, 1988c). EPA can also require additional data from reg i strants, when necessary , throug h va rious mechanisms, including the DCI process. The purpose of the first DCI

, dated J une and October 1987, “Data Call-I n Notice for Product Chemistry Re lating to Potential F o rmati on of Halog e nated Dibenz o -p- diox in or
Dibenz ofuran Contaminants in Certain Active I ng r e d ie nts,” wa s to ide n tif y , using a n a n a l y sis of

raw m a t e ri al s and process chem i s tr y , those pe stic ide s tha t mig ht contain halog e nated dibenz o- p

diox in (HDD) and halog e nated dibenz ofuran (HDF) contaminan ts. The 93 pesticides (76 pesticide active ing r edients) to which th e DCI applied, along with their corresponding Shaug hnessey and Chemical Ab stract code numbers, are pr esented in Table 8-29. (The
S h aug hnessey code i s an i n t e rnal EP A t r acki n g sy st em

. I t i s of i n t e rest because chem i cal s wi t h
similar code numbers are similar in chemical nature [ e .g ., salts, esters, and acid forms of 2,4-D] .) All reg i strants supporting reg i strations fo r these chemicals were subject to the requirements of the DCI unless their product qualified for a Gene ric Data Ex emption (i.e., a

reg i strant ex clusively used a F I F R A-reg i stered pesticide pr oduct as a source of an active ing r edient identified in Table 8-29 in formula ting a product). Reg i stra nts whose products did not

me e t the Ge ne r i c Da ta Ex e m ption we r e r e quir e d to submit the ty pe s of da ta liste d be low to
enable EP A to assess the potential for form ation of tetra- thr oug h hepta-HDD or -HDF contaminants during manufacture.

• P roduct identity and disc losure of ing r edients

. EPA r e quir e d submitta l of a C onfi d ent i a l S t at em ent of Form ul a (C S F ), based on the requirements specified in 40 CF R 158.108 and 40 CF R 158.120, Subdivision D: Product Chemistry

. Reg i strants who ha d pr e v iously submitte d still- c u r r e nt CSF s we r e not r e quir e d to r e submit this i n form at i on.

• D escription of beg i nning materi als and manufacturing process

. Under the requirements mandated by 40 CF R 158.120, Subdivision D, EPA required submittal of a m a nufact uri n g process descri pt i on for each st ep of t h e m a nufact u ri ng process, including specification of the rang e of accepta ble conditions of temp erature, pressure, or pH at each st ep.

8-61Table 8-29.Status offirst pesticide Data Call-In:pesticides suspected ofhavingthe potential to becomecontaminated with dioxins ifsynthesizedunder conditions favoring dioxin formation



### 8-62ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired000014Dichlorodifluoromethane75-71-8Yes-­008706O-(4-Bromo-2,5-dichlorophenyl) O,O-dimethylphosphorothioate2104-96-3Yes-­009105Dimethylamine 2,3,5-triiodobenzoate17601-49-9Yes-­012001Neburon555-37-3Yes-­012101Crufomate299-86-5Yes-­019201MCPB, 4-butyric acid [4-(2-Methyl-4-chlorophenoxy)butyric acid]94-81-5NoYes019202MCPB, Nasalt[Sodium4-(2-methyl-4-chlorophenoxy)butyrate]6062-26-6NoNo0194014-Chlorophenoxyacetic acid122-88-3NoYes025501Chloroxuron1982-47-4Yes-­027401Dichlobenil1194-65-6NoYes28201Propanil [3',4'-Dichloropropionanilide]709-98-8NoNo028601Dichlofenthion[O-(2,4-Dichlorophenyl) O,O-diethylphosphorothioate)]97-17-6Yes-­029201DDT[Dichloro diphenyltrichloroethane]50-29-3Yes-­29601Dichlone[2,3-dichloro-1,4-naphthoquinone]117-80-6Yes-­029902Ammoniumchloramben[3-amino-2,5-dichlorobenzoic acid]1076-46-6Yes-­029906Sodiumchloramben[3-amino-2,5-dichlorobenzoic acid]1954-81-0Yes-­030602Sodium2-(2,4-dichlorophenoxy)ethylsulfate136-78-7Yes-­031301DCNA[2,6-Dichloro-4-nitroaniline]99-30-9NoYes031503Potassium2-(2-methyl-4-chlorophenoxy)propionate1929-86-8Yes-­031516MCCP, DEASalt[Diethanolamine 2-(2-methyl-4-chlorophenoxy)propionate]1432-14-0Yes-­031563MCPP, IOE [Isooctyl2-(2-methyl-4-chlorophenoxy)propionate]28473-03-2NoNo034502Dicapthon[O-(2-chloro-4-nitrophenyl) O,O-dimethylphosphorothioate]2463-84-5Yes-­035502Monurontrichloroacetate [3-(4-chlorophenyl)-1,1-dimethylurea trichloroacetate]140-41-0Yes-­35505Diuron[3-(3,4-dichlorophenyl)-1,1-dimethylurea]330-54-1NoNo35506Linuron[3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea]330-55-2NoNo35901Metobromuron[3-(p-bromophenyl)-1-methoxy-1-methylurea]3060-89-7Yes-­Table 8-29.Status offirst pesticide data call-in:pesticides suspectedofhaving the potential to becomecontaminated with dioxins ifsynthesized under conditions favoring dioxin formation (continued)



### 8-63ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired53501Methylparathion[O,O-DimethylO-p-nitrophenylphosphorothioate]298-00-0NoNo55001Dichlorophene [Sodium2,2'-methylenebis(4-chlorophenate)]97-23-4Yes-­55005Dichlorophene, sodiumsalt[Sodium2,2'-methylenebis(4-chlorophenate)]10254-48-5Yes-­552011,2,4,5-Tetrachloro-3-nitrobenzene117-18-0Yes-­57501Ethylparathion[O,O-diethylO-p-nitrophenylphosphorothioate]56-38-2NoNo58102Carbophenothion[S-(((p-chlorophenyl)thio)methyl) O,O-diethylphosphorodithioate]786-19-6Yes-­58301Ronnel[O,O-dimethylO-(2,4,5-trichlorophenyl) phosphorothioate]229-84-3Yes-­58802MitinFF [Sodium5-chloro-2-(4-chloro-2-(3-(3,4-dichlorophenyl)ureido)phenoxy)benzenesulfonate]3567-25-7NoNo59401Orthodichlorobenzene95-50-1Yes-­61501Paradichlorobenzene106-46-7NoNo62201Chlorophene [2-Benzyl-4-chlorophenol]120-32-1NoNo62202Potassium2-benzyl-4-chlorophenate35471-49-9NoInreview62203Sodium2-benzyl-4-chlorophenate3184-65-4NoInreview622042-Chlorophenol95-57-8Yes-­622062-Chloro-4-phenylphenol92-04-6Yes-­62207Potassium2-chloro-4-phenylphenate18128-16-0Yes-­622084-Chloro-2-phenylphenolNAYes-­622094-Chloro-2-phenylphenol,potassiumsalt53404-21-0Yes-­622106-Chloro-2-phenylphenol85-97-2Yes-­622116-Chloro-2-phenylphenol,potassiumsalt18128-17-1Yes-­622124-Chloro-2-phenylphenol,sodiumsalt10605-10-4Yes-­622136-Chloro-2-phenylphenol,sodiumsalt10605-11-5Yes-­622144 and 6-Chloro-2-phenylphenol,diethanolaminesalt53537-63-6Yes-­622152-Chloro-4-phenylphenol,sodiumsalt31366-97-9Yes-­642024-Chloro-2-cyclopentylphenol13347-42-7Yes-­Table 8-29.Status offirst pesticide data call-in:pesticides suspectedofhaving the potential to becomecontaminated with dioxins ifsynthesized under conditions favoring dioxin formation (continued)



### 8-64ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired64208Fentichlor [2,2'-Thiobis(4-chloro-6-methylphenol)]4418-66-0Yes-­64209Fentichlor [2,2'-Thiobis(4-chlorophenol)]97-24-5Yes-­642144-Chloro-2-cyclopentylphenol, potassiumsaltof35471-38-6Yes-­642184-Chloro-2-cyclopentylphenol, sodiumsalt53404-20-9Yes-67707Chlorophacinone3691-35-8NoNo69105ADBAC[Alkyl*dimethylbenzylammoniumchloride *(50%C14, 40%C12, 10%C16)]68424-85-1NoNo69144ADBAC[Alkyl*dimethyl3,4-dichlorobenzylammoniumchloride *(61%C12, 23%C14, 11%C16, 5%C18)]NANoNo77401Niclosamide [2-Aminoethanol salt of2',5-dichloro-4'-nitrosalicylanilide]1420-04-8NoNo774065-Chlorosalicylanilide4638-48-6Yes-­787802-Methyl-4-isothiazolin-3-oneNAYes-­79202Tetradifon[4-chlorophenyl2,4,5-trichlorophenylsulfone]116-29-0Yes-­79301Chloranil[tetrachloro-p-benzoquinone]118-75-2Yes-­804036-Chlorothymol89-68-9Yes-­80811Anilazine[2,4-Dichloro-6-(o-chloroanilino)-s-triazine]101-05-3Yes-­81901Chlorothalonil[tetrachloroisophthalonitrile]1897-45-6NoYes82602Sodium2,3,6-Trichlorophenylacetate2439-00-1Yes-­84101Chlorfenvinphos470-90-6Yes-­84901O-(2-Chloro-1-(2,5-dichlorophenyl)vinyl) O,O-diethylphosphorothioate1757-18-2Yes-­86801PCMX[4-Chloro-3,5-xylenol]88-04-0NoNo97003Piperalin[3-(2-Methylpiperidino)propyl3,4-dichlorobenzoate]3478-94-2NoNo100601FenamiphosNANoNo101001p-Chlorophenyldiiodomethylsulfone20018-12-6Yes-­101101Metribuzin21087-64-9NoNo104301Bifenox[methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate]42576-02-3Yes-­106001Methazole[2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione]20354-26-1Yes-­Table 8-29.Status offirst pesticide data call-in:pesticides suspectedofhaving the potential to becomecontaminated with dioxins ifsynthesized under conditions favoring dioxin formation (continued)



### 8-65ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired108201Diflubenzuron[N-(((4-chlorophenyl)amino)carbonyl)-2,6-difluorobenzamide]35367-38-5NoYes109001Oxadiazon[2-tert-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-delta2 -1,3,4­oxadiazoline-5-one]19666-30-9NoYes109301Fenvalerate51630-58-1NoInreview109302Fluvalinate [N-2-Chloro-4-trifluoromethyl)phenyl-DL-valine (+-)-cyano(3-phenoxyphenyl)methyl ester]69409-94-5NoNo109801Iprodione [3-(3,5-Dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1­imidazolidinecarboxamide (9CA)]36734-19-7NoNo109901Triadimefon[1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone]43121-43-3NoNo110902Diclofop -methyl[methyl2-(4-(2,4-dichlorophenoxy)phenoxy)propanoate]51338-27-3NoYes111401Profenofos[O-(4-Bromo-2-chlorophenyl)-O-ethylS-propylphosphorothioate]41198-08-7NoInreview111601Oxyfluorfen[2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene]42874-03-3NoInreview111901Imazalil [1-(2-(2,4-Dichlorophenyl)-2-(2-propenyloxy)ethyl)-1H-imidazole]35554-44-0NoNo112802Bromothalin[N-Methyl-2,4-dinitro-n-(2,4,6-tribromophenyl)-6­(trifuloromethyl)benzenamine]63333-35-7NoNo113201Vinclozolin[3-(3,5-Dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione(9CA)]50471-44-8NoNo119001Fenridazon[Potassium1-(p-chlorophenyl)-1,4-dihydro-6-methyl-4-oxo-pyridazine3-carboxylate]83588-43-6NoInreview123901Tridiphane[2-(3,5-Dichlorophenyl)-2-(2,2,2-trichloroethyl) oxirane]58138-08-2NoNo125601Paclobutrazol76738-62-0NoNo128838Linalool78-70-6NoInreview206600Fenarimol[a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol]60168-88-9NoNoNA= Not available-- =Noinformation given

### • D isc u ssion of the f o r m a tion of impur itie s

. Under the require ments mandated by 40 CF R 158.120, Subdivision D, EPA required s ubmittal of a detaile d discussion and assessment of the possible formation of HDDs and HDFs.

Reg i strants had the option of voluntarily cancelin g their product or “refor mulate to remove an

a c tive ing r e d ie nt” to a void ha ving to c o mply with the DCI

. The second DCI

, dated J une and October 1987, “Data Call-I n for Analy tical Chemistry Data on Poly halo g e nated Dibenz o -p- Diox ins/Dibenz ofurans (HDDs and HDFs),” was issued for 68 pe stic ide s ( 16 pe stic ide a c tive ing r e d ie nts) suspe c t e d to be c onta mina t e d with CDDs/CDF s (see Table 8-30). All reg i strants supporting reg i stra tions for these pesticides were subject to the requirements of this DCI unle ss the product qualified for various ex emptions or waivers. Pesticides covered by the second DCI were strong ly suspected by EPA of containing detectable
levels of CDDs/CDF s. Under the second DCI

, reg i strants whose products did not qualify for an

e x e m ption or wa ive r we r e r e quir e d to g e ne r a te a nd submit the f o llowing ty pe s of da ta in a ddition to the data requirements of the first DCI :

• Q uantitative method for measuring CDDs or CDF s

. Reg i strants were required to develop an analy tical met hod for measuring the HDD/HDF content of their products. The DCI established a reg imen for defining the precision of the analy tical method. Targ et L OQs were est a bl i s hed i n t h e DC I for speci fi c C DD/ C DF cong eners (see Table 8-25).

• C e r tif ic a tion of limits of CDDs or CDF s

. Re g i str a nts we r e r e quir e d to submit a “Certification of L imits” in accordance with 40 CF R 158.110 and 40 CF R 158.120, Subdivision D. Analy tical re sults were required that me t the g u idelines described above.

Reg i strants could select one of two options to comply with the second DCI

. The first option wa s to submit r e le va nt e x isting da ta , de ve lop ne w da ta , or sha r e the c o st of de ve loping new data with other reg i strants. The sec ond option was to alleviate the DCI requirements throug h several ex emption processes, incl uding a Generic Data Ex emption, voluntary cancellation, reformulation to remove the active ing r edient of con cern, an assertion that the data requirements did not apply , or the application or award of a low-volume, minor-use waiver.
The data contained in CSF s , as well as any other data g e nerated under 40 CF R 158.120, Subdivision D, are ty pically considered conf idential business information (CB I ) under the

g u i d el i n es prescri b ed i n FI FR A because t h ey usual l y cont ai n i n form at i on reg a rdi n g propri e t a ry manufacturing processes. I n g e ne ral, all analy tical results submitted to EPA in response to both
DCI s are considered CB I and cannot be releas ed by EPA into the public domain. Summaries

8-66Table 8-30.Status ofsecondpesticide Data Call-In:pesticides suspected ofbeing contaminated with dioxins



### 8-67ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired29801Dicamba [3,6-dichloro-o-anisicacid]1918-00-9NoYes29802Dicamba dimethylamine [3,6-dichloro-o-anisicacid]2300-66-5NoYes29803Diethanolaminedicamba [3,6-dichloro-2-anisicacid]25059-78-3Yes-­300012,4-Dichlorophenoxyacetic acid94-75-7NoYes30002Lithium2,4-dichlorophenoxyacetate3766-27-6NoNo30003Potassium2,4-dichlorophenoxyacetate14214-89-2Yes-­30004Sodium2,4-dichlorophenoxyacetate2702-72-9NoNo30005Ammonium2,4-dichlorophenoxyacetate2307-55-3Yes-­30010Alkanol*amine 2,4-dichlorophenoxyacetate *(saltsofthe ethanol andispropanolseries)NAYes-­30011Alkyl*amine 2,4-dichlorophenoxyacetate *(100%C12)2212-54-6Yes-­30013Alkyl*amine 2,4-dichlorophenoxyacetate *(100%C14)28685-18-9Yes-­30014Alkyl*amine 2,4-dichlorophenoxyacetate *(asinfattyacidsoftall oil)NAYes-­30016Diethanolamine2,4-dichlorophenoxyacetate5742-19-8NoNo30017Diethylamine2,4-dichlorophenoxyacetate20940-37-8Yes-­30019Dimethylamine 2,4-dichlorophenoxyacetate2008-39-1NoNo30020N,N-Dimethyloleylamine2,4-dichlorophenoxyacetate53535-36-7Yes-­30021Ethanolamine2,4-dichlorophenoxyacetate3599-58-4Yes-­30023Heptylamine 2,4-dichlorophenoxyacetate37102-63-9Yes-­30024Isopropanolamine2,4-dichlorophenoxyacetate6365-72-6Yes-­30025Isopropylamine2,4-dichlorophenoxyacetate5742-17-6NoNo30028Morpholine 2,4-dichlorophenoxyacetate6365-73-7Yes-­30029N-Oleyl-1,3-propylenediamine 2,4-dichlorophenoxyacetate2212-59-1Yes-­30030Octylamine2,4-dichlorophenoxyacetate2212-53-5Yes-­30033Triethanolamine 2,4-dichlorophenoxyacetate2569-01-9Yes-­30034Triethylamine 2,4-dichlorophenoxyacetate2646-78-8NoNo30035Triisopropanolamine2,4-dichlorophenoxyacetate32341-80-3NoNoTable 8-30.Status ofsecondpesticide Data Call-In:pesticides suspected ofbeing contaminated with dioxins(continued)



### 8-68ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired30039N,N-Dimethyloleyl-linoleyl amine 2,4-dichlorophenoxyacetate55256-32-1Yes-­30052Butoxyethoxypropyl 2,4-dichlorophenoxyacetate1928-57-0Yes-­30053Butoxyethyl 2,4-dichlorophenoxyacetate1929-73-3NoNo30055Butoxypropyl 2,4-dichlorophenoxyacetate1928-45-6Yes-­30056Butyl 2,4-dichlorophenoxyacetate94-80-4Yes-­30062Isobutyl 2,4-dichlorophenoxyacetate1713-15-1Yes-­30063Isooctyl(2-ethylhexyl) 2,4-dichlorophenoxyacetate1928-43-4NoYes30064Isooctyl(2-ethyl-4-methylpentyl) 2,4-dichlorophenoxyacetate25168-26-7Yes-­30065Isooctyl(2-octyl) 2,4-dichlorophenoxyacetate1917-97-1Yes-­30066Isopropyl 2,4-dichlorophenoxyacetate94-11-1NoNo30072Propyleneglycol butyl ether 2,4-dichlorophenoxyacetate1320-18-9Yes-­308014-(2,4-Dichlorophenoxy)butyric acid94-82-6NoYes30804Sodium4-(2,4-dichlorophenoxy)butyrate10433-59-7NoNo30819Dimethylamine 4-(2,4-dichlorophenoxy)butyrate2758-42-1NoNo30853Butoxyethanol4-(2,4-dichlorophenoxy)butyrate32357-46-3Yes-­30856Butyl4-(2,4-dichlorophenoxy)butyrate6753-24-8Yes-­30863Isooctyl4-(2,4-dichlorophenoxy)butyrate1320-15-6Yes-­314012-(2,4-Dichlorophenoxy)propionicacid120-36-5NoYes31419Dimethylamine 2-(2,4-dichlorophenoxy)propionate53404-32-3NoNo31453Butoxyethyl2-(2,4-dichlorophenoxy)propionate53404-31-2NoNo31463Isooctyl2-(2,4-dichlorophenoxy)propionate28631-35-8NoNo31501MCPP acid [2-(2-Methyl-4-chlorophenoxy)propionicacid]7085-19-0NoYes31519MCPP, DMA[Dimethylamine2-(2-methyl-4-chlorophenoxy)propionate]32351-70-5NoNo35301Bromoxynil[3,5-dibromo-4-hydroxybenzonitrile]1689-84-5NoYes44901Hexachlorophene [2,2'-Methylenebis(3,4,6-trichlorophenol)]70-30-4Yes-­Table 8-30.Status ofsecondpesticide Data Call-In:pesticides suspected ofbeing contaminated with dioxins(continued)



### 8-69ShaughnesseycodePesticide [activeingredient]CAS No.SupportwithdrawnTestingrequired44902Hexachlorophene, Nasalt[Monosodium2,2'-methylenebis(3,4,6-trichlorophenate)]5736-15-2Yes-­44904Hexachlorophene, Ksalt[Potassium2,2'-methylenebis(3,4,6-trichlorophenate)]67923-62-0Yes-­54901Irgasan[5-Chloro-2-(2,4-dichlorophenoxy)phenol]3380-34-5NoYes63004Tetrachlorophenols25167-83-3Yes-­63005Tetrachlorophenols,sodiumsalt25567-55-9Yes-­63006Tetrachlorophenols,alkyl*amine salt*(asinfattyacidsofcoconutoil)NAYes-­63007Tetrachlorophenols,potassiumsalt53535-27-6Yes-­64203Bithionolatesodium[Disodium2,2'-thiobis(4,6-dichlorophenate)]6385-58-6Yes-­64212Phenachlor [2,4,6-Trichlorophenol]88-06-2Yes-­64219Potassium2,4,6-trichlorophenate2591-21-1Yes-­642202,4,6-Trichlorophenol, sodiumsalt3784-03-0Yes-­64501Phenothiazine92-84-2Yes-­78701Dacthal-DCPA[Dimethyltetrachloroterephthalate]1861-32-1NoYes79401Endosulfan[hexachlorohexahydromethano-2,4,3-benzodioxathiepin-3-oxide]115-29-7NoNo82501Silvex[2-(2,4,5-trichlorophenoxy)propionicacid]93-72-1Yes-­83701Tetrachlorvinphos[2-Chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate]961-11-5NoYes104101Edolan[Sodium1,4',5'-trichloro-2'-(2,4,5-trichlorophenoxy)methanesulfonanilide]69462-14-2Yes-­NA= Not available-- =Noinformation given

### based on the trends identified in those data as well as in data made public by EPA are

summa r i ze d be low.
The two DCI s included 161 pesticides. Of these, 92 are no long er supported by

reg i strants. F ollowing evaluation of the pro cess chemistry submissions required under the DCI s , OPP de te r mine d tha t f o r m a tion of CDDs/CDF s was not likely during the manufacture of 43 of
the r e ma ining 69 pe stic ide s; thus, a n a l y sis of sa mple s of the se 43 pe stic ides was not required by
OPP. Evaluation of process che mistry data is ong oing at OPP for an additional 7 pesticides. Table 8-30 indicates which pesticides are no long er supported and those for which OPP has requi red furt her t e st i n g t o det e rm i n e whet her C DDs/ C DFs are present as cont am i n ant s (U.S

. EPA, 1995g ). OPP required that analy s is of production samples be perfo rmed on the remaining 19 pesticides (see Table 8-31). The status of the anal y t i cal dat a g e nerat i on/evaluation to date is
summariz e d as follows: (a) no detection of CDDs/CDF s above the L OQs in reg i strant submissions for 13 active ing r edients, (b) det ection of CDDs/CDF s above the L OQs for 2,4-D acid (two submissions) and 2,4-D 2-ethy l hex y l acetate (one submission), and (c) ong oing data

g e neration or evaluation for four pesticides. Table 8-32 presents a summary of results obtained by EPA for CDDs/CDF s in eig ht technical 2,4-D herbicides; these data were ex tracted from prog ra m files in OP P

. B ecause some of

the se f ile s c onta i ne d CB I
, the da ta in this ta ble were reviewed by OPP staff to ensure that no
CB I was being disclosed (mem orandum dated May 28, 1996, from S. F unk, U.S. EPA, to W

. Haz e l, U.S. EPA). F i g u re 8-5 presents a cong ener profile for 2,4-D based on the averag e
cong ener concent r at i ons reported in Table 8-32. Schecter et al. (1997) reporte d the results of analy s es of samples of 2,4-D manufactured in Europe, Russia, and the United States (s ee Table 8-33). The to ta l TEQ c onc e n tr a tions

me a sur e d in the Eur ope a n a nd Russia n sa mple s we r e simila r to those me a sur e d in the EPA DCI

sa mple s; howe v e r , the le ve ls r e ported by Schecter et al. for U.S. sa mple s we r e sig n if ic a n tly
lower. Similarly , Masunag a et al. (2001) reported the analy s es of two ag rochemical formulations containing 2,4-D manufactured in J a pan (Table 8- 33). The total TEQ concentration measured in one of the samples was similar to what Schecter et al. (1997) re ported for the U.S. samples; no TEQ was detected in the other sample. As discussed in Section 11.2.1 (Chapter 11) , an estimated 28,100 metr ic tons of 2,4-D were used in the United States in 2000, making it one of the top 10 pesticid es in terms of quantity used (EPA proprietary data). The pesticide 2,4-D is the only produc t judg ed to have the potential
f

o r

e nvir onme n ta l r e le a se thr oug h its a g r i c u ltur a l use

. Howe ve r , no e stima te of e nvir onme n ta l
release can be made for 2000. Since 1995, the chemical manufacturers of 2,4-D have been undertaking voluntary actions to sig nificantly re duce the diox in content of the product. No
information is available on the level of diox in c ontamination, if any , that may have been present

8-70Table 8-31.Summary ofanalytical data submittedto EPA in response to pesticide Data Call-In(s)



### 8-71ShaughnesseycodePesticideNumber ofpositiveasubmissions todateCommonnameChemicalname019201MCPB, 4-butyric acid4-(2-methyl-4-chlorophenoxy)butyric acid00194014-CPA4-Chlorophenoxyacetic acid0027401Dichlobenil2,6-Dichlorobenzonitrile0029801Dicamba3,6-Dichloro-o-anisic acid0029802Dicamba, dimethylamine3,6-Dichloro-o-anisicacid, dimethylamine salt00300012,4-D2,4-Dichlorophenoxyacetic acid20300632,4-D, 2EHIsooctyl(2-ethylhexyl)2,4-dichlorophenoxyacetate10308012,4-DB4-(2,4-Dichlorophenoxy)butyric acid0031301DCNA2,6-Dichloro-4-nitroanilinePending0314012,4-DP2-(2,4-Dichlorophenoxy)propionicacid0031501Mecoprop (MCPP)2-(2-methyl-4-chlorophenoxy)propionicacid0035301Bromoxynil3,5-Dibromo-4-hydroxybenzonitrile0054901Irgasan5-Chloro-2-(2,4-dichlorophenoxy)phenol0078701Dacthal(DCPA)DimethyltetrachloroterephthalatePending081901ChlorothalonilTetrachloroisophthalonitrilePending083701Tetrachlorvinphos2-Chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate0108201DiflubenzuronN-(((4-chlorophenyl)amino)carbonyl)-2,6-difluorobenzamide0109001Oxadiazon2-Tert-butyl-4(2,4-dichloro-5-isopropoxyphenyl)-delta2-1,3,4-oxadiazoline-5-onePending110902Dichlofop-methylMethyl-2-(4-(2,4-dichlorophenoxy)phenoxy) propanoate0aPositive is definedas the detectionofanycongener at a concentrationequal toorexceedingthe limits ofquantitationlistedinTable 8-27.Sources:U.S.EPA(1995f);facsimiledated March27, 1996 fromS.Funk,U.S.EPA,toD.Cleverly,U.S.EPA.

### Table 8-32. Sum m ary of results f or CDDs/CDF s in technical 2,4-D and 2,4-D ester h erb i c i d es

C ongener EP A LO Q a 

### (μg/kg) Tot a l no. of technicals N u mber of technicals greater than LO Q Observed

max i mu m

conc. (μg/kg) Average

conc. b 

### (μg/kg)
2,3,7,8- T C DD 0.1 8 2 0.13 0.06 1,2,3,7,8- PeCDD 0.5 8 3 2.6 0.78 1,2,3,4,7,8- HxCDD 2.5 8 0 0.81 0.31 1,2,3,6,7,8- HxCDD 2.5 8 0 0.77 0.39 1,2,3,7,8,9- HxCDD 2.5 8 0 0.68 0.24 1,2,3,4,6,7,8- HpCDD 100.0 8 0 1.5 0.21

O C D D

-­ -­ -­ -­ -­ 2,3,7,8- T C DF 1 8 0 0.27 0.07 1,2,3,7,8- PeCDF 5 8 0 0.62 0.38 2,3,4,7,8- PeCDF 5 7 0 0.73 0.07 1,2,3,4,7,8- HxCDF 25 8 0 1.6 0.36 1,2,3,6,7,8- HxCDF 25 8 0 1.2 0.11 1,2,3,7,8,9- HxCDF 25 8 0 1.4 0.16 2,3,4,6,7,8- HxCDF 25 8 0 1.1 0.14 1,2,3,4,6,7,8- HpCDF 1,000 8 0 8.3 2.17 1,2,3,4,7,8,9- HpCDF 1,000 8 0 1.2 0.18

O C D F

-­ -­ -­ -­ -- TO TA L c 

### 5.6

I-T E Q DF 

### 0.7

TE Q DF 

### -W H O 98 

### 1.1

a L OQ req u ired b y EP A in th e d a ta call- in

. b A v erag e o f th e m ean resu lts f o r m u ltip le an aly s es o f f

o u r tech n i cal 2

, 4

- D an d / o r 2
, 4

- D ester p r o d u cts f o r w h ich detectable C DD/C D F con g en er con cen tration s les s th an th e L OQs w ere qu an tif ied; n o n d etect v alu es w ere

as s u m e d t o be zero.

c T o tal equ als th e s u m of th e in div i du al con g en er av erag es

.

L OQ = L i m it o f q u an titatio n

- - = A n aly s es n o t perf orm e d

Sou r ce: U.S. EP A Of f i ce of P es ticide P r og ram s f ile.



### in 2,4-D in 2000. An estimated 26,300 and 30,400 me tric tons were used during 1995 and 1987, respectively (U.S. EPA, 1997e, 1988d). On th e basis of the averag e CDD/CDF cong ener concentrations in 2,4-D presented in Tabl e 8-33 (not including OCDD and OCDF ), the corresponding TEQ DF 

### -W HO 98 

### concentration is 1.1 μg /kg (0.7 μg I

- TEQ DF 

### /kg )

. Combining this

8-722, 3,7,

8-T

C D D

1 , 2,3

, 7, 8-P

e C DD

1, 2 ,3,

4 ,7,

8 -H

xC

D D

1 ,2 ,3 ,6 ,7 ,8 -H

xC

D D

1 ,2 ,3 ,7

, 8,9

- H xC

D D

1, 2,3

, 4,6

, 7,8

- Hp

C DD OC D D

2, 3 , 7 ,8-

T C DF

1 ,2 ,3 ,7

, 8- P eC

D F

2 , 3,4

, 7, 8- P e C DF

1 ,2,

3 ,4 ,7 ,8 -H

x C D F

1 ,2 ,3 ,6 ,7

, 8-H

x C D F

1 , 2,3

, 7,8

, 9-H

x C DF

2, 3 , 4, 6 , 7, 8

- H xC

DF

1 , 2,3

, 4, 6, 7, 8 -H

p C D F

1, 2 , 3, 4 , 7 ,8,

9 -H

pC

D O C D F 0% 5% 10 % 15 % 20 % 25 % 30 % 35 % 40 % 45 %PercentofTotal CDDsandCDFs

Congener



### F i gure 8-5. Congener prof ile f o r 2,4-D (salts and esters) (based on m e an

con cen trati o n s rep or ted in Table 8-34).

TEQ concentration with the activity level estimates for 1995 and 1987 indicates that 28.9 g TEQ DF 

### -W HO 98 

### (18.4 g I

- TEQ DF 

### ) were released in 1995 and 33.4 g TEQ DF 

### -W HO 98 

### (21.3 g I TEQ DF 

### ) in 1987. The release estimates for 1987 and 1995 are assig n ed a hig h confidence rating

, indicating hig h confidence in both the production and the emission factor estimates. B ecause no estimate can be made for 2000, it is rated as Categ o ry E (no estima te of environmental release of
CDDs/CDF s can be made because of th e poor quality of ex isting information).

8.4. OTHER CHEMICAL MANUF ACT URING AND P R OCESSING SOURCES
8.4.1. Municipal Wastew a ter Treatm ent P l ants
8.4.1.1. Sourc e s CDDs/CDF s have been measured in nearly all sewag e sludg es tested, althoug h the concentrations and, to some ex tent, the cong ener profiles and patterns di ffer widely

. Potential
sources of the CDDs/CDF s incl ude microbial formation (discu ssed in Chapter 9), runoff to ­

8-73Table 8-33.CDD/CDFconcentrations (μg/kg) in samples of2,4-D and pesticide formulations containing 2,4-D



### 8-74Congener/congenergroupAcbarSuper(GazaCitya)AmcoSuper(GazaCitya)(Bethlehem)aChimprom(Russia)DragonLawnWeedKillerKGRO(U.S.)ProCarePremium(U.S.)OrthoWeed-BGone(U.S.)SigmaCo.(U.S.)AmericanBrandChemicalCo. (U.S.)IshiharaSangyoKaisha,Ltd.(Japan)NissanChemicalIndustries,Ltd.(Japan)2,3,7,8-TCDDND(0.1)ND(0.1)ND(0.1)ND(0.02)ND(0.001)-­-­-­-­-­0.0021ND(0.002)1,2,3,7,8-PeCDD0.1ND(0.1)1.20.030.0014-­-­-­-­-­0.011ND(0.002)1,2,3,4,7,8-HxCDDND(0.1)ND(0.1)ND(0.1)0.02ND(0.001)-­-­-­-­-­ND(0.005)ND(0.005)1,2,3,6,7,8-HxCDDND(0.1)0.20.60.050.0024-­-­-­-­-­ND(0.005)ND(0.005)1,2,3,7,8,9-HxCDDND(0.1)ND(0.1)0.4ND(0.02)0.001-­-­-­-­-­ND(0.005)ND(0.005)1,2,3,4,6,7,8-HpCDD0.11.20.30.230.0017-­-­-­-­-­ND(0.005)ND(0.005)OCDD0.12.60.10.850.0063-­-­-­-­-­ND(0.01)ND (0.01)2,3,7,8-TCDF1,2,3,7,8-/1,2,3,4,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-/1,2,3,4,7,9-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF0.3ND(0.1)ND(0.1)ND(0.1)ND(0.1)ND(0.1)ND(0.1)0.1ND(0.1)0.2ND(0.1)0.2ND(0.1)0.1ND(0.1)ND(0.1)ND(0.1)0.8ND(0.1)3.8ND(0.1)0.70.10.40.1ND(0.1)0.10.1ND(0.1)0.4ND(0.1)1.20.060.080.11ND(0.02)0.050.240.020.460.00360.0010.00110.0013ND(0.001)ND(0.001)0.00110.0016ND(0.001)0.0039-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­ND(0.002)0.0038ND(0.002)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND(0.010)ND(0.002)ND(0.002)ND(0.002)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND(0.005)ND (0.01)Total2,3,7,8-CDD(nondetect = 0)0.342.61.180.01280.01440.01430.00910.1270.02780.013-­Total2,3,7,8-CDF(nondetect = 0)0.64.91.92.220.01360.16280.42530.10953.05070.08220.004-­Total I-TEQDF(nondetect = 0)b0.0820.0660.850.1420.00230.00090.00120.00140.00130.0019NDTotal TEQDF-WHO98(nondetect = 0)b0.1340.0611.4490.1560.0030.0078NDTotal TCDDTotal PeCDDTotal HxCDDTotal HpCDDTotal OCDDTotal TCDFTotal PeCDFTotal HxCDFTotal HpCDFTotal OCDF-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­-­0.0130.0410.0180.008ND(0.005)ND(0.01)2.70.890.0190.006ND(0.01)ND(0.002)ND(0.002)ND(0.005)ND(0.005)ND (0.01)0.0093ND(0.002)ND(0.005)ND(0.005)ND (0.01)TotalCDD/CDF-­-­-­-­-­-­-­-­-­-­3.70.0093Table 8-33.CDD/CDFconcentrations (μg/kg) in samples of2,4-D and pesticide formulations containing 2,4-D(continued)a2,4-D manufactured inEurope and packaged inPalestine.bCalculated assumingnondetect valuesare zero.ND = not detected(valueinparenthesis is the detectionlimit)-- =Noinformation givenSources:Schecter etal. (1997);Masunagaetal. (2001).



### 8-75

### sewers from lands or urban su rfaces contaminated by product uses or deposition of previous emissions to air (discussed in Chapter 11, Section 11.2.1), household wa stewater, industrial wastewater, and chlorination ope rations within the wastewater treatment fac ility (Rappe, 1992b; Rappe et al., 1994; Horstmann et al., 1992; Sewart et al., 1995; Cramer et al., 1995; Horstmann
and McL achlan, 1995). The major source(s) for a g i ven publicly owne d tr e a tme nt wor k s ( P OTW) is like l y to be site specific, particularly in industrializ ed areas. F o r ex ample, Rieg er and B a llschmiter (1992) traced the orig in of CDDs/CDFs found in municipa l sewag e sludg e in Ulm, Germany , to metal

ma nuf a c t ur ing a nd ur ba n sour c e s. The c h a r a c t e r istic s of both sour c e s we r e simila r a nd sug g e ste d

g e neration via thermal processing

. However, a series of st udies by Horstmann et al. (1992, 1993a, b) and Horstmann and Mc L achlan (1994a, b, 1995) demonstrated that wastewater

g e nerated by laundering and bathing could be the major sour ce at many , if not all, POTW s that serve primarily residen tial populations. Althoug h runoff from streets during precipitation events,

pa r tic ula r ly f

r o m str e e t s with hig h tr a f f i c density , was reported by these researchers as contributing measurably , the total contributi on of TEQ from household wastewater was eig h t times g r eater than that from surface runoff at the study city

. Horstmann et al. (1992) provided initial eviden ce that household wastewater could be a sig n ificant source. Horstmann et al. (1993a) measured CDD/CDF le vels in the effluent from four different loads of laundry from tw o different domestic washing mach ines. The concentrations of
total CDDs/CDF s in the four samples rang ed from 3,900 to 7,100 pg /L and were very similar in

cong ener profile, with OCDD being the dominant cong ener, followed by the hepta- and hex a

CDDs. B ecause of the similar concentrations a nd cong ener profiles found, the authors concluded

t h at t h e presence of C DDs/ C DFs i n washi n g m achi n e wast ewat er i s wi despread. A si m p l e m a ss balance performed using the results (Hors tmann and McL achlan, 1994a) showed that the CDDs/CDFs found in the four washing machin e wastewater samples could account for 27 to
94% of the tota l CDDs/CDF s me a sur e d in the sludg e of the loc a l wa ste w a t e r tr e a tme nt pla n t. Horstmann et al. (1993a) performed additional ex periments that showed that deterg ents, commonly used bleaching ag ents, and the washing cy cle process itself were not responsible for
the obse r ve d CDDs/CDF s. To de te r mine whe t he r the te x tile f a br ic or f

a br ic f i nishing pr oc e sse s could account for the observed CDDs/CDF s, Horstmann et al. (1993b), Horstmann and
McL achlan (1994a, b), and Klasme ier and McL achlan (1995) analy z ed the CDD/CDF content of raw cotton cloth, white sy nthetic materials, and more than 100 new tex tile finished products.
L o w concentrations were found in most products (less than 50 ng /kg of total CDDs/CDF s), but a small percentag e contained hig h concentrations, up to 290 μg /kg of total CDDs/CDF s. On the
basis of the concentrations a nd patterns found, the authors concl uded that neither unfinished new fabrics nor common cotton finishing processe s could ex plain the CDD/CDF levels found in

8-76

### wa ste w a t e r ; r a the r , the use of CDD- /CDF

- c onta i ning te x tile dy e s a nd pig m e n ts a nd the use in some developing countries of PC P to treat unfinished cotton appear ed to be the sources of the
det ect ed C DDs/ C DFs.
Horstmann and McL achlan ( 1994a, b, 1995) reported the results of additional

e x pe r ime nts showing tha t the sma ll pe r c e n ta g e of clothing items with hig h CDD/CDF levels could be responsible for the quantity of C DDs/CDF s observed in household wastewater and

sewag e sludg e. They demonstrated that th e CDDs/CDF s can be g r adually removed from the fabric during washing ; they can be transferred to the skin, subseque ntly transferred back to other

te x tile s, a nd the n wa she d out, or the y c a n be tr a n sf e r

r e d to othe r te x tile s dur ing wa shing a nd the n removed during subsequent washing

.

8.4.1.2. Re le ase s to Wate r 8.4.1.2.1. Em issions data

. The presence of C DDs/ C DFs in sewag e sludg e sug g e sts that
C DDs/ C DFs m a y al so be present i n t h e wast ewat er effluent discharg es of POTW s; however, few studies reporting the results of effluent an aly s es for CDDs/CDF s have been published. Rappe et al. (1989a) tested the efflue nt from two Swedish POTW s for all 2,3,7,8­
substitute d CDD/CDF c ong e n e r s. OCDD wa s de te c t e d in the e f f l ue nts f r o m both f a c ilitie s a t concentrations rang ing from 14 to 39 pg /L

. The investig ators detected 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCDF in the effluent of one facility at concentr ations of 2.8 and 2 pg /L
, respectively

. No 2,3,7,8-substituted tetra-, penta-, and hex a -CDDs or CDF s were detected (DL s of 0.2 to 20 pg /L ). Ho and Clement (1990) reported the results of sampling during the late 1980s of 37
P O TW s in Ontario, Canada, for each of the five CDD/CDF cong ener g r oups with four to eig h t
chlorines. The sampled fac ilities included 27 secondary trea tment facilities, seven primary treatment facilities, one tertiary plant, a nd two lag oons. The facilities accounted for about 73% of the sewag e discharg ed by POTW s in Ontario. No C DDs/C DFs were detected (DL in the low

ng /L rang e) in the effluents from the lag oons a nd the tertiary treatment facility

. Only OCDD and
TCDF we r e de te c t e d in the e f f l ue nts f r o m the pr ima r y tr e a tme nt f a c ilitie s ( t wo a nd one e f f l ue nt samples, respectively )

. HpC DD, OC DD, TC DF, a nd OCDF were detected i n t h e effl uent s from the secondary treatment f acilities (detected in four or fewer samples at levels rang ing from 0.1 to 11 ng /L ). Gobran et al. (1995) analy z ed the raw sewag e and final effluent of an Ontario, Canada, wastewater treatment plant for CDD/CDF cong eners over a 5-day period. Althoug h HpCDD, OCDD, HpCDF
, and OCDF were detected in th e raw sewag e (12 to 2,300 pg /L ), no CDDs/CDF s were det ect ed i n t h e fi nal e ffluent at cong ener-specific DL s rang ing from 3 to 20 pg /L

.

8-77

### The Ca lif or nia Re g i ona l Wa te r Qua lity Contr o l B o a r d r e por te d the r e sults of e f f l ue nt testing at nine POTW s in the San F r ancisc o area (memorandum date d March 21, 1996, from L ila
Ta ng , Ca lif or nia Re g i ona l Wa te r Qua lity Contr o l B o a r d, to Da vid Cle v e r ly , U.S. EPA)

. A tota l of 30 samples were collected between 1992 and 1995, and 1 to 6 sa mples were analy z ed for each
POTW

. The mean concentrations of CDDs/C DF s are shown in Table 8-34. The overall mean TEQ concentration was 0.27 pg TEQ DF 

### -W HO 98 

### /L (0.29 pg I

- TEQ DF 

### /L )

. With the e x c e p tion of OCDD, most 2,3,7,8-substituted CDD/CDF c ong eners were seldom detected. Rappe et al. (1998) analy z ed effluent samples from 17 POTW s in Mississippi, 10 of which receive input from industria l facilities. Treatment processes at the facilities include the use of one or more of the following : lag oons , activated sludg e, aerated dig e stion, wetlands,

ox ida tive ditc h, a nd tr ic kling f ilte r

. Additiona lly , 12 of the f a c ilitie s use c h lor i ne g a s in the
treatment process. The wastewater flows at the facilities rang e from 0.11 to 39.75 million L / day ; however, wastewater flow rate s were not known for two facilitie s. Table 8-35 presents the
concentrations of diox ins measured in the effluent samples for each facility and total TEQ
emission factors. Concentrations were cong ener-specific for only 2,3,7,8-TCDD; 2,3,7,8-TCDF ; 1,2,3,7,8-PeCDD; 2,3,4,7,8-PeCDF ; OCDD; and OCDF

. Al so provided were concentrations for

tota l Hx CDD a nd tota l HpCDD. The tota l I

- TEQ concentrations repor ted by Rappe et al. (assuming nondetect values equal to one-hal f the DL ) rang ed from 0.274 to 3.84 pg I

- TEQ DF 

### /L (averag e of 0.81 pg /I -TEQ DF 

### / L ). Because concent r at i ons fo r al l cong eners were not provi ded,
emission factors could not be calculated in TEQ DF 

### -W HO 98 

### . The CRW QCB data (memorandum dated Ma rch 21, 1996, from L ila Tang , California
Re g i ona l Wa te r Qua lity Contr o l B o a r d, to Da vid Cle v e r ly , U.S. EPA) we r e c o lle c t e d to pr ovide representative effluent concen trations for the San F r ancisco area. These data cannot be considered to be representative of CDD/CDF e ffluent concentrations at the 16,000-plus POTW s

na tionwide

. The r e f or e , the da ta c a n be use d only to g e ne r a te a pr e limina r y e stima te of the potential mass of CDD/CDF TEQ that may be released annually by U.S. POTW s.

8.4.1.2.2. A c t i v i t y l evel i n form at i o n . B a sed on the results of the 1996 and 2000 Clean W a ter Needs Survey s, an estimated 122 billion L and 148 b illion L of wastewater were treated daily by
POTW s in the United States in 1996 a nd 2000, respectively (U.S. EPA, 1997c, 2004).
W a stewater treatment data were not available for 1987; however, an estimate was developed using the population of the United States as a surrog a te. I n 2000, the population of the United States was appr ox imately 281 million people. Using th e estimate of water treated daily by POTW s in 2000, approx imately 527 L / person of wastewater were treated daily by POTW s. I n 1990, the population of the United States was a pprox imately 249 million people. Assuming the

8-78

### Table 8-34. Mean CDD/CDF concentratio ns and range of detection lim its ( D Ls) ( p g/L) in e fflue nt s fr om nine U

. S. public ly owne d t r e a t m e n t wor k s (P OTWs)

Congener/congener grou p No . o f det ect io ns/

sa m ple s Ra ng e o f DLs Range of detected concentrations ( P O T W m e a n ba sis) Overall m e an concentrations a

M i nim u m M a x im um No ndet ect

s e t to 0 No ndet ect

s e t to 1⁄2 DL 2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 0/ 30 0/ 30 0/ 30 0/ 30 0/ 30 3/ 30 13/ 30 0.31–8.8 0.45–15 0.43–9.8 0.81–10 0.42–9.7 0.75–18

6.2–57 ND ND ND ND ND ND ND ND ND ND ND ND 5 99.75 0 0 0 0 0 1.06 29.51 0.98 1.32 1.38 1.42 1.31 3.61 37.95
2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 1/ 27 1/ 30 1/ 30 1/ 30 1/ 30 1/ 30 1/ 30 2/ 30 0/ 30 1/ 30 0.74–4.4 0.64–9.4 0.61–14 0.25–6.8 0.23–6.8 0.57–10 0.25–7.9 0.36–6.9 0.19–11 0.86–28 ND ND ND ND ND ND ND ND ND ND 1.3 2 2.8 2.4 1.5 2 ND 4.6 ND 3.2 0.14 0.22 0.31 0.27 0.17 0.22 0 0.68 0 0.36 0.98 1.58 1.68 1.22 0.97 1.72 0.93 1.83 1.18 3.4

T o t a l 2,3,7,8- C D D T o t a l 2,3,7,8- C D F T o tal I- T E Q DF T o tal T E Q DF -W H O 98 -­ -- ND ND ND ND 104.75 19.8

2.42 2.33 30.57 2.37 0.29 0.27 47.97 15.49

3.66 4.28

T o tal T C DD T o tal P e CDD T o tal Hx CDD T o tal Hp CDD T o tal OCDD T o tal T C DF T o tal P e CDF T o tal Hx CDF T o tal Hp CDF T o tal OCDF 4/ 27 0/ 27 1/ 30 3/ 30 13/ 30 2/ 30 1/ 30 1/ 30 2/ 30 1/ 30 1.2–8.8 0.62–200 0.84–11 0.75–18

6.2–57 0.39–6.8 0.64–25 0.93–17 0.36–19 0.86–28 ND ND ND ND ND ND ND ND ND ND 9.7 ND 1.7 8.4 99.75 25 20 13

4.6 3.2 1.23 0 0.19 1.83 29.51

6.61 2.22 1.44 0.68 0.36 2.61 6.27 1.93 4.77 37.95

7.7 4.72 3.43 2.41 3.4

T o t a l C D D / C D F N D 185.35 44.07 75.19

a T h e ov erall m ean s are th e m ean s of th e in div i du al P O T W m ean con cen tration s rath er th an th e m ean s of th e in d i v i d u al sam p le co n cen tratio n s

.

DL = Detectio n lim it ND = No t d e tected

-- = N o i n fo r m a t i o n gi ve n

Sou r ce: Mem o ran d u m dated March 21, 1996, f r om L ila T a n g , C a lif orn i a R e g i on al W a ter Qu ality C o n t rol B o ard, to Dav i d C l ev erly , U.S. EP A

.



### 8-79Table 8-35.Effluent concentrations(pg/L) ofCDDs/CDFs frompubliclyowned treatment works in Mississippi



### 8-80Facility2,3,7,8­TCDD2,3,7,8­TCDF1,2,3,7,8­PeCDD2,3,4,7,8­PeCDFTotalHxCDDTotalHpCDDOCDDOCDFTotalI-TEQWaynesboroND(0.17)0.18ND(0.2)ND(0.1)ND3.5131.80.316Meridian0.180.12ND(0.16)ND(0.09)1.37.6581.80.445PascagoulaND(0.13)0.15ND(0.15)0.11ND0.823.60.460.264W. Biloxi0.180.24ND(0.15)0.082ND0.94ND(0.34)0.378Gulfport0.160.24ND(0.15)0.094ND2.39.90.780.371LaurelND(0.18)0.15ND(0.23)ND(0.12)ND2.938ND(0.48)0.334BrookhavenND(0.18)0.540.450.160.853.2281.70.796NatchezND(0.16)0.410.60.342.52.49.11.81.03PicayuneND(0.22)0.56ND(0.27)ND(0.14)6.53812020.715PicayuneaND(0.13)0.54ND(0.12)ND(0.07)630531060.397WavelandND(0.18)170.220.66ND3142.4CorinthND(0.15)0.17ND(0.16)ND(0.09)0.772.7180.90.276NewAugustaND(0.1)1.30.280.085211202,5001.13.84BeaumontND(0.1)0.14ND(0.13)0.0880.642.4110.660.274LeaksvilleND (0.12)0.720.250.158.9467803.21.6McLainND(0.06)ND(0.05)ND(0.10)ND(0.06)2.5142000.377HattiesburgSouthND (0.16)ND (0.24)ND (0.24)ND (0.11)1.24.5590.770.32HattiesburgNorthND (0.19)0.18ND (0.26)ND (0.13)0.969.1732.90.457AVERAGE0.171.420.360.24.4316.3221.768.990.81aBlind double.ND = Not detected(valueinparenthesis is the detectionlimit).Whencalculatingthe average, NDswere not included.Source:Rappe etal. (1998).

### population did not chang e drastically betw een 1987 and 1990, and assuming that the daily
domestic wastewater treatment per person remained cons tant between 1987 and 2000, EPA estimates that approx imate ly 131 billion L of wastewater were treated daily at POTW s in 1987.

8.4.1.2.3. Em ission Estim ates

. Multiply ing the amount of wastewater treated by 365 day s /y r by the overall mean TEQ concentrations repor ted by CRW QCB (memor andum dated March 21, 1996, from L ila Tang , California Re g i onal W a ter Quality Control B o ard, to David Cleverly , U.S. EPA) (0.27 pg TEQ DF 

### -W HO 98 

### /L [ 0.29 pg I

- TEQ DF 

### /L ] ) y i elds annual TEQ release estimates of
12.9 g TEQ DF 

### -W HO 98 

### (13.9 g I

- TEQ DF 

### ), 12 g TEQ DF 

### -W HO 98 

### (13 g I

- TEQ DF 

### ), and 14.6 g TEQ DF 

### WH O 98 

### (15.7 g I

- TEQ DF 

### ) for 1987, 1995, and 2000, respectively

. These estimates should be

r e g a r d e d a s pr e limina r y indic a tions of possible e missions f r o m this sour c e

.

8.4.1.3. Sewage Sludge Land Disposal Sewag e sludg e is the solid, semi-solid, or li quid residue g e nerated dur ing the tr e a tme nt of

wastewater. During wastewater treatment, nutrients, pathog en s, inorg a nic compounds (metals and trace elements), and org a nic compounds (CDDs/CDFs, P C B s , and surfactants) from the incoming wastewater are partitioned to the re sulting sewag e sludg e (NRC, 2002). The sludg e is either disposed of throug h methods such as incineration or landfill/surface disposal or beneficially used throug h met hods such as land application. Sewag e sludg e that is applied to land is referred to as biosolid s. I n order to be applied to land, the biosolids must be treated to meet la nd application reg u latory requirements (F ederal Reg i ster, 1993a). B i osolids are often used for crop production, g a rdening

, forestry , turf g r owth, and landscaping

. Some other uses include st rip mine and g r avel pit reclamation and wetland
restoration. L a nd application of biosolids is beneficial because it improves the phy sical and
chem i cal propert i e s of t h e soi l needed for pl an t g r owth, it reduces the need for other disposal methods, and it reduces or eliminates the need fo r commercial fertiliz ers. Commercial fertilizers often have hig her nutrient contents than do bioso lids; therefore, the application of biosolids to
la nd in lie u of c o mme r c ia l f e r tilize r s ma y r e duc e the impa c t s of hig h le ve ls of e x c e ss nutr i e n ts entering the environment (U.S. EPA, 1999b).

8.4.1.3.1. Em issions data

. EPA conducted the National Se wag e Sludg e Survey in 1988 and
1989 to obtain national data on sewa g e sludg e quality and manag e ment. As part of this survey

, EPA analy z ed sludg es from 174 POTW s that employ ed at least secondary wastewater treatment for more than 400 analy t es, including CDDs/C DF s. Althoug h sludg es from only 16% of the
POTW s had detectable levels of 2,3,7,8-TCDD, all sludg es had detect able levels of at least one
CDD/CDF cong ener (U.S. EPA, 1996e). I

- TEQ DF 

### concentrations as hig h as 1,820 ng /kg dry

8-81

### weig ht were measured. The cong ener-specific results of the surv ey are presented in Table 8-36.

I f

all nondetect values found in the study are assu med to be z e ro, then the mean and median I TEQ DF 

### concentrations of the sludg es from the 174 POTW s are 50 and 11.2 ng /kg (dry -weig h t basis), respectively

. I f the nondetect values ar e set equal to the DL , then the mean and median
I

- TEQ DF 

### concentrations are 86 and 50.4 ng /kg

, resp ectively (U.S. EPA, 1996e; Rubin and W hite, 1992).

Table 8-36. CDD/CDF concentrations (ng/kg) m e asu red in the 1998/1999 National Sew age Sludge Survey a

Congener Percent detected M a x i mu m concentration detected M edian concentration M e an concentration

No ndet ect

s e t to detection

lim it No ndet ect

s e t to

zero No ndet ect

s e t to detection

lim it No ndet ect

s e t to

zero
2,3,7,8- T C D D 1,2,3,7,8- PeC D D 1,2,3,4,7,8- H x C D D 1,2,3,6,7,8- H x C D D 1,2,3,7,8,9- H x C D D 1,2,3,4,6,7,8- H p C D D OCDD 16 18 25 49 39 98 100 116 736 737 737 737 52,500 905,000 6.86 9.84 22.5 27.3 28 335 3,320 0 0 0 0 0 335 3,320 -­

-­

-­

-­

-­

-­

-­ -­

-­

-­

-­

-­

-­

-­ 2,3,7,8- T C D F 1,2,3,7,8- PeC D F 2,3,4,7,8- PeC D F 1,2,3,4,7,8- H x C D F 1,2,3,6,7,8- H x C D F 1,2,3,7,8,9- H x C D F 2,3,4,6,7,8- H x C D F 1,2,3,4,6,7,8- H p C D F 1,2,3,4,7,8,9- H p C D F OCDF 65 22 26 43 35 16 27 71 26 80 337 736 736 1,500

737 1,260

737 7,100

842 69,500 17 9.6 10.4 28 18 18 18 57 23 110 3.9 0 0 0 0 0 0 36

0 80 -­

-­

-­

-­

-­

-­

-­

-­

-­

-­ -­

-­

-­

-­

-­

-­

-­

-­

-­

-­

T o tal I- T E Q DF 1,820 50.4 11.2 8 6 b 50 b

T o t a l 2,3,7,8- C D D / C D F

- ­ - ­ - ­ - ­ - ­

a Fo r p u b licly o w n e d treatm e n t w o rk s w ith m u ltip le sam p les, th e p o llu tan t co n cen tratio n s w e re av erag ed b e f o re th e

su m m a ry statistics p r esen ted in th e tab l e w e re calcu lated

. b V a l u es pres en t e d by R u bi n an d Wh i t e (1992) f o r 175 rat h er t h an 174 pu bl i c l y ow n e d t reat m e n t w o rk s

.

-- = N o i n fo r m a t i o n gi ve n

S o u rce: U

. S

. EPA (1996e).



### 8-82

### Green et al. (1995) and Cramer et al. (1995) re ported the results of analy s es of 99 samples of sewag e sl udg e col l ect ed from wast ewat er t r eat m e nt pl ant s across t h e Uni t e d S t at es duri n g t h e summer of 1994 as part of the 1994/1995 Associ ation of Metropolitan Sewerag e Ag encies (AMSA) survey

. These data are summariz e d in Ta ble 8-37. To calculate averag e results in units
of

TEQ, Gr e e n e t a l . a v e r a g e d the r e sults f r o m a ll sa mple s c o lle c t e d f r o m the sa me f a c ility to ensure that the results were not biased toward the concentrations f ound at facilities from which more than one sample was collected. Also, ei g h t sa mple s we r e e x c l ude d f r o m the c a l c u la tion of the overall TEQ averag es because it was unclear whether they were duplicate samples from other
POTW s. POTW averag e TEQ concentrations we re calculated for 74 POTW s. I f all nondetect
values are assumed to be z e ro, then the overall study mean and median I

- TEQ DF 

### concentrations were 47.7 and 33.4 ng I

- TEQ DF 

### /kg (dry weig ht basis), respectiv ely (standard deviation of 44.7 ng
I

- TEQ DF 

### /kg )

. The corresponding mean and median TEQ DF 

### -W HO 98 

### concentrations were 36.3 and
25.5 ng /kg

, respectively (s tandard deviation, 38.6). The mean and median results reported by Green et al. (1995) and Cramer et al. (1995) are

ve r y simila r in te r m s of tota l TEQ to those r e por te d by EPA f o r

sa mple s c o lle c t e d 5 y e a r s e a r lie r (U.S. EPA, 1996e; Rubin and W hite, 1992). The pre dominant cong eners in both data sets are the octa- and hepta-CDDs and CDF s

. Althoug h not present at hig h concentrations, 2,3,7,8-TCDF

was com m onl y det ect ed.
I n addition to effluents, Rappe et al. ( 1998) analy z ed the levels of CDDs/CDF s in municipal sewag e sludg e from the 17 POTW s in Mississippi. Table 8-38 presents the
concentrations of diox ins measured in the sewa g e sludg e samples and to tal TEQ emission factors reported by Rappe et al. C oncentrations were only cong ener specific for 2,3,7,8-TCDD; 2,3,7,8­
TCDF ; 1,2,3,7,8-PeCDD; 2,3,4,7,8-PeCDF ; OCDD; and OCDF

. Also provided were

c onc e n tr a tions f o r

tota l Hx CDD a nd tota l HpCDD. The TEQ e mission f a c t or s ( a ssuming nondetects equal to one-half the DL ) rang ed from 2.26 to 1,270 ng I

- TEQ DF 

### /kg

. The

pr e domina n t c ong e n e r s in a ll sa mple s we r e th e octa- and hepta-CDDs. The sludg e with the hig hest concentrations of oc ta- and hepta-CDDs was from th e Picay une POTW , which receives industrial inputs, including effluents from wood tr eatment facilities that lik ely contain PCP. I n
g e neral, the sludg es with the lowest TEQ va lues were from the facilities that do not receive
effluent from industrial facilities. Additionally

, the samples with the two lowest TEQ values

we r e f r o m f a c ilitie s tha t do not use f r e e c h lor i ne a s a disinf e c t a n t.
I n 1999, sewag e sludg e samples from a POTW in Ohio were collected and analy z ed for
CDDs/CDF s (U.S. EPA, 2000b). The facility

, which accepts both domestic and industrial wastewater, employ s secondary wastewater technolog y

. Assu ming nondetects are z e ro, the mean TEQ emission factor was 21.9 ng TEQ DF 

### -W HO 98 

### / k g (dry -wei g h t basi s). These resul t s are presented in Table 8-39.

8-83Table 8-37.CDD/CDFconcentrations(ng/kg) measured in 99 sludges collected fromU.S. publicly ownedtreatment works (POTWs) during 1994



### 8-84CongenerPercentdetectedMaximumconcentrationdetectedMedian concentrationMean concentrationNondetectset todetectionlimitNondetectset tozeroNondetectset todetection limitaNondetectset tozeroa2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD4023348764989912.337.545.613088.85,38065,5001.958.235.2525.612.36426,63000024.79.486426,6302.72(2.4)10.9(7.8)11.1(8.13)33.8(27.6)20.2(17.7)981(977)11,890(12,540)1.71(2.86)3.34(7.43)6.03(10.2)32.2(28.8)17(19.8)981(977)11,890(12,540)2,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF762142481743564319315660.31551702001153561,46021311,2007.537.919.711.5147.539.8591.711.72866.2800000031.8028112.8(19.6)10.7(11.3)15.7(19.8)20.4(25.3)30.4(53.6)11.1(13.6)21.8(40.4)223(271)27.1(34.8)786(1,503)11.1(20.2)3.53(9.36)10.5(21.6)14(25.9)5.13(21.9)1.56(11.7)13.6(41)97.5(207)15(33.4)775(1,506)Average I-TEQDF(facilitybasis)b24649.633.464.5(50.1)47.7(44.7)Total2,3,7,8-CDD/CDF85,279.57,782.87,625.314,108.7(15,573)13,878.2(15,484.2)Average TEQDF-WHO98(facilitybasis)b44.625.557.2(44.4)36.3(38.6)aValue inparenthesis is the standarddeviation.bFor POTWs withmultiple samples, the sample TEQ concentrationswere averagedtoPOTWaverages before calculationofthe total TEQ meanand medianvalues presentedinthe table.Atotal of74POTWaverage concentrationswere usedinthe calculations.Inaddition,the following sampleIDnumberswerenot included inthe averagingbecause, accordingto Greenet al. (1995), it wasnot possible to determine whether theywere duplicate ormultiple samples fromother POTWs:87, 88, 89, 90, 91, 97, 98, and 106.Sources:Greenetal. (1995);Cramer etal. (1995).Table 8-38.Concentrations ofCDDs/CDFs (ng/kg dry matter) in sewage sludge frompublicly owned treatmentworks in Mississippi



### 8-85Facility2,3,7,8­TCDD2,3,7,8­TCDF1,2,3,7,8­PeCDD2,3,4,7,8­PeCDFTotalHxCDDTotalHpCDDOCDDOCDFTotalI-TEQWaynesboro2.12.93.51.4859207,40041023.7MeridianND(0.06)2.16.42.8101007,40041027.6Pascagoula23.65.33.51709704,30017026.4W. Biloxi0.842.43.21.3782801,8007013.7Gulfport1.99.19.53.42001,1007,70031030.9Laurel0.170.30.370.25221602,700214.83Brookhaven22.5112.51301,4009,30023036.7NatchezND(0.58)8.38.4ND(1.5)2701,1006,80027037.7Picayune5.369742417,000250,000480,00016,0001,270Picayunea4.166601716,000210,000420,00017,0001,240Waveland1.62.65.11.91305803,50015031.7Corinth0.31.80.970.93422303,300367.4NewAugustaND(0.13)0.170.150.094211401,4008.82.67Beaumont0.170.670.780.37594701,900426.18LeaksvilleND (0.051)0.140.320.111692560262.26McLain0.0760.170.110.031391402,6000.743.55HattiesburgS11.19.12.21701,30004,40018033HattiesburgNND (0.035)1.7423103,60027,00098070.4Average1.79.711.23.81,930.726,904.655,114.42,017.5159.4 ± 399aBlind double.ND = Not detected(valueinparenthesis is the detectionlimit).Whencalculatingthe average, NDswere not included.Source:Rappe etal. (1998).

### Table 8-39. CDD/CDF m e di an concentrations (n g/kg) m e asured in 1999 fr om a public ly ow ne d t r e a t m e n t w o r k s fac ilit y in Ohio

C o ngener N o ndetect set to z ero Nondet ect set t o 1⁄2 d e tection limit
2,3,7,8- T C DD 1,2,3,7,8- PeCD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND ND 2.67 21.33 30.33 298 2,963 0.0018 0.0082 2.67 21.33 30.33 298 2,963
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 26.67 4.33 10 21

5.33 ND 9 171 ND 364.67 26.67 4.34 10 21

5.33 0.0033 9 171 0.01 364.67

A v erag e total T E Q DF 

### -W H O 98 

### 21.87 21.88

ND = No t d e tected

S o u rce: U

. S

. EPA (2000b).



### I n 2000 and 2001, AMSA conducted another survey of diox in-like compounds in sewag e sludg e (Alvarado et al., 2001). A total of 200 sewag e sludg e samples were collected from 171
POTW s located in 31 states. Assuming nondetect s are z e ro, TEQ emission factors rang e from
0.08 to 3,578.61 ng TEQ DF 

### -W HO 98 

### /kg

. The mean and median TEQ emission factors were 34.5 and 11.79 ng TEQ DF 

### -W HO 98 

### /kg

, r e spe c tive l y

. EPA conducted another Na tional Sewag e Sludg e Survey to characteriz e the diox in and
diox in-like equivalence levels in biosolids produced by 6,857 POTW s operating in the United States in 2001 (U.S. EPA, 2002d). Samples were collected from 94 POTW s using secondary or hig h er treatment practices. A ll facilities had been sa mpled previously as part of the 1988/1989 National Sewag e Sludg e Survey

. The overall mean and median TEQ DF 

### -W HO 98 

### concentrations were 75 and 15 ng /kg

, respectively

. However, whe n the da ta we r e we ig hte d using the da ily
inf l ue nt wa ste w a t e r f

l ow r a te s ( i .e ., the numbe r of f

a c ilitie s with wa ste w a t e r f

l ow r a te

8-86

### >100 Mg /day , >10 but 

### # 100 Mg /day , >1 but 

### # 10 Mg /day , and 

### # 1 Mg / d ay ), t h e overal l m ean and median TEQ DF 

### -W HO 98 

### concentrations were 21.7 and 15.5 ng /kg , respectively

. These dat a are summariz e d in Table 8-40.

Table 8-40. CDD/CDF m e an concentrat ions (ng/kg) m e as ured in the 2001 National Sew age Sludge Survey

C o ngener N o ndetect set to z ero Nondet ect set t o 1⁄2 d e tection limit
2,3,7,8- T C DD 1,2,3,7,8- PeCD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 1.41 5.76 11.8 21.3

3.6 492 6,780 1.1 4.57 7.49 15.1

2.22 273 2,730
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 3.11 2.61 6.03 1.37 0.27 5.21 5.5 9.13 167 802 2.3 1.5 2.8 1 0 2.6 3.36 2.8 88.2 279

A v erag e total T E Q DF 

### -W H O 98 

### 21.7 15.5

S o u rce: U

. S

. EPA (2002d).



### The CDD/CDF concentrations and cong ener g r oup patterns observed in the U.S. survey s are similar to those reported for sewag e sludg es in several other W e stern count ries. Stuart et al. (1993) reported mean CDD/CDF c oncentrations of 23.3 ng I

- TEQ DF 

### / k g (dry wei g ht ) for t h ree sludg es from rural areas, 42.3 ng I

- TEQ DF 

### /kg for six sludg es from lig ht industry / domestic areas, and 52.8 ng I

- TEQ DF 

### /kg for six sludg es from industria l/domestic areas collected during 1991–1992 in Eng l and and W a les. Näf et al. (1990) reported concentrati ons rang ing from 31 to 40 ng I

- TEQ DF 

### /kg (dry weig ht) in primary and dig e st ed sl udg es col l ect ed from t h e P O TW i n Stockholm, Sweden, during 1989. Gobran et al. (1995) reported an averag e concentration of
15.7 ng I

- TEQ DF 

### /kg in anaerobically dig e sted sludg es from an industrial/domestic POTW in Ontario, Canada. I n all three studies, the c ong ener g r oup concentrations increased with

8-872, 3,7

,8

- TC

D D

1,2

,3 ,7, 8- P eC

DD
1,2,3

, 4,7

, 8- Hx

C D D
1,2,3

, 6,7,

8- Hx

CD

D

1,2,

3 ,7,8

, 9- Hx

CD

D

1,2

, 3,4,

6,7,8

- H p CDD O CDD

2 ,3 ,7, 8- T CDF

1,2,

3 ,7,8

- P e CDF

2,3

,4 ,7, 8- P eC

DF

1 , 2,3,

4 ,7,8

- H x CDF

1 ,2,3

,6 ,7, 8 - Hx

CD

F

1, 2 , 3 ,7 ,8,9

- Hx

CD

F

2 ,3,4

,6 ,7, 8 - Hx

C DF

1,2

, 3,4,6 , 7,8

- Hp

CDF

1,2,

3,4,7 , 8,9-

Hp

CDF O CDF 0% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % 100 %Percent ofTotalCDDs andCDFs

Congener



### F i gu re 8-6. Con g en er p r of i l e s f o r sew age sl u d g e (created f r om d a ta i n T a b l e 8-38).

increasing deg r ees of chlorination, with OCDD the dominant cong ener. F i g u re 8-6 presents

cong ener profiles, using the mean concen trations reported by Green et al. (1995).
Because t h e m ean I

- TEQ DF 

### concentration values reporte d in the 1988/1989 sewag e sludg e
survey (U.S. EPA, 1996e) and the 1995 survey (G reen et al., 1995; Cramer et al., 1995) were

very similar, the estimated amounts of TEQs that may have been present in sewag e sludg e and
released to the environment in 1987 and 1995 were assumed to be the same. These values were

e stima te d using the a v e r a g e ( 49 ng I

- TEQ DF 

### /kg ) of the me a n I

- TEQ DF 

### concentration values (nondetects equal to DL s) reported by U.S. EPA (1996e) (50 ng I

- TEQ DF 

### /kg ) and by Green et al. (1995) and Cramer et al. (1995) (36.3 ng TEQ DF 

### -W HO 98 

### /kg [ 47.7 ng I

- TEQ DF 

### /k g ] ). Therefore, the overall averag e mean emission factor for reference y ears 1987 and 1995 is 36.3 ng TEQ DF 

### WH O 98 

### /kg (48.9 ng I

- TEQ DF 

### /kg )

. The emission factor of 21.7 ng TEQ DF 

### -W HO 98 

### /kg

, a s calculated from the 2001 survey , appears to be th e most reasonable TEQ emission factor estimate for reference y ear 2000 because this estimate is nationally weig hted on the basis of wastewater
flow rates of POTW s operating in the United States in 2001.

8.4.1.3.2. A c t i v i t y l evel i n form at i o n . According to the results of its 1988/1989 National Sewag e Sludg e Survey , EPA estimated that appr ox imately 5.4 million dry me tric tons of sewag e

8-88

### sludg e were g e nerated in 1989 (F ederal Reg i ster, 1993a). EPA also used the results of the 1984
to 1996 Clean W a ter Needs Survey s to estimate th at 6.3 million dry metric t ons of sewag e sludg e
were g e nerated in 1998. B ecause estimates for reference y ear s 1987 and 1995 are not available, the 1989 and 1998 activity level es timates were used for 1987 a nd 1995, respectively

. Tables 8-41 and 8-42 list the volumes, by use and disposal practices, of sludg e disposed of annually for reference y ears 1987 and 1995, respectively

. U.S. EPA (1999b) estimated that 6.6 million dry metric tons of sewag e sludg e would be

g e nerated in 2000. Table 8-43 lists the volumes , by use and disposal practices, of sludg e disposed of annually for reference y ear 2000. Similarly , the Nationa l Research Council (NRC) analy z ed the amount of biosolids being app lied to land in 2002 (NRC, 2002). Citing 2001 data (unpublished) from the W i sconsin Department of Na tional Resources, the NRC estimated that

approx imately 8,650 of the 16,000 POTW s operating in the Unite d States g e nerated sewag e sludg e r e quir i ng use or disposa l

. Using da ta f

r o m 37 sta t e s, the inve stig a t or s e stima te d tha t 5,900 of these sewag e sludg e g e nerators either la nd applied or publicly distributed more than 3.4 million dry tons of biosolids annually

. The volume of biosolids, by use and disposal practices, is presented in Table 8-44. The volume of bios olids and their distribution among the various

c a t e g or ie s e stima te d by the NRC a r e ve r y c l ose to those e stima te d by EPA.

8.4.1.3.3. Em ission estim ates

. Annual potential releases of CDDs/CDF s were determined by multiply ing the me a n tota l TEQ c onc e n tr a tions by the sludg e volume s g e ne r a te d. The me a n tota l TEQ concentrations in sewag e sludg es fo r reference y ears 1987, 1995, and 2000 are reported in Tables 8-41, 8-42, and 8-43, respectively

. F o r 1987, the total annual potential release from nonincinerated sludg es was 151 g TEQ DF 

### -W HO 98 

### . Of this amount, 2.6 g TEQ DF 

### -W HO 98 

### (3.5 g I

TEQ DF 

### ) entered commerce as a product for di stribution and marketing and 76.6 g TEQ DF 

### -W HO 98 

### (103 g I

- TEQ DF 

### ) was applied to land. The remaining 71.8 g TEQ DF 

### -W HO 98 

### did not result in an
environmental release because it was sent to RCRA Subtitle D landf ills or disposal sites. F or 1995, the total annual potential release fro m nonincinerated sludg es was 178 g TEQ DF 

### -W HO 98 

### . Of this amount, 3 g TEQ DF 

### -W HO 98 

### (4 g I

- TEQ DF 

### ) entered commerce as a product for distribution and marketing and 116.1 g TEQ DF 

### -W HO 98 

### (156.5 g I

- TEQ DF 

### ) was applied to land. The remaining
58.9 g TEQ DF 

### -W HO 98 

### did not result in an environmenta l release because it was sent to RCRA Subtitle D landfills or disposal sites. F or 2000, the total annual release of nonincinerated sludg es was 111 g TEQ DF 

### -W HO 98 

### . Of this amount, 1.9 g TEQ DF 

### -W HO 98 

### (1.9 g I

- TEQ DF 

### ) ent e red commerce as a product for distri bution and marketing and 78.2 g TEQ DF 

### -W HO 98 

### (78.2 g I

TEQ DF 

### ) was applied to land. The remaining 30.9 g TEQ DF 

### -W HO 98 

### did not result in an
environmental release because it was sent to RCRA Subtitle D landfills or disposal sites.

8-89

### Table 8-41. Quantity of sew age sludg e disposed of and potential dioxin TEQ releases f r om prim ary, secondary, a nd advanced treatm ent publicly ow ned treatm en t w o rk s f o r ref eren ce year 1987

Use/disposal practice Volu m e disposed of (1,000 dry

me t r i c ton s / y r) P ercen t of total vol u m e P o t e nt ial dioxin r e le a se a 

### ( g TEQ/yr )

I- TEQ DF 

### TEQ DF 

### ­ WHO 98 

### L a nd application 1,714 32 b 

### 84 62.2 Distribution and marketing 71 1.3 3.5 2.6

S urface disposal site/other 396 7.4 19.4 14.4 Sewag e sludg e landfill 157 2.9 7.7 5.7

Co- d isposa l la ndf ills c 

### 1,819 33.9 89.1 66 Sludg e incinerators and co-i nci n erat ors d 

### 865 16.1 e e



### Ocean disposal (336) f 

### (6.3) f f f



### T O T A L 5,358 100 203.7 150.9

a P o ten tial d i o x in T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (s econ d colu m n ) by th e av erag e of th e m ean I- T E Q DF con cen t rat i o n s i n s l u d g e report e d by R u bi n an d Wh i t e (1992) (i .e., 50 n g / k g dry w e i g h t ) an d G r een et al . (1995) an d C r am er et al . (1995) (47.7 n g / k g )

. T h e cal cu l a t i o n s of TE Q DF -W H O 98 u s ed th e m ean con cen tration of 36.3 n g T E Q DF -W H O 98 /k g f o r th e res u lts reported by Green et al. (1995) an d C ram er et al . (1995).

b In cl u d es 21.9% appl i e d t o ag ri cu l t u ral l a n d , 2.8% appl i e d as com pos t , 0.6% appl i e d t o f o res t ry l a n d , 3.1% appl i e d
to “ p u b lic co n t act” lan d , 1

. 2 % ap p lied to reclam atio n sites, an d 2

. 4 % ap p lied in u n d ef in ed settin g s

.
c L a n d f ills u s ed f o r d i sp o s al o f sew a g e slu d g e an d so lid w a ste resid u als.

d Co

- i n c in erato r s treat sew a g e slu d g e in co m b in atio n w ith o t h e r co m b u s tib le w a ste m a terials.

e See Section 3.5 f o r es tim ates of C DD/C D F releas e s t o a i r fr o m se w a ge sl ud ge i nc i ne r a t o r s

. f T h e Ocean Du m p in g Ban A c t of 1988 g e n e rally proh ibited th e du m p in g of s e w a g e s l u d g e in to th e ocean af ter Decem ber 31, 1991. Ocean du m p in g of s e w a g e s l u d g e en ded in Ju n e 1992 (F ederal R e g i s t er, 1993a). T h e cu rren t

m e th od of dis pos al of th e 336,000 m e tric ton s of s e w a g e s l u d g e th at w e re dis pos ed of in th e ocean s in 1988 h a s n o t been determ in ed.



### These release estimates are a ssig n ed a hig h confidence rating for both the production and
the emission factor estimates. The hig h rating is based on the judg ment that the 174 facilities tested as part of the 1988/1989 National Sewa g e Sludg e Survey (U.S. EPA, 1996e), the 74 facilities tested as part of the 1994/1995 AMSA Survey (Green et al., 1995 and Cramer et al., 1995), and the 94 facilities tested as part of the 2001 National Se wag e Sludg e Survey (U.S. EPA, 2002d) were reasonably representative of the variability in POTW t echnolog ies and sewag e charact eri s t i c s nat i onwi d e.

8-90

### Table 8-42. Quantity of sew age sludg e disposed of and potential dioxin TEQ releases f r om prim ary, secondary, a nd advanced treatm ent publicly ow ned treatm en t w o rk s f o r ref eren ce year 1995

Use/disposal practice Volume disposed of

(1,000 dry metric ton s/yr) P ercent of total volume Poten t ial d i ox in release a 

### (g T E Q/yr)

I

- TEQ DF 

### TEQ DF 

### ­ WHO 98 

### Land application b 

### 2,500 40 122.3 90.7

A d v anced treatm ent c 

### 700 11 34.2 25.4

Other beneficial use d 

### 500 8 24.5 18.2 Surface disposal/landfill 1,100 17 53.8 39.9

I n cineration 1,400 22 e e 

### Other disposal m e thod 100 2 4.9 3.6

T O T A L 6,300 100 239.7 177.8

a P o ten tial d i o x in T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (s econ d colu m n ) by th e av erag e of th e m ean I- T E Q DF con cen t rat i o n s i n s l u d g e report e d by R u bi n an d Wh i t e (1992) (50 n g / k g dry w e i g h t ) an d G r een et al . (1995) an d C r am er et al . (1995) (47.7 n g / k g )

. T h e cal cu l a t i o n s of T EQ DF WH O 98 u s ed th e m ean con cen tration of 36.3 n g T E Q DF -W H O 98 / k g f o r t h e res u l t s report e d by G reen et al . (1995)

an d C r am er et al . (1995).

b W ith o u t f u rth e r p r o cessin g o r stab ilizatio n , su ch as co m p o s tin g

.
c Su ch as com pos tin g

. d E P A a ssum e s t h a t t h i s c a t e g o r y i n c l ud e s d i st r i b u t i o n a n d m a r k e t i ng ( i

. e

. , sa l e o r gi ve -a w a y o f sl ud ge fo r use i n h o m e g a rden s ). Bas e d on t h e 1988 N a t i o n a l S e w a g e S l u d g e S u rv ey an d 1988 N eeds S u rv ey , approx i m at el y 1.3% of

t h e t o t a l v o l u m e of s e w a g e di s pos ed i s di s t ri bu t e d an d m a rk et ed (F ederal R e g i s t er, 1993a). T h eref ore, i t i s

es tim ated th at 3 g T E Q DF -W H O 98 (4 g I- T E Q DF ) w e r e r e l e a s e d t hr o ugh d i st r i b ut i o n a nd m a r ke t i ng i n 1995.

e See Section 3.5 f o r es tim ates of C DD/C D F releas e s t o a i r fr o m se w a ge sl ud ge i nc i ne r a t o r s

.

S o u rces : F e deral R e g i s t er (1990, 1993a).



### 8.4.2. Drinking Water Treatm ent P l ants There is no strong evidence that chlorination of water for drinking purposes results in the
formation of CDDs/CDF s. F e w survey s of CDD/CDF content in finished drinking water have
been conducted. Those that have been published have only rarely reported the presence of any
CDDs/CDF s, e ve n a t low pic og r a m pe r lite r DL s, a nd in those c a s e s , CDDs/CDF s we r e a l so present i n t h e unt reat ed wat e r. Rappe et al. (1989b) reported th e formation of tetra- throug h octa-CDF s when tap water
and double-distilled water we re chlorinated using chlorine g a s. The CDF levels found in the sing le samples of tap wa ter and double-distilled wate r were 35 and 7 pg I

- TEQ DF 

### /L , r e spe c tive l y

. No CDDs were detected at DL s rang ing from 1 to 5 pg /L

. Howe ve r , the wa te r sa mple s we r e

8-91

### Table 8-43. Quantity of sew age sludg e disposed of and potential dioxin TEQ releases f r om prim ary, secondary, a nd advanced treatm ent publicly ow ned treatm en t w o rk s f o r ref eren ce year 2000

Use/disposal practice Volume disposed of (1,000 dry metric ton s/yr) P ercent of total volu m e Poten t ial d i ox in release a 

### (g T E Q/yr)
TEQ DF 

### -WHO 98 

### Land application b 

### 2,800 42 60.80

A d v anced treatm ent c 

### 800 12 17.40

Other beneficial use d 

### 500 8 10.90 Surface disposal/landfill 900 14 19.50

I n cineration 1,500 23 e 

### Other disposal m e thod 100 2 2.17

T O T A L 6,600 100 111.00

a P o ten tial d i o x in T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (s econ d colu m n ) by th e av erag e of th e m ean T E Q DF -W H O 98 con cen t rat i o n s i n s l u d g e report e d i n U

. S

. EPA (2002d).

b W ith o u t f u rth e r p r o cessin g o r stab ilizatio n , su ch as co m p o s tin g

.
c Su ch as com pos tin g

. d EP A as s u m es th at th is categ ory in clu d es dis t ribu tion an d m a r ke t i ng ( s a l e o r gi ve -a w a y o f sl ud ge fo r use i n ho m e g a rden s ). Bas e d on t h e 1988 N a t i o n a l S e w a g e S l u d g e S u rv ey an d 1988 N eeds S u rv ey , approx i m at el y 1.3% of t h e t o t a l v o l u m e of s e w a g e di s pos ed i s di s t ri bu t e d an d m a rk et ed (F ederal R e g i s t er, 1993a). T h eref ore, i t i s es t i m at ed
t h at 1.9 g T EQ DF -W H O 98 w e r e r e l e a s e d t hr o ugh d i st r i b ut i o n a nd m a r ke t i ng i n 2000.

e See Section 3.5 f o r es tim ates of C DD/C D F releas e s t o a i r fr o m se w a ge sl ud ge i nc i ne r a t o r s

.



### Tab l e 8-44. Biosolid s d i sp osal p r actices f o r ref eren ce year 2000

Use/disposal practice Volume disposed of (1,000 dry metric ton s/yr) P ercent of total volu m e Land application 3,100 61

S u rface disposal/landfill 940 18

I n cineration 1,000 20

Ot he r 6 4 1

T O T A L 5,104 100
S o u rce: N R C (2002).



### chlorinated at a dosag e rate of 300 mg /L , which is considerably hig h er (by one to two orders of

ma g n itude ) tha n the r a ng e of dosa g e r a te s ty pic a lly used to disinfect drinki ng water. The authors hy pothesiz e d that the CDF s or their pr ecursors were present i n chl o ri ne g a s.

8-92

### Rappe et al. (1990c) analy z ed a 1,500-L samp le of drinking water from a municipal drinking water treatment plant in Sweden. Althoug h the untreat ed water was not analy z ed, a sludg e sa mple f r o m the sa me f a c ility wa s a n a l y z e d. The la r g e sa mple volume e n a b le d DL s on

the order of 0.001 pg /L

. The TEQ contents of the water and the sludg e were 0.0029 pg I TEQ DF 

### /L and 1.4 ng /kg

, respectively

. The cong ener patterns of the dri nking water and sludg e

sa mple we r e ve r y simila r , sug g e sting tha t the CDDs/CDF s de te c t e d in the f i nishe d wa te r we r e present i n t h e unt reat ed wat e r.

8.4.3. Soaps and Detergents As discussed in Section 8.4.1, CDDs/CDF s were detected in nearly all sewag e sludg es tested, whether the sludg es were obtained from i ndustrializ ed areas or from rural areas. B e cause of the ubiquitous presence of CDDs/CDF s in sewa g e sludg e, several studi es have been conducted to determine their source(s). A log i cal categ ory of products to test, becau se of their widespread use, is deterg ents, particularly t hose t h at cont ai n or rel e ase chl o rine during use (i.e., hy pochloritecontaining and dichloroisocy a nuric acid-containing deterg ents). The results of studies conducted

t o dat e , sum m a ri z e d bel o w, i ndi cat e t h at C DDs/ C DFs are not form ed duri n g use of chl o ri ne-free
det e rg ent s , chl o ri ne-cont ai ni ng or chl o ri ne-rel easi n g det e rg ent s , or chl o ri ne bl each duri n g household bleaching operations. Sweden’s Office of Nature Conservancy (1991) reported that the re sults of a preliminary study conducted at one household indicated th at CDDs/CDF s may be formed during use of dichloroisocy a nurate-containing dishwa she r de te r g e n ts. A mor e e x te nsive ma in study with multiple runs was then conducte d using standardiz ed food, dish es, cutlery , and other household
items. Testing of laundry wash ing and fabric bleaching and ac tual testing of the CDD/CDF content of deterg ents was also performed. The study ex amined (1) hy pochlorite- and
di chl o roi s ocy a nurat e-cont ai ni ng di shwasher det e rg ent s , (2) sodi um hy pochl ori t e -based bl each (4.4% NaOCl) in various comb inations with and without la undry deterg ent, and (3) sodium hy pochlorite-based bleach, used at a hig h enoug h concentration to effect bleaching of a pair of imported blue jeans.
CDDs/CDF s we r e not de te c t e d in e ithe r the c h lor i ne

- f r e e de te r g e n t or the de te r g e n t with hy pochlorite; 0.6 pg TEQ/g we re detected in the deterg ent cont aining dichloroisocy a nurate. The
results of all dishwasher a nd laundry washing machine tests showed very low levels of
CDDs/CDF s, often nondetected values. There wa s no sig n ificant difference between the controls

a nd the te st sa mple s; in f a c t , the c ontr o l sa mple s had a hig her TEQ content than did some of the

te st sa mple s. The dr a i nwa t e r f

r o m the dish washer tests contained <1 to <3 pg I

- TEQ DF 

### /L (the water-only control sample contained <2.8 pg I

- TEQ DF 

### /L ). The CDD/CDF content of the laundry

8-93

### drainwater samples rang ed from <1.1 to <4.6 pg I

- TEQ DF 

### /L (the water-onl y c ontr o l sa mple contained <4.4 pg I

- TEQ DF 

### /L )

. Thus, under the study ’s test conditions, CDDs /CDF s were not formed during dishwashing or laundry washing or during bleaching with hy pochlorite-containing bleach. No definitive
reason could be found for the difference in resu lts between the preliminary study and the main study for dishwashing with dichloroisocy a nurate-c ontaining deterg ents. The authors of the study

sug g e sted that differences in the foods used and the prewashing procedures employ ed in the two
studie s we r e the like l y c a u se s of the va r i a tion in the r e sults. Rappe et al. (1990b) analy z ed a sample of a Swedish commercial so ft soap, a sample of tall oil, and a sample of tall resin for CDD/CDF content. Tall oil and tall re sin, by -products of the pulping industry

, are the starting materials fo r the production of soft liquid soap. Crude tall oil, collected after the Kraft pulping process, is distilled under reduced pr essure at temperatures of up to 280 to 290°C, y i elding tall oil and tall resin. The measured TEQ content of the liquid soap was found to be 0.647 ng TEQ DF 

### -W HO 98 

### /L (0.447 ng I

- TEQ DF 

### /L ). P e C DDs were the dominant cong ener g r oup, followed by HpCDDs , Hx CDDs, PeCDF s , and OCDD, with some
tetra-CDF s and CDDs also present. Th e TEQ contents of the tall oil (12 ng TEQ DF 

### -W HO 98 

### /kg [ 9.4 ng I

- TEQ DF 

### /kg ] ) and tall resin (196 ng TEQ DF 

### -W HO 98 

### /kg [ 200 ng I

- TEF DF 

### / k g ] ) were sig nificantly hig her than the level found in the li quid soap. The tall oil c ontained primarilytetraand penta-CDDs and CDF s , whereas the tall re sin contained primarily HpCDDs, Hx CDDs, and
OC DD. The i nvest i g at ors com p ared t h e cong ener pat t e rns of t h e t h ree sam p l e s and not ed t h at althoug h the absolute values for the tetra- and penta-CDDs and CDF s di ffered among the tall oil, tall resin, and liquid soap samples, t h e sam e cong eners were present

. The cong ener pat t e rns for
the hig h e r

- c hlor ina t e d c ong e n e r s we r e ve r y simila r

. Ta ble 8- 45 pr e se n ts the r e sults of the study

. I n 1987, 118 million L of liquid household soaps we re shipped in the United States (U.S. DOC, 1990b); shipment quantity data are not ava ilable in the 1992 U.S. Economic Census (U.S. DOC, 1996). B ecause only one sample of liquid so ap has been analy z ed for CDD/CDF content (Rappe et al., 1990b), no estimate of e nvironmental release can be made.

8.4.4. Textile Manuf acturi ng and Dry Cleaning As discussed in Section 8.4.1, CDDs/CDF s have been detected in almost all sewag e sludg es tested, whether they were obtained from i ndustrializ ed areas or rura l areas. To determine
whether tex tile fabric or fabr ic finishing processes could acc ount for the observed CDDs/CDF s, several studies were conducted in Germany

. These st udies, summariz e d in the following

parag r aphs, indicate that some finished tex tile products do contain detectable levels of
CDDs/CDF s and that they can be released from the tex tile durin g laundering or dry cleaning ;

8-94

### Table 8-45. CDD/CDF concentrations in Sw edish liquid soap, tall oil, and t a ll r e s in

C o ngener/congener group Li qui d soap (n g/L ) T a ll oil (ng/kg) T a ll resin (ng/kg)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD ND (0.009) 0.4 ND (0.02) 0.32 0.18 1.9 1 3.6 5.3 ND ( 2 ) ND ( 2 ) ND ( 2 ) ND ( 1 ) 5.3 ND ( 1 ) 3.1 ND ( 4 ) 810 500 5,900 6,000
2,3,7,8- T C DF 1,2,3,4,8- /1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8/9- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.62 0.29 0.2 0.013 ND (0.004) ND (0.004) ND (0.004) ND (0.005) ND (0.01) NA 17 4.2 1.9 1.4 0.7 ND (0.7) ND (0.5) ND (0.8) ND ( 2 ) NA ND ( 2 ) ND (0.4) ND (0.5) 24

-­ ND ( 1 ) ND (0.7) 10

9.0 NA

T o tal 2,3,7,8- CDD a 

### T o tal 2,3,7,8- CDF a 

### Total I

- T E Q DF a 

### Total TE Q DF 

### -W H O 98 a 

### 3.8 1.123 0.447 0.647 14.2 25.2

9.4 12 13,213.1 43 200 196

Total TC D D Total P e C D D Total H x C D D Total H p C D D Total O C D D Total TC D F Total P e C D F Total H x C D F Total H p C D F Total O C D F 0.12 15

3.4 3.6 1 1 1.3 0.15 ND (0.01) NA 31 380 3.3 ND ( 1 ) 5.3 26 41

4.9 ND ( 2 ) NA ND ( 1 ) 25 6,800 11,000

6,000 ND ( 2 ) ND (0.5) 56 19 NA

Total C D D / C D F a 

### 25.57 491.5 23,900

a C alcu l ation s as s u m e n o n d etect v alu es w ere zero.

NA = Not an aly zed ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)

-- = N o i n fo r m a t i o n gi ve n

S o u r ce: R a ppe et al . (1990b).



### 8-95

### however, tex tile finishing proce sses are ty pically not sources of CDD/CDF formation. Rather,
the use of CDD/CDF

- containing dy es and pig m ents and the use in some countries of PCP to treat unfinished cotton appear to be the sources of t h e det ect ed C DDs/ C DFs. Horstmann et al. (1993b) analy z ed the C DD/CDF content of eig h t different raw (unfinished) cotton cloths cont aining fiber from different count ries and five different white

sy nt het i c m a t e ri al s (acet at e, vi scose, bl eached pol y e st er, pol y a m i d e, and pol y acry l i c ). The

max imum concentrations found in the tex tile fabrics we re 30 ng /kg in the cotton products and 45

ng /kg in the sy nthe tic ma te r i a l s. Also, a c o tt on finishing scheme was developed that subjected one of the cotton materials to a series of 16 ty pical cotton finishing pro cesses; one sample was
anal y z ed fol l o wi ng each st ep. The fabri c fi ni shi n g processes showi n g t h e g r eat est effect on C DD/ C DF concent r at i on were t h e application of an indanthren e dy e and t h e “wash and wear” finishing process, which tog e ther resulted in a CDD/CDF concentration of about 100 ng /kg

. On the basis of the concentrations found, the author s concluded that neither unfinished new fabrics nor common cotton finishing processes could ex plain the CDD/CDF levels found in laundry

wast ewat er. F u chs et al. (1990) reported that the dry

- cl eaning solvent redistillation residues collected
from 12 commercial and industria l dry

- cleaning operations cont ained considerable amounts of
CDDs/CDF s. The reported I

- TEQ DF 

### content rang ed from 131 to 2,834 ng /kg , with the dominant

cong eners being OCDD and HpCDD. Towara et al . (1992) demonstrated that neither the use of
chlorine-free solvents nor variation of the dry

- cl eani n g process pa r a me te r s lowe r e d the
CDD/CDF content of the residues. Umlauf et al. (1993) conducte d a study to characteriz e th e mass balance of CDDs/CDF s i n t h e dry

- cl eani n g process. The soi l e d cl ot hes (containing 16 pg total CDDs/CDF s per kg )
accounted for 99.996% of the CDD/CDF input. I nput of CDDs/CDF s from indoor air containing
0.194 pg /m 3 

### accounted for the remainder (0.004%). The dry

- cleaning process removed 82.435%
of the CDDs/CDF s in the soiled clothing

. Mo st of the input CDDs/CDF s (82.264%) were found
in the solvent distillation residue s. Air emissions (at 0.041 pg /m 3 

### ) accounted for 0.0008% of the total input, which was less than the input from i ndoor air. The fluff (at a concentration of 36 ng /kg ) accounted for 0.1697%, and water efflue nt (at a concentration of 0.07 pg /L ) accounted
for 0.0000054%.
Horstmann and McL achlan (1994a, b, 1995) anal y z ed 35 new tex tile samples (primarily cotton products) obtained in Germany for CDDs/C DF s. L o w levels were found in most cases (total CDD/CDF <50 ng /kg )

. The dominant cong eners were OC DD and HpC DD. However,

se ve r a l c o lor e d T- shir ts f r o m a number of clothing producers ha d ex tremely hig h levels, with concentrations up to 290,000 ng /kg

. B ecause the c oncentrations in identical T-shirts purchased at the same store varied by up to a factor of 20, the authors concluded that the source of

8-96

### CDDs/CDF s was not a tex tile finishing process, because a process source would have resulted in
a more consistent level of contamination. Klasmeier and McL achlan (1995) subsequently analy z ed 68 new tex tile products obtained in Ge rmany for OCDD and OCDF

. Most samples had nondetectable levels (42 samples <60 ng /kg )

. Only four sa mples had levels ex ceeding 500 ng /kg

. Horstmann and McL achlan (1994a , b) reported finding two different cong ener g r oup patterns in the more contaminated of the 35 te x tile products. One pattern ag reed with the

cong ener pattern for PCP repor ted by Hag e nmaier and B r unner (1987), whereas the other pattern was similar to that reported by Remmers et al. (1992) for chlora nil-based dy es. The authors hy pothesiz e d that the use of PCP to preserve co tton, particularly when it is randomly strewn on
bal e s of cot t on as a preservat i v e duri n g sea t r an sport, was the likely source of the hig h levels occasionally observed. Althoug h the use of P C P for nonwood uses was prohibited in the United States in 1987 (see Section 8.3.8), PCP is still us ed in developing countries, especially to preserve cotton during sea trans port (Horstmann a nd McL achlan, 1994a).
Horstmann and McL achlan (1994a, b) c onducted additional ex periments that demonstrated that the small percentag e of clot hing items with hig h CDD/CDF levels could be responsible for the quantity of CDDs/CDF s obs erved in household wastewater (see Section 8.4.1.1).

8-97

### 9. INDICATIONS OF P O SSIBLE NATURAL SOURCES OF CDDs/CDF s

Numerous laboratory and field research studies have demons t r at ed t h at bi ochem i cal and photoly tic formation of CDDs/CDF s from chlor ophenol precursors is possible. I n addition, under certain conditions, some CDDs/CDF s can be biodeg r aded to form less chlorinated (and possibly mor e tox i c ) CDDs/CDF s. B o th of the se me c h a n isms a r e disc usse d in this c h a p te r ; however, t h e ex t e nt t o whi c h C DDs/ C DFs are form ed by ei t h er m echani s m i n t h e envi ronm ent i s not known at present. The poten tial for releases of CDDs/CDF s from the application of animal
manure to farmland and the mining and use of ball clay is also discussed.

9.1. BIOLOG ICAL SOURCES OF CDDs/CDF s 9.1.1. Biotransf orm ation of Chlorophenols
B i ochemical formation of CDDs/CDF s—partic ul arl y t h e hi g h er-chl ori n at ed cong eners— from chlorophenol precursors is possible, as indi cated in laboratory studies with solutions of trichlorophenols and pentachlor ophenol (PCP) in the presence of perox i dase enz y mes and hy drog en perox i de (Svenson et al., 1989; Ober g et al., 1990; W a g n er et al., 1990; Oberg and Rappe, 1992; Morimoto and Kenji, 1995) and with sewag e sludg e spik ed with PCP (Oberg et al., 1992). However, the ex tent to which CDDs/C DF s are formed in the environment via this
mechanism cannot be estimated at this time.
I n 1991, L a hl et al. (1991) reported finding CDDs/CDF s in all 22 samples of the various
ty

pe s of c o mposts a n a l y z e d. The he pta

- a nd oc ta

- substitute d CDDs/CDF s we r e ty pic a lly the dominant cong ener g r oups found. The I

- TEQ DF 

### content of the composts rang ed from 0.8 to 35.7

ng I

- TEQ DF 

### /kg

. The CDDs/CDF s found in compost may primarily resu lt from atmospheric deposition onto plants that are subsequently com posted, but they may also be caused by uptake of
CDDs/CDF s from air by the active compost (Krauss et al., 1994). CDDs/CDF s are also
f r e que ntly de te c t e d in se wa g e sludg e s, a nd the y ma y c o me pr ima r ily f

r o m the sour c e s ide n tif ie d
in Section 8.4.1.
Pe r o x i da se s a r e c o mmon e n zy me s in na tur e

. F o r e x a m ple

, the initia l de g r a d a tion of the lig nin poly m er by white- and brown-rot fung i is perox i dase cataly z ed (W ag ner et al., 1990). The conversion efficiency of chlori nated phenols to CDDs/CDF s that has been observed is low. I n the solution studies, Oberg and Rappe (1992) and Morimoto and Kenji (1995) reported
conversion efficiencies of PC P to OCDD of about 0.01% and 0.8% , respectively

, and W a g n er et al. (1990) reported a conversion efficiency of trichlorophenol to HpCDD of about 0.001%. Oberg et al. (1990) reported a conversion effici ency of trichlorophenols to CDDs/CDF s of about
0.001%. I n their sewag e sludg e study , Oberg et al. (1992) reported a conversion efficiency of
PCP to total CDDs of 0.0002 to 0.0004%.

9-1

### Several researchers have c onducted both laboratory and fiel d studies in an attempt to
better understand the ex tent of, a nd factors affecting

, the fate or formation of CDDs/CDF s in composts and sewag e sludg es. The finding s of several of these studies are discussed in the
fol l o wi ng parag r aphs. These fi ndi ng s are not al way s consi s t e nt because t h e cong ener profi l e s and patterns detected—and the ex tent of CDD/CDF formation, if any

— may vary with compost materials studied, differences in ex perimental or field compos ting desig n, and duration of the
studies. Harrad et al. (1991) analy z ed finished composts and active compost windrows from a municipally operated y a rd waste composting f acility in L ong I s land, NY. Concentrations measured in 12 finished composts rang ed from 14 to 41 ng I

- TEQ DF 

### /kg (mean, 3 ng I

- TEQ DF 

### /kg )

. The concentrations in the five active compost samples (1 to 30 day s in ag e) rang ed from 7.7 to 54

ng I

- TEQ DF 

### /kg (mean, 21 ng I

- TEQ DF 

### /kg )

. The authors observed that CDD/CDF concentrations

me a sur e d in two soil sa mple s f r o m the imme dia t e vic i nity of the c o mposting f a c ility we r e sig nificantly lower (1 and 1.3 ng I

- TEQ DF 

### /kg ) than the levels found in the composts, sug g e sting
tha t the sour c e ( s) of CDDs/CDF s in the c o mposts wa s dif f

e r e nt f r o m the sour c e ( s) a f f

e c ting loc a l
soils. Harrad et al. (1991) also noted a strong simila rity between the cong ener profiles observed in the composts and the cong ener profile of a PCP formulation (i.e., predominance of 1,2,4,6,8,9­
Hx CDF and 1,2,3,4,6,8,9-HpCDF in their respective cong ener g r oups), which seemed to indicate that leaching of CDDs/CDFs fro m P C P

- treated wood in the compost piles was the likely source of the observed CDDs/CDF s. The levels of PC P in the 12 finished composts rang ed from 7 to 190 μg /kg (mean, 33 μg /kg ) , and the PCP levels in the active compost samples rang ed from 17 to 210 μg /kg (mean, 68 μg /kg )

. The PCP le vel in both soil samples was 1.5 μg /kg

. Goldfarb et al. (1992) and Malloy et al. (1993) reported the results of testing composts at
thr e e munic i pa l y a r d wa ste c o mposting f a c ilitie s ( 5 to 91 ng I

- TEQ DF 

### /kg ; mean, 30 ng I TEQ DF 

### /kg ) , two munic i pa l solid wa ste c o mposting f a c ilitie s ( 19 to 96 ng I

- TEQ DF 

### /kg ; mean, 48

ng I

- TEQ DF 

### /kg ) , a nd one munic i pa l f a c ility c o mposting solid wa ste a nd de wa te r e d se wa g e sludg e (37 to 87 ng I

- TEQ DF 

### /kg ; mean, 56 ng I

- TEQ DF 

### /kg )

. All f a c ilitie s we r e loc a t e d in the Unite d
States. Two g e neral trends were observed for the three ty pes of composts: a prog ressive increase in analy t e levels, with an increasing deg r ee of chlorination for each compound ty pe (CDDs,
CDF s , chlorophenols, and chlorobenz enes), and a prog ressive increase in concentration of each

cong ener or homolog ue g r oup from y a rd waste to solid waste to solid waste/sewag e sludg e composts. As noted above, the mean TEQ concen trations showed this same trend, which was primarily due to increasin g levels of 1,2,3,4,6,7,8-HpCDD and OCDD. The mean PCP concentrations in the three compost ty pes were 20 μg /kg (y ard waste), 215 μg /kg (solid waste), and 615 μg /kg (solid waste/sewag e sludg e).

9-2 ­

### Comparison of cong ener profiles by the aut hors indicated that the CDD/CDF residue in PCP-treated wood in the compost feedstock was a major but not ex clusive contributor of the
observed CDDs/CDF s. The authors postulated th at biolog ical formati on of Hx C DDs, HpC DDs, and OCDD from chlorophenols (tri, te tra, and penta) in the compos t could be responsible for the elevated levels of these cong ener g r oups relative to their presence in PCP. Oberg et al. (1993) measured the ex tent of CDD/CDF formation in three conventional

g a r d e n c o mposts; two we r e spike d with PCP a nd one was spiked with hex achlorobenz ene. One PCP-spiked compost was monitored for 55 day s and the other for 286 day s

. A sig n ificant
i n crease i n t h e concent r at i ons of t h e m o re hi g h ly chlorinated cong en e r s, pa r tic ula r ly the HpCDDs, OCDD, and, to a lesser ex tent, OCDF
, were observed. Similar results were reported
for the hex achlorobenz ene-spiked compost, which was monitored for 49 day s

. Oberg et al. stated that for a “ty p ical” co mposting event, a two- to threefol d increase in TEQ content corresponded with an elevation of 0.2 to 0.5 ng I

- TEQ DF 

### /kg dry weig ht.
W e ber et al. (1995) subjected sewag e sludg es from two German communities to anaerobic dig e stion in laboratory reactors for 60 day s

. The two sludg es were spiked with 2,3,5­ trichlorophenol (10 to 25 mg /kg ) , a mix ture of 2,3,5-trichlorophenol and dichlorophenols (2.5 to 25 mg /kg ) , or a

mix tur e of di-

, tr i- , a nd te tr a c h lor obe nze n e s ( 4 to 40 mg /kg )

. The initia l
CDD/CDF c onc e n tr a tions in the tw o sludg es were 9 and 20 ng I

- TEQ DF 

### /kg

. I n nearly all of the dig e stion ex periments, the addition of the precurs ors did not lead to any sig nificant chang e s in
concentrations. The only ex ceptions were in creased 2,3,7,8-TCDF concentrations in the mix ed chlorophenol ex periments and decreased 2,3,7,8-TCDF concentrations in the mix ed
chlorobenz ene ex periments. Howe ver, t h e sam e i n creases or decreases for t h i s cong ener were also observed in the controls (i.e., no precursors added). Researchers at the U.S. Department of Ag ri culture (USDA) (F ries et al., 1997) reported that dairy cows that were fed PCP-treated wood ex creted amounts of OCDD almost four times

g r eater than the amounts ing e sted. F e il and Tier nan (1997) reported that rats fed technical PCP
had liver concentrations of Hx CDD, HpCDD, Hp CDF
, OCDD, and OCDF two to three orders of

mag n itude hig h er than those of rats fed purif ied PCP. These results sug g e st the in vivo
formation of CDDs/CDF s from pre-diox ins (i.e., chlorinated phenox y phenols present as contaminants in the PCP). A follow-up USDA study (Huwe et al., 1998) investig ated the metabolic conversion of a pr e-diox in (monochloro-2-phenox y phenol) to OCDD in a feeding study with rats. The results of the study de m onst r at ed t h e form at i on of OCDD from the prediox in, althoug h the conversion wa s estimated to be less than 2%. I nteresting l y , the study noted

t h at t h e presence of added OC DD i n t h e feed m a t e ri al i n creased t h e percent a g e of pre-di ox i n conversion.

9-3

### W ittsiepe et al. (1998) demonstrated that CDDs/CDF s can be formed throug h reaction of chlorophenols with my eloperox i da se (a component of neutroph ile g r anulocy t es, a subg roup of human leucocy t es). The C DDs/CDF s formed showed diffe rent homolog ue patterns and formation rates depending on the deg r ee of chlo rination of the chlorophenol substrate. The formation rates rang ed from 1 to 16 μmol of CDD/CDF per mol of chlorophenol substrate.

9.1.2. Biotransf orm ation of Higher CDDs/CDF s Results of several studies th at ex am i n ed t h e fat e of a rang e of C DD/ C DF cong eners i n pure cultures, sediments, and sludg es indicat e that under certain conditions some CDD/CDF

cong eners will underg o biodeg r adation to form lower-chlorinated (and possibly more tox i c)
CDDs/CDF s. Howe ve r , the e x te nt to whic h mor e tox i c CDDs/CDF s a r e f or m e d in the
environment via this mechanism cannot be estimated at this time. Several reports indicate that CDDs and CD F s may underg o microbial dechlorination in
anaerobic sediments. Adriaens and Grbic-Galic (1992, 1993) and Adriaens et al. (1995) reported
the results of a series of microcosm studies using Hudson River sedime nt (contaminated with Aroclor 1242) and aquifer material (contaminated with CDDs) from Pensacola, F L

. B oth ty pes of substrates were spiked with se veral CDDs (1,2,3,4,6,7,8-HpCDD; 1,2,3,4,7,8-Hx CDD; and 1,2,4,6,8,9-/1,2,4,6,7,9-Hx CDD) and CDF s ( 1,2,3,4,6,7,8-HpCDF and 1,2,4,6,8-PeCDF ) and monitored over a 16-month period at an incuba tion temperature of 30°C. The Hudson River sediment was spiked with 144 μ g /kg of each cong ener, and the P e nsacola aquifer material was spi k ed wi t h 63 μ g / k g of each cong ener. All of the cong eners, with the ex cepti on of 1,2,3,4,6,7,8-HpCDF

, showed a slow decrease
in c onc e n tr a tion ove r time , whic h wa s a ttr ibute d to biolog ic a lly me dia t e d r e duc tive dechlorination, with net disapp earance rates rang ing from 0.0031 wk -1 

### to 0.0175 wk -1 

### (i.e., halflives of approx imately 1 to 4 y r). However, Adriaens et al. conc luded that actual half-lives may be orders of mag n itude hig h er. The ex pe riment with 1,2,3,4,6,7,8-HpCDD y i elded formation of 1,2,3,4,7,8-Hx CDD and 1,2,3,6,7,8-Hx CDD. Thus, re moval of the peri-substituted (1,4,6,9) chlorines was favored, with en richment of 2,3,7,8-substituted cong eners. No lower-chlorinated

cong eners were identified from incubation with the other test ed cong eners. 1,2,4,6,8-PeCDF was also ex amined in dichlorophenol -enriched cultures. After 6 months of incubation, several
TCDF s we r e ide n tif ie d, whic h a l so indic a t e d tha t peri-dechlorination was the preferred route of
reduction.
B a rkovskii and Adriaens (1995, 1996) reporte d that 2,3,7,8-TCDD ex tracted from Passaic River sediments was susceptible to reductive dechlorination when incubated at 30°C under

me tha nog e n ic c onditions in a mix tur e of a liphatic and org a nic acids inoculated with microorg a nisms obtained from the sediments. The initial concentration of 2,3,7,8-TCDD (20 ± 4

9-4

### μg /L ) decreased by 30% to 14 ± 2 μg /L over a period of 7 months, with the consecutive appearance and disappearance of tri-, di-, and mono-CDDs. Ex periments were also conducted by spiking the sediment with Hx C DDs, HpC DDs, and OC DD. Up to 10% of the spiked OC DD was converted to hepta-, hex a -, penta- , tetra-, tri-, di-, and mono-chlo rinated isomers, but the reaction
stoic h iome tr y wa s not de te r mine d. Two distinct pathway s of dech lorination were observed: the peri-dechlorination pathway of 2,3,7,8-substituted hepta- to pe nta-CDDs, resulting in the production of 2,3,7,8-TCDD, and the peri-lat eral dechlorination pathway of non-2,3,7,8­
substitute d c ong e n e r s. Several studies have repor ted that CDDs/CDF s can be formed during composting operations throug h biolog ical action on chlorophenol s present in the compost feed material. The results of studies that specify likely involvement of chlorophenols are de scribed in Section 9.1. Another possible formation mechanism was sug g e st ed by Vikelsoe et al. (1994), who reported

t h at hi g h er-chl ori n at ed C DD/ C DF cong eners are form ed when hum i c aci d i s react ed wi t h a
perox i dase enz y me, hy drog en pero x i de, and sodium chloride. I t is ex pected that some org a nic

ma te r i a l in c o mpost a nd se wa g e sl udg e has a hum i c -l i k e st ruct ure. Several additi onal studies are
described below in which the potential involvement of chlor ophenols could not be assessed because chlorophenol concentrations in the composts were not reported. Schäfer et al. (1993) monitored the seasonal chang e s in the CDD/CDF content, as well as
the ex tent of CDD/CDF formation, in composts from a veg e table and g a rden waste composting operation in Germany

. F i nished compost sample s were col l ect ed and anal y z ed every 2 m ont hs for 1 y r

. An annual cy cle was observed in TEQ c oncentrations, with peak concentrations in the summer (approx imately 8.5 ng I

- TEQ DF 

### /kg ) being 2.5 times hig her than the lowest concentrations observed in the winter (approx imately 3.5 ng I

- TEQ DF 

### /kg )

. No seasonal source was apparent that
could ex plain the observed diffe rences in seasonal levels.
The C DD/ C DF cont ent of t h e st art i n g wast e m a t e ri al s for t wo com post cy cl es (March and September) was measured to mon itor the ex tent of CDD/CDF formation during composting

. F or the March cy cle sample, most 2,3,7,8-subs tituted CDD/CDF cong eners decreased in concentration during composting

. F our CDF cong en ers showed a sl i g ht i n crease i n concent r at i o n (l ess t h an 10%). For t h e S e pt em ber cy cl e sam p l e , OC DD and HpC DD concent r at i ons i n creased 300% during composting

. I n creases of less than 10% were observed for Hx CDDs and OCDF ; all other 2,3,7,8-substituted CDD/CDF cong eners show ed decreases in concentrations during

c o mposting

. Krauss et al. (1994) measured the ex tent of CDD/CDF formation during the composting of household waste using a laboratory compost r eactor. After 11 wk, the TEQ content of the compost increased from 3 to 4.5 ng

. The larg es t increases in mass content were observed for HpCDD (primarily 1,2,3,4,6,7,8-HpCDD) and OCDD. TCDD, PeCDD, and Hx CDD showed no

9-5

### chang e in mass content. All CDF cong ener g r oups showed decreases in mass content; however,

t h e concent r at i ons i n bot h t h e st art i n g and t h e fi ni shed com post were cl ose t o t h e anal y t i cal
de te c tion limits. Oberg et al. (1994) reported the results of monitoring two household waste composts and
two g a rden composts. The total CDD/CDF cont ent of both household waste composts decreased over the 12-wk test period. Total CDD conten t and PCB content decreased, but total CDF content increased, in contrast to the finding s of Krauss et al. (1994). However, a small increase in OCDD content in both composts was observed. The two g a rden composts were monitored for a 60-wk period. Total CDD/CDF concentration incr eased, with the larg est increases observed for
OC DD and HpC DDs. The l o wer-chl ori n at ed C D Fs decreased i n concent r at i on. As a follow-up to a preliminary study (Heng s tmann et al., 1990) that indicated CDD/CDF

concent r at i ons m a y i n crease and cong ener pr ofiles may chang e during anaerobic dig e stion of

sewag e sludg e, W e ber et al. (1995) subjected sewag e sludg es from two German communities to
anaerobi c di g e st i on and aerobi c di g e st i on i n l a borat ory react ors for 60 day s and 20 day s ,

r e spe c tive l y

. The initia l a v e r a g e I

- TEQ DF 

### concentrations in the ra w sludg es were 20 and 200 ng
I

- TEQ DF 

### / k g

. No si g n i f i cant i n crease or decrease i n t o t a l C DD/ C DF cont ent or cong ener g r oup content was observed with either sludg e. I n c ont rast , a si g n i f i cant decrease i n C DD/ C DF cont ent was observed in the aerobic dig e stion ex periment s with both sludg es. The g r eatest percentag e decreases in cong ener g r oup concentrations (g reater than 40%) were observed for TCDF

, Pe CDF
, Hx CDF
, TCDD, a nd Pe CDD in the sludg e initia lly c onta i ning 20 ng I

- TEQ DF 

### /kg and for
TCDF , TCDD, HpCDD, a nd OCDD in the initia lly hig h- c onte nt sludg e

. The g r e a t e st pe r c e nta g e decreases in cong ener concentrations (g reater than 40%) were observed for non-2,3,7,8­
substitute d c ong e n e r s. The data presented in this section and in Section 9.1.1 do not provide a basis for making a

r e le a se e stima te via biotr a nsf o r m a tion; the r e f or e , biotr a nsf o r m a tion r e le a se s a r e c l a ssif i e d a s Categ o ry E (not quantifiable).

9.1.3. Dioxin-Like Com p ounds in Anim al M a nur e I n 2000, approx imately 9 billion individual lives tock and poultry animals were raised on commercial farms in the United States (U.S. Ce nsus B ureau, 2001). I t is estimated that beef animals, dairy cows, chickens, turkey s, and pi g s , combined, produced in ex cess of 190 billion kg (dry weig ht) of manure in 2000 (Table 9-1). B ecause livestock and poultry manure can provide valuable org a nic material and nutrients for crop and pasture g r owth, most of the animal manure

g e ne r a te d a t c o mme r c ia l f a r m s a nd a n ima l f e e d lots is a pplie d to f a r mla nd a s f e r tilize r

. To the

ex tent diox in-like compounds may contaminate animal manures, the prac tice of land-spreading

a n ima l wa ste ma y r e sult in r e le a se s of CDDs/CDF s to the ope n a nd c i r c ula ting e nvir onme n t.

9-6

### Table 9-1. Estim ated quantit y of anim al m a nure pr od u ced i n th e Un i ted States in 2000

Species N u mbers of i ndi vi dual s on f a rms in 2000 a 

### Average

w e ight of

animal

(lb s ) b 

### T o tal live

w e ight on fa r m s ( l b s ) Manure generation rate f a ctor (d ry w e igh t lb /lb live u n i t

w eigh t /d ay) c 

### Manure generated ( l b/ yr dry

we i g h t ) Manure produced (kg/yr dry

we i g h t )

Swine 6.73e+07 135 9.09e+09 8.2e



### ! 03 2.72e+10 1.23e+10 Lay e r 4.35e+08 4 1.74e+09 1.6e



### ! 02 1.02e+10 4.61e+09

Broiler 8.26e+09 2 1.65e+10 2.1e



### ! 02 1.27e+11 5.74e+10

T u rk ey 2.7e+08 1 5 4.05e+09 1.2e



### ! 02 1.77e+10 8.04e+09

Beef 9.73e+07 800 7.78e+10 6.9e



### ! 03 1.96e+11 8.89e+10 Dairy cow 9.21e+06 1,400 1.29e+10 1 e



### ! 02 4.71e+10 2.13e+10

T o tal 4.25e+11 1.93e+11

a S o u rce: U

. S

. C e n s u s Bu reau (2001).

b S o u rce: U

. S

. EPA (2001d).

c S o u rce: S t ev en s an d Jon e s (2003).



### Stevens and J ones (2003) publishe d results of CDD and CDF det ection in animal manure applied
to f a r mla nd in the Unite d King dom. Ma nur e f r o m six milking da ir y c o ws wa s sa mple d a t six farms in the northern United King dom. I n add ition, sing le samples of sheep, chicken, and pig
manure were collected from other farms in the re g i on. The samples were shipped to a laboratory
for t r ace chem i cal anal y s i s

. S a m p l e s were anal y z ed usi n g hi g h -resol u t i on g a s chrom a t o g r aphy coupled with hig h-resolution mass spectrometry a nd a capillary column for the identification of
CDD/CDF cong eners. Recoveries of the intern al standard rang ed from 51 to 94%, with a mean
of 74% for CDD/CDF cong eners. Table 9-2 summa riz e s the results of the study

. The pig and chicken manure contained appr ox imately 0.2 ng W HO-TEQ/kg

, and the cow manure averag ed
3.6 ng W HO-TEQ/kg in concentration. This study pr ovide s e x tr e m e l y limite d da ta on the possible le ve ls a nd oc c u r r e nc e s of
diox in-like compounds in farm animal manure, and, therefore, these data are clearly not representative of national releas es of diox in-like compounds from the land applica tion of all farm

a n ima l ma nur e in the Unite d Sta t e s. Ac c o r d ing l y , EPA c u r r e ntly c onside r s this sour c e to be unquantifiable (Categ ory E) in terms of diox in emissions.

9-7

### T a b l e 9-2. CDD an d CDF con cen tration s (n g/k g d r y w e igh t) in sam p les of anim al m anure in th e Un i t ed Ki n g d o m

C ongener Cow s (n = 6) (mean) Sheep (n = 1) P i g (n = 1) Chi c ken (n = 1)
2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 0.17 0.46 2.4 4.5 2.6 120 460 0.11 0.41 0.9 0.86 0.56 9.4 53 0.01 0.07 0.26 0.1 0.07 0.8 11 0.01 0.04 0.03 0.09 0.12 1.4 14

T otal 2,3,7,8- CDD 590.1 65.2 12.3 15.7
2,3,7,8- T C DF 1,2,3,7,8- PeCDF 2,3,4,7,8- PeCDF 1,2,3,4,7,8- HxCDF 1,2,3,6,7,8- HxCDF 1,2,3,7,8,9- HxCDF 2,3,4,6,7,8- HxCDF 1,2,3,4,6,7,8- HpCDF 1,2,3,4,7,8,9- HpCDF OCDF 0.3 0.3 0.28 0.6 0.51 1.9 0.4 7.6 12 35 1.2 1.1 1.2 1.4 1.1 0.15 1.4 5.2 0.56 5 0.03 0.04 0.06 0.05 0.06 0.04 0.06 0.48 0.04 0.73 0.03 0.09 0.12 0.15 0.07 0.05 0.14 0.37 0.09 0.8

T otal 2,3,7,8- CDF 58.9 18.3 1.6 1.9

T otal CDD/CDF 649 83.5 13.9 17.6

WHO- T E Q 3.6 2.1 0.2 0.2

S o u rce: S t ev en s an d Jon e s (2003).



### 9.2. P HOTOTRANSF O RMATIO N OF CHLOROP H ENOLS
Several researchers have dem onstrated that CDDs/CDF s can be formed via photoly s is of PCP under laboratory conditions. Ho wever, the ex tent to which CDDs/CDF s are formed in the
environment via this mechanism cannot be estimated at this time.
L a mparski et al. (1980) conducte d laboratory studies to deter mine the effect of simulated summer sunlig ht on the formation of OCDD, Hp CDDs, and Hx CDDs in wood pressure-treated in the laboratory with PCP. I n the first set of ex periments, wood veneer s (southern pine) treated with purified PCP or Dowicide EC- 7, using me thy l e n e c h lor i de as t h e P C P carri er, were ex posed to lig ht for 70 day s

. The PCP concentration in the treated wood was 5% by weig ht, which

approx imates the concentr ation in the outer lay e r of PCP-tr eated wood utility poles. Photoly tic
condensation of PCP to form OCDD was observe d, with the OCDD concentration increasing by

a max imum factor of 3,000 for the purified PCP and by a factor of 20 for EC-7 at about day 20

9-8

### before leveling off. HpCDD and Hx CDD we re also formed, apparently by photoly tic deg r adation of OCDD rather than by condensa tion of PCP and tetrachlo rophenols. The Hx CDD concentration increased by a factor of 760 for the purified PCP and by a factor of 50 for EC-7 over the 70-day ex posure period. The pre dominant HpCDD cong ener formed was 1,2,3,4,6,7,8­ HpC DD as a resul t of an apparent l y preferent i a l loss of chlorine at the peri position (positions 1, 4, 6, and 9).
I n a second set of ex perime nts conducted by L a mparski et al. (1980), a hy drocarbon oil (P-9 oil) was used as the carrier to treat the wood. The increases observed in the OCDD, HpCDD, and Hx CDD were reported to be much lo we r r e la tive to the inc r e a se s obse r ve d in the
first set of ex periments, which used methy l ene ch l o ri de as t h e carri er. Results were reported only
for OCDD. The OCDD concentra tion increased by a max imum factor of 1.5 for both EC-7 and technical PCP and by a factor of 88 for purified PCP. The author s c onc lude d tha t the oil e ithe r reduced condensation of P C P to OCDD or accelerat ed deg r adation to other species by providing a hy drocarbon trap for free-radical species. Vollmuth et al. (1994) studied the effect of irradiating laborat ory water and landfill

seepag e water that contained PCP under conditions simulating those used to purify water with ultraviolet (UV) radiation (5-hr ex posure to 254 nm radiation from low-pr essure mercury lamps).
B e fore irradiation, the three solu tions tested containe d approx imately 1 mg /L of PCP or PCP-Na,
but the CDD/CDF content of one solution varied dramatically from those of the other two (1.5 vs. 2,066 and 2,071 pg I

- TEQ DF 

### /L ). I rradiation resulted in n e a r ly tota l de str u c tion of PCP ( g r e a t e r tha n 99% loss) in a ll thr e e e x pe r ime nts. An ove r a ll ne t inc r e a se in I

- TEQ DF 

### -content was
obse r ve d in the initia lly low I

- TEQ DF 

### -content water, but a net decrease was observed for the two
initia lly hig h I

- TEQ DF 

### - c onte n t wa te r s. I rradiation of laboratory wa ter containing purified PCP showed an increase in I

- TEQ DF 

### concentration from 1.5 pg /L to 214.5 pg /L

. The increase was due entirely to the formation of 1,2,3,4,6,7,8-HpCDD, OCDD, and 1,2,3,4,6,7,8-HpCDF

. F ormation of non-2,3,7,8-substituted HpCDDs and HpCDF s was also observed. The ratios of the concentrations of these non-2,3,7,8­

cong eners to the concentrations of the 2,3,7,8-cong eners were 0.6 for HpCDDs and 5 for HpC D Fs. The HpC DD and HpC D F cong eners fo rm ed i ndi cat e t h at t h e operat i v e m echani s m was photoinduced dechlorination of OCDD at a peri position a nd dechlorination of OCDF at only the 1 and 9 peri positions.
I rradiation of water containing te c hnic a l PCP- Na ( D owic ide

- G) r e sulte d in a ne t loss in I

TEQ DF 

### content, from 2,065.5 pg /L to 112.7 pg /L

. The only 2,3,7,8-substituted cong ener showing an increased concentration was 1,2,3,6,7,8-Hx CDD. The other cong eners orig inally present in
the technical PCP-Na showed reductions of 80.6 to 100%.

9-9

### The I

- TEQ DF 

### content of seepag e water from a landfill (2,071 pg I

- TEQ DF 

### / L ) was reduced by a factor of 2, to 1,088 pg I

- TEQ DF 

### /L

. However, several 2,3,7,8- substituted cong eners did increase in concentration (1,2,3,6,7,8-Hx CDD; 1,2,3,4,6,7,8-HpCDD; 1,2,3,4,6,7,8-HpCDF ; and
OC DF).
W a ddell et al. (1995) also studied the effect of irradiating dis tilled laboratory water containing PCP under conditions simulating those used to purify water with UV radiation. The
results obtained were similar to those of Vollmuth et al. (1994). Analy tical-g rade PCP at a concentration of 10 mg /L was ex posed for 12 min to 200 to 300 nm radiation from a mediumpressure mercury lamp. All CDD/CDF cong ener g r oups incr eased in concentration over the 12­
min ex posure period, with the g r eatest increases observed for OCDD (75-fold increase) and

­ HpC DDs (34-fol d i n crease). The I

- TEQ DF 

### content of the solution increased from 4.2 pg I TEQ DF 

### /L to 137 pg I

- TEQ DF 

### /L over the 12-min period. The domin ant cong eners formed, in terms
of both concentration and contribution to I

- TEQ DF 

### , were 1,2,3,4,6,7,8-HpCDD, OCDD, and 1,2,3,7,8,9-Hx CDD.

9.2.1. P h otolysis of Higher CDDs/CDF s Photoly s is appears to be one of the fe w e nvir onme n ta lly sig n if ic a n t de g r a d a tion
mechanisms for CDDs/CDF s in water, air, and soil. Alt houg h g ood mass balances were not obtained and the photoly tic pathwa y s for CDDs/CDF s were not fully identified in most studies, a major photoly s is pathway appears to be photod echlorination, resulting in formation of lowerc h lor i na te d CDDs/CDF s. A pr e f e r e n tia l loss of chlorines from the peri positions (1, 4, 6, and 9) rather than from the lateral positions (2, 3, 7, and 8) was reported fo r some cong ener g r oups when irradiated as dry films and sorbed to soil and in g a s-phase CDDs/CDF s (Choudhry and
W e bster, 1989; Kieatiwong et al., 1990; Sivils et al., 1994, 1995; Ty sklind et al., 1992). Several researchers reported that carbon-ox y g en cleavag e and other mechanisms may be similarly or more important pathway s for CDDs/CDF s containing four or fewer chlorines.
B ecause of the difficulties inherent in c ontrolling ex perimental variables for nonvolatile and hig hly lipophilic compounds such as CDDs /CDF s, few photoly s is studies have been performed on natural waters, soils , atmospheric particulates, and a tmosphe r i c g a se s to e x a mine the rates and products of photoly s is under environmentally releva nt conditions. Thus, it is not possible a t this time to qua ntita tive l y e stima te the ma ss of va r i ous CDD/CDF c ong e n e r s f o r m e d in the environment annually via photoly tic mechan isms. The following sections summariz e the key finding s of environmentally sig nificant studies for water, soil, veg e tation, and air.

9-10

### 9.2.2. P h otolysis in Water
Numerous studies have demonstrated th at CDDs/CDF s will underg o photodechlorination following first-order kinetics in org a nic soluti on, with preferential loss of chlorine from the lateral positions. Photoly s is is slow in pure wa t e r, but i t i n creases dram at i cal l y when sol v ent s serving as hy drog en donors such as hex a ne, be nz ene, methanol, acetonitr ile, hex a decane, ethy l oleate, diox ane, and isooctane are present. However, only a few studies have ex amined the photoly sis of CDDs/CDF s using natural waters and sunlig ht. Choudhry and W e bster (1989) ex per imentally determined the s unlig ht photoly sis half-life of 1,3,6,8-TCDD in pond water to be 3.5 day s (mor e than 10 times g r eater than the half-life predi c t e d by l a borat ory ex peri m e nt s usi n g a wat e r/ acet oni t r i l e sol u t i on). The aut hors at t r i but ed this sig nificant difference in photoly s is rates to the lig ht screening / quenching effects of dissolved

or g a nic ma tte r

. F r iesen et al. (1990) ex amined the photoly tic behavior of 1,2,3,4,7-PeCDD and 1,2,3,4,6,7,8-HpCDD in water:acetonitrile (2:3, v/v) and in pond water under sunlig ht at 50 deg r ees North latitude. The observed half-lives of these two compounds in the water:acetonitrile solution were 12 and 37 day s , respectively

, but were much shorter in pond water, 0.94 and 2.5 day s , respectively

. Similarly

, F r iesen et al . (1993) studied the photodeg r adation of 2,3,7,8-TCDF and 2,3,4,7,8-P e CDF by sunlig ht using water:acetonitrile (2:3, v/v) and lake water. The observed half-lives were 6.5 and 46 day s , respectively

, in the water: acetonitrile solution and 1.2 and 0.19
da y s, r e spe c tive l y , in la ke wa te r

. The sig n if ic a n t dif f

e r e nc e s be twe e n the na tur a l wa te r a nd the
water:acetonitrile solution results we re attributed to indirect or sensitiz ed photoly sis due to the presence of naturally occurring co mponents in the lake and pond water. Dung and O’Keefe (1992), in an investig a tion of aqueous photoly s is of 2,3,7,8-TCDF and 1,2,7,8-TCDF , reported finding s similar to those of F r iesen et al. (1993). The photoly s is rates of
the two TCDF cong eners observed in river and la ke water (half-lives of about 4 to 6 hr) were double those observed in pure water (half-lives of a bout 8 to 11 hr). The authors attributed the
di fference i n rat e s t o t h e presence of natural org a nics in the rive r a nd la ke wa te r tha t ma y a c t a s

se nsitize r s.

9.2.3. P h otolysis on Soil Photoly s is of CDDs/CDF s on soil has not been wel l charact eri z ed. Accordi n g t o t h e dat a
g e nerated to date, however, photol y s is is an operative deg r adation process onlyin the nearsurface soil where UV lig ht penetrates (the top few millimeters or less of soil), and
de c h lor i na tion of pe r i

- substitute d c h lor i ne s a ppe a r s to oc c u r pr e f e r e n tia lly

. Miller et al. (1989) studied the CDD deg r ad ation products resultin g from irradiation of

13 

### C-labeled OCDD on two soil ty pes using sunlam ps. Approx imately 38 to 42% of the OCDD

9-11

### was deg r aded by day 5 of the ex periment; no si g n ificant further loss of OCDD was observed over the following 10 day s

. Althoug h the authors de termined that photodechlorination was not the dominant photoly s is pathway , it was observed in both soils; approx imate ly 10 to 30% of the
lowe r

- c hlor ina t e d c ong e n e r s we r e pr oduc e d f r o m the imme dia t e hig h e r

- c hlor ina t e d c ong e n e r s. The HpCDD and Hx CDD cong eners observed as deg r adation products were present in proportions similar to the number of cong ener s in each cong ener g r oup. However, the investig ators observed g r eater y i elds of 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD than would be

ex pected on the basis of the number of poten tial TCDD and PeCDD cong eners. One-fifth to one-third of the total y i eld of PeCDDs was 1,2,3,7,8-PeCDD, and one-half of the total y i eld of TCDDs was 2,3,7,8-TCDD. Kieatiwong et al. (1990) performed ex perime nts similar to those of Miller et al. (1989) using na tur a l sunlig ht r a the r th an sunlamps for irradiation of 13 

### C-labeled OCDD on soils.
Photodechlorination was estimated to account fo r approx imately 10% of the loss of OCDD. One-third to one-half of the total y i eld of PeCDDs was 1,2,3,7,8-PeCDD, and one-half of the total y i eld of TCDDs was 2,3,7,8-TCDD. These fi nding s, along with those of Miller et al., indicate that the 2,3,7,8-substituted TCDD and Pe CDD cong eners were either preferentially formed or were photochemically less reactive than the other cong eners that were formed. Ty sklind et al. (1992) studied the sunlig ht photoly s is of OCDD on soil and reported results similar to those of Miller et al. (1989) and Kieatiwong et al. (1990). Photodechlorination was observed with production of HpCDDs, Hx CDDs, PeCDDs, and TCDDs over the 16-day irradiation period. Photodechlo rination at the peri-substitute d positions was the preferred photodechlorination mechanism; the proportions of 2,3,7,8-substituted cong eners present in the soils after 16 day s for each cong ener g r oup were as follows: Hx CDD, 65%; P e CDD, 40%; and TCDD, 75%. Ty sklind et al. (1992) also studied the sunlig ht photoly sis of OCDF on soil. Photodechlorination was observed; however, un like the case with OCDD, photodechlorination of the lateral-substituted positions was found to be the dominant photodechlorination mechanism, resulting in a relative decreasing proporti on of 2,3,7,8-substituted cong eners during the irradiation period. 2,3,7,8-TCDF was not obser ved in any of the irradiated samples.

9.2.4. P h otolysis on Vegetation
P hot ol y s i s of C DDs/ C DFs sorbed on t h e surface of veg e t a t i on has not been wel l
charact eri z ed, and t h e fi ndi ng s t o dat e are so mewhat contradictory

. McCrady and Mag g a rd (1993) reported that 2,3,7,8-TCDD sorbed on the surface of reed canary g r ass ( Phalaris
arundinacea L. ) underwent photoly tic deg r adation, with a ha lf-life of 44 hr in natural sunlig ht.
I n contrast, W e lsch-Pausch et al. (1995) found little difference in the CDD/CDF cong ener

9-12

### patterns between g r ass ( Lolium multiflorum ) g r own on an outdoor plot and g r ass g r own in a

g r eenhouse (i.e., UV lig ht transmission blocked).
I n an attempt to clarify this contradic tion, W e lsch-Pausch and McL a chlan (1995) studied the photodeg r adation of CDDs/CDF s on pasture g r ass ( Arrhenatherion elatioris ) dur ing two

g r owing cy cles (summer and autumn) using tw o g r eenhouses. One g r eenhouse was constructed of g l ass that blocks UV transmission and the othe r was constructed of pl e x ig la ss ( 4 mm) with a UV lig ht transmission of g r eater than 50% in th e 280 to 320 nm rang e. I n both the summer and
the autumn ex posure periods, the concentrati ons of CDDs/CDF s (on a cong ener-g roup basis)

we r e simila r in the g r a ss e x pose d to UV lig ht a nd the g r a ss tha t wa s not e x pose d. The a uthor s concluded that if photodeg r adati on was occurring , it was a relativel y insig nificant factor in the

accum u l a t i on of C DDs/ C DFs i n past ure g r ass.

9.2.5. P h otolysis in Air Photoly s is of CDDs/CDF s in the atmosphere has not been well characteriz ed. On the basis of data g e nerated to date, however, photoly s is appears to be a sig nificant mechanism for
de g r a d a tion ( p r i nc ipa lly , de c h lor i na tion of the pe r i

- substitute d c h lor i ne s) of those CDDs/CDF s present in the atmosphere in the g a s phase. F o r airborne CDDs/CDF s so rbed to particulates, photoly s is appears to proceed very slowly , if at all. B ecause of the low volatility of CDDs/CDF s, few studies have been attempted to measur e actual rates of photode g r adation of g a s-phase CDD/CDF, and only recently have studies ex a mined the relative importance of photoly s is to particulate-bound CDDs/CDF s. Sivils et al. (1994, 1995) studied the g a s- phase photoly s is of several CDDs (2,3,7­ TrCDD; 2,3,7,8-TCDD; 1,2,3,4-TCDD; 1,2,3,7,8-PeCDD, and 1,2,4,7,8-PeC DD) by irradiating
the e f f l ue nt f r o m a g a s c h r o ma tog r a ph with br oadband radiation in the UV/visible reg i on for periods of up to 20 min. The irradiated sa mple was then introduced into a second g a s chromatog r aph to measure the ex tent of dechlo rination. The results showed that deg r adation
followed first-order kinetics a nd that an inverse relationshi p ex isted between the deg r ee of chlorination and the rate of disappearance. Althoug h the lack of photoproducts prevented an
inde pe nde nt c onf ir ma tion of the pr e f e r e n tia l loss me c h a n ism, the r e sults indic a t e tha t la te r a lly
substitute d c ong e n e r s ( c hlor ine s a t the 2, 3, 7, a nd 8 positions) de g r a d e a t a slowe r r a te tha n do the peri-substituted cong eners (chlorines at the 1, 4, 6, and 9 positions). Althoug h Sivils et al. (1994) did not present the rate constants, the deg r adation rate for 2,3,7,8-TCDD (30% loss in 20 min) was reported to be slower than the rates for all other tested CDDs. Also, 1,2,4,7,8­ PeCDD (with two perichlorines) deg r aded si g nificantly faster than did 1,2,3,7,8-PeCDD (with only one perichlorine).

9-13

### Mill et al. (1987) studied the photoly s is of 2,3,7,8-TCDD sorbed onto small-diameter fly ash particulates suspended in air. The results indicated that fly ash confers photostability on 2,3,7,8-TCDD. L ittle (8%) to no loss was observed on the two fly ash samples after 40 hr of
illumination. Ty sklind and Rappe (1991) and Koester and Hite s (1992) reporte d similar results of photoly s is studies with fly ash. Ty skli nd and Rappe subjected fly ash from two German
incinerators to various simu lated environmental conditions. The fraction of photoly tically deg r adable CDD/CDF after 288 hr of ex posure was in the rang e of 20 to 40% of the ex tractable
CDD/CDF

. However, a 10 to 20% reduction was al so observed in the darkened control samples.
W ith the ex ception of HpCDD and HpCDF

, the con centration of all other cong ener g r oups either increased or stay ed the same during the ex posure period from hour 144 to hour 288. Koester and Hites (1992) studied the photodeg r adation of CDDs/CDF s naturally adsorbed

t o fl y ash col l ect ed from fi ve el ect rost at i c precipitators. They observed no sig n ificant deg r adation in 11 photodeg r adati on ex periments performed on the ash for periods rang ing from 2 to 6 day s

. The authors concluded that (a) th e absence of photodeg r adation was not due to the absence of a hy drog en-donor org a nic substance; (b) other molecules on the ash, as determined by a photoly s is ex periment with an ash ex tract, i nhibited photodeg r adation, either by absorbing lig ht and dissipating energ y or by quenc hi ng t h e ex ci t e d st at es of t h e C DDs/ C DFs; and (c) t h e surface of the ash itself may have hindered photoly s is by shielding the CDDs/CDF s from lig ht.

9.3. CDDs/CDF s IN BALL CLAY
9.3.1. Initial Discovery of CDD/CDF Contam ination of Ball Clay The presence of diox in-like compounds in ba ll clay was discovered in 1996 as a result of an investig ation to determine the sources of relatively hig h levels of diox in found in two chicken fat samples during a national surv ey of poultry

. The survey was conducted jointly by USDA, the
U.S. F ood and Drug Administration (F DA), a nd EPA to assess the national prevalence and concentrations of CDDs, CDF s , and coplanar PCB s in poultry (F errario et al., 1997). The results of the investig ation indicated that soy b ean meal added to chicken feed was the
source of diox in contamination (F errario et al ., 2000). F urther investig ation showed that the
C DD cont am i n at i on cam e from t h e bal l cl ay added t o t h e soy m eal as an ant i caki n g ag ent

. The ball clay was added at approx ima tely 0.3 to 0.5% of the soy bean meal. Samples of raw ball clay were subsequently taken at the mine of orig in in Mississippi. Analy s is of the samples showed elevated levels of CDDs with a cong ener profile similar to the C DD profiles found in the

soy m e a l , c h ic ke n f e e d, a nd imma tur e c h ic ke ns.

9-14

### 9.3.2. Characteristics of Missi ssippi Em baym ent Ball Clays The ball clay s from the mine discussed above are part of a larg er ball clay resource that spans portions of western Kent ucky , Tennessee, and Mississippi. These cl ay s were deposi t e d along the shores of the Mississippi embay m ent during the early to middle Eocene epoch, which

oc c u r r e d a ppr ox ima te ly 40 to 45 million y e a r s a g o. The Mississippi e m ba y m e n t ba ll c l a y s a r e secondary clay s composed mainly of poorly defi ned cry s talline kaolinite. Other minerals present include illite, smectite, and chlor ite. Quartz sand is the majo r nonclay mineral. These deposits of ball clay occur in lenses surrounded by lay e rs of sand, silt, and lig nite. The clay s can have a

g r ay appearance caused by t h e presence of fi ne ly divided carbonaceous pa r tic le s. I t is not
uncommon to find black carboniz e d imprints of foss il leaves and other plant debris in the clay (Patterson and Murray

, 1984). The plasticity of ball clay make s it an important natural res ource for the ceramic industry

. The breakdown of the ceramic uses of ball clay is 33% for floor and wa ll tile, 24% for sanitary ware, 11% for pottery , and 32% for other industr ial and commercial uses (Virta, 2000). A minor
use of bal l cl ay was as an ant i caki n g ag ent i n an imal feeds, but this use has been banned by the
F DA (Headrick et al., 1999). Total mining of ball clay in 1999 was 1.14 million metric tons (Virta, 2000).

9.3.3. Le ve ls of D ioxin- Like C o m p ounds in Ball C lay
The joint EPA/F DA a nd USDA inve stig a ti on of ball clay as a source of diox in

c onta mina tion in a n ima l f e e d s r e sulte d in sa mpling the c l a y a t a n ope r a tiona l mine in we ste r n Mississippi. Eig ht samples of ra w (unprocessed) ball clay were collected from an open mining pit at a depth of about 10 to 15 m. Samples were prepared and analy z ed by EPA using EPA Method 1613 (F errario et al., 2000). The concentra tions of the CDDs/CDF s present in the raw
ba ll c l a y sa mple s f r o m the one mine a r e shown in Ta ble 9- 3. The r a tio of the limits of de te c tion to the limits of quantification for the CDDs/CDF s in the clay samples were 0.5:1 pg /g (ppt, dry weig ht) for the tetras; 1:2 pg /g for the pentas, hex a s, and heptas; and 5:10 pg /g for the octas. The
mean concentrations of all of th e CDDs ex ceeded 100 ppt (dry weig ht). OCDD was found at the hig hest concentration in all of the samples, followed by either 1,2,3,4,6,7,8-HpCDD or 1,2,3,7,8,9-Hx CDD. The max imum OCDD concentration in the eig ht samples was approx ima tely 59,000 pg /g

. The most tox i c tetr a and penta cong eners were present at unusually hig h concentrations in all of the samples, with averag e c oncentrations of 711 pg /g and 508 pg /g for 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD, re spectively

. Althoug h the ball clay s showed elevated levels of 2,3,7,8-substituted C DDs, they showed very low levels of 2,3,7,8­
substituted CDF s

. I n addition, there was a c onsistent ratio within the Hx CDD cong ener

9-15

### T a b l e 9-3. Con cen tration s of CDDs (p g/g, d r y w e igh t) in eigh t b a ll clay

sam p le s in t h e Unit e d St at e s

C o ngener Mean Median M inimum Max i mum T E Q DF 

### -WHO 98 

### 2,3,7,8- T C DD 1,2,3,7,8- PeCDD 1,2,3,4,7,8- HxCDD 1,2,3,6,7,8- HxCDD 1,2,3,7,8,9- HxCDD 1,2,3,4,6,7,8- HpCDD OCDD 711 508 131 456 2,093 2,383 20,640 617 492 134 421 1,880 2,073 4,099 253 254

62 254 1,252 1,493 8,076 1,259 924 193 752 3,683 3,346 58,766 711 508

13 46 209

24

2

Total TE Q 1,513

S o u r ce: F e rrari o et al . (2000).



### distribution across all samples (1,2,3,7,8,9-Hx CDD was present at hig h er concentrations than the other 2,3,7,8-substituted Hx CDD cong eners). The averag e percent distribution of the three individual 2,3,7,8-hex a cong eners wa s 5, 17, and 78%, respectively

. This cong ener pattern was observed i n al l t h e raw bal l cl ay sam p l e s anal y z ed.
The me a n tota l TEQ DF 

### -W HO 98 

### for the raw ball clay was de termined to be 1,513 pg /g dry weig ht; 2,3,7,8-TCDD accounted for 47% of the TEQ DF 

### -W HO 98 

### , followed by 1,2,3,7,8-PeCDD
at 34%. As ex pected, even thoug h present at the hig h est concentrati on, OCDD contributed less
tha n 1% pe r c e n t of the tota l TEQ DF 

### -W HO 98 

### due to its r e la tive l y sma ll WHO- TEF

. I n comparison, the ty pical rang es of backg r ound TEQ DF 

### -W HO 98 

### concentrations in North American urban and rural surface soil sample s were found to be 2 to 21 pg /g and 0.1 to 6 pg /g , respectively (U.S. EPA, 2000c). I n soil samples, all 2,3,7,8-CDD/CDF cong eners we re detected, and 2,3,7,8­
TCDD r e pr e se n te d le ss tha n 1% of tota l CDD/CD F present

. The m o st preval ent cong eners i n soils were OCDD, followed by OCDF

. Table 9- 4 com p ares t h e m ean C DD/ C DF cong ener g r oup concentrations in ball clay with those in ru ral and urban backg r ound soils. This comparison
indic a t e s the r e a r e f e w simila r itie s be twe e n the ba ll c l a y a nd soils in the c ong e n e r g r oup distributions.

9.3.4. Evid en ce f o r Ball Clay as a Natu ral S o u rce Several lines of evidence sug g e st that diox in -like compounds in ball clay are of natural orig in. The clay samples were obtained fro m undisturbed deposits. I t is unknown how human activity could have contaminated these deposits without disturbi ng them. The EPA laboratory in Athens, GA, analy z ed the Mississippi mine cl ay s using a broad screen for anthropog enic contaminants and no compounds we re found outside of the normal rang e (F errario et al., 2000).

9-16

### T a b l e 9-4. Com p arison of th e m e an CDD/CDF con g en er grou p

c o nc e n t r at ions in ball c l ay w i t h t h ose in ur ban and r u r a l soils in Nor t h Am erica (pg/g, dry w e ight)

Congener group M e an concentration

Ra w ba ll cla y Urba n ba ck g r o und so il Rura l ba ck g r o und so il

TC D D TC D F 3,729 6 36.1 23.5 2.3 6.8

Pe C D D Pe C D F 4,798 2 18.1 40.8 4.1 12.7

Hx CDD Hx CDF 6,609 6 31.7 23.5 22.7 21.9
Hp CDD Hp CDF 6,194 9 194.4 46.4 114.7 37.3

OCDD OCDF 11,222 11 2,596 40.2 565.1 33.5

T o t a l C D D / C D F 32,586 3,050.7 821.1

S o u rces : A d apt e d f rom U

. S

. EPA (2000c); F e rrari o et al . (2000)



### All known anthropog enic sources of diox in have a ssociated with them a wide variety of other
contaminants. The absence of el evated levels of other compounds is strong evidence that the
diox ins found in the clay were not the result of waste disposal. The cong ener profiles of ball clay do not match those of known anthropog enic sources. Cleverly et al. (1997) reported on the cong ener profiles that are ty pical of known anthropog enic
sources of diox in-like compounds in the United St ates. The results of this study , presented below, were used as a basis of comp arison for the profiles of raw ball clay

. The cong ener pat t e rn charact eri s t i c of wast e com bust i on sources di ffers si g n i f i cant l y from the ball clay profile in several aspect s. I n combustion source emissions, all 2,3,7,8­
substituted CDD and CDF cong eners are meas ured, and 2,3,7,8-TCDD is usually 0.1 to 1% of
total CDD/CDF mass emitted. I n ball clay , 2,3,7,8-TCDD is approx imately 5% of total mass of
diox ins present. As with the ball clay , th e most prevalent 2,3,7,8-Cl-substituted CDD cong eners in most incinerator emissions are OCDD and 1,2,3,4,6,7,8-HpCDD; however, combustion emissions contain appreciable amounts of CDF s , of which the 1,2,3,4,6,7,8-HpCDF , OCDF
, 1,2,3,4,7,8-Hx CDF
, 2,3,7,8-TCDF , and 2,3,4,6,7,8-Hx CDF cong eners dominate. The combustion of wood g e nerates a cong en er profile not unlike that of waste

c o mbustion ( i .e ., the r a tio of CDD:CDF is < 1 )
, a nd a ll la te r a lly substitute d c ong e n e r s c a n be
detected in emissions. The co mbustion of tree bark produces a cong ener profile in which the

9-17

### CDD:CDF ratio is >1, showing onl y minima l a nd ba r e ly de te c t a b le le ve ls of CDF s in the smoke

, the ex ception being that 2,3,7,8-TCDF is present at approx imately 2% of total mass. The dominant cong ener in tree bark combustion e missions is OCDD ( > 30% tota l CDD/CDF ma ss)
, followed by 1,2,3,4,6,7,8-HpCDD and 1,2,3,7,8,9-Hx CDD. The cong ener profile of 2,4- D salts and esters seems to mimic a combustion source profile in the number of cong eners repres ented and in the minimal amount of 2,3,7,8-TCDD relative to all 2,3,7,8-Cl-substitute d cong eners. Nevertheless, unlike the combustion source profile, the 1,2,3,7,8-PeCDD and the 1,2,3,4,6,7,8-HpCDF constitute ma jor fractions of total
CDD/CDF contamination present in 2,4-D. The cong ener profile of technical-g rade PCP is clearly dominated by OCDD and 1,2,3,4,6,7,8-Hp CDD; however, only trace amounts of 2,3,7,8­ TCDD are detected in PCP, and 1,2,3,4,6,7,8-HpCD F and OCDF constitute roug hly 15% of
ty pical formulations. Metal smelting and refining pr ocesses, such as secondary aluminum, copper, and lead smelting , also have all the 2,3,7,8-Cl-substituted CDD/CDF cong eners in stack emissions. I n secondary aluminum smelting , 2,3,7,8-TCDD is le ss than 0.1% of total CDDs/CDF s, whereas
PeCDF is nearly 25% of tota l emissions of diox in-like compounds, and the CDD/CDF ratio is

< 1. Secondary copper operations show a similar pattern of C DD/CDF emissions, but with six compounds dominating emissions: 1,2,3,4,7,8-Hx CDF ; 1,2,3,6,7,8-Hx CDF ; 1,2,3,4,6,7,8­ HpCDF ; OCDF ; OCDD; and 1,2,3,4,6,7,8-HpCDD. I n iron ore sintering

, the dominant cong ener in emissions of 2,3,7,8-Cl-substituted compounds is 2,3,7,8-TCDF

. A number of studies have shown that natura l processes can produce c h lor i na te d a r oma tic compounds, including diox in-like compounds. Gribble (1994) review ed the biolog ical production of a wide variety of halog e nated org a nic compounds in nature. The Mississippi salt

m a rsh g r ass “needl e rush” ( Juncus roemerianus ) contains the aromatic compound 1,2,3,4­

t e t r achl o robenz ene, and t h e bl ue-g reen al g a Anacystis marina naturally contains chlorophenol. The soil fung us Pe nic illium sp. produces 2,4-dichlorophenol, and the common g r asshopper is known to secrete 2,5-dichlorophenol.
Urhahn and B a llschmiter (1998) al so provide a g ood review of the chemistry of the biosy nthesis of chlorinated org a nic com pounds under natural conditions. I t has been hy pothesiz e d that CDDs, CDF s , and other chlo rinated aromatic com pounds can be naturally formed from halog e nated humic substances, and halomethanes can be formed throug h chloroperox i dase-mediated reac tions in undisturbed peat bog s (Silk et al., 1997). A similar chloroperox i dase-mediated bi ochemical formation of CDDs /CDF s from chlorophenols was achieved under laboratory conditions by Oberg and Rappe (1992).
I t has been observed that chlorophenols can be biosy nthesiz ed (Gribble, 1994; Silk et al., 1997), and that chorophenols are readily adsorbed into peat-bentonite mix tures (Virarag havan

9-18

### and Sloug h, 1999). Hoekstra et al. (1999) offers the hy pothesis that 2,3,7,8-TCDD, 1,2,3,7,8­ PeCDD, and 1,2,3,7,8,9-Hx CDD can be naturally form ed in soils of coniferous forests from
chl o ri nat e d phenol

. These sam e cong eners are al so t h e predom i n ant cong eners i n t h e bal l cl ay from the Mississippi embay m ent. Althoug h none of these natural pro cesses can be directly

connect ed wi t h t h e presence of di ox i n i n bal l cl ay , t h e ex i s t e nce of such m echani s m s l e nds pla u sibility to a hy pothe sis tha t the y a r e of na tur a l or ig in.
CDDs/CDF s have been found in other clay s quite distant from Mississippi embay m ent ball clay deposits. No evidence of anthropog enic sources have been discovered in these areas

e ithe r

. The pr e se nc e of CDDs ha s be e n disc ove r e d in ka olinitic c l a y mine d in Ge r m a ny ( J obst and Aldag

, 2000). B ecause no anthropog enic source could be determined to ex plain the presence

a nd le ve ls of CDDs in the ba ll c l a y , the a u thor s spe c u la te d tha t the y we r e the r e sult of a n unknown g e olog ic process. I n addition, the German clay also has a cong ener profile similar to that observed in the Mississippi ball clay , with an absence of C DFs at com p arabl e concent r at i ons and the predominance of 1,2,3,7,8,9-Hx CDD among the tox i c hex a -CDDs. The similarity in the

c ong e n e r pr of ile s in ba ll c l a y mine d in the Un ited States and Germany sug g e sts a common orig in to the CDDs present in thes e clay s (F errario et al., 2000).
I n summary , no anthropog enic sources have b een identified that ex plain the levels and profiles of CDDs/CDF s present in ball clay

. On the other hand, no defin itive scientific evidence has been broug ht forward that identifies the pr incipal chemical and phy sical mechanism involved in the selective chemical sy nt hesis of CDDs under the conditions inherent in the formation of
ba ll c l a y s some 40 million y e a r s a g o.

9.3.5. Envir o nm e n tal Re le ase s of Dioxin-Like Com p ounds f r om the M i ning and P r oc e ssing of

Ball Clay
I n 1995, approx imately 993 million kg of ball clay was mined in the United States (Virta, 2000). Multiplication of the mean TEQ DF 

### -W HO 98 

### c onc e n tr a tion in mine d ba ll c l a y by the tota l amount of ball clay mined in 1995 g i ves an estimate of 1,502 g TEQ DF 

### -W HO 98 

### contained in all the ball clay mined in 1995. I t is unknown whethe r any of these CDDs are released to the environment during the mining , initial refining

, and product handling

. As discussed above, most ball clay is used to produce ceramics throug h a pr ocess of hig h -temperatu re vitrification. The temperatures found in ceramic k ilns are well above the levels n eeded for both volatilization and
destruction of CDDs. Despite th ese hi g h t e m p erat ures, i t i s uncl ear whet her som e rel ease occurs, and no stack measurements have y e t been made. Therefore, i n suffi ci ent evi d ence i s avai l a bl e t o

ma ke e v e n a pr e limina r y e stima te of r e le a se s, a nd this a c tivity is c l a ssif i e d a s a Ca te g o r y E

source.

9-19

### 10. SOURCES OF DIOXIN-LIK E P O LYCHLORINATED BIP H ENYLS (P CBs )

The purpose of this chapter is twofold: (1) to ide n tif y

sour c e s tha t r e le a se diox in- like
PCB c ong e n e r s into the e nvir onme n t a nd ( 2 ) to de r i ve na tiona l e stima te s f o r

r e le a se s f r o m the se sources in the United States. PCB s have been found in all media and in all parts of the world.
PCB s were manufactured in re latively larg e quantities for use in commercial products such as dielectrics, hy draulic fluids, pl astics, coating s and paints, and althoug h PCB s are no long er

c o mme r c ia lly pr oduc e d in the Unite d Sta t e s, the y continue to be released to the environment throug h the use and disposal of these products. PCB s may also be inadvertently produced as by

products during the manufacture of certain org a nic chemicals a nd also as products of the
inc o mple te c o mbustion of some wa ste ma te r i a l s.

10.1. G E NERAL F INDING S OF THE EMISSIONS INVENTORY Table 10-1 provides a compilation of known or suspected diox in-like PCB

- emitting

source cat eg ori e s i n t h e Uni t e d S t at es for whi c h emission measurements of diox in-like PCB

cong eners, Aroclors, or PCB cong ener g r oups ha ve been reported in g overnment, industry , and trade association reports; conference proceeding s and journal articles; and comments submitted to EPA on previous versions of this document. The intent of Table 10-1 is to clearly identify those source categ ories and media (air, water, land, and products) fo r which the available data are adequate for reliably quantify i ng emissions of diox in-like PCB s a nd those for which the data are
ina d e qua te

. Na tionwide e mission e stima te s f o r

the Unite d Sta t e s inve ntor y a r e pr e se n te d in Table 10-2 (emissions to air, water, land, and product) for t hose source categ ories for which

e stima te s c a n be r e lia bly qua ntif ie d ( t he c a t e g or y ha s be e n a ssig n e d a c onf ide n c e r a ting of A, B
, or C) (see Section 1.2.3 for details on confidence rating s ). Table 10-2 also lists preliminary estimates of the potential mag nit ude of emissions from “unquan tified” sources (i.e., sources assig n ed a confidence rating of D) in referen ce y ear 2000. B ecause of larg e uncertainties for
the se Ca te g o r y D e stima te s, the y a r e not inc l ude d in the qua ntita tive inve ntor y

. Currently , no sig n ificant releases of newly fo rmed diox in-like PCB s are occurring in the
Unite d Sta t e s. Unlike CDDs/CDF s, PCB s we r e inte ntiona lly ma nuf a c t ur e d in the Unite d Sta t e s in larg e quantities from 1929 until production was banned in 1977. Re leases to the environment
of “old” diox in-like PCB s (diox i n-like PCB s manufactured prior to the production ban) can occur from ong oing use and disposal practices. Pr ior to r e g u la tions e n a c t e d be g i nning in the la te 1970s that limited the manufacture/use/disposal of PCB s , sig nificant quan tities were released to
the e nvir onme n t in a ssoc i a tion with ( a ) th e manufacture of PCB s , (b) the manufacture of products containing PCB s , and (c) the use and dis posal of products containing PCB s as well as

10-1

### Table 10-1. Conf idence rating classes f or 2000 f or releases f r om all know n and

su sp ected sou rce categori e s of d i oxi n - l i k e P C B s a



### Source category A ir L a nd Water Approv ed PCB disposal E

A ccidental PC B releasees E E E Municipal w a stew ater treatm ent sludg e A Municipal waste com bustion E

I ndustrial wood com bustion E

Medical w a ste incineration E

T i re com bustion E

C i g arette com bustion D Sewag e sludg e incineration C

Back y ard barrel burning E

Petroleum refining cataly st reg e neration E

a B l an k cells m ean n o t ap p licab le o r n o d a ta.

A = Ch aracterizatio n o f th e so u r ce categ o r y j u d g ed to b e ad eq u a te f o r q u an titativ e estim atio n w ith h i g h co n f id en ce in th e em is s i on f actor an d h i g h con f iden ce in th e activ ity lev el. C= Ch aracterizatio n o f th e so u r ce categ o r y j u d g ed to b e ad eq u a te f o r q u an titativ e estim atio n w ith lo w co n f id en ce in th e em issio n f acto r an d / o r th e activ ity lev e l. D= T h ese are p r elim in ary in d i catio n s o f th e p o t en tial m a g n itu d e o f em issio n s f r o m “ u n q u a n tif ied ” so u r ces in R e f e ren ce Y ear 1995. T h es e es t i m at es w e re as s i g n e d a “ c on f i den ce cat eg ory ” rat i n g of D an d are n o t i n cl u d ed i n t he I nve nt o r y

. E= No t q u an tif iab l e.



### m a t e ri al s t h at m a y have been cont am i n at ed wi t h t r ace l e vel s of P C Bs from pri o r P C B use or disposal. Following the ban on P C B production, re leases from these first two categ o ries ceased. The third ty pe of releases, thos e associated with product use a nd disposal, will continue in at least four way s :

1. Disposal of products containing g r eater th an 2 lb of PCB s (e.g ., dielectric fluids in
tr a n sf or me r s a nd la r g e c a p a c itor s)
, whic h is controlled by disposal reg ulations that ha ve minimize d e nvir onme n ta l r e le a s e s ;

2. Disposal of products containing small quantities of PCB s (e .g ., small capacitors, fluorescent lig hting fix t ures) or trace quantitie s of PCB s (e.g ., wastepapers), which is subject to disposal as municipal solid wa ste but whic h ma y r e sult in some r e le a se to the g e neral environment;

10-2Table 10-2.Inventory ofcontemporary releases ofdioxin-like PCBs in the United States for 1987, 1995, and2000 and preliminary release estimates ofdioxin-like PCBs for 2000 (g TEQp-WHO98/yr)



### 10-3Emissions source category2000 Inventory1995 Inventory1987 InventoryPreliminaryestimate for2000ABCABCABCDReleases to airCombustion sourcesCigarettes0.01Sewagesludge incineration0.71.10.4Total quantified releases to air0.71.10.40.01Releases to landMunicipal sludge (landapplication and farming)18.877.451.1Total quantified releases to land18.877.451.1Releases to productsMunicipal sludge as soilammendment0.52.01.7Total quantified releases toproducts0.52.01.7A=Characterizationofthe source categoryjudgedtobeadequate for quantitative estimationwithhighconfidence inthe emissionfactor and highconfidence inthe activitylevel.C=Characterizationofthe source categoryjudgedtobeadequate for quantitative estimationwithlowconfidence inthe emissionfactorand/orthe activitylevel.D=These are preliminaryindicationsofthe potentialmagnitude ofemissionsfrom“unquantified” sourcesinReference Year 1995.These estimateswereassigned a “confidence category”ratingofD and are not included inthe Inventory.E=Not quantifiable.

### 3. L e a k s a nd spills of still- in- se r vic e PCB s; a n d

4. I lleg a l disposal of PCB s.

Althoug h it has been demonstrated that sm all quantities of diox in-like PCB s can be emitted into the air during waste combustion, no str ong evidence ex ists that they are emitted in sig nificant quantities as by -products during com bustion. The widespread occurrence of diox inl i k e P C Bs i n t h e U.S

. envi ronm ent m o st l i k el y refl ect s past rel e ases associ at ed wi t h P C B production, use, and disposal. F urther support for this finding is based on observations of
reductions since the 1980s in PCB concentrations in Great L a kes sediment and in other areas.

10.2. RELEASES OF COM M E RCIAL P C Bs
PCB s we r e c o mme r c ia lly ma nuf actured by the direct batch chlorination of molten bipheny l with anhy drous chlorine in the pres ence of a cataly st, followed by separation and purification of the desired ch lorinated bipheny l fractions. The deg r ee of chlorination was controlled by the chlorine contact time in the reactor. Commercial PCB production is believed to
have been confined to 10 countries. Total PC B s produced worldwide since 1929 (the first y ear of known production) has been es timated at 1.5 million metric tons.
I n itia lly , PCB s we r e use d pr ima r ily a s die l e c t r i c f l uids in tr a n sf or me r s. Af te r Wor l d Wa r I I , PCB s found steadily increasing use as dielectri c fluids in capacitors, as heat-conducting fluids
i n heat ex chang e rs, and as heat -resi st ant hy draulic fluids in mining equipment and vacuum

pumps. PCB s also were used in a variety of “open” applications (i .e, uses from which PCB s cannot be recollected), including plasticiz ers, carbonless copy pape r, lubricants, inks, laminating

a g e n ts, impr e g n a ting a g e n ts, pa ints, a dhe sive s, wa x e s, a dditive s in c e m e n t a nd pla ste r , c a sting

a g e n ts, de dusting a g e n ts, se a ling liquids, f i r e r e ta r d a n ts, imme r sion oils, a nd pe stic ide s ( D e V oog t
and B r inkman, 1989).
U.S. production peaked in 1970, with a volume of 39,000 metric tons. I n 1971, Monsanto Corporation, the major U.S. producer, vol untarily restricted the sale of PCB s for all applications, with the ex ception of “closed el ectrical sy stems.” Annual production fell to 18,000
metric tons in 1974. Monsanto ceased P C B manufacture in mid-1977 and shipped the last inventory in October of that y ear. Reg ulations issued by EPA beg i nning in 1977, principally
under the Tox i c Substances Control Act (TSC A) (40 CF R 761), have strictly limited the production, import, use, and disposal of PC B s

. The estimated cumulative production and consumption volumes of PCB s in the Un ited States from 1930 to 1975 were 635.03 million kg produced, 1.36 million kg imported (primarily from J a pan, I t aly , and F r ance), 568.35 million kg

10-4

### sold in the United States, and 68.04 million kg ex ported (ATSDR, 1993; DeVoog t and
B r inkman, 1989). The reliability of these va lues is + 5 % and –20% (Versar, I n c., 1976). Monsanto Corporation market ed technical-g rade mix tures of PCB s primarily under the

tr a d e na me Ar oc lor

. The Ar oc lor mix tur e s a r e identified by a four-dig it numbering code in
whic h the la st two dig its indic a t e the c h lor i ne c ontent by weig ht percent. The ex ception to this coding scheme is Aroclor 1016, which contains only mono- thr oug h hex achlorinated cong eners with an averag e chlorine content of 41%. F r om 1957 until 1972, Monsanto also manufactured
several blends of PCB s and pol y c hlorinated terpheny ls (PCTs) under the trade names Aroclor 2565 and Aroclor 4465; manufacture a nd sales volumes are not availa ble for these blends. L i sted below are the percentag e s of total Aroclor production during th e y ears 1957 to 1977 by Aroclor
mix ture, as reported by B r own (1994).

1957–1977 U.S. production Aroclor (%)

1016 12.88 1221 0.96 1232 0.24 1242 51.76 1248 6.76 1254 15.73 1260 10.61 1262 0.83 1268 0.33

The tr a d e na me s of the ma jor c o mme r c ia l PCB te c hnic a l

- g r a de mix tur e s ma nuf a c tur e d in other countries included Clophen (Germany ), F e nc lor and Apirolio (I taly ), Kanechlor (J apan), Phenoclor and Py ralene (F rance) , Sovtel (USSR), Delor and De lorene (Cz echoslovakia), and Orophene (German Democratic Republic) (DeVoog t and B r i nkman, 1989). The mix tures
marketed under these trade names had similar chlo rine content (by weig ht percent and averag e number of chlorines per molecule) to those of various Aroclor mix tures. L i sted below are comparable mix tures in terms of chlorine content marketed under several trade names.

Aroclor Clophen Pyr a le ne Phenoclor F e nclor Kanechl o r

1232 2000 200 1242 A-30 3000 DP-3 42 300 1248 A-40 DP-4 400 1254 A-50 DP-5 54 500 1260 A-60 DP-6 64 600

10-5

### Major advances in analy tical separation a nd resolution techniques beg i nning in the 1970s
enabl e d vari ous researchers t o i d ent i f y

and quantify PCB cong eners present in Aroclors, Clophens, and Kanechlors (J ensen et al., 1974; Albro and Parker, 1979; Huckins et al., 1980; Albro et al., 1981; Duinker and Hillebrand, 1983; Kannan et al., 1987; Tanabe et al., 1987; Duinker et al., 1988; Schulz et al., 1989; Himberg and Sippola, 1990; L a rsen et al., 1992; deB o er et al., 1993; Schwartz et al., 1993; F r ame et al., 1996a, b; F r am e, 1997). Schulz et al. (1989)

we r e the f i r st to ide n tif y

a nd qua ntif y

a ll PCB c ong e n e r s pr e se n t in a se r i e s of Ar oc lor s a n d Clophens. F r ame (1995) reported preliminary results of a nearly completed round robin study

, one g o al of which was to de termine the distribution of a ll PCB cong eners above 0.05 weig ht percent in various Aroclors (1221, 1016, 1242, 1260, and 1262) using 18 state-of-the-art g a s chrom a t o g r aphy / m a ss spect rom e t r y (GC / MS ) or el ect ron capt u re det ect or (GC / EC D) sy st em s. Table 10-3 presents mean summary statistics on the concentrations of the diox in-like
P C B s in each mix ture g r oup (e.g ., Aroclor 1248, Clophen A-40, and Kanechlor 400 are in one
mix ture g r oup) reported by these researchers. Table 10-3 also presents the mean TEQ concentration of each cong ener in each mix ture g r oup as well as the total mean TEQ
concentration in the mix ture g r oup. B ecause of the wide variability in the reported results, the

uncert a i n t y associ at ed wi t h t h ese m ean concent r at i ons i s very l a rg e. F o r each mix ture g r oup, the cong eners detect ed were g e nerally similar. There was,
howe v e r , wide va r i a b ility in the c onc e n tr a tions r e por te d by some r e se a r c h e r s f o r

some c ong e n e r s. B r own et al. (1995) compiled simila r statistics using a somewhat different set of studies and
de r i ve d sig n if ic a n tly lowe r me a n concentrations of some cong ener s in several Aroclors. F r ame (1995) and L a rsen (1995) attributed such diffe rences to either potential limitations in the GC

c o lumns use d by va r i ous r e se a r c h e r s to se pa r a te simila r e l uting c ong e n e r s or a c t ua l dif f

e r e nc e s in the cong ener concentrations in the Aroclor, Clophen, and Kanechlor lots analy z ed by various research g r oups. The cong ener distributions al so vary among the different mix tures. Therefore, the calculated TEQs also vary

. The cong ener distri butions for various lots of Aroclor 1254, and the corresponding TEQs, are presented in another study (F rame, 1999) in which the relative TEQs for late production lots we re reported to be much hig h er than those for the earlier production lots; however, the late production lots were estimated to account for only about 1% of the total production volume of Aroclor 1254. Therefore, th e data for the later production lots were not included in the averag e TEQ calcula tion for Aroclor 1254 in Table 10-3.
I n the e nvir onme n t, PCB s a l so oc c u r a s mix tur e s of c ong e n e r s, but the i r c o mposition
di ffers from t hose of t h e com m e rci a l m i x t u res because aft e r rel ease t o t h e envi ronm ent t h e mix tures chang e over time throug h partitioning , chemical transforma tion, and preferential bioaccumulation (U.S . EP A, 1996f). Diox in-lik e P C B cong eners differ by up to one to two

10-6Table 10-3.Weightpercent concentrationsofdioxin-like PCBsinAroclors, Clophens, andKanechlors



### 10-7Dioxin-like PCBcongenerIUPACnumberNo.ofsamplesanalyzedNo.ofdetectionsMeanconc.(nondetect set tozero) (g/kg)TEQP-WHO98conc.(nondetect set tozero) (mg/kg)Meanconc.a(nondetect set to1⁄2detectionlimit)(g/kg)TEQP-WHO98conc.a(nondetectset to1⁄2 detectionlimit) (mg/kg)Aroclor10163,3',4,4'-TCB3,4,4',5-TCB2,3,3',4,4'-PeCB2,3,4,4',5-PeCB2,3',4,4',5-PeCB2',3,4,4',5-PeCB3,3',4,4',5-PeCB2,3,3',4,4',5-HxCB2,3,3',4,4',5'-HxCB2,3',4,4',5,5'-HxCB3,3',4,4',5,5'-HxCB2,2',3,3',4,4',5-HpCB2,2',3,4,4',5,5'-HpCB2,3,3',4,4',5,5'-HpCB77811051141181231261561571671691701801895344444444544400101000000000000.037500.0125000000000000.0037500.00125000000000000.10900.091000000000000.01100.009000000000Total TEQP-WHO980.0050.0200Total TEQP-WHO940.0050.0200Aroclor12213,3',4,4'-TCB3,4,4',5-TCB2,3,3',4,4'-PeCB2,3,4,4',5-PeCB2,3',4,4',5-PeCB2',3,4,4',5-PeCB3,3',4,4',5-PeCB2,3,3',4,4',5-HxCB2,3,3',4,4',5'-HxCB2,3',4,4',5,5'-HxCB3,3',4,4',5,5'-HxCB2,2',3,3',4,4',5-HpCB2,2',3,4,4',5,5'-HpCB2,3,3',4,4',5,5'-HpCB778110511411812312615615716716917018018944444444444334413040000000001.0750.08750.387501.7250000000000.10750.008750.0387500.17250000000001.0780.1160.401.7250000000000.1080.0120.0400.173000000000Total TEQP-WHO980.3280.333Total TEQP-WHO940.7490.752Table 10-3. Weightpercent concentrationsofdioxin-like PCBsinAroclors, Clophens, andKanechlors (continued)



### 10-8Dioxin-like PCBcongenerIUPACnumberNo.ofsamplesanalyzedNo.ofdetectionsMeanconc.(nondetect set tozero) (g/kg)TEQP-WHO98conc.(nondetect set tozero) (mg/kg)Meanconc.a(nondetect set to1⁄2detectionlimit)(g/kg)TEQP-WHO98conc.a(nondetectset to1⁄2 detectionlimit) (mg/kg)Aroclor1242, ClophenA-30, and Kanechlor3003,3',4,4'-TCB7715153.30.333.3010.333,4,4',5-TCB8761.090.111.0890.1092,3,3',4,4'-PeCB10511114.020.44.0240.4022,3,4,4',5-PeCB114851.130.571.2010.6012,3',4,4',5-PeCB118998.040.88.0440.8042',3,4,4',5-PeCB123971.120.111.1570.1163,3',4,4',5-PeCB1261480.0494.940.0949.4042,3,3',4,4',5-HxCB156980.390.20.4240.2122,3,3',4,4',5'-HxCB157820.0210.0110.0960.0482,3',4,4',5,5'-HxCB167820.0210.000210.0960.0013,3',4,4',5,5'-HxCB1691420.0000130.000130.0480.4762,2',3,3',4,4',5-HpCB170620.1900.24402,2',3,4,4',5,5'-HpCB180520.1600.21802,3,3',4,4',5,5'-HpCB189700000Total TEQP-WHO987.4712.5Total TEQP-WHO948.7013.74Aroclor1248, ClophenA-40, and Kanechlor4003,3',4,4'-TCB3,4,4',5-TCB2,3,3',4,4'-PeCB2,3,4,4',5-PeCB2,3',4,4',5-PeCB2',3,4,4',5-PeCB3,3',4,4',5-PeCB2,3,3',4,4',5-HxCB2,3,3',4,4',5'-HxCB2,3',4,4',5,5'-HxCB3,3',4,4',5,5'-HxCB2,2',3,3',4,4',5-HpCB2,2',3,4,4',5,5'-HpCB2,3,3',4,4',5,5'-HpCB7781105114118123126156157167169170180189136978711877125461348687683334414.361.7610.123.3920.981.480.111.130.190.160.010.961.240.00180.440.181.011.692.10.1510.550.560.090.00160.1006000.00018334.361.7710.123.420.981.480.141.130.20.160.0410.971.240.060.440.181.011.72.10.1513.510.560.10.00160.41000.006Total TEQP-WHO9816.8720.16Total TEQP-WHO9418.5521.83Table 10-3. Weightpercent concentrationsofdioxin-like PCBsinAroclors, Clophens, andKanechlors (continued)



### 10-9Dioxin-like PCBcongenerIUPACnumberNo.ofsamplesanalyzedNo.ofdetectionsMeanconc.(nondetect set tozero) (g/kg)TEQP-WHO98conc.(nondetect set tozero) (mg/kg)Meanconc.a(nondetect set to1⁄2detectionlimit)(g/kg)TEQP-WHO98conc.a(nondetectset to1⁄2 detectionlimit) (mg/kg)Aroclor1254, ClophenA-50, and Kanechlor5003,3',4,4'-TCB3,4,4',5-TCB2,3,3',4,4'-PeCB2,3,4,4',5-PeCB2,3',4,4',5-PeCB2',3,4,4',5-PeCB3,3',4,4',5-PeCB2,3,3',4,4',5-HxCB2,3,3',4,4',5'-HxCB2,3',4,4',5,5'-HxCB3,3',4,4',5,5'-HxCB2,2',3,3',4,4',5-HpCB2,2',3,4,4',5,5'-HpCB2,3,3',4,4',5,5'-HpCB778110511411812312615615716716917018018915612911814109101487712111611812108968720.87.8535.8312.1781.654.590.9911.081.912.740.085.065.790.0450.07950.793.586.088.170.4699.465.540.950.02740.8000.00454290.837.8635.8312.2381.654.591.0211.081.932.740.125.065.790.130.080.793.586.118.170.46101.75.540.970.031.23000.013Total TEQP-WHO98125.94128.67Total TEQP-WHO94126.04128.78Aroclor1260, ClophenA-60, and Kanechlor6003,3',4,4'-TCB3,4,4',5-TCB2,3,3',4,4'-PeCB2,3,4,4',5-PeCB2,3',4,4',5-PeCB2',3,4,4',5-PeCB3,3',4,4',5-PeCB2,3,3',4,4',5-HxCB2,3,3',4,4',5'-HxCB2,3',4,4',5,5'-HxCB3,3',4,4',5,5'-HxCB2,2',3,3',4,4',5-HpCB2,2',3,4,4',5,5'-HpCB2,3,3',4,4',5,5'-HpCB7781105114118123126156157167169170180189156119118141181014878611041017118958780.130.081.590.719.510.00051.816.891.592.870.1632.9482.611.740.012560.00750.160.350.950.00005180.893.450.790.031.64000.17397920.170.11.590.779.510.081.846.891.592.870.1932.9482.611.740.0170.010.160.390.950.008183.823.450.790.031.92000.17Total TEQP-WHO98188.45191.71Total TEQP-WHO94192.62195.89Table 10-3. Weightpercent concentrationsofdioxin-like PCBsinAroclors, Clophens, andKanechlors (continued)aCalculated for a congener onlywhenat least one sample contained detectable levelsofthat congener.Sources:Adapted fromSchulz et al. (1989); Duinker and Hillebrand (1983; deBoer et al. (1993);Schwartz et al. (1993); Larsen, etal. (1992);Kannanetal.(1987);Huckinsetal. (1980);Albro and Parker (1979;Jensenetal. (1974);Albro etal. (1981);Duinker etal. (1988);Tanabe etal. (1987);HimbergandSippola (1990);Frame etal. (1996a, b);Frame (1997).



### 10-10

### or de r s of ma g n itude in the i r wa te r solubility , va por pr e ssur e , K
ow 

### value, and Henry ' s L a w
constant. Thus, althoug h all the diox in-like PC B cong eners are poorly soluble in water and have

very low vapor pressures, they will volatiliz e and leach at different rates. Similarly , because the

cong eners differ somewhat in their rate s of biodeg r adation, bioaccumulation, and photodeg r adation, the cong ener pa tterns found in environmental me dia and biota will vary from
those found in commercial mix tures. Althoug h environmental mix ture s are often characteriz ed in terms of Aroclors, this

c h a r a c t e r iza tion c a n be both impr e c i se a nd ina ppr opr ia te

. Qua lita tive a nd qua ntita tive e r r o r s c a n ari s e from j udg em ent s i n com p ari n g GC / M S peaks for a sam p l e wi t h t h e charact eri s t i c peak
pat t e rns for di fferent Arocl o rs, particularly for environmenta lly a lte r e d pa tte r n s ( U .S. EPA, 1996f). F o r the same reason, it can be both impreci se and inappropr iate to infer concentrations
of diox in-like PCB cong eners in an environmenta l sample on the basis of charact eri z at i on of t h e sample’s Aroclor content and know ledg e of the diox in-like cong en er content in the commercial
Aroclor. Safe (1994) wrote, “Reg ulatory ag enci es and environmental scie ntists have recog n iz ed that the composition of PCB s in most environm e n ta l e x tr a c ts doe s not r e se mble the c o mpositions of the commercial product.” Simila rly , ATSDR (1993) stated, “I t is important to recog nize that
the PCB s to which people may be ex posed are likel y to be different from the orig inal PCB source because of chang e s in cong ener and impurity composition resulting from differential partitioning
and transformation in the environment a nd differential metabo lism and retention.”

10.2.1. Approved P C B Dispos al/Destruction Methods
I n 1978, EPA beg a n reg ulating the disposal of PCB s and PCB

- contaminated waste under TSCA, PL 94-469. The disposal reg ulations, publis hed in the Code of F e deral Reg ulations, 40
CF R, Part 761, state that the preferred disposal method is incineration at 1,200°C or hig her. I f
the waste contains material th at cannot be destroy e d by in cineration, EPA clearance must be
obta i ne d to dispose of the wa ste in a c h e mic a l wa ste la ndf ill or by a nothe r a ppr ove d ma nne r

. The PCB disposal reg ulations de scribe disposal of three di stinct ty pes of PCB waste:
PCB s , PCB a r tic le s ( ite ms c onta i ning PCB s ), and PCB containe r s. Within the se c a t e g or ie s, further distinctions are made on the ba sis of the PCB c onc e n tr a tion in the wa ste , with the acceptable disposal methods being based on the concentrations in the specific waste to be destroy e d. The acceptable disposal methods are Annex I incinera tors, hig h -efficiency boilers,
Annex I I chemical waste landfills , and other approved methods. The following parag r aphs and Table 10-4 provide brief de scriptions of these disposal methods

. More complete descriptions of the specific methodolog ies are provided in 40 CF R, Part 761.

10-11Table 10-4.Disposal requirements for PCBs and PCB items



### 10-12PCBs/itemsWaste characterizationDisposal requirementsPCBsMineral oil dielectric fluids fromPCB transformersThose analyzing>500 ppmPCBAnnex IincineratoraMineral oil dielectric fluids fromPCB-contaminated transformersThose analyzing50–500ppmPCBAnnex IincineratorHigh-efficiencyboiler (40 CFR761.10(a)(2)(iii))Other approved incineratorbAnnex IIchemical waste landfillcPCB liquid wastes other thanmineral oil dielectric fluidThose analyzing>500 ppmPCBThose analyzing50–500ppmPCBAnnex IincineratorAnnex IincineratorHigh-efficiencyboiler (40 CFR761.10(a)(2)(iii))Other approved incineratorbAnnex IIchemical waste landfillcNonliquid PCB wastes (e.g.,contaminated materials fromspills)Annex IincineratorAnnex IIchemical waste landfillDredged materials and municipalsewage treatment sludgescontainingPCBsAnnex IincineratorAnnex IIchemical waste landfillOther approved disposal method, 40 CFR761.10(a)(5)(iii)PCBarticlesTransformersPCBtransformersPCBcontaminatedtransformersAnnex IincineratorDrained and rinsed transformers maybe disposed ofin Annex IIchemical waste landfillDisposal of drained transformers is not regulatedPCBcapacitorsdAnnex IincineratorPCB hydraulic machinesThose containing>1,000ppmPCBThose containing<1,000ppmPCBDrained and rinsed machinesmaybe disposed of asmunicipal solid waste or salvagedDrained machines maybe disposed of as municipalsolid waste or salvagedTable 10-4.Disposal requirementsforPCBs and PCB items (continued)



### 10-13PCBs/itemsWaste characterizationDisposal requirementsOther PCBarticlesThosecontainingPCB fluidsThose not containingPCBfluidsDrained machines maybe disposed of byAnnex IorAnnex IIAnnex Iincinerator or Annex IIchemical wastelandfillPCB containersThose usedto contain onlyPCBsat a concentration <500 ppmAs municipal solid wasteprovided anyliquid PCBsare drained prior to disposalOther PCB containersAnnex IincineratorAnnex II,provided anyliquid PCBs are drainedprior to disposalDecontaminate per Annex IVaAnnexI incinerator isdefined in40 CFR761.40.bRequirementsfor other approved incineratorsare defined in40 CFR761.10(e).cAnnexII chemical waste landfillsare described in40 CFR761.41.AnnexII disposal ispermitted ifthe PCBwaste containslessthan500 ppmPCB and isnot ignitable asper 40 CFRPart 761.41(b)(8)(iii).dDisposal ofcontainerized capacitorsinAnnexII landfillswaspermitted until March1, 1981; thereafter, onlyAnnexI incinerationhas beenpermitted.Source:U.S.EPA(1987d).

### 10.2.1.1. Approv e d Inc i ne rators/High- Ef f

i c i e n c y Boile rs P C B Annex I i n ci nerat o rs m u st m eet t h e speci fi c t echni cal st andards and cri t e ri a l i s t e d i n Annex I of EPA’s PCB reg ulations. The minimum operating requirements for disposal of liquid wastes are 2 sec at 1,200°C with 3% ex cess ox y g en (measured in the stack g a s) or 1.5 sec at 1,600°C with 2% ex cess ox y g en (measured in the st ack g a s). Monitoring requirements, approval conditions, and trial burn requirements are prescribed in Anne x I

. Operators of commercial or
industrial incinerators who in tend to destroy liquid PCB wastes must demonstrate the
inc i ne r a tion’ s c o mplia nc e with the Anne x I r e quir e me nts thr oug h a c o mpr e he nsive tr ia l bur n
prog ram. Annex I incinera tors operating at optimum perfo rmance level should destroy 99.997% of liquid PCB waste, with a resulting max imum emission factor of 0.03 g / kg

. C r i t e ri a for Annex I i n ci nerat o rs were est a blished for the destruction of liquid PCB

wast es; however, t h ese i n ci nerat o rs al so m a y be used for disposal of nonliquid PCB items (such as capacitors), provided that a destruction a nd removal efficiency of 99.9999% and a max imum emission factor of 0.001 g / kg are met. Hig h -efficiency boilers may be used to de st roy P C Bs and P C B-cont am i n at ed wast e wi t h
PCB concentrations not ex ceeding 500 ppm. Conve ntional industrial and utility boilers may be desig n ated as hig h -efficiency boilers if th ey are operated under the prescribed combustion
conditions defined in the PCB disposal reg ula tions. The PCB reg ulations do not specify a

m i n i m u m dest ruct i on effi ci ency for hi g h -effi ciency boilers; however, EPA-approved boilers operated according to the reg u lati ons have reported dest ruction efficiencies in ex cess of 99.99%, with a corresponding max imum emission factor of 0.1 g / kg (U.S. EPA, 1987d).

10.2.1.2. Approv e d Che m ic al Waste Landf ills Appr ove d c h e mic a l wa ste la ndf ills c a n be use d f o r

the disposa l of some but not a ll PCB

wastes. PCB

- contaminated mate rials acceptable for land disposal in an approved landfill include
PCB mix tur e s ( e .g ., c e r ta in PCB

- c onta mina t e d soil/solid de br is, PCB

- c onta mina t e d dr e d g e d materials, and PCB

- contaminated municipal sewag e sludg e), PCB articles that cannot feasibly be
inc i ne r a te d ( e .g ., dr a i ne d a nd f l ushe d tr a n sf or me r s)
, a nd dr a i ne d PCB c onta i ne r s. Wr itte n

a ppr ova l must be obta i ne d f r o m EPA in or de r to la ndf ill PCB a r tic le s othe r tha n tr a n sf or me r s. PCB

- contaminated materials not acceptable for land disposal in an approved landfill include nonliquid PCB mix tures in the form of contaminated soil, rag s , or other solid debris, and sealed capacitors. Ty pically , PCB s disposed of in these landfills are placed in seal ed containers, thereby minimizing a n y PCB e missions.

10-14

### 10.2.1.3. Other Approved Disposal Methods
Other thermal and nonthermal destruction techniques may be approved by EPA Reg i onal
Adm i n i s t r at ors i f t h ese processes can effect a l e ve l of destruction of PCB s equivalent to that of
incinerators or boilers. Afte r April 29, 1983, all other PCB dispos al technolog ies (thermal and nonthermal) used in more than one EPA Reg i on had to be approved by EPA Headquarters.
Ex amples of thermal technolog ies approved for commercial-scal e use or for research and development projects include a py roly sis process to treat contaminated soils, a fluid wall reactor, a cement kiln, a diesel eng i ne, a steam-stripping operation, an aluminum melting furnace, and a molten salt process. Ex amples of appr oved nonthermal proce sses include chemical dechlorination processes, phy si cal/chemical ex traction technique s, and biolog ical reduction
methods. The phy sical/chemical techniques ex tr act the PCB s from transformers or capacitors
and concent r at e t h em for di sposa l; they do not destroy the PCB s

.

10.2.2. Em ission Estim a tes
Tables 10-5 and 10-6 list the amounts of PC B s reported in EPA’s Tox i cs Release
I nventory (TRI ) as transferred o ff site for treatment, energ y rec overy , or disposal and the amounts released between 1988 and 2000, respectively

. These quantities do not necessarily represent

e n tr y of PCB s into the e nvir onme n t. I f it is a ssume d tha t a ll tr a n sf e r r e d PCB s a r e inc i ne r a te d in hig h -efficiency boilers with a destruction and removal efficiency of 99.99%, then annual
emissions of PCB s to air during 1988, 1995, and 2000 could have been as hig h as 264 kg , 31 kg

, and 15 kg , respect i v el y

. Because no st ack t e st i n g dat a are avai l a bl e for di ox i n -l i k e P C Bs, i t i s not possible to e stima te wha t f r a c tion of the se pote n tia l PCB r e le a se s would ha ve be e n diox inl i k e cong eners.

10.2.3. Accidental Releases of Still-in-Service P C Bs After the 1977 ban on production of PCB s , rel eases of commercially produced PCB s to
the e nvir onme n t ( a side f r o m minima l r e le a s e s oc c u rring during approved dis posal or destruction)
have been limited to accidental release of in -service PCB s (U.S. EP A, 1987d). Accidental releases are the result of leaks or spills durin g failure/breakag e of an ex isting piece of PCB

containing equipment or of incomplete co mbustion during accidental fires involving P C B

cont ai ni ng equi pm ent

. These t w o t y pes of acci dent al rel eases are di scussed i n t h e fol l o wi ng sections.

10-15

### Table 10-5. Of f

- site transf ers of P C Bs reported in th e Toxics Release Inventory (TRI) (1988–2000)

Yea r No. of TRI fo r m s fi l e d R e ported transf ers (kg)

T ransf ers to POT W s Transf ers f o r treatment/disposal T otal transf ers
2000 NA 102 150,888 150,990

1999 NA 0 434,666 434,666

1998 NA 0 386,903 386,903

1997 NA a 

### 471,319 471,319

1996 NA 0 160,802 160,802

1995 NA 0 308,347 308,347

1994 NA 0 466,948 466,948

1993 16 120 463,385 463,505

1992 20 0 766,638 766,638

1991 26 0 402,535 402,535

1990 NA 0 1,181,961 1,181,961

1989 NA 0.5 2,002,237 2,002,237

1988 122 113 2,642,133 2,642,246

a Facilities lef t th at p a rticu l ar cell b l an k o n th e Fo rm R su b missio n s.

NA = No t av ailab l e P OT W s = P u b licly o w n e d treatm e n t w o rk s

S o u r ces : U

. S

. EPA (1993f , 1995h , 1998b, 2003c).



### 10.2.3.1. Le aks and Spills
PCB s tha t r e ma in in a c tive se r v ic e a t this time a r e those c onta i ne d in “ c l ose d sy ste m s” (i .e., t hose pi eces of el ect ri cal equi pm ent t h at com p l e t e l y encl ose t h e P C Bs and do not provi de
di rect at m o spheri c access for t h e P C Bs duri n g norm a l use). Thi s equi pm ent i n cl udes P C B

tr a n sf or me r s, c a p a c itor s, volta g e r e g u la tor s, c i r c u i t breakers, and recl osures. W i t h t h e ex cept i o n of PCB transformers—a nd probably small PCB capacitors—the majority of the PCB

- containing electrical equipment in serv ice during 1981 was owned by the electrical utility industry

. Approx imately 70% of the es timated 140,000 PCB transfor mers in service in 1981 were owned by nonutilities. No information was availabl e on the relative distribution of small PCB capacitors (Versar, I n c., 1988).

10-16Table 10-6.Releases ofPCBs reported inthe Toxics ReleaseInventory (TRI) (1988–2000)



### 10-17Reported releases (kg)Fugitive orOn-siteTotalNo. ofTRInonpointairStack or pointSurface waterUndergroundreleases toon-siteYearformsfiledemissionsair emissionsdischargesinjectionlandReleases2000NA1582,497130.5648,128650,796.51999NA00aa0.01998NA000a60,85460,854.01997NA000a3,0813,081.01996NA2.3114004,1794,295.31995NA000000.01994NA000000.01993160000120120.019922000000.50.5199126000000.01990NA2.300032,37232,374.31989NA001200453573.019881222.704.50341348.2aFacilities leftthat particular cell blankonthe FormR submissions.NA= Not availableSources:U.S.EPA(1993f, 1995h, 1998b, 2003c).

### The number of each of these items owned by the utility industry , the quantity of PCB s contained in each, and an estimate of the annual quantity of PC B s leaked and/or spilled were
inve stig a t e d by the Edison Ele c t r i c I n stitute a nd the Utility Solid Wa ste s Ac tivity Gr oup (EEI /USW AG) for EPA in 1981. The finding s of th is investig ation, whic h were reported in a proposed modification to the PCB reg ulations (F ed eral Reg i ster, 1982a), i ndicated that more than 99% of the total quantity of PCB s contained in utility -owned electrical equipment in 1981 (73,700 metric tons) was in 40,000 PC B transformers (those contai ning >500 ppm of PCB s ) and larg e PCB capacitors (those contai ning > 3 lb of PCB s ). An upper-bound estimate of the mass of
PCB s that leached or spilled from this equipm ent in 1981 was 177 metric tons. Approx imately
95% of the e stima te d r e le a se s we r e the r e sult of le a k s f r o m la r g e PCB c a p a c itor s ( F e d e r a l Reg i ster, 1982a). L eaks/spills ty pically occur in transformers when the g a sket joining the top to the body corrodes, tears, or phy sically fails. PC B s can then leak past this failed section and potentially spill onto the surrounding g r ound. PC B capacitors ty pically fail by rupturing

,

ex posing the contained PCB s to the environmen t. F a ilure is caused by environmental and weathering effects (e.g ., lig htning ) or ma te r i a l f a ilur e s ( e .g ., me ta l f a tig ue )

. As of mid-1988, the total population of in-s ervice PCB transformers and larg e PCB capacitors was estimated to have decreas ed from 140,000 to 110,000 and from 3.3 million to 1.9 million, respectively (Versar, I n c ., 1988). PCB transformers ha ve normal opera ting lifetimes of 30 y ears and 40 y ears, respectively

. EPA’s PC B Electrical Use Rule (F ederal Reg i ster, 1982b) required the removal of 950 food/feed i ndustry transformers by 1985 and 1.1 million unrestricted-access larg e PCB capac itors by October 1988. I n a ddition, EPA’s PCB Transformer
F i res Rule (F ederal Reg i ster, 1985b) require d the removal by 1990 of 7,600 480-volt network
transformers.
More recent i nvent ori e s of P C B-cont ai ni ng el ect ri cal equi pm ent are not avai l a bl e. Howe ve r , a n I n f o r m a tion Colle c tion Re que st submitte d by EPA to the Of f i c e of Ma na g e me nt
and B udg et for information on uses, locations , and conditions of PCB electrical equipment estimated that there may be 150,000 owners of PCB

- containing tr ansformers used in industry

, utilities, g overnment building s , and private buildin g s (F ederal Reg i ster, 1997b). I t is ex pected, and is demonstrated by the re por te d PCB tr a n sf e r s in the EPA’ s TRI (see Table 10-5), that many

owne r s of PCB e l e c t r i c a l e quipme n t ha ve r e move d PCB

- c onta i ning e quipme n t to e limina t e pote n tia l lia bility

.

10.2.3.2. Accidental Fires The available information is not adequate to support an estimate of potential annual
releases of diox in-like P C B s fro m accidental electri cal equipment fires. For fires involving P C B transformers or capacitors, the amount of PCB s re leased is dependent on the ex tensiveness of the

10-18

### f i r e a nd the spe e d a t whic h it is e x ting u ishe d. A number of these fires are documented. A New York fire involving 200 g a l of transformer fluid containing some 65% by weig ht PCB s resulted in a release of up to 1,300 lb of PCB s

. A cap acitor fire that burned uncontrolled for 2 hr in
Swe d e n r e sulte d in the de str u c tion of 12 la r g e utility c a p a c itor s c onta i ning a n e stima te d 25 pounds each of P C B s , for a total potential release of 300 lb. However, data are incomplete on the

ex act amount of PCB s released as a result of these two fires. EPA has imposed reporting requirements to en sure that the National Response Center is informed immediately of fires involving PCB tr ansformers (40 CF R 761). The recordkeeping requirements are used to document the use, location, and condition of PCB equipment. Responses are mandatory , but the submitter may cla im them to be confidential information. The
numbe r of PCB tr a n sf or me r f

i r e s is e stima te d to be a ppr ox ima te ly 20 pe r y e a r ; the numbe r of
P C B capacitor fires is unknown (U.S . EP A, 1987d). As these P C B

- containing items reach the

e nd of the i r use f ul live s a nd a r e r e tir e d, the i r susc e p tibility to f i r e s will be e limina t e d, a nd the

ove r a ll numbe r of PCB tr a n sf or me r a nd c a p a c itor f

i r e s will be r e duc e d

.

10.2.4. Municipal Wastew ater Treatm ent
EPA conducted the National Se wag e Sludg e Survey in 1988 and 1989 to obtain national
da ta on se wa g e sludg e qua lity a nd ma na g e me nt. As pa r t of this sur v e y , EPA te ste d f o r

mor e tha n 400 analy t es, including seven of the Aroclors , in sludg es from 175 publicly owned treatment works (POTW s ) that employ ed at least secondary wastewater treatment. Sludg es from 19% of
the POTW s had detectable levels of at leas t one of the following Aroclors: 1248, 1254, or 1260;
none of the other Aroclors were detected in any sample (the detec tion limit [ D L ] was ty pically about 200 μg /kg dry weig ht) (U.S. EPA, 1996e). Analy s es were not performed for diox in-like
P C B cong eners. The Arocl o r-speci fi c resul t s of the survey are presented in Table 10-7. Gutenmann et al. (1994) reporte d similar results in a survey of sludg es from 16 larg e U.S.
cities for Aroclor 1260 content. At a DL of 250 μg /kg (dry weig ht), the investig ators detected Aroclor 1260 (4,600 μg /kg ) at only one facility

. Th ese results indicate that PCB s are not likely
to be formed at P O TW s, but rather are pr esent because of disposal of P C B products or recirculation of previously disposed of PCB s

. Althoug h PCB s , measured as Aroclors, were not commonly detected in sewag e sludg e at microg r am-per-kilog r am levels in studies by EPA (U.S. EPA, 1996e) and Gutenmann et al. (1994), the presence of diox in-like PCB cong en ers at lower concentrations may be more

common. Green et al. (1995) and Cramer et al. (1995) reported the results of analy s es of 99 samples of sewag e sludg e for PCB cong ener numbers 77, 81, 126, and 169. The sludg e samples
were col l ect ed from 74 wast ewat er t r eat m e nt pl ant s across t h e Uni t e d S t at es duri n g t h e sum m e r

10-19

### Table 10-7. Aroclor concentrations (ng/kg) m e asured in EP A’s National Se wage Sludge Sur ve y a



### Aroclor P ercent detected Max i mum concentration Median concentration

N o ndetects set to

d e tection limit N o ndetects set to z ero
1016 0

- ­ - ­ 0

1221 0

- ­ - ­ 0

1232 0

- ­ - ­ 0

1242 0

- ­ - ­ 0

1248 9 5.2 0.209 0

1254 8 9.35 0.209 0

1260 10 4.01 0.209 0 Any Aroclor (total) 1 9 14.7 1.49 0

a Fo r p u b licly o w n e d treatm e n t w o rk s w ith m u ltip le sam p les, th e p o llu tan t co n cen tratio n s w e re av erag ed b e f o re th e

su m m a ry statistics p r esen ted in th e tab l e w e re calcu lated

.

-- = N o i n fo r m a t i o n gi ve n

S o u rce: U

. S

. EPA (1996e).



### of 1994. These data are summariz e d in Table 10- 8. Results from all samples collected from the

sa me f a c ility we r e a ve r a g e d by Gr e e n e t a l . a nd Cr a m e r e t a l . to e nsur e tha t r e sults we r e not biased toward the concentrations found at f acilities from which more than one sample was
collected. I f all nondetect values were a ssumed to be z e ro, then the POTW mean TEQ P 

### -W HO 94 

### and TEQ P 

### -W HO 98 

### concentrations were 25.1 and 24.2 ng TEQ /kg (dry -weig h t basis), respectively

. I f

the nondetect values we re set equal to the DL s, then the POTW mean TEQ P 

### -W HO 94 

### and TEQ P 

### -W HO 98 

### concentrations were 25.2 a nd 24.3 ng TEQ/kg , respectively

. I n 1999, sewag e sludg e samples from a POTW in Ohio were collected and analy z ed for
PCB s (U.S. EPA, 2000b). The facility , which accep ts both domestic and i ndustrial wastewater, employ s secondary wastewater technolog y

. Assuming nondects were z e ro, the mean TEQ emission factor was 141 ng TEQ P 

### -W HO 98 

### /kg

. These results are presented in Table 10-9.
I n 2000 and 2001, the Association of Metropo litan Sewag e Ag encies conducted a survey
of diox in-like PCB compounds in sewag e sludg e (Alvarado et al., 2001). A total of 200 sewag e sludg e samples were collected from 171 POTW s lo cated in 31 states. Assuming nondetects were

z e ro, the mean and median TEQ emission factors were reported as 8.3 and 3.37 ng TEQ P 

### WH O 98 

### /kg

, r e spe c tive l y

.

10-20Table 10-8.Dioxin-like PCB concentrationsmeasuredinsludges collected from74 U.S. publicly ownedtreatment works (POTWs) during 1994a,b



### 10-21CongenerIUPACnumberPercentdetectedMaximumconcentration(ng/kg)Median concentration (ng/kg)Mean concentration (ng/kg)Nondetect set to1⁄2 detectionlimitNondetectset to zeroNondetectsetto 1⁄2 detectionlimitNondetectsetto zero3,3',4,4'-TCB7710022,9007837832,2432,2433,4,4',5-TCB81861,25027.32765.263.52,3,3',4,4'-PeCB1052,3,4,4',5-PeCB1142,3',4,4',5-PeCB1182',3,4,4',5-PeCB1233,3',4,4',5-PeCB126993,02091.691.62372372,3,3',4,4',5-HxCB1562,3,3',4,4',5'-HxCB1572,3',4,4',5,5'-HxCB1673,3',4,4',5,5'-HxCB169221,4708.5032.526.22,2',3,3',4,4',5-HpCB1702,2',3,4,4',5,5'-HpCB1802,3,3',4,4',5,5'-HpCB189Total TEQP-WHO989.39.224.324.2aFor POTWswithmultiple samples,the sampleconcentrationswere averaged byCramer etal. (1995) to POTWaveragesbefore calculationofthe total TEQmeanand medianvaluespresented inthe table.The TEQP-WHO94and TEQP-WHO98values were calculatedona facility-level basis.bBlankcellsindicate that nomeasurementsofthese congenerswere made.Source:Greenetal. (1995);Cramer etal. (1995).

### Table 10-9. Dioxin-like P C B concentrations in sew age sludge collected f r om U.S. publicly ow ned treatm ent w orks during 1999

C ongener IU P A C

num ber Mean emission f a ctor (ng/kg)

N o n d e tect set to 1⁄2

detection limit N o ndetect set to z ero 3,3' ,4,4'

- T CB 77 42,467 42,467
2,3,3' ,4,4'

- P eCB 105 7,230 7,230
2,3,4,4' ,5- PeCB 114 701 701

2' ,3,4,4' ,5- PeCB 123 249 249
2,3' ,4,4' ,5- PeCB 118 12,867 12,867
3,3' ,4,4' ,5- PeCB 126 1,270 1,270
2,3,3' ,4,4' ,5- HxCB 156 1,843 1,843
2,3,3' ,4,4' ,5'

- H xCB 157 524 524
2,3' ,4,4' ,5,5'

- H xCB 167 935 935
3,3' ,4,4' ,5,5'

- H xCB 169 570 570
2,2' ,3,3' ,4,4' ,5- HpCB 170 2,627 2,627
2,2' ,3,4,4' ,5,5'

- H pCB 180 6,497 6,497
2,3,3' ,4,4' ,5,5'

- H pCB 189 199 199

Total TE Q P 

### -W H O 98 

### 141 141

S o u rce: U

. S

. EPA (2000b).



### F o r 2001, EPA conducted another National Sewag e Sludg e Surv ey to characteriz e the
diox in and diox in-like equiva lence levels in biosolids pr oduced by the 6,857 POTW s operating in the United States in 2001 (U.S. EPA, 2002d). Sewag e sludg e samples were collected from 94
POTW s that used secondary or hi g h er treatment practices. All the facilities had been sampled as part of the 1988/1989 National Sewag e Sludg e Surv ey

. To determine the mean and median TEQ

e mission e stima te s of the diox in- like PCB s, EPA we ig hte d the va lue s on the ba sis of wa ste w a t e r f l ow r a te s of a ll POTWs in the Unite d Sta t e s ( i .e ., numbe r of f

a c ilitie s with wa ste w a t e r f

l ow r a te >100 mg /day , >10 but 

### # 100 mg /day , >1 but 

### # 10 mg /day , and 

### # 1 m g / d ay ). The wei g ht ed m ean and median TEQ P 

### -W HO 98 

### concentrations of the diox in- like PCB cong eners were 5.22 and 2.05

ng /kg

, r e spe c tive l y

. According to the results of its 1988/1989 Na tional Sewag e Sludg e Survey , EPA estimated that approx imately 5.4 million dry me tric tons of sewag e sludg e were g e nerated in 1989 (F ederal Reg i ster, 1993a). EPA also used the results of the 1984 to 1996 Clean W a ter Needs Survey s to

10-22

### estimate that 6.3 million dry metr ic tons of sewag e sludg e were g e nerated in 1998 and 6.6 million dry metric tons were g e nerated in 2000 (U.S. EPA, 1999b). B ecause estimates for 1987 and 1995 are not available, the 1989 and 1998 activ ity level estimates are used for reference

y ears 1987 and 1995, respectively

. Tables 10-10, 10-11, and 10-12 list the volume, by use and disposal practices, of sludg e disposed of annually for reference y ears 1989, 1995, and 2000.

Table 10-10. Quantity of se w age sludge dispose d of annually in 1989 by prim ary, secondary, or advanced treatm en t p u b l i c l y ow n e d treatm en t w o rk s ( P OTWs) and pot e nt ial dioxin- like P C B TEQ r e le a se s

Use/disposal practice Vol u m e disposed of (1,000 dry metric ton s/yr) P ercent of total volume Poten tial T E Q P 

### ­ WHO 98 

### release a



### (g of TEQ/yr) Poten tial T E Q P 

### ­ WHO 94 

### release a



### (g of TEQ/yr) Land application 1,714 32 b 

### 41.5 43

Distribution and m ark eting 7 1 1.3 1.7 1.8 Surface disposal site/other 396 7.4 9.6 9.9 Sewag e sludg e landfill 157 2.9 4.2 3.9

C o

- d isposal landfills c 

### 1,819 33.9 44 45.6 Sludg e incinerators and coincinerators d 

### 865 16.1 e e



### O cean disposal f 

### 336 6.3 0 0

T O T A L 5,358 100 101 104.2

a P o ten tial T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (col u m n 2) by t h e m ean di ox i n

- l i k e PC B T E Q con cen t rat i o n i n 74 PO T W s l u d g e s report e d by G reen et al . (1995)

an d C r am er et al . (1995) (i .e., 24.2 n g T EQ P -W H O 98 / k g an d 25.1 n g T E Q P -W H O 94 / kg)

. b In cl u d es 21.9% appl i e d t o ag ri cu l t u ral l a n d , 2.8% appl i e d as com pos t , 0.6% appl i e d t o f o res t ry l a n d , 3.1%
ap p lied to “ p u b lic co n t act” lan d , 1

. 2 % ap p lied to reclam atio n sites, an d 2

. 4 % ap p lied in u n d ef in ed settin g s

.
c L a n d f ills u s ed f o r d i sp o s al o f sew a g e slu d g e an d so lid w a ste resid u als.

d Co

- i n c in erato r s treat sew a g e slu d g e in co m b in atio n w ith o t h e r co m b u s tib le w a ste m a terials.

e S ee S ect i o n 10.4.6 f o r a di s c u s s i on of di ox i n

- l i k e PC B rel eas es t o ai r f rom s e w a g e s l u d g e i n ci n e rat o rs

. f T h e Ocean Du m p in g Ban A c t of 1988 g e n e rally proh ibited th e du m p in g of s e w a g e s l u d g e in to th e ocean af ter Decem ber 31, 1991. Ocean du m p in g of s e w a g e s l u d g e en ded in Ju n e 1992 (F ederal R e g i s t er, 1993a). T h e

cu rren t m e th od of dis pos al of th e 336,000 m e tric ton s of s e w a g e s l u d g e th at w e re dis pos ed of in th e ocean s in 1988 h a s n o t been det e rm i n ed.

S o u r ces : F e deral R e g i s t er (1990, 1993a); G r een et al . (1995); C r am er et al . (1995).



### 10-23

### Table 10-11. Quantity of se w age sludge dispose d of annually in 1995 by prim ary, secondary, or advanced treatm en t p u b l i c l y ow n e d treatm en t w o rk s ( P OTWs) and pot e nt ial dioxin- like P C B TEQ r e le a se s

Use/disposal practice Volume disposed of (1,000 dry metric ton s/yr) P ercent of total volume Poten t ial d i ox in release a 

### (g T E Q/yr)

TEQ P 

### -WHO 98 

### TEQ P 

### -WHO 94 

### Land application b 

### 2,500 39.7 60.5 62.8

A d v anced treatm ent c 

### 700 11.1 16.9 17.6

Other beneficial use d 

### 500 7.9 12.1 12.6 Surface disposal/Landfill 1,100 17.5 26.6 27.6

I n cineration 1,400 22.2 e e 

### Other disposal m e thod 100 1.6 2.4 2.5

T O T A L 6,300 100 118.5 123.1

a P o ten tial T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (col u m n 2) by t h e m ean di ox i n

- l i k e PC B T E Q con cen t rat i o n i n 74 PO T W s l u d g e s report e d by G reen et al . (1995)

an d C r am er et al . (1995) (i .e., 24.2 n g T EQ P - W H O 98 / k g an d 25.1 n g T E Q P -W H O 94 / kg)

. b W ith o u t f u rth e r p r o cessin g o r stab ilizatio n , su ch as co m p o s tin g

.
c Su ch as com pos tin g

. d E P A a ssum e d t h a t t h i s c a t e g o r y i n c l ud e s d i st r i b u t i o n a n d m a r k e t i ng ( i

. e

. , sa l e o r gi ve -a w a y o f sl ud ge fo r use i n h o m e g a rden s ). Bas e d on t h e 1988 N a t i o n a l S e w a g e S l u d g e S u rv ey an d 1988 N eeds S u rv ey , approx i m at el y 1.3% of t h e t o t a l v o l u m e of s e w a g e di s pos ed w a s di s t ri bu t e d an d m a rk et ed (F ederal R e g i s t er, 1993a). T h eref ore, i t i s

es tim ated th at 2 g (T EQ P -W H O 98 an d T EQ P -W H O 94 ) w e r e r e l e a s e d t hr o ugh d i st r i b ut i o n a nd m a r ke t i ng i n 1995.

e See Section 3.5 f o r es tim ates of C DD/C D F releas e s t o a i r fr o m se w a ge sl ud ge i nc i ne r a t o r s

.

S o u rces : U

. S

. EPA (1999b); G reen et al . (1995); C ram er et al . (1995).



### These tables also list the estimated amount of diox in-like PCB TEQs that may be present in sewag e sludg e and potentially released to the environment. F o r reference y e ars 1987 and 1995, these values were estimated using the POTW mean TEQ P 

### -W HO 98 

### concentration calculated from the results reported by Green et al. (1995) and Cramer et al. (1995). F o r reference y ear 2000, they were estimated using the POTW mean TEQ P 

### -W HO 98 

### concentration reported by EPA (U.S. EPA, 2002d) as part of the 2001 National Sewag e Sludg e Survey

. Multiply ing these TEQ concentrations by the sludg e volumes g e nerated y i elds annual potential to tal releases of 101 g TEQ P 

### -W HO 98 

### (104.2 g TEQ P 

### -W HO 94 

### ) in 1987, 118.5 g TEQ P 

### -W HO 98 

### (123.1 g TEQ P 

### -W HO 94 

### ) i n 1995, and 26.6 g TEQ P 

### -W HO 98 

### in 2000 for nonincinerated sludg es.

10-24

### Table 10-12. Quantity of se w age sludge dispose d of annually in 2000 by prim ary, secondary, or advanced treatm en t p u b l i c l y ow n e d treatm en t w o rk s ( P OTWs) and pot e nt ial dioxin- like P C B TEQ r e le a se s

Use/disposal practice Volume disposed of (1,000 dry metric ton s/yr) P ercent of total volume Po te n t ia l TEQ DF 

### -WHO 98 

### release a 

### (g T E Q/yr) Land application b 

### 2,800 42.4 14.6

A d v anced treatm ent c 

### 800 12.1 4.2

Other beneficial use d 

### 500 7.6 2.6 Surface disposal/landfill 900 13.6 4.7

I n cineration 1,500 22.7 e 

### Other disposal m e thod 100 1.5 0.5

T O T A L 6,600 100 26.6

a P o ten tial d i o x in T E Q release f o r n o n i n c in erated slu d g e s w a s estim ated b y m u ltip ly in g th e slu d g e v o lu m e g e n e rated (colu m n 2) by th e av erag e of th e m ean T E Q DF -W H O 98 co n cen tratio n s in slu d g e rep o r ted b y U.S. EP A (2002c) (i .e., 5.22 n g T E Q DF -W H O 98 / kg)

. b W ith o u t f u rth e r p r o cessin g o r stab ilizatio n , su ch as co m p o s tin g

.
c Su ch as com pos tin g

. d E P A a ssum e d t h a t t h i s c a t e g o r y i n c l ud e s d i st r i b u t i o n a n d m a r k e t i ng ( i

. e

. , sa l e o r gi ve -a w a y o f sl ud ge fo r use i n h o m e g a rden s ). Bas e d on t h e 1988 N a t i o n a l S e w a g e S l u d g e S u rv ey an d 1988 N eeds S u rv ey , approx i m at el y 1.3% of t h e t o t a l v o l u m e of s e w a g e di s pos ed of w a s di s t ri bu t e d an d m a rk et ed (F ederal R e g i s t er, 1993a). T h eref ore, i t is es tim ated th at 0.5 g T E Q DF -W H O 98 w e r e r e l e a s e d t hr o ugh d i st r i b ut i o n a nd m a r ke t i ng i n 2000.

e See Section 3.5 f o r es tim ates of C DD/C D F releas e s t o a i r fr o m se w a ge sl ud ge i nc i ne r a t o r s

.

S o u r ces : U

. S

. EPA (1999b, 2002d).



### Of the 101 g TEQ P 

### -W HO 98 

### released in 1987, 1.7 g entered commerce as a product for distribution and marketing and th e remainder was applied to land (41.5 g to land application and
9.6 g to surface disposal sites) or landfilled (48.2 g )

. Of the 118.5 g TEQ P 

### -W HO 98 

### rel eased i n 1995, 60.5 g were applied to land without furthe r processing or stabiliz ation, 16.9 g underwent advanced treatment such as composting

, 26.6 g we re disposed of on the surface or landfilled, and the remainder was either used or disposed of in other way s

. Of the 26.6 g TEQ P 

### -W HO 98 

### rel e ased in 2000, 14.6 g were applied to land without furt her processing or stabiliz ation, 4.2 g underwent advanced treatment such as composting

, 4.7 g we re disposed of on the surface or landfilled, and
the r e ma inde r wa s e ithe r use d or dispose d of in othe r wa y s. The PCB s in la ndf ille d sludg e we r e not considered releases to the environment unde r the definition established in this document. The other disposal practi c e s we r e c onside r e d r e le a se s a nd we r e summe d to g e t tota l la nd r e le a se s, as shown in Table 10-2 (above).

10-25

### The 1987 and 1995 release estimates are assig n ed a confidence rating of B

, indicating hig h confidence in the production estimate and medium confidence in the emission factor
estimates. The medium rating was based on the judg ment that , althoug h the 74 facilities tested by Green et al. (1995) and Cramer et al. ( 1995) may be reasonably representative of the variability in POTW technolog ies and sewag e characteristics nati onwide, the sample siz e was still relatively small, and not a ll diox in-like PCB cong eners we re monitored. The 2000 release

e stima te s a r e a ssig n e d a c onf ide n c e r a ting of A, indic a ting hig h c onf ide n c e in both the production estimate and th e emission factor estimates. Hig h confidence was placed in the
emission factors estimated because they were weig hted on the basi s of wastewater flow rates of

a ll POTWs in the Unite d Sta t e s

.

10.3. CHEMICAL MANUF ACTURING AND P R OCESSING SOURCES
I n the early 1980s, EPA investig ated the ex tent of inadvertent g e ne ration of PCB s during the manufacture of sy nthetic org a nic chemical s (Hammerstrom et al., 1985). F o r ex ample, phtha loc y a n ine dy e s a nd dia r y lide pig m e n ts we r e r e por te d to c onta i n PCB s in the millig r a m- pe r

kilog r am rang e. EPA subsequently issued re g ulations under TSCA (40 CF R 761.3) that ban the distribution in commerce of any products containi ng an annual averag e PC B concentration of 25

mg /kg (50 mg /kg max imum concentration at any time). I n addition, EP A requires manufacturers with processes that inadverten tly g e nerate PCB s and importe rs of products that contain inadvertently g e nerated PCB s to report to EPA any process or import for which the PCB

concent r at i on i s g r eat er t h an 2 m g / k g for any resol v abl e P C B g a s chrom a t o g r aphi c peak.

10.4. COMBUSTION SOURCES
10.4.1. Municipal Waste Com bustors Municipal waste combustors (MW C s) have long be e n ide n tif ie d a s pote n tia l PCB a i r emission sources. Stack g a s concentrations of PCB s for three MW Cs were reported (U.S. EPA, 1987d); the averag e test results y i elded an emi ssion factor of 18 μg /kg refuse. Stack g a s emissions of PCB s from the three MW Cs were quantified without dete rmining the MW Cs’ PCB
dest ruct i on effi ci ency

. EPA also analy z ed the PCB content of va rious consumer paper products (U.S. EPA, 1987d). The results indicated that paper products such as mag a z i ne c overs and paper towels contained up to 139 μg /kg paper. These levels, which were repor ted in 1981, were attributed to the repeated recy cling of wast e paper containing PCB s

. F o r ex ample, carbonless copy paper manufactured prior to 1971 contained P C B levels as hig h as 7%. This copy paper then became a component of waste paper, which was recy cled. The PCB s were inevitably introduced into other paper products, resulting in conti nued measurable levels in muni cipal refuse some four y ears

10-26

### after the PCB manufacturing ban was imposed. Refuse-derived fuel m a nufact ured from t h ese paper products had PCB le vels of 8,500 μg /kg , indicating that this fuel could be a source of

at m o spheri c P C Bs. Therefore, it wa s a ssume d tha t munic i pa l refuse does contain detectable
le ve ls of PCB s a nd tha t some of the se PCB s ma y e n te r the a tmosphe r e whe n the r e f u se is incinerated (U.S. EPA, 1987d). Shane et al. (1990) analy z ed fly ash from fi ve MW Cs for PCB cong ener g r oup content. Total PCB levels rang ed from 99 to 322 μg /kg in th e ash, with the tri, tetra, and penta cong ener
g r oups occurring in the hig hest concentrations. The investig ators also analy z ed seven bottom ash and eig ht bottom ash/fly ash mix tures for total PCB measured as Aroclor 1254. The DL for this Aroclor analy s is was 5 μg /kg

. Aroclor 1254 wa s detected in two of the seven bottom ash samples (26 and 8 μg /kg ) and in five of the eig ht fly ash/bottom ash mix tures (rang e, 6 to 33

μg /kg )

. Sakai et al. (2001) analy z ed the PCB leve ls in fly ash and bottom ash from a newly
constructed MW C in J a pan. The I

- TEQ values derived from the da ta g i ve a tota l TEQ va lue of
31.6 ng /kg for fly ash and 0.85 ng /kg for bottom ash. The development of more sensitive analy ti cal methodolog ies has enabled researchers in

recent y ears t o det ect di ox i n -l i k e P C B cong eners i n t h e st ack g a ses and fl y ash from ful l

- scal e and pilot-scale MW Cs (Sakai et al., 1993a , b, 1994, 2001; B oers et al., 1993; Schoonenboom et al., 1993). Similarly , the advances in analy tical techniques have enabled re searchers to determine
that diox in-like PCB s can be formed during the ox ida tive solid c o mbusti on phase of incineration, presumably due to dimeriz a tion of chlorobe nz enes. L a boratory

- s cale studies have also
demonstrated that diox in-like PCB s can be fo rmed from heat treatment of fly ash in air (Schoonenboom et al., 1993; Sakai et al., 1994); howev er, the available data are not adequate to support development of a quantita tive estimate of a diox in-like PCB emission factor for this

source cat eg ory

. MW C s are desi g n at ed as a C a t e g o ry E source.

10.4.2. Industr ial Wood Com bustion
Emissions of PCB cong ener g r oups (but not individual cong eners) were measured during stack testing at two industria l wood-burning facilities (CARB

, 1990d, e). Table 10-13 presents the averag e of the cong ener g r oup (monochl orobipheny l [ M CB ] throug h decachlorobipheny l [DCB ]) e mission f a c t or s f o r

the se two f a c ilitie s. No te tr a

- or hig h e r

- c hlor ina t e d c ong e n e r s ( t he

cong ener g r oups containing the diox in-like PCB s ) were detected at either facility at DL s corresponding to emission factors in the lo w rang e of nanog ram per kilog r am of wood
combusted.

10-27

### Table 10-13. P C B c o nge n e r gr oup e m ission f a c t or s f o r industr ial w ood

com b u s tors a



### C ongener group N u mber of det ect i ons Max i mum concentration detected (ng/kg w ood) Mean concentration (ng/kg)

Nondet ect set

to detection limit Nondet ect set to z ero Monochlorobipheny ls 1 32.1 39.4 16 Dichlorobipheny ls 1 2 3 50.9 11.5

T r ichlorobipheny ls 1 19.7 42.3 9.8

T etrachlorobipheny ls 0

- ­ 22.7

- - Pentachlorobipheny ls 0

- ­ 17.6

- - Hexachlorobipheny ls 0

- ­ 1 7

- - Heptachlorobipheny ls 0

- ­ 17.9

- - Octachlorobipheny ls 0

- ­ 15.8

- - Nonachlorobipheny ls 0

- ­ 2 5

- - D ecachlorobipheny ls 0

- ­ 36.3

- ­

a T w o s ites f o r each con g e n e r g r ou p.

-- = N o i n fo r m a t i o n gi ve n

S o u rce: C A R B (1990d, e).



### I n CARB (1990d), PCB s were measured in the emissions from two spreader stoker woodf i r e d boile r s ope r a te d in pa r a lle l by a n e l e c t r i c utility f

o r

g e ne r a ting e l e c t r i c ity

. The e x ha ust g a s
st ream from each boi l e r was passed t h roug h a dedi cat ed el ect rost at i c preci pi t a t o r (ES P ) , aft e r whic h the g a s str e a m s we r e c o mbine d a nd e mitte d to the a tmosphe r e thr oug h a c o mmon sta c k.
Stack tests were conducted both wh en the facility burned fuels a llowed by ex isting permits and when the facility burned a mix ture of permitted fuel supplemented by urban wood waste at a ratio
of 70:30.
I n CARB (1990e), PCB s were measured in the emissions from twin fluidiz e d-bed combustors desig ned to burn wood chips to g e nera te electricity

. The ai r pollution control device ( A PCD) sy ste m c onsiste d of a mmonia inje c tion f o r

c ontr o lling nitr og e n ox ide s a nd a multic lone and an ESP for controlling PM. During testing

, the facility burned wood wastes and ag ricultural wastes allowed by ex isting permits

. The available data are not adequate to support development of a quantitative estimate of di ox in-like PCB emissions from this source. I ndustrial wood combustion is desig n ated as a Categ o ry E source.

10-28

### 10.4.3. Medical Waste Incineration As discussed in Chapter 3, Section 3.3, EPA has issued nationally applicable emission standards and g u idelines that address CDD/CDF emissions fro m me dic a l wa ste inc i ne r a tor s (MW I s). Althoug h PCB s are not addressed in thes e reg u lations, the database of stack test results

a t MWI s c o mpile d f o r

this r u le ma king doe s c onta i n limite d da ta on PCB c ong e n e r g r oup

em i ssi on fact ors. Dat a are avai l a bl e for t w o MW I s lacking add-on APCD equipment and for two
MW I s with add-on AP CD equipment in place. The averag e cong ener g r oup emission factors
derived from these test data are presented in Table 10-14. B ecause data are available for only 4 of the estimated 1,065 facilities that make up this industry , and b ecause these data do not provide

c ong e n e r

- spe c i f i c e mission f a c t or s, no na tiona l e stima te s of tota l PCB or diox in- like PCB

e missions a r e be ing ma de a t this time

. Me dic a l wa ste inc i ne r a tion is de sig n a t e d a s a Ca te g o r y E

source.

Table 10-14. P C B congener group em ission f actors f or m e dical w aste i n ci n erators (MWIs) a



### C ongener group Mean emission f a ctor (ng/kg) ( 2 M W I s w i t h out AP CD) Mean emission f a ctor (ng/kg) ( 2 M W I s w i t h AP CD)

N o ndetects set to

d e tection limit Nondet ect s set to z ero N o ndetects set to d e tection limit Nondet ect s set to z ero Monochlorobipheny ls 0.059 0.059 0.311 0 Dichlorobipheny ls 0.083 0.083 0.34 0

T r ichlorobipheny ls 0.155 0.155 0.348 0

T e trachlorobipheny ls 4.377 4.377 1.171 0 Pentachlorobipheny ls 2.938 2.938 17.096 9.996 Hexachlorobipheny ls 0.238 0.238 1.286 1.078 Heptachlorobipheny ls 0.155 0.155 0.902 0 Octachlorobipheny ls 0.238 0.238 0.205 0 Nonachlorobipheny ls 0.155 0.155

- ­ - -
D ecachlorobipheny ls 0.155 0.155 0.117 0

a See Sectio n 3

. 3 f o r d e tails o n tested f acilities.

A P CD = A i r p o llu tio n co n t ro l d e v i ce

-- = N o i n fo r m a t i o n gi ve n



### 10-29

### 10.4.4. Tire Com bustion As discussed in Chapter 3, Section 3.6, tires ar e burned in a variety of facilities, including dedicated tire burners, cement kilns, industrial boilers, and pulp and pape r combustion facilities.
Emissions of PCB cong ener g r oups (but not i ndividual cong eners) were measured during stack testing of a tire incinerator (CARB

, 1991). Th e facility consisted of two ex cess air furnaces equipped with steam boilers to recover the energ y from the heat of combustion. Discarded whole
tires were fed to the incineration units at ra tes rang ing from 2,800 to 5,700 kg /hr during the three testing day s

. The furnaces were equipped to burn natural g a s as aux iliary fuel. The steam produced from the boilers drove electrical turb ine g e nerators that produced 14.4 meg a watts of electricity

. The facility was equipped with a dr y acid g a s scrubber and a fabric filter for the control of emissions prior to ex iting the stac k. Table 10-15 presents the cong ener g r oup (MCB
thr oug h DCB ) e mission f a c t or s f o r

this f a c ility

. The e mission f a c t or f

o r

the tota l of the te tr a

throug h heptachlorinated cong en er g r oups was about 1.2 μ g /kg tir e processed. B ecause these
da ta do not pr ovide PCB c ong e n e r

- spe c i f i c e mission f a c t or s, no e stima te s of e missions of diox inlike PCB s can be made. Tire combustion i s desi g n at ed as a C a t e g o ry E source.

Table 10-15. P C B congener group em i ssion f a ctors f o r a tire com bustor a



### C ongener group N u mber of det ect i ons Max i mum emission f a ctor (ng/kg) Mean emission f a ctor (ng/kg)

N o n d e tect set to d e tection limit Nondet ect set to z ero Monochlorobipheny ls 0

- ­ 0.04

- - Dichlorobipheny ls 1 34.8 11.7 11.6

T r ichlorobipheny ls 1 29.5 11.8 9.8

T etrachlorobipheny ls 0

- ­ 1 0

- - Pentachlorobipheny ls 2 2,724 1,092 1,092 Hexachlorobipheny ls 1 106.5 55.9 35.5 Heptachlorobipheny ls 1 298.6 107.7 99.5 Octachlorobipheny ls 0

- ­ 20.9

- - Nonachlorobipheny ls 0

- ­ 17.7

- - D ecachlorobipheny ls 0

- ­ 41.9

- ­

a T h ree s a m p les f o r each con g e n e r g r ou p.

-- = N o i n fo r m a t i o n gi ve n

S o u rce: C A R B (1991).



### 10-30

### 10.4.5. Cigarette Sm oking Using hig h-resolution mass spectrometry , Mats ueda et al. (1994) analy z ed tobacco from 20 brands of commercially ava ilable cig a rettes collected in 1992 from J a pan, the United States, Taiwan, China, the United King dom, Germany

, and Denmark for the PCB cong eners 77, 126,
and 169. Table 10-16 presents the results of the study

. However, no studies ex amining tobacco smoke for the presence of these cong eners have been reported. Thus, it is not known whether the
PCB s present in the tobacco are destroy e d or volatiliz ed during combustion or whether PCB s are formed during combustion. At least 1,200 tobacco constituents (e.g ., nicotine, n-paraffin, some terpenes) are transferred intact from the tobacco into the smoke stream by distillation in this area, and it is plausible that PCB s present in th e unburned tobacco would be subject to similar
distilla tion. Cig a rette consumption and the combustion processes operating dur ing cig a rette smoking are discussed in Chapter 5, Section 5.5. A pr e limina r y r oug h e stima te of pote n tia l e missions of diox in- like PCB s c a n be ma de using the f o llowing a ssumptions: ( a ) the a v e r a g e TEQ P 

### -W HO 98 

### content of seve n brands of U.S. cig a rettes reported by Ma tsueda et al. (1994), 0.64 pg /pack (0.032 pg /cig arette), is representative of cig a rettes smoked in the United States; (b) diox in-like PCB s are neither formed nor destroy e d, and the cong ener profile reporte d by Matsueda et al. (1994) is not altered during combustion of
ci g a ret t e s; and (c) al l di ox i n -l i k e P C Bs cont ri but i n g t o t h e TEQ are rel eased from t h e t obacco during smoking

. On the basis of these assump tions, the calculated annual emissions would be
0.018 g TEQ P 

### -W HO 98 

### , 0.016 g TEQ P 

### -W HO 98 

### , and 0.014 g TEQ P 

### -W HO 98 

### for reference y ears 1987, 1995, and 2000, respectively

. These estimates are assig n ed a confidence rating of D
because t h e em i ssi on fact or i s cl earl y not represent a t i v e of ci g a ret t e sm oke.

10.4.6. Sew age Sludge Incineration EPA (U.S. EPA, 1996g ) derived an emission factor of 5.4 μg PCB s /kg dry sewag e sludg e incinerated. This emission fact or was based on measurements conducted at five multiple-hearth
incinerators controlled with we t scrubbers. However, it is not known what fraction of the
emissions was diox in-like PCB s

. I n 1999, stack tests were conducted at a multip le-hearth incinerator in Ohio equipped
with a venturi scrubber and a th ree-tray imping e ment conditioni ng tower (U.S. EPA, 2000b). Of the four test runs conducted, the fi rst test run was aborte d and the results from the fourth test run

we r e de te r mine d to be sta tistic a l outlie r s ( p >0.05). The back-half CDD/ CDF concentrations for
test run 4 were 50 to 60% lower than back-half emission concentrations for test runs 2 and 3.
Because of t h e probl em s associ at ed wi t h t e st r un 4, t h e resul t s were not used t o cal cul a t e an

em i ssi on fact or for di ox i n -l i k e P C Bs. The averag e TEQ emission factor (e x c luding test run 4)

10-31Table 10-16.Dioxin-like PCB concentrations in cigarette tobacco in brands fromvarious countries (pg/pack)a



### 10-32CongenerIUPACnumberU.S.(avg. of7brands)Japan(avg. of6brands)UnitedKingdom(avg. of3brands)Taiwan(1brand)China(1brand)Denmark(1brand)Germany(1brand)3,3',4,4'-TCB77105.770.253133.912.621.739.33,4,4',5-TCB812,3,3',4,4'-PeCB1052,3,4,4',5-PeCB1142,3',4,4',5-PeCB1182',3,4,4',5-PeCB1233,3',4,4',5-PeCB1266.27.86.114.52.42.27.32,3,3',4,4',5-HxCB1562,3,3',4,4',5'-HxCB1572,3',4,4',5,5'-HxCB1673,3',4,4',5,5'-HxCB1690.90.90.92.40.40.51.62,2',3,3',4,4',5-HpCB1702,2',3,4,4',5,5'-HpCB1802,3,3',4,4',5,5'-HpCB189Total TEQP-WHO980.640.80.621.490.240.230.75aBlankcellsindicate that nomeasurementsofthese congenerswere made.Source:Matsueda etal. (1994).

### was 0.51 ng TEQ P 

### -W HO 98 

### /kg (see Table 10-17). This emi ssion factor was assig n ed a low confidence rating because it is based on limited survey s that are judg ed to be possibly nonrepresentative.

Table 10-17. Dioxin-like P C B concentratio ns in stack gas collected f r om a U.S

. sew age sl u d g e i n ci n erator

C ongener IU P A C

num ber Mean emission f a ctor (ng/kg)

Nondet ect set t o 1⁄2

detection limit N o ndetect set to z ero 3,3' ,4,4'

- T CB 77 92.37 92.37
2,3,3' ,4,4'

- P eCB 105 18 18
2,3,4,4' ,5- PeCB 114 2.56 2.56

2' ,3,4,4' ,5- PeCB 123 0.82 0.82
2,3' ,4,4' ,5- PeCB 118 38.65 38.65
3,3' ,4,4' ,5- PeCB 126 4.51 4.51
2,3,3' ,4,4' ,5- HxCB 156 4.25 4.25
2,3,3' ,4,4' ,5'

- H xCB 157 1.41 1.41
2,3' ,4,4' ,5,5'

- H xCB 167 2.55 2.55
3,3' ,4,4' ,5,5'

- H xCB 169 3.61 3.61
2,2' ,3,3' ,4,4' ,5- HpCB 170 7.19 7.19
2,2' ,3,4,4' ,5,5'

- H pCB 180 17.79 17.79
2,3,3' ,4,4' ,5,5'

- H pCB 189 0.6 0.6

Total TE Q P 

### -W H O 98 

### 0.51 0.51

S o u rce: U

. S

. EPA (2000b).



### Approx imately 0.865 million dry metric tons of sewag e sludg e were incinerated in 1988 (F ederal Reg i ster, 1993a), appr ox imately 2.11 million dry metric tons in 1995 (e-mail dated J uly 13, 1998, from K. Maw, Pacific Environmental Serv ices, to G. Schweer, Versar, I n c.), and an estimated 1.42 million dry me tric tons in 2000 (U.S. EPA, 1999b). Using the above estimated amounts of sewag e sludg e incinerated per y ear and the averag e TEQ emission factor of 0.51 ng TEQ P 

### -W HO 98 

### /kg

, the estimated annual releases of total PCB s to air were 0.44 g TEQ P 

### -W HO 98 

### in 1987, 1.1 g TEQ P 

### -W HO 98 

### in 1995, and 0.72 g TEQ P 

### -W HO 98 

### in 2000. These emissions were
assi g n ed a l o w confi d ence rat i n g (C at eg ory C ) because t h e em i ssi on fact or was g i ven a l o w

r a ting

.

10-33

### 10.4.7. Back yard Barrel Bu rn in g The l o w com bust i on t e m p erat ures and ox y g en-st a rved condi t i ons associ at ed wi t h
ba c k y a r d ba r r e l bur ning ma y r e sult in inc o mple te combustion and increased pollutant emissions (L emieux , 1997). EPA’s Control Technolog y Cent er, in cooperation with New York State’s departments of health and environmental conservation, conducted a study to ex amine,
characteriz e, and quantify emissions from th e simulated open burning of household waste materials in barrels (L emieux

, 1997). A representative waste to be burned was prepared on the basis of the ty pical percentag e s of various wa st e m a t e ri al s di sposed of by New York State residents (i.e., nonavid recy clers); haz a rdous wastes such as chemi cals, paints, and oils were not
included in the test waste. A variety of co mpounds, including diox in-like PCB s , were measured
in the e missions f r o m the simula te d ope n bur ni ng

. The measured TEQ emission factors for waste that had not been separated for recy cling purposes were 1.02 × 10 -2 

### μg TEQ P 

### -W HO 94 

### /kg
and 5.26 × 10 -3 

### μg TEQ P 

### -W HO 98 

### /kg wa ste bur ne d ( se e Ta ble 10- 18)

. The se limite d e missions
da ta we r e judg e d to be ina d e qua te f o r

e stima ting na tiona l e missions ( a Ca te g o r y E sour c e )

. The activity level for backy a rd barrel bur ning is discussed in Section 6.5.2.

10.4.8. P e troleum Ref i ning Catalyst Regeneration As discussed in Section 5.4, re g e neration of spent cataly s t used in cataly tic reforming to produce hig h -octane refo rmates is a potential source of CDD/CDF air emissions. I n 1998,
emissions from the caustic scrubber used to treat g a ses from the ex ternal cataly s t reg e neration unit of a refinery in Californi a were tested for CDDs/CDF s as well as PCB cong ener g r oups (CARB
, 1999) (see Chapter 5, Section 5.4 for details).
All P C B cong ener g r oups were detected in each of the three samples collected. The

averag e cong ener g r oup emission factors in units of nanog rams per barrel of reformer feed are presented in Table 10-19. The total PCB emissi on factor was 118 ng /barrel. This emission
factor assumes that emissions are proportional to reforming capacity ; emission factors may be
more related to the amount of coke burned, APCD equipment pr esent, and/or other process

pa r a me te r s

. Because em i ssi ons dat a are avai l a bl e for onl y one U.S

. pet r ol eum refi nery (whi ch
represent s l e ss t h an 1% of t h e cat al y t i c reform i n g capaci t y at U.S

. refi neri es), and because t h ese da ta do not pr ovide c ong e n e r

- spe c i f i c e mission f a c t or s, no na tiona l e stima te s of tota l PCB or diox in- like PCB e missions a r e be ing ma de a t this time

. This is a Ca te g o r y E sour c e

.

10-34

### Table 10-18. Dioxin-like P C B em issi on f actors f r om backyard barrel bur ning a

Congener IUP A C

num ber Em issio n f a c t o r s ( 

### : g/ k g)
T e s t 1 T es t 2 A verage 3,3' ,4,4'

- T C B 7 7 9 .3 15.2 12.3 3,4,4' ,5- T C B 81 2,3,3' ,4,4'

- PeC B 105 5.9 4 .9 5.4 2,3,4,4' ,5- P eC B 114 2,3' ,4,4'
, 5- PeC B 118 8.3 14.3 11.3
2' ,3,4,4'
, 5- PeC B 123 18.6 28.7 23.7 3,3' ,4,4'
, 5- PeC B 126 2,3,3' ,4,4'
, 5- H x C B 156 2,3,3' ,4,4'
, 5'

- H x C B 157 2,3' ,4,4'
, 5,5'

- H x C B 167 3,3' ,4,4'
, 5,5'

- H x C B 169 2,2' ,3,3'
, 4,4' ,5- H pC B 170 2,2' ,3,4,4'
, 5,5'

- H pC B 180 2,3,3' ,4,4'
, 5,5'

- H pC B 189

T o tal T E Q P -W H O 98 4.21e



### ! 03 6.31e



### ! 03 5.26e



### ! 03

a B l an k cells in dicate th at th e con g en er w as n o t detected in eith er of th e tw o du plicate s am p les

. S o u rce: L e m i eu x (1997).



### Table 10-19. P C B congener group em ission f a ctors f o r a petroleum catalytic

r e f or m ing unit a

Congener group Me a n concentration

(n g/d s cm ) (at 12% O 2 ) M e an em i s s i on rate ( lb/hr) M e an em i s s i on factor (l b / 1000 b b l ) M e an em i s s i on factor (ng/barrel)

Mon o ch l o robi ph en y l s 166 5.51e



### ! 08 7.11e



### ! 09 3.23e+00

D i ch l o robi ph en y l s 355 1.17e



### ! 07 1.52e



### ! 08 6.89e+00

T r i c h l orobi ph en y l s 743 2.45e



### ! 07 3.17e



### ! 08 1.44e+01

T e t rach l o robi ph en y l s 849 2.81e



### ! 07 3.62e



### ! 08 1.64e+01
Pen t ach l o robi ph en y l s 914 3.02e



### ! 07 3.88e



### ! 08 1.76e+01

H e x ach l o robi ph en y l s 780 2.57e



### ! 07 3.30e



### ! 08 1.50e+01

H e pt ach l o robi ph en y l s 1 ,430 4.73e



### ! 07 6.01e



### ! 08 2.73e+01
O c t ach l o robi ph en y l s 698 2.32e



### ! 07 2.95e



### ! 08 1.34e+01
N o n ach l o robi ph en y l s 179 5.99e



### ! 08 7.59e



### ! 09 3.44e+00
Decach lorobiph en y l s 41.3 1 .39e



### ! 08 1.76e



### ! 09 7.98e



### ! 01

T ot a l PC Bs 6,155.3 2.04e



### ! 06 2.61e



### ! 07 1.18e+02

a T h ree s a m p les an d th ree detection s f o r each con g e n e r g r ou p.
S o u rce: C A R B (1999).



### 10-35

### 10.5. NATURAL SOURCES
This section discusses biotransformation and photochemical tran sformation of other
PCB s

. Althoug h there is some evidence that th ese processes occur, the data were considered
insuf f i c i e n t f o r

de ve loping r e le a se e stima te s.

10.5.1. Biotransf orm ation of Other P C Bs
Studies show that under anaerobic conditi ons, biolog ically mediated reductive dechlorination to lower-chlorinated cong ener s, followed by slow anaerobic and/or aerobic biodeg r adation, is a major pathway for destruc tion of PCB s in the environment. Research reported to date and su mmariz e d below indicates that biode g r adation should result in a net
decrease rat h er t h an a net i n crease i n t h e envi ronm ent a l l o ad of di ox i n -l i k e P C Bs.
L a boratory studies (e.g ., B e dard et al ., 1986; Pardue et al., 1988; L a rsson and
L e mkemeier, 1989; Hickey , 1995; Schr einer et al., 1995) have reveal ed that more than two doz en
st rai n s of aerobi c bact eri a and fung i t h at are capabl e of deg r adi n g m o st P C B cong eners wi t h fi ve or fewer chlorines are widely dist ributed in the environment. Many of these org a nisms are of the

g e nus Pseudomonas or Al cal i g enes

. The major metabolic pathwa y involves addition of ox y g en at the 2,3-position by a diox y g enase enz y me, with subsequent dehy drog en ation to the catechol
fol l o wed by ri ng cl eavag e. S e veral bact eri a l st rains have been shown to possess a diox y g enase

enz y me that attacks the 3,4-position. Only a

f

e w str a ins ha ve de monstr a t e d the a b ility to de g r a d e he x a c h lor obiphe ny l ( H x C B ) and the hig h er-chlorinated bipheny ls. The rate of aerobic biodeg r adation decreases with increasing chlorination. The half-lives for bi odeg r adation of tetrachlo robipheny ls (TCB s) in
fresh surface wat e r and soi l are 7 t o 60+ da y s and 12 t o 30 day s , respect i v el y

. For pentachlorobipheny ls (PeCB s ) and the hig her-chlorinated PCB s , th e hal f-l i v es i n fresh surface

wat e r and soi l are l i k el y t o ex ceed 1 y ear. P C Bs wi t h al l or m o st chl o ri nes on one ri ng and P C Bs
with f e we r tha n two c h lor i ne s in the or tho positi on tend to deg r ade more rapidly

. F o r ex ample,
Gan and B e rthouex (1994) monitored over a 5-y r period the disappearance of PCB cong eners

a pplie d to soil with se wa g e sludg e. Three of t h e t e t r a- and pentachlorinated diox in-like PCB s (I UPAC Nos. 77, 105, and 118) followed a first- order disappearance model, with half-lives

rang ing from 43 to 69 months. A hex a -substitu ted cong ener (I UPAC No. 167) and a heptasubstituted cong ener (I UPAC No. 180) showed no sig nificant loss over the 5-y r period. Prior to the early 1990s, little investig ation focused on anaerobic microbial dechlorination or deg r adation of PCB s , even thoug h most PCB s eventually accumulate in anaerobic sediments (Abramowicz , 1990; Risatti, 1992). Environmental dechlorination of PCB s via losses of meta and para chlorines has been re ported in field studies for fresh wa te r , e stua r ine

, a nd ma r i ne anaerobic sediments, including those from th e Acushnet Estuary

, the Hudson River, the

10-36

### Sheboy g a n River, New B e dford Harbor, Escam bia B a y , W a ukeg a n Harbor, the Housatonic River, and W oods Pond (B rown et al., 1987; Rhee et al., 1989; Van Dort and B e dard, 1991;
Abramowicz , 1990; B e dard et al., 1995; B e dard and May

, 1996). The altered PCB cong ener distribution patterns found in these sediments (i .e., different patterns w ith increasing depth or
distance from known sources of PCB s ) have been interpreted as evidence that bacteria may
dechlorinate PCB s in anaerobic sediment. Reported results of la boratory studies confirm anaerobic deg r adation of PCB s

. Chen et al. (1988) found that “PCB -deg rading ” bacter ia from the Hudson River could sig nificantly deg r ade the MCB

, dichlorobiphey l (DiCB ) , a nd trichlorobipheny l (TrCB ) components of a 20 ppm Aroclor 1221 solution within 105 day s

. Thes e cong ener g r oups make up 95% of Aroclor
1221. No deg r adation of hig h er-c hlorinated cong eners (present at 30 ppb or less) was observed, and a separate 40-day ex pe r ime nt with TCB a l so showed no deg r adation. Rhee et al. (1989) reported deg r adation of mono- to penta-substituted PCB s in
contaminated Hudson River se diments held under anaerobic c onditions in the laboratory (N 2 

### atmosphere) for 6 months at 25°C. Amendment of the te st sa mple s with biphe ny l r e sulte d in

g r eat er l o ss of P C Bs. No si g n i f i cant decreases i n t h e concent r at i ons of t h e hi g h er-chl ori n at ed

cong eners (more than five chlorines) were obs erved. No evidence of deg r adation was observed
in sa mple s inc uba te d in CO 2 

### /H 2 

### atmospheres. Abramowicz (1990) hy pothesiz e d that this result could be an indication that, in the absence of CO 2 

### , a selection is imposed favoring org a nisms capable of deg r ading PCB s to obtain CO 2 

### a nd/or low- mole c u la r

- w e i g h t me ta bolite s a s e l e c t r o n recept o rs. Risatti (1992) ex amined the de g r adation of PCB s at vary ing concentrations (10,000 ppm, 1,500 ppm, and 500 ppm) in the laboratory with “PCB -deg rading ” bacteria from W a ukeg a n Harbor. After nine months of incubation at 22°C, the 500 ppm and 1,500 ppm samples showed no chang e in PCB cong ener distributions or concen trations, thus indicating a lack of deg r adation. Sig nificant deg r adation was observed in the 10,000 ppm sediment, with at least 20 cong eners

r a ng ing f r o m the Tr CB s thr oug h the Pe CB s showing de c r e a se s. Quensen et al. (1988) also demonstrated that microorg a nisms from PCB

- contaminated sediments (Hudson River) dechlorinated most TrCB s throug h Hx CB s in Aroclor 1242 under anaerobic laboratory conditions. The Aroclor 1242 used to spike the sediment contained predominantly TrCB s and TCB s (85 mol percent). Three con centrations of the Aroclor, corresponding to 14, 140, and 700 ppm on a sed iment dry

- weig ht ba sis, were used.
Dechlorination was most ex tensive at the 700 ppm te st concentration: 53% of the total chlorine was removed in 16 weeks, and the proportion of TCB s throug h Hx CB s decreased from 42 to 4%. Much less deg r adation was observed in the 140 ppm sediment, and no obs ervable deg r adation was found in the 14ppm sediment. These results and those of Risatti (1992) sug g e st that the

10-37

### org a nism(s) responsible for this dechlorination ma y require relatively hig h levels of PCB s as a terminal electron acceptor to maintain a g r owing population. Quensen et al. (1990) reported that dechlo rination of 500 ppm spike concentrations of Aroclor 1242, 1248, 1254, and 1260 by microorg a nism s from PCB

- contaminated sediments in
the Hudson River and Silver L a ke occurred prima r ily a t the me ta a nd para positions; orthosubstituted MCB s and DiCB s increased in con centration. Sig n ificant decreases over the incubation period (up to 50 weeks) were re ported for diox in-like PCB s 156, 167, 170, 180, and
189. Of the four diox in-like TCB s and PeCB s de tected in the Aroclor spikes (I UPAC Nos. 77, 105, 114, and 118), all decreased sig nificantly in concentration, with the possible ex ception of
PeCB 114 in the Aroclor 1260-spiked sediment. Nies and Vog e l (1990) reporte d similar results with Hudson River sediment s incubated anaerobically and enriched with acetone, metha nol, or g l ucose. Approx imately 300 ppm of Aroclor 1242 (31 mol percent TCB s , 7 mol per cent PeCB s, and 1 mol percent Hx CB s) were added to the sediments prior to incubation for 22 weeks under an N 2 

### atmosphere. Sig nificant dechlorination was observed, primar ily at the meta and para pos itions on the hig h er-chlorinated

cong eners (TCB s, PeCB s, and Hx CB s), resulting in the accumu lation of lower-chlorinated, primarily ortho-substitu ted mono- throug h tri- substituted cong eners. No sig nificant
dechlorination was observed in the control sa mples (samples containing no added org a nic
chem i cal subst r at e and sam p l e s t h at were aut o cl aved).
B e dard and May (1996) also reported similar finding s in th e sediments of Woods Pond,
which was believed to be contaminated with Aroclor 1260. Si g n ificant decreases in the sediment
concentrations of PCB s 118, 156, 170, and 180 (relative to their c oncentrations in Aroclor 1260)
were observed. No i n creases or decreases we re reported for the other diox in-like PCB s

. B e dard et al. (1995) demonstrated that it is possible to stimulate substantial microbial dechlorination of the hig hly chlorinated PCB mix tu re Aroclor 1260 in situ with a sing le addition of 2,6-dibromobipheny l. The investig ators added 365 g of 2,6-di bromobipheny l to 6-ft-diameter submerg e d caissons containing 400 kg sediment (d ry weig ht) and monitored the chang e in PCB

cong ener concentrations for a period of one y ear. At the end of the observation period, the
MCB s throug h Hx CB s decreased by 74% in the t op of the sediment and by 69% in the bottom. The averag e number of chlorines per molecule dropped 21%, from 5.83 to 4.61, with the larg est reduction observed in meta chlori nes (54% reduction) followed by para chl o ri nes (6%). The dechlorination stimulated by 2,6- dibromobipheny l selectively rem oved meta-chlorines positioned

nex t to other chlorines.
The fi ndi ng s of t h ese l a t t e r st udi es are si g n i f i cant , because rem oval of m e t a and para
chlorines from the diox in-like P C B s should redu ce their tox i city and bioaccumulative potential

10-38

### and al so l ead t o t h e form at i on of l o wer-chl ori n at ed cong eners t h at are m o re am enabl e t o aerobi c biodeg r adation.
Van Dort and B e dard (1991) re ported the first ex perimental demonstration of biolog ically
mediated ortho-dechlorination of a PCB and st oichiometric conversion of that PCB cong ener (2,3,5,6-TCB ) to lower-chlorinated forms. I n that study , 2,3,5,6-TC B was incubated under
anaerobic conditions with unacclimated metha nog enic pond sediment for 37 weeks, with reported dechlorination to 2,5-DiCB (21 %); 2,6-DiCB (63%); and 2,3,6-TrCB (16%).

10.5.2. P h otochem i cal Transf orm ation of Other P C Bs Photoly sis and photo-ox idation may be major pathway s for de struction of PCB s in the

e nvir onme n t. Re se a r c h r e por te d to da te a nd summa r i ze d be low indic a t e s tha t or tho- substitute d chlorines are more susceptible to photoly s is than are meta- and para-subs tituted cong eners; thus, photoly tic formation of more tox i c diox in-like PC B s may occur. Ox idation by hy drox y l radicals,
howe v e r , a ppa r e ntly oc c u r s pr e f e r e n tia lly a t the me ta a nd pa r a positions, r e sulting in a ne t
decrease rat h er t h an a net i n crease i n t h e envi ronm ent a l l o ad of di ox i n -l i k e P C Bs. On the basis of the data available in 1983, L e ifer et al. (1983) conc luded that all PCB s, especi al l y t h e hi g h er-chl ori n at ed cong eners and t hose that contain two or more chlorines in the ortho position, photodechlorinate. I n g e neral, as the chlorine content increases, the photoly s is
rate increases. More recently , L e pine et al. ( 1992) ex posed dilute solutions (4 ppm) of Aroclor 1254 in cy clohex a ne to sunlig ht for 55 day s in December and J a nuary

. Cong ener-specific analy s is indicated that the amounts of many hi g h er-chlorinated cong en ers, particularlymonoor tho- substitute d c ong e ne r s, de c r e a se d, whe r e a s those of some lowe r

- c hlor ina t e d c ong e ne r s increased. The results for the diox in-like PC B s indicated a 43.5% d ecrease in the amount of
PeCB 114, a 73.5% decrease in the amount of Hx CB 156, and a 24.4% decrease in the amount of
Hx CB 157. However, TCB 77 and PeCB 126 (the mo st tox i c of the diox in-like PCB cong eners),
which were not detected in unirradiated Aroclor 1254, represen ted 2.5% and 0.43%, respectively

, of

the ir r a dia t e d mix tur e

. W ith reg a rd to photo-ox idation, Atkinson (1987) and L e ifer et al. (1983), using assumed

st eady

- st at e at m o spheri c OH concent r at i ons and m easured ox idation rate constants for bipheny l
and MCB , estimated atmospheric d ecay rates and half-lives for g a s-phase PCB s

. Atmospheric
transformation was estimate d to proceed most rapidly for thos e PCB cong eners containing either
a small number of chlorines or t hose containing all or most of the chlorines on one ring

. Kwok et al. (1995) ex tended the work of Atkinson (1987) by measuring the OH radical reaction rate constants for 2,2' -, 3,3' -, and 3,5-DiCB

. These reac tion rate constants, wh en taken tog e ther with Atkinson’s measurements for bipheny l and MCB and the estimation method described in Atkinson (1991), were used to g e nerate more relia ble estimates of the g a s-phase OH radical

10-39

### reaction rate constants for the di ox i n -l i k e P C Bs. The persi s t e nce of t h e P C B cong eners i n creased with increasing deg r ee of chlorination. Table 10- 20 presents these estimate d rate constants and the corresponding tropospheric lifetimes and half-lives.

Table 10-20. Estim ated tropospheric ha lf -lives of dioxin-like P C Bs w i th resp ect to gas-p h a se reacti o n w i th th e O H rad i cal

C ongener group D i ox in -lik e congener E s timated OH reaction rate constant

(10 -1 2 

### cm 3 

### / molecule-sec) E s timated tropospheric lif etime (days) a 

### E s timated tropospheric h a lf -lif e (days) a



### T e trachlorobipheny ls 3,3' ,4,4'

- T CB 3,4,4' ,5- T C B 0.583 0.71 20 17 14 12
Pentachloropheny ls 2,3,3' ,4,4'

- P eCB 2,3,4,4' ,5- PeCB 2,3' ,4,4' ,5- PeCB 2' ,3,4,4' ,5- PeCB 3,3' ,4,4' ,5- PeCB 0.299 0.383 0.299 0.482 0.395 40 31 40 25 30 28 22 28 17 21
Hexachlorobipheny ls 2,3,3' ,4,4' ,5- HxCB 2,3,3' ,4,4' ,5'

- H xCB 2,3' ,4,4' ,5,5'

- H xCB 3,3' ,4,4' ,5,5'

- H xCB 0.183 0.214 0.214 0.266 65 56 56 45 45 39 39 31
Heptachlorobipheny ls 2,2' ,3,3' ,4,4' ,5- HpCB 2,2' ,3,4,4' ,5,5'

- H pCB 2,3,3' ,4,4' ,5,5'

- H pCB 0.099 0.099 0.125 121 121

95 84 84 66

a Ca l c ul a t e d usi ng a 2 4

- hr

, se a s o n a l

, a nnua l

, a n d gl o b a l t r opos ph eri c av erag e O H radi cal con cen t r at i o n of 9.7 × 10 5 m o lecu le/cm 3 (Pri n n et al ., 1995).

S o u rce: T e l e ph on e con v e rs at i o n on N o v e m b er 16, 1995, bet w een R o g e r A t k i n s on , A i r Pol l u t i o n R e s earch C e n t er, U n i v ers i t y of C a l i f orn i a, an d G reg S c h w eer, V e rs ar, In c. (bas ed on A t k i n s on , 1991, an d K w ok et

al ., 1995).



### Sedlak and Andren (1991) dem onstrated in laboratory studies that OH radicals g e nerated
with F e nton’s reag ent rapidly ox idiz ed PCB s (2-MCB and the DiCB s throug h PeCB s present in Aroclor 1242) in aqueous solutions. The results i ndicated that the reacti on occurs via addition of a hy drox y l g r oup to one nonhalog e na ted site; reaction rates are inve rsely related to the deg r ee of chlorination of the bipheny l. The results also indi cat ed t h at m e t a and para si t e s are m o re react i v e than ortho sites due to stearic hi ndrance effect s. On t h e basi s of t h ei r ki net i c m easurem ent s and reported steady

- state aqueous sy stem OH concentrations or es timates of OH ra dical production

r a te s, the a u thor s e stima te d e nvir onme n ta l ha lf

- live s f o r

dissolve d PCB s ( MCB thr oug h

10-40

### octachlorobipheny l) in fresh su rface water and in cloud water to be 4 to 11 day s and 0.1 to 10 day s , respectively

.

10.6. P A ST USE OF COMMERCIAL P C Bs
An estimated total of 1.5 milli on metric tons of PCB s were produced worldwide (DeVoog t and B r inkman, 1989). Slig htly more than one-third of these PCB s (568,000 metric tons) were used in the United States (Versar, I n c., 1976). Althoug h the focus of this section is on past uses of PCB s within the United States, it is necessary to note that the use and disposal of
PCB s in many countries, coupled with the persis tent nature of PCB s , have resulted in their movement and presence throug hout the g l obal e nvironment. The ultimate sink of most PCB s

r e le a se d to the e nvir onme n t is a qua tic se dime nts. Cur r e ntly , howe v e r , la r g e qua ntitie s of PCB s

a r e e stima te d to be c i r c ula ting be twe e n the a i r a nd wa te r e nvir onme n ts or a r e pr e se n t in la ndf ills and dumps, some of which may o ffer t h e pot ent i a l for re-rel ease of P C Bs i n t o t h e ai r. Tanabe (1988) presented a g l obal mass bala nce for PCB s that indicated th at as of 1985, 20% of the total
P C Bs produced were present i n seawat er, wher eas only 11% were present in sediments (see Table 10-21). Nearly two-thirds of total g l obal PCB production wa s estimated by Tanabe to still
be in use in e l e c t r i c a l e quipme n t or to be pr e se n t in la ndf ills a nd dumps. As discussed in Section 10.2, an estimated 568,000 me tric tons of PCB s were sold in the United States between 1930 and 1975 (Versar, I n c., 1976). Table 10-22 presents annual estimates of domestic sales by y ear for each Aroclor from 1957 to 1974. Estimates of PCB usag e in the United States by usag e categ ory from 1930 to 1975 are presented in Table 10-23. Prior to voluntary restrictions by Monsanto Corporati on in 1972 on sales for uses other than “closed
el ect ri cal sy st em s,” approx i m a t e l y 13% of t h e P C B s were used in “semi-closed applications,” and 26% were used in “open-end applications.” Most of the us ag e for semi-closed and open-end applications occurred between 1960 and 1972 (Versar, I n c., 1976). Table 10-24 presents estimates of the amounts of individual Aroclors that were directly released to the environment (w ater, air, or soil) between 1930 and 1974. B ecause detailed usag e data were not available for the period 1930 to 1957, Versar, I n c. (1976) assumed that the usag e pattern for this period followed the averag e pa ttern for the period of 1957 to 1959. The basic

a ssumption use d by Ve r sa r in de r i ving the se e stima te s wa s tha t PCB s we r e r e le a se d on the or de r of 5% of those used in closed el ect ri cal sy st em s, 60% of those used in semi-closed applications, and 25% of those used for plasticiz ers and that 90% of PCB s used fo r miscellaneous industrial

use s ha d e sc a p e d. The r e lia bility of the se r e le a se e stima te s wa s a ssume d to be ±30%

. Versar, I nc. (1976) also estimated that 132,000 me tric tons of PCB s were landfilled. This total comprised 50,000 metric tons from capac itor and transformer production wastes, 36,000 metric tons from disposal of obsolete electrical equipment, and 46,000 metric tons from disposal

10-41

### Table 10-21. Estim a ted P C B loads in the global enviro nm ent as of 1985

E n vironment P C B load (metric ton s ) P ercentage of P C B load P ercentage of

w orl d product i on

T e rrestrial and coastal Ai r Riv er and lak e water Seaw ater Soi l Sedim e nt Biota To ta l 500 3,500 2,400 2,400 130,000

4,300 143,100 0.13 0.94 0.64 0.64 35

1.1 39

O p en ocean Ai r Seaw ater Sedim e nt Biota To ta l 790 230,000 110 270 231,170 0.21 61

0.03 0.07 61

Total load in env i ronm ent D eg r aded and incinerated Land- stock e d a 

### World production 374,000 43,000 783,000 1,200,000 b 

### 100 31 4 65 100

a Still in u s e in electrical eq u i p m en t an d o t h e r p r o d u cts, an d d e p o s ited in lan d f ills an d d u m p s. b T h i s v a l u e i s f rom T a n a be (1988). D e V oog t an d Bri n k m an (1989) es t i m at ed w o rl dw i d e produ ct i o n t o h a v e been 1,500,000 m e t r i c t o n s

.

S o u rce: T a n a be (1988).



### of material from open-end app lications. An estimated additi onal 14,000 metric tons of PCB s , althoug h still “in service” in various semi-cl osed and open-end app lications in 1976, were
ultima te ly de stine d f o r

disposa l in la ndf ills. An estimated 3,702 kg of TEQ P 

### -W HO 98 

### were released directly to the U.S. environment between 1930 and 1977 (see Table 10-25). These estimates are based on the Aroclor release

e stima te s pr e se n te d in Ta ble 10- 22 a nd the me a n TEQ P 

### -W HO 98 

### concentrations in Aroclors presented in Table 10-3.

10-42Table 10-22.Estimated domesticsales ofaroclors and releases ofPCBs, 1957–1974 (metric tons)



### 10-43YearEstimateddomestic salesTotalPCBreleasesAroclor1016Aroclor1221Aroclor1232Aroclor1242Aroclor1248Aroclor1254Aroclor1260Aroclor1262Aroclor12681957010898,2658072,0233,44114014,649195807514,7371,1613,0352,713833311,820195901151096,1681,5353,0643,0021634614,2021960047708,2541,2822,7613,3251488615,97319610431098,9931,8252,8552,9661647217,02719620641029,3681,5712,8692,9911969517,2561963016468,3962,2742,6813,45918812917,29719640270610,6922,3762,8493,8712028620,35219650167314,3032,5243,5092,6452538923,49319660239717,9432,2753,1912,66534812926,797196702001119,5292,1343,0372,91138113028,33319680624120,3452,2204,0332,38232712729,5371969023012420,6342,5634,4552,01332313630,4781970067011822,0391,8475,6342,21846415033,14019711,5121,005789,970972,1147820015,55819729,4817803303661,5851380011,978197310,6731602,81203,61800017,11919749,9592602,81502,80500015,605TOTAL31,6253,413924195,59326,85756,11841,5223,2541,308360,614% of Total8.80.90.354.27.415.611.50.90.4100Source:Versar, Inc. (1976).

### Table 10-23. Estim ated U.S. usage of P C Bs by use category, 1930–1975

Use class U se category Am ount used (1,000 metric ton s) P ercent of total usage R e liab ility of estimate (% )

C l osed electrical

sy stem s Capacitors 286 50.3 ± 2 0

T r ansform ers 152 26.8 ± 2 0

Sem i

- c l o sed

applications H eat transfer fluids 9 1.6 ± 10

H y draulics and lubricants 36 6.3 ± 10

Open- e nd

applications Plasticiz er uses 52 9.2 ± 1 5 Carbonless copy
paper 20 3.5 ± 5

Misc. industrial 1 2 2.1 ± 1 5

Petroleum additiv es 1 < 1 ± 5 0

T O T A L 568 100

S o u r ce: V e rs ar, In c. (1976).



### 10-44

### Tab l e 10-24. Estim a ted d i rect releases of Aroclors to th e U.S

. en viron m en t, 1930–1974 a 

### (m etri c ton s )

Yea r E stimated environmental releases

Tot a l P C B releases Aroclor

1016 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor 1260

1930–56 0 8,486 2,447 2,269 1,614 14,816

1957 0 903 319 307 423 1,952

1958 0 649 483 416 355 1,903

1959 0 1,042 724 518 507 2,791

1960 0 1,340 556 449 540 2,885

1961 0 1,852 792 587 611 3,842

1962 0 1,811 659 554 571 3,595

1963 0 1,655 935 529 682 3,801

1964 0 2,085 980 555 755 4,375

1965 0 2,689 1,025 660 497 4,871

1966 0 3,180 876 566 472 5,094

1967 0 3,376 814 525 504 5,219

1968 0 3,533 853 733 433 5,552

1969 0 4,165 993 985 452 6,595

1970 0 4,569 697 1,168 474 6,908

1971 76 1,466 51 325 121 2,039

1972 474 22 0 104 9 609

1973 534 141 0 181 0 856

1974 498 141 0 140 0 779

T O T A L 1,582 43,105 13,204 11,571 9,020 78,482



### % of Total 2.0 54.9 16.8 14.7 11.5 100

a Does n o t in clu d e an addition a l 132,000 m e tric ton s es tim ated to h av e been lan d f illed du rin g th is period.

S o u r ce: V e rs ar, In c. (1976).



### 10-45

### Table 10-25. Estim ated releases of dioxin-like P C B TEQs to the U.S. environm ent, 1930–1977

Aroclor P ercent of U.S. s a l e s a 

### (1957–1974) E s timated P C B releases (1930–1974) b 

### (metric tons) E s timated mean TEQ P 

### ­ WHO 98 

### concentration c 

### (mg/k g) E s timated t o t a l TEQ P 

### ­ WHO 98 

### released (k g)

1016 12.88 1,582 d d



### 1221 0.96

- ­ 0.328

- ­
1232 0.24

- ­ - ­ - ­
1242 51.76 43,103 7.47 322

1248 6.76 13,205 16.87 223

1254 15.73 11,572 125.94 1,457

1260 10.61 9,019 188.45 1,700

1262 0.83

- ­ - ­ - ­
1268 0.33

- ­ - ­ - ­
T O T A L 3,702

a Sales du rin g th e period 1957–1974 con s titu ted 63% of all P C B s a les du ri n g 1930–1977. Sales data f o r i n di v i du al A rocl o rs are n o t av ai l a bl e f o r y ears pri o r t o 1957; h o w e v e r, s a l e s of A rocl o rs 1221, 1232, 1262, an d 1268 w e re m i n o r ev en pri o r t o 1957.

b F r om T a bl e 10- 24.

c From T a ble 10- 3 (as s u m e s n o n d etect v a lu es are zero).

d D a t a are av ai l a bl e f o r on l y a f e w s a m p l e s of A rocl o r 1016 w h ere on l y t w o di ox i n

- l i k e PC B con g e n e rs w e re detected. T h e total T E Q P -W H O 98 released is less th an 0

. 0 1 k g

.

- - = In dicates th at releas e es tim ates w ere n o t m ade becau s e of relativ ely low u s ag e am ou n t s

S o u r ce: V e rs ar, In c. (1976).



### 10-46

### 11. RESERVOIR SOURCES OF CDDs/CDF s AND DIOXIN-LIK E P C Bs

National CDD/CDF source invent ories have been conducted in severa l nations, including the United King dom (U.K.), the Netherlands, Germ any , Aust ri a, and S w eden, t o charact eri z e emissions from various source categ ories and es timate annual CDD/CDF e missions to air (and

some time s othe r me dia )

. The se inve ntor ie s f o c u se d ma inly on e missions f r o m pr ima r y sour c e s (i .e., em i ssi ons from t h e si t e or process where t h e C DDs/ C DFs are form ed). The authors of these inventories (Rappe, 1991; Harrad and J ones, 1992; B r emmer et al., 1994; Thomas and Spiro, 1995, 1996; Eduljee and Dy ke, 1996; J ones and Alcock, 1996; DuarteDavidson et al., 1997) indicated th at the annual estimates of releas es to air provided in these inventories may

, for several reasons, be unde restimates of actual e missions. F i rst, on an empirical basis, estimates of the amounts of CDDs/CDF s deposited annually from the atmosphere were g r eater than the estimates of annual CDD/CDF emissions to the atmosphere. Second, because the emission test data were limited, the inventories may have underestimated releases from known sources or may not have identified all primary sources. Third, the investig ators were not able to reliably quantify emissions fro m potential reservoir (secondary ) sources, including volatiliz ation of CDDs/CDF s from PCP-treated wood, volatilization from soil,

a nd r e suspe n sion of soil pa r tic le s. Re la tive l y little r e se a r c h of e ithe r a

monitor i ng or a the o r e tic a l na tur e ha s be e n pe r f o r m e d to ide n tif y

reservoir sources and to qua ntif y

the ma g n itude of current or potential future rel eases from t h ese sources. This chapter presents backg r ound inform ation on the major reservoir sources of
CDDs/CDF s and PCB s , including the potential ma g nitude (mass) of CDDs/CDF s and PCB s in each reservoir, the chemical/phy sical mechanisms responsible fo r releases of these compounds, and estimates of potential annual releases from each reservoir, if such estimates are feasible.

11.1. P O TENTIAL RESERVOIRS Chapters 2 throug h 10 of this document discuss both known and suspected sources of releases of newly formed diox in-like compounds to the environment in the United States. Once

r e le a se d into the ope n e nvir onme n t, CDDs, CDF s, a nd PCB s pa r tition to a i r , soils, wa te r , sedi m e nt s, and bi ot a accordi n g t o bot h t h e nat u re of t h e rel ease and t h e cont am i n ant ’ s chem i c al and phy sical properties.
For t h i s anal y s i s , reservoi rs are defi ned as m a t e ri al s or pl aces t h at cont ai n previ ousl y formed CDDs/CDF s or diox in-like PCB s and have the potential for redistributing and circulating these compounds into the environment. Potentia l reservoirs include so ils, sediments, biota, water, and some anthropog enic ma terials. The atmosphere is not considered a reservoir, but serves as a medium for transporting and dist ributing CDDs and CDF s over larg e g e og raphical

11-1

### areas. At m o spheri c deposi t i on of C DDs/ C DFs t o t h e eart h ’s surface resul t s i n an ex chang e of
C DDs/ C DFs from t h e at m o sphere t o surface wat e rs and soi l s

. Diox in-like compounds are sequestered by a reservoir only un til phy sical processes

c a u se the se c onta mina n ts to be c o me r e le a se d into the ope n e nvir onme n t ove r a

de f i ne d time a n d

space. W h en this occurs, reservoirs become s ources of diox in-like compounds in the circulating

e nvir onme n t. Re se r voir sour c e s a r e not inc l ude d in the qua ntita tive inve ntor y of c onte m por a r y sources because they do not involve orig inal releases but rather th e re-circulation of past releases from anthropog enic sources. They can, however , contribute to human ex posure and, therefore, are important to consider.
The rate of movement from one environmental medium to a not her i s t e rm ed “fl u x , ” and
it r e f e r s to the dir e c tion a nd ma g n itude of f

l ow a nd e x c h a n g e ove r a

r e f e r e nc e time pe r i od a n d

space. Fi g u re 11-1 present s a concept u al di ag ram of fl ux and ex chang e of di ox i n -l i k e compounds to multiple environmenta l compartments such as soils, water, air, sediments, and
biota. This dy namic sy stem consists of flux es in and out of the atmo sphere as well as other

ex chang e s bet w een reservoi rs and t h e at m o sphere ( r e c a ll tha t the a tmosphe r e is not f o r m a lly
considered an environmental rese rvoir, rather it is a transport media for diox in-like compounds).
Movement of diox in-like compounds between medi a can be induced by the phy sical processes of
volatiliz ation, wet and dr y atmospheric particle and vapor deposition, adsorption, erosion and runoff, resuspension of soils into air, and resuspension of se dime nts into wa te r

.

F i gure 11-1. F l uxes am ong en vi ron m en tal reservoi rs.

11-2

### 11.2. CHARACTERIZ ATION OF RESERVOIR SOURCES
Thi s sect i on i s org a ni z e d accordi n g t o each pri n ci pl e reservoi r, i

. e., soi l

, wat e r, sedi m e nt , and bi ot a. The di scussi on of each envi ronm ent a l reservoi r provi des i n form at i on i n t h ree part s: (1) the potential amount or mass of diox in-like co mpounds contained within the reservoir, (2) the chemical/phy sical mechanisms re sponsible for releases of thes e compounds back into the open and circulating environment, a nd (3) estimates of poten tial annual releases from the reservoir if such estimates are feasible, g i ven the available state of knowledg e. Althoug h anthropog enic structures (e.g ., PCP-treated fe nceposts, telephone poles) are poten tial reservoir sources, they are
not di scussed here because t h ey are covered i n C h apt e r 8 (t he m o st det a i l e d di scussi on i s on PCP, Section 8.3.8).

11.2.1. Soil
11.2.1.1. Potential Mass of Dioxin-Like Com pounds Present
I n estimating burdens for the U.K., Harrad a nd J ones (1992) and Duarte-Davidson et al. (1997) assumed that the majority of CDDs/CDF s in soil is present in the top 5 cm (ex cept possibly in cropland, where they may be present at g r eater depths due to plowing ) and that the soil density is 1,000 kg /m 3



### . Coupling these assumptions with the rural and urban U.S. surface areas and TEQ concentrations y i el ded soil burden estimates of 1,350 kg TEQ DF 

### -W HO 98 

### (1,530 kg I

- TEQ DF 

### ) in rural soils and 220 kg TEQ DF 

### -W HO 98 

### (250 kg I

- TEQ DF 

### ) in urban soils in the
Unite d Sta t e s. The se c a l c u la tions a r e not de f i nitive

, a nd only se r v e to indic a t e a ppr ox ima te amounts of CDDs/CDF s that may be contained in soils in rural and urban areas of the United
S t at es. Hig h er concentrations of CDDs/CDF s for backg r ound urban and rural soils may be present in soils underlain by municipal and i ndustrial waste and in soils at contaminated
industrial sites. Hig her concentr ations may also be present in th e soils of areas that have been

tr e a t e d with pe stic ide s c onta mina t e d with CDDs/CDF s. The la c k of c o mpr e he nsive da ta on CDD/CDF c onc e n tr a tions in the se soils, a s we ll a s the la c k of da ta on the ma ss of the se soils nationwide, precludes estimating tota l national soil burdens of CDDs /CDF s. B ecause of the lack
of

da ta , it is not possible to e stima te c u r r e nt soil bur de ns of CDDs/CDF s a ssoc i a t e d with pa st
pe stic ide use ; howe v e r , e stima te s c a n be ma de of the tota l ma ss of CDD/CDF TEQs tha t ha ve been applied to soil from past use of the pes ticides 2,4-dichlorophenox y acetic acid (2,4-D) and 2,4,5-trichlorophenox y ace tic acid (2,4,5-T). 2,4-D (and its salts and esters) are widely used as post-emerg e nce herbicides in

ag ricultural and nonag r icultural setting s in the Un ited States for control of broadleaf weeds and
brush. Commercial produc tion of 2,4-D in the United States started in 1944 (Esposito et al., 1980), and it has been in larg e-scale, larg e-vol ume commercial use for many y ears (U.S. EPA, 1975). I n terms of annual volume, 2,4-D ranks am ong the top 10 pesticides used in the United

11-3

### States (U.S. EPA, 1994d, 1997e). Table 11-1 pr esents a compilation of domestic production, sales, and usag e volumes for 2,4-D and its salts and esters.

Table 11-1. Historical production, sa les, and usage of2,4-dichlorophenoxyacetic acid (2,4-D) (m etric tons) a

Yea r 2,4-D , aci d 2,4-D, es ters and s a lts (as rep orted ) b

P r o duct io n

vol u m e Sa les vol u m e D o m e s ti c u s age/ disa ppea r a n ce P r o duct io n vol u m e Sa les vol u m e 2000 — — 23,600–28,100 c — — 1998/ 99 — — 23,600–28,100 d
— — 1996/ 97 — — 23,600–27,200 d
— — 1994/ 95 — — 21,800–26,300 e — —

1993 — — 16,800–20,400 f
— — 1992 — — 16,800–20,400 f
— — 1991 — — 18,100–29,500 g — — 1990 — — 18,100–29,500 g — — 1989 — — 18,100–29,500 h
— — 1988 — — 23,600–30,400 i
— — 1987 — — 23,600–30,400 j
— — 1986 — — - ­ 8,618 12,150
1985 — — - ­ — 0
1984 — — - ­ — 0
1983 — — - ­ 7,702 8,234
1982 — — - ­ 8,762 8,400
1981 5,859 3,275

- ­ 8,987 8,002
1980 6,164 3,137

- ­ 11,313 11,147
1979 5,763 6,187

- ­ 11,874 13,453
1978 — — - ­ 8,958 9,256
1977 — — - ­ 12,552 10,196
1976 — — 17,418 k 10,913 7,813
1975 — — - ­ 16,134 13,414
1974 — — - ­ 6,558 5,991
1973 — — - ­ 13,400 13,698
1972 24,948 b
— 21,772 k 10,192 10,899
1971 — 5,619 15,700 k
— 18,654
1970 19,766 7,159

- ­ — 19,920
1969 21,354 8,521

- ­ 25,854 20,891
1968 35,953 10,352

- ­ 42,690 30,164
1967 34,990 15,432

- ­ 37,988 29,300
1966 30,927 12,710 28,985 l 32,895 25,075



### 11-4

### Table 11-1. Historical production, sa les, and usage of2,4-dichlorophenoxyacetic acid (2,4-D) (m etric tons) a 

### ( c ont i nue d)

Yea r 2,4-D , aci d 2,4-D, es ters and s a lts (as rep orted ) b

P r o duct io n

vol u m e Sa les vol u m e D o m e s ti c u s age/ disa ppea r a n ce P r o duct io n vol u m e Sa les vol u m e 1965 28,721 11,816 22,906 l 28,740 21,454
1964 24,364 11,343 19,958 l 24,660 18,263
1963 21,007 9,446 15,059 l 20,178 16,333
1962 19,503 7,716 16,284 l 16,831 13,075
1961 19,682 7,591 14,107 l 16,683 12,533
1960 16,413 — 14,107 l 15,436 13,661
1959 13,282 7,240 15,468 l 12,438 7,070
1958 14,036 6,234 9,662 l 11,295 5,649
1957 15,536 6,871

- ­ 12,392 7,125
1956 13,079 6,465

- ­ 9,635 7,294
1955 15,656 5,924

- ­ 13,390 8,121
1954 — 4,838

- ­ 10,268 6,886
1953 11,761 — - ­ 10,733 8,855
1952 13,933 — - ­ 11,358 9,637
1951 — — - ­ — — 1950 6,421 4,301

- ­ 5,274 3,219
1949 6,852 2,991

- ­ 5,829 3,211
1948 9,929 4,152

- ­ 2,458 1,598
1947 2,553 2,320

- ­ 1,468 1,108
1946 2,479 2,330

- ­ 515 81
1945 416 286

- ­ — —

a A l l v a l u es are f rom U S IT C (1946–1994) u n l es s f oot n o t e d ot h e rw i s e. b N o dat a w e re report e d f o r dom es t i c u s ag e/ di s a ppearan ce of 2,4- D es t e rs an d s a l t s

.
c S o u rce: U

. S

. EPA (1991c).

d S o u rce: U

. S

. EPA (2000a).

e S o u rce: U

. S

. EPA (1997e).

f S o u rce: U

. S

. EPA (1994d).

g S o u rce: U

. S

. EPA (1992g ).

h S o u rce: U

. S

. EPA (1991d).

i S o u rce: U

. S

. EPA (1990c). j S o u rce: U

. S

. EPA (1988d).

k S o u rce: U

. S

. EPA (1975).

l S o u rce: U S D A (1970).

— = N o t report e d t o av oi d di s c l o s u re of propri e t a ry dat a

-- = N o i n fo r m a t i o n gi ve n



### 11-5

### As described in Section 8.3.8, CDDs/CDF s were detected in several formulations of 2,4­ D and its derivatives during analy s es performed to comply with EPA’s 1987 Data Call-I n (DCI )
for CDDs/CDF s. Althoug h the an aly tical results of these test s indicated that CDDs/CDF s were seldom above the reg u latory limits of quantification (L OQs) es tablished by EPA for the DCI

, several reg i strants detected a nd quantified CDDs/CDF s at lower L OQs. The results of these
tests are summariz e d in Table 8-28 (Chapter 8). The averag e TEQ in these tests was 1.1 : 

### g TEQ DF 

### -W HO 98 

### /kg (0.7 : 

### g I

- TEQ DF 

### /kg )

. Schecter et al. (1997) reported similar c oncentrations in 2,4-D samples manufactured in Eur ope and Russia; lower levels we re observed in U.S. products.
S o m e of t h e resul t s from S c hect er et al

. are presented in Table 8-34 (Chapter 8).
I f

it is assumed that the EPA DCI results are ty pical of CDD/CDF levels in 2,4-D pesticides over the past 20 y r and that the aver ag e annual use of these pesticides in the United States has been approx imately 25,000 metric tons, then the estimated CDD/CDF TEQ released to the environment from 2,4-D use during the period of 1975 to 1995 was 550 g TEQ DF 

### -W HO 98 

### (350 g I

- TEQ DF 

### ). 2,4,5-T was used in the United States for a vari ety of herbicidal app lications until the late 1970s to early 1980s. The major use of 2,4,5-T (a bout 41% of annual usag e) was for control of woody and herbaceous weed pests on rig h ts-of-w ay

. The other major herbicidal uses were forestry (28% of usag e), rang eland (20% of us ag e), and pasture (5% of usag e). Uses of 2,4,5-T for home or recreation areas and for lakes, ponds , and ditches were su spended by EPA in 1970; rig h ts-of-way , forestry , and pasture uses were suspended by EPA in 1979; and all uses were
canceled in 1983. Table 11-2 presents a compilation of domestic production, sales, and usag e volumes for 2,4,5-T and its salts and esters. As shown in Table 11-2, production a nd use of 2,4,5-T g e nerally increased each y ear following its introducti on in the 1940s until the late 1960s. Production, sales, and usag e information for the 1970s are g e nerally not available but are reported to have steadily declined during that decade (Fed eral Reg i ster, 1979; Esposito et al., 1980).
Some information is available on the 2,3,7,8-TCDD content of 2,4,5-T, but little
information is available on the concentrati ons of the other 2,3,7,8-substituted CDD/CDF s that

may have been present. P limmer (1980) reported that 2,3,7,8-TCDD concentrations as hig h as 70,000 : 

### g / kg were detected in 2,4,5-T during the late 1950s. I n a study of 42 samples of 2,4,5-T manufactured before 1970, W ools on et al. (1972) found 500 to 10,000 : 

### g / kg of TCDDs in 7 samples, and another 13 sa mples contained 10,000 to 100,000 : 

### g / kg of TCDDs. Hx CDDs were found in 4 samples at le vels between 500 and 10,000 : 

### g / kg and in 1 sample at a concentration

ex ceeding 10,000 : 

### g / kg but less than 100,000 : 

### g / kg

. The de te c tion limit in the study wa s 500

: 

### g /kg

.

11-6

### Table 11-2. Historical production, sa les, and usage of2,4,5-trichlorophenoxyacetic acid (2,4,5-T) (m etric tons) a

Yea r 2,4,5-T 2,4,5-T , es ters an d s a l t s (as rep orted ) b

P r o duct io n

vol u m e Sa les vol u m e D o m e s ti c u s age/ disa ppea r a n ce P r o duct io n vol u m e Sa les vol u m e
1993 — — - ­ — — 1992 — — - ­ — — 1991 — — - ­ — — 1990 — — - ­ — —

1989 — — - ­ — —
1988 — — - ­ — — 1987 — — - ­ — — 1986 — — - ­ — — 1985 — — - ­ — — 1984 — — - ­ — — 1983 — — - ­ — — 1982 — — - ­ — — 1981 — — - ­ — — 1980 — — 900 c — — 1979 3,200–4,100 d
— - ­ — — 1978 — — 3,200 e — — 1977 — — 4,100 d
— — 1976 — — - ­ — — 1975 — — 3,200 e — — 1974 — — 900 f
— — 1973 — — - ­ — — 1972 — — - ­ — — 1971 — — 694 g — 1 ,675

1970 — — 3,200 e 5,595 3,272

1969 2,268 — - ­ 5,273 2,576

1968 7,951 1,329 ~7,000 h, i 19,297 15,021

1967 6,601 757 ~7,000 h, i 12,333 11,657

1966 7,026 2,312 7,756 h 8,191 4,553

1965 5,262 — 3,266 h 6,131 5,977

1964 5,186 1,691 4,037 h 5,880 3,128

1963 4,123 1,928 3,266 h 4,543 2,585

1962 3,796 1,021 3,674 h 4,765 2,543



### 11-7

### Table 11-2. Historical production, sa les, and usage of2,4,5-trichlorophenoxyacetic acid (2,4,5-T) (m etric tons) a 

### ( c ont i nue d)

Yea r 2,4,5-T 2,4,5-T , es ters an d s a l t s (as rep orted ) b

P r o duct io n

vol u m e Sa les vol u m e D o m e s ti c u s age/ disa ppea r a n ce P r o duct io n vol u m e Sa les vol u m e
1961 3,134 1,196 2,449 h 3,536 2,372

1960 2,874 — 2,676 h 3,594 1,891

1959 2,516 1,039 2,495 h 3,644 1,843

1958 1,668 692 1,724 h 2,372 1,151

1957 2,419 — - ­ 3,098 1,337

1956 2,345 816

- ­ 3,196 1,473

1955 1,327 662 1,300 e 1,720 1,077

1954 1,223 639

- ­ 1,761 615

1953 2,395 — - ­ 2,443 1,817

1952 1,583 — - ­ 1,423 569

1951 — — 1,100 e — — 1950 852 297

- ­ — — 1949 — — - ­ — — 1948 — — - ­ — — 1947 — — - ­ — — 1946 — — - ­ — — 1945 — — - ­ — —

a A l l v a l u es are f rom U S IT C (1946–1994) u n l es s f oot n o t e d ot h e rw i s e. b N o dat a w e re report e d f o r dom es t i c u s ag e/ di s a ppearan ce of 2,4,5- T es t e rs an d s a l t s

.
c S o u r ce: Es pos i t o et al . (1980).

d S o u rce: F e deral R e g i s t er (1979).

e S o u rce: T h om as an d S p i ro (1995).

f S o u rce: U

. S

. EPA (1977).

g S o u r ce: U S D A (1971); ref l ect s f a rm u s ag e on l y

. h Sou r ce: USDA (1970); v alu es in clu d e m ilitary s h ipm en t s abroad.

i S o u rce: K earn e y et al . (1973) report s s l i g h t l y l o w e r dom es t i c con s u m pt i o n f o r t h e y ears 1967 an d 1968 t h an f o r 1966.

— = N o t report e d t o av oi d di s c l o s u re of propri e t a ry dat a

-- = N o i n fo r m a t i o n gi ve n



### The averag e 2,3,7,8-TCDD concentration in 200 samples of Ag ent Orang e , a defoliant containing about a 50/50 mix ture of the buty l es ters of 2,4,5-T and 2,4-D that was used by the
U.S. Air F o rce in Vietnam, was 1,910 : 

### g / kg (Kearney et al., 1973). Of the 200 samples, 64 (32%) contained more than 500 : 

### g / kg of 2,3,7,8-TCDD, with the hi g h est concentration reported to be 47,000 : 

### g / kg

. Storherr et al. (1971) reporte d detecting 2,3,7,8-TCDD at concentrations

11-8

### rang ing from 100 to 55,000 : 

### g / kg in five samples of 2,4,5-T. Kearney et al. (1973) reported that production samples of 2,4,5-T obtai ned from the three principa l 2,4,5-T manufacturers in 1971 contained 2,3,7,8-TCDD at levels of <100 : 

### g / kg , 100 : 

### g / kg , and 2,300 : 

### g / kg

. A 1975 survey of 10 lots of a commercial formulation containing 2,4,5-T showed 2,3,7,8­ TCDD concentrations rang ing from 10 to 40 : 

### g / kg (L ewert, 1976). Analy s es by EPA of 16 technical-g rade 2,4,5-T samples from five different manufacturers revealed 2,3,7,8-TCDD contents rang ing from <10 to 25 : 

### g / kg (F ederal Reg i ster, 1979). Schecter et al. (1997) reported the analy tical results of one sample of 2,4,5- T purchased from Sig m a Chemical Co. (product number T-5785, lot number 16H3625). The results, presented in Table 11-3, indicate a total TEQ DF 

### -W HO 98 

### concentration of 3.26 : 

### g / kg (2.88 : 

### g I

- TEQ DF 

### /kg )

. B ecause of the wide variability (three orde rs of mag nitude) in the limited available information on the 2,3,7,8-TCDD content of 2,4,5-T (particularly the 2,4,5-T used in the 1950s) and incomplete information on domestic usag e, it is difficult to reliably estimate the amount of 2,3,7,8-TCDD that was released to the U.S. envi ronment as a result of 2,4,5-T use. A very
uncertain estimate can be ma de using the following assumptions: (1) averag e annual consumption during the 1950s, 1960s, and 1970s was 2,000, 4,000, and 1,500 metric tons/y r, respectively ; and (2) the averag e 2,3,7,8-TCDD c oncentration in 2,4,5-T used over these three decades was 10,000 : 

### g / kg in the 1950s, 4,000 : 

### g / kg in the 1960s, and 100 : 

### g / kg in the 1970s.
B a sed on these assumptions, the very uncerta in estimate of 2,3,7,8-TCDD input from 2,4,5-T use over the period of 1950 to 1979 was 36,000 g

. Another contributing source to the soil reser voir is CDD/CDF in sewag e sludg e applied to land (i.e., surface disposal or land fa rming ) , estimated to have been 75 g TEQ DF 

### -W HO 98 

### (103

g I

- TEQ DF 

### ) in 1995 (see Section 8.4.1 for details). I f th is same amount of TEQ had been applied each y ear during the period of 1975 to 1995, the total amount applied would have been 1,500 g TEQ DF 

### -W HO 98 

### (2,000 g I

- TEQ DF 

### ).

11.2.1.2. Mechanism s Responsible for Releases from Surface Soils The atmospheric deposition of diox in-like compounds is believed to be the primary means whereby surface soils, in g e neral, beco me contaminated with diox in-like compounds.
CDDs/CDF s a nd PCB s a r e hig h ly lipid soluble a nd ha ve low vola tility , a nd the y te nd to pa r tition
to soil r a the r tha n into a i r or wa te r

. Onc e pr esent in or on soils, phy sical/chemical and biolog ical mechanisms (photoly s is and biodeg r adation) can slowly alter the composition and amount of compound present. Studies indi cate that the diox in-like com pounds (particularly the hig h erc h lor i na te d CDDs/CDF s) e x hibit little downwa r d mobility to lowe r soil de pths a f te r the y a r e deposited in or on soil (Puri et al. 1989; F r eeman and Schroy , 1985; Oraz io et al., 1992; Paustenbach et al., 1992). Howeve r, re-mobiliz ation of the conta minants to the atmosphere is possible thr oug h vola tiliza tion a nd r e suspe n sion of soil pa r tic le s.

11-9

### T a b l e 11-3. CDD/CDF con cen tration s ( : 

### g/ k g ) i n recen t sam p l e of 2,4,5-trichloro-phenoxya cetic acid (2,4,5-T)

Congener/congener group 2,4,5-T sam p le
2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-Hx CDD 1,2,3,6,7,8-Hx CDD 1,2,3,7,8,9-Hx CDD 1,2,3,4,6,7,8-HpCDD OC DD 1.69 0.412 0.465 2.28 1.35 18.1 33.9
2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-Hx CDF 1,2,3,6,7,8-Hx CDF 1,2,3,7,8,9-Hx CDF 2,3,4,6,7,8-Hx CDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OC DF 0.087 0.102 0.183 1.72 0.356 ND (0.012) 0.126 2.9 0.103 3.01 Total 2,3,7,8-CDD a 

### Total 2,3,7,8-CDF a 

### Total I

- TEQ DF a 

### Total TEQ DF 

### -W HO 98 a 

### 58.2 8.59 2.88 3.05

Tota l TCDD Tota l Pe CDD Tota l Hx CDD Tota l HpCDD Tota l OCDD Tota l TCDF Tota l Pe CDF Tota l Hx CDF Tota l HpCDF Tota l OCDF -­

-­

-­

-­

-­

-­

-­

-­

-­

-­
Tota l CDD/CDF

- ­

a C alcu l ated as s u m i n g n o n d etect v alu es w ere zero.

ND = No t d e tected (v alu e in p a ren t h e sis is th e d e tectio n lim it)

-- = N o i n fo r m a t i o n gi ve n

S o u r ce: S c h ect er et al . (1997).



### 11-10

### Young (1983) conducted field studies on th e persistence and movement of 2,3,7,8-TCDD from 1973 to 1979 on a military test area that ha d been aerially spray e d with 73,000 kg of 2,4,5-T from 1962 to 1970. TCDD levels of 10 to 1,500 ng /kg were found in the top 15 cm of soil 14 y r after the last appli cation of herbicide at the site

. Althoug h actual data were not available on the amount of 2,3,7,8-TCDD orig inally applied as a contamin ant of the 2,4,5-T, best
estimates indicated that less than 1% of th e applied 2,3,7,8-TCDD remained in the soil after 14 y r

. Young sug g e sted that photodeg r adation at the time of and imme diately after aerial application was responsible for most of the di sappearance; however, once incorporated into the soil, the data indicated a half-life of 10 to 12 y r

. Similarly , Paustenbach et al. (1992) concluded that the half-life of 2,3,7,8-TCDD in soils at the surface mig ht be 9 to 15 y r and the half-life below the surface could be 25 to 100 y r

. Ay ris and Harrad (1997) studied the mechanisms affecting volatiliz ati on flux es of several
PCB cong eners (PCB 28, 52, 101, 138, and 180) from soil and found positive correlations
between flux and soil temperature, soil moisture content, and so il PCB concentration. F or PCB s , secondary releases from soils (primarily via volatiliz ation) are belie ved to currently ex ceed primary emissions in the U.K. (Harner et al ., 1995; J ones and Alcock, 1996). L ee et al. (1998)

qua ntif ie d PCB s in a i r sa mple s ta ken every 6 hr over a 7-day peri od in the summe r a t a r u r a l site in Eng l and and found a strong correlation between air temperature and PCB cong ener concentrations. The concentrations followed a cl ear diurnal cy cle, thus providing some evidence
tha t r a pid, te mpe r a t ur e

- c ontr o lle d soil- to- a ir e x c h a n g e of PCB s influences air concentrations and enables reg i onal/g lobal scale cy cling of these compounds.
CDDs/CDF s and PCB s sorbed to soil and ur ban dust particles can also be moved from
the terrestrial environment to the aquatic environment throug h contaminated storm water runoff
and surface erosi on of cont am i n at ed soi l s

. R e sul t s of recent research i ndi cat e t h at , for at l east some water bodies, soil erosion a nd storm water runoff can be an important way of transporting
CDDs/CDFs into the surface water. This is especially true for water bodies lacking nonpoint
sources of diox in-like compounds. Smith et al . (1995) analy z ed CDD/CDF concentrations in sediment cores, air, precipitati on, soil, and storm water runoff in an effort to determine the contributing sources of these compounds to the lower Hudson River. The mass balance estimates developed from these da ta for 1990 to 1993 are as follows: stormwater runoff entering tributaries (76% of total CDD/ CDF input), anthropog enic wastes (19%), atmospheric deposition (4%), and shoreline erosion (less than 1%). The authors projected the percent contribution of these same sources for 1970 as anthropog enic wast es (70%), stormwater runoff into tributaries (15%), atmospheric deposition (15 %), and shoreline erosion (0.1%). Studies conducted by Paustenbach et al. (1996) , Mathur et al. (1997) and F i sher et al. (1999) discerned the relative concen trations of CDDs and CDF s in storm water. Paustenbach et al. and Mathur et al. reported that stormwater runoff from 15 sites in the San F r ancisco area

11-11

### contained CDD/CDF TEQ at levels rang ing from 0.01 to 65 pg I

- TEQ DF 

### /L ; most sa mple s contained less than 15 pg I

- TEQ DF 

### /L

. The sites differed widely in la nd use ; the hig h e st le ve ls
measured were obtained from an urban but nonindus trializ ed area. A distinct variability was noted in the results obtained at the same samp ling location during different rain events. The

pr of ile s of CDDs/CDF s in the ur ba n stor mwa t e r sa mple s we r e simila r , pa r tic ula r ly in sa mple s collected at the onset of rain events. Stow e (1996) reported similar finding s from analy s es of

se dime nts f r o m thr e e stor mwa t e r ba sins c o lle c ting r unof f f

r o m a milita r y ba se , a c ity str e e t , a n d

pa r k ing lots.
F i sher et al. (1999) reported that urban r unoff samples from eig ht sites (15 samples) in
the Santa Monica B a y watershed contained CDD/CDF TEQ at le vels rang ing from 0.7 to 53 pg
I

- TEQ DF 

### /L (all but one sample were in the rang e of 0.7 to 10 pg I

- TEQ DF 

### /L )

. The sa mple s we r e collected in 1988/1989 from continuously flowin g storm drains during both dry and storm periods. The mean concentration meas ured during storm events, 18 pg I

- TEQ DF 

### /L , was hig her
than concentration observed during dry periods, 1 pg I

- TEQ DF 

### /L

. Atmospheric deposition of CDDs and CDF s to lakes and the wate rshed area of water bodies is another important mean s of contaminating bo ttom sediments. F o r ex ample, L e beuf et al. (1996) analy z ed sediment cores from differe nt locations in the lower St. L a wrence River Estuary and the Gulf of St. L a wrence. Th e cong ener g r oup profile s found in the samples indicated that the input of C DDs/CDF s was primarily from the a tmosphere. Comparison of the
C DD/ C D F concent r at i ons i n sedi m e nt s col l ect ed from areas where sedi m e nt accum u l a t i on i s due pri m a ri l y t o fl uvi al t r ansport wi t h sedi m e nt s from areas where sedi m e nt accum u l a t i on i s due

pr ima r ily to dir e c t a tmosphe ric deposition onto the water indi cates that the contribution of
CDDs/CDF s f r o m dir e c t a tmos pheric deposition represents le ss than 35% of the sediment
burden. Thus, the primary source of CDDs/CDF s is emissions to the atmosphere upwind of the

e stua r y tha t a r e de posite d within the wa te r she d and subsequently tr ansported downstream by
fluvial waters.

11.2.1.3. Estim ate d Annual Re le ase s f r

om Soil to Wate r Nonpoint sources of CDDs/CDF s to waterw ay s include stormwater runoff from urban

a r e a s a nd soil e r osion in r u r a l a r e a s dur ing stor ms. Appr oa c h e s f o r

e stima ting na tiona l loa d ing s
to wa te r f

o r

both of the se sour c e s a r e de sc r i be d be low. The e stima te de r i ve d f o r

the pote n tia l annual national loading of CDDs/C DF s in urban runoff to waterway s is uncertain, but it sug g e sts that the loading may be comparable to the c ontribution from known industrial point sources (at
l east 20 g I

- TEQ DF 

### in 1995). Similarly , the estimate de rived for the potential annual national
loa d ing of CDDs/CDF s in r u r a l e r ode d soils to waterway s is uncertain, but it has a strong er

a n a l y tic a l ba se tha n doe s the ur ba n r unof f e stima te

. This loa d ing e stima te , howe v e r , is sig nificantly hig her than the contri bution from known industrial point sources.

11-12

### U r ban r unoff. F e w data on CDD/CDF concentra tions in urban runoff have been reported. The most recent and la rg est data sets were reported in studies conducted in the S a n F r ancisco B a y and Santa Monica B a y reg i ons (Mat hur et al., 1997; F i sher et al., 1999). These studies found a wide rang e of CDD/CDF levels in samples of stormwat er runoff from 23 sites,

vary ing from 0.01 to 83 pg I

- TEQ DF 

### /L

. The wide va r i a b ility a nd limite d g e og r a phic c ove r a g e of
the se da ta pr e c l ude de r i va tion of a

na tiona l e missions e stima te a t this time

. Howe ve r , by ma king

a

numbe r of a ssumptions, a pr e limina r y e stima te of the pote n tia l CDD/CDF ma g n itude f r o m this
source can be made.
I n order to estimate the amount of rainfall in urbaniz e d ar eas of the conterminous United
S t at es, a Geog raphi c I n form at i on S y st em (GI S ) anal y s i s was perform ed t o det e rm i n e t h e t o t a l area of every U.S

. Census urbaniz e d area and th e 30-y r annual averag e rainfall for each of those areas and to calculate the product of the total areas of urbaniz e d areas with the annual averag e rainfall (L ockheed Martin Co rp., 1998). This approach y i elds an estimate of 1.9 × 10 14 

### L / yr

. I f it is assumed that urban runoff in the United States averag es 1 pg TEQ DF 

### -W HO 98 

### /L (1 pg I

TEQ DF 

### /L ) (i.e., approx imately the midpoint of the rang e reported by Mathur et al., 1997, and
F i sher et al., 1999), this source c ould contribute a total of 190 g TEQ DF 

### -W HO 98 

### or I

- TEQ DF 

### /y r to U.S. wa te r w a y s. No da ta we r e a v a ila ble to ma ke simila r e stima te s f o r

PCB s. A similar analy s is was conducted using histor ical precipitation data from the National Oceanic and Atmospheric Administration (NOAA, 2004) and metropolitan/ urban area statistics
from the 1990 and 2000 census. The 30-y ear a nnual averag e rainfall for each state was calculated for 1987, 1995, and 2000. An approx imati on of the urban area for each state was estimated by summing the acreag e for each metr opolitan area identified in the 1990 census. Assuming that the amount of land classified as urban did not chang e sig nificantly from 1987 to 1990, the urban areas for each state in 1990 were assumed to be equal to those in 1987. Similarly

, an approx imation for urban area for each state was estimated by summing the urban

area acreag e available from the 2000 census. An approx imation of the 1995 urban area for each State was estimated by taking the averag e of the 1990 and 2000 estimates. Multiply ing the 30­

y ear averag e rainfall by the urban area for each state and summing the results provides an
estimated amount of urban runoff for the conter minous United States. The urban runoff was
1.24 × 10 14



### , 1.33 × 10 14 

### , and 1.42 × 10 14 

### L / y ear for 1987, 1995, and 2000, respectively

. Apply i ng the emission factors g e nerated a bove, urban runoff contributed 124, 133, and 142 g I TEQ DF 

### or TEQ DF 

### -W HO 98 

### to U.S. waterway s in 1987, 1995, and 2000, respectively

. These numbers are in ag reement with the estimate developed using L o ckh eed Martin Corp. (1998)
data.
Rur a l soil e r o sion. Using acreag e and erosion factor s for cropland provided in the 2001
Annual National Resources I nventory (USDA, 2003), 1.36, 1.07, 0.96, and 0.91 billion metric tons of soil and rill erosion were g e nerated in 1987, 1992, 1997, and 2001, respectively

. ­

11-13

### L i kewise, using acreag e data for rang eland fro m USDA (2003) and a soil and rill erosion factor of 4.2 tons/acre/y r (USDA, 1995), approx imately 1.55 billi on metric tons of soil and rill erosion

were g e nerated in 1987, 1992, 1997, and 2001. F o r pur poses of estimating values for reference

y ears 1995 and 2000, it was assumed that the 1995 er osion estimate was the averag e of soil and
rill erosion estimates developed for 1992 and 1997, and that the 2001 numbers approx imated those g e nerated in 2000. The total amount of er oded soil entering waterway s was g r eater than

t h i s val u e, because t h i s val u e di d not i n cl ude soi l erosi on from const r uct i on areas, forest s, and other non-croplands and non-rang elands.
The data summariz e d in U.S. EPA (2000c) sug g e st that ty pical concentrations of
CDDs/CDF s in soils in rural areas is about 2.8 ng TEQ DF 

### -W HO 98 

### /kg

. I t is not known how well this estimate represents erode d soil from cropland and rang eland. I f these soils contain an

averag e of 1 ng TEQ DF 

### /kg (i.e., a lower value than the b ackg r ound value for all ty pes of rural soil), they would have contributed 2,900, 2,600, and 2,500 g TEQ DF 

### -W HO 98 

### to the nation’s waterway s in 1987, 1995, and 2000, respectively

. Gi ven the uncertainties in both the amount of

e r ode d soil a nd diox in le ve ls, the se e stima te s a r e c onside r e d pr e limina r y ( i .e ., Ca te g o r y D)

. As
with ur ba n r unof f

, no da ta we r e a v a ila ble to ma ke simila r e stima te s f o r

PCB s.

11.2.1.4

. Estim ate d Annual Re le ase s f r

om Soil to Air No quantitative estimates of th e mass of diox in-like compounds that may be released to the atmosphere annually from U. S. soils have been published in the literature and none were developed for this report. As noted above, the vapor flux of these compounds from soil to air is dependent on the soil and air c oncentrations of diox in-like compounds and the temperature, moisture content, and org a nic carbon content of the soil. Most of these parameters are not
characteriz ed well enoug h for the United States as a whole to enable a reliable estimate to be

ma de a t pr e s e n t. Pa r tic le f l ux is dependent on many factors, including wind speed, veg e tative

c ove r , a c tivity le ve l, pa r tic le size , soil ty pe /c onditions, moistur e c onte n t, a nd pa r tic le de nsity

. Throug h use of models and various assumpti ons, Kao and Venkatarama n (1995) estimated the
fraction of ambient air CDD/CDF concentrations in the upper mid western section of the United
Sta t e s tha t ma y be the r e sult of a tmosphe r i c r e

- e ntr a inme nt of soil pa r tic le s. Simila r l y , thr oug h use of models and various assumptions, J one s and Alcock (1996) and Harner et al. (1995)
reached tentative conclusions about the relative importance of volatiliz ation of diox in-like compounds from soils in the U.K. Modeling re-entrainment of soil to the atmosphere was conducted by Kao and Venkataraman (1995). Their mode l incorporated information on particle si zes, deposition

ve loc itie s, a nd c onc e n tr a tions of CDDs/CDF s in soils. Sma lle r pa r tic ula t e s, with me dia n diameters rang ing from about 0.01 : 

### m to 0.3 : 

### m, are primarily formed from combustion sources when hot vapors condense and th roug h accumulation of secondary reaction products on smaller

11-14

### nuclei. Particle s at the upper end of this siz e rang e will deposit to the g r ound in several day s

. L a rg e or coarse particles, havi ng median diameters of about 8 : 

### m, are g e nerated from windblown dust, sea spray

, and mechanically g e ne rated particles. CDDs/CDF s absorbed onto
re-entrained soil would be included in this la r g e r pa r tic le size

. The se la r g e r pa r tic le s ha ve a lifetime in the atmosphere from a few to many hours.
The f r a c tion of a m bie n t a i r c onc e n tr a tion of CDDs/CDF s tha t r e sults f r o m soil

re-ent rai n m e nt was est a b lished on the basis of the contribution of crustal sources to the ambient
aerosol. Data on ty pical crustal so il concentrations in air (15 to 50 : 

### g/ m 3 

### for rural areas and 5 t o 25 : 

### g/ m 3 

### for urban areas) were combined with data on the averag e concentrations of
CDDs/CDF s in soils (73 ng /kg for rural, 2,075 ng /kg for urban, and 8,314 ng /kg for industrial soils) published by B i rming ham (1990) for Ontari o, Canada, and several U. S. midwestern states.
This a n a l y sis e stima te d the c onc e n tr a tions of CDDs/CDF s in the a m bie n t a e r osol tha t or ig ina t e from soils to be 1 × 10 -3 

### to 4 × 10 -3 

### pg /m 3 

### in rural areas and 0.01 to 0.05 pg /m 3 

### in urban areas. These part i c ul at e di ox i n concent r at i ons were com p ared wi t h averag e t o t a l part i c ul at e di ox i n levels of 1.36 pg /m 3 

### in Eitz er and Hites (1989) to arrive at the conclu sion that soil re-entrainment could account for only 1 to 4% of the particulate diox ins in the atmosphere in urban areas and
0.1 to 0.3% of those in rural re g i ons (Kao and Venkataraman, 1995).
This information on the siz e distribution of ambient aerosols and relative CDD/CDF

c onc e n tr a tions in dif f

e r e nt pa r tic le size f r a c tions wa s inte g r a t e d with pa r tic le size de position

ve loc itie s to e stima te the r e la tive c ontr i bution to the tota l ma ss de position f l ux f o r

sma ll a n d larg e particle siz e s. Even t houg h re-entrained soil may constitu te only a small fraction of the

at m o spheri c l e vel s of C DDs/ C DFs, t h e cont ri but i on of di ox i n s i n re-ent rai n ed surface soi l t o t h e total deposition flux could be sig nificant becau se coarse particles do minate in dry deposition. Soil re-entrainment could possibly account for as much as 70 to 90% of the total dry deposition
of CDDs/CDF s in urban areas and 20 to 40% in rural reg i ons (Kao and Venkataraman, 1995). Two approaches were used by J ones a nd Alcock (1996) to assess the potential sig nificance of CDD/CDF volatiliz ation from soils: the fug acity quotient concept and a simple equilibrium partitioning model. The fug acity quotient model compares the fug acity (the tendency of a chemical to escape from a phase ) of individual CDD/CDF compounds in different
environmental media to determine the tendency for these co mpounds to accumulate in particular environmental compartments (McL achlan, 1996)

. F ug a cities for individual compounds, by

me dia

, we r e e stima te d by J one s a nd Alc o c k on the ba sis of phy sic a l/c he mic a l pr ope r tie s of the compounds as well as the concentrations in the me dia. I n this instance, fug acity quotients were calculated for air and soil by dividing each co mpound’s fug acity for air by that of soil. Quotients near 1 indicate equilibrium conditions be tween media; values g r eater than 1 represent

a

te nde nc y f

o r

f

l ux ( vola tiliza tion) f r o m soil to a i r , a nd va lue s le ss tha n 1 indic a t e a ne t f l ux to the soil f r o m the a i r

. The e quilibr i um pa r titioning mode l use d by J one s a nd Alc o c k pr e d ic ts the

11-15

### max imum (possible “worst case”) flux of CDDs /CDF s f r o m soil to the a tmosphe r e

. Air pha se

to- soil pa r tition c o e f f i c i e n ts we r e c a l c u la te d using the r a tios of soil a nd a i r f

u g a c ity c a p a c itie s. Equilibr i um a i r c onc e n tr a tions we r e the n c a l c u la te d using ty pic a l U.K. soil c onc e n tr a tions f o r both ur ba n a nd r u r a l se tting s. F r om the fug acity quotient model, J ones a nd Alcock (1996) concluded that the lowerc h lor i na te d CDDs/CDF s ma y be c l ose to soil- a i r e quilibr i um in the U.K., whe r e a s f o r

othe r
cong eners, soi l i s a si nk rat h er t h an a source t o the atmosphere. The authors reported that the equilibrium partitioning model pr edicted that 0.15 kg I

- TEQ vola tiliz es annually from soil in the
U.K. However, they discounted this estimate a nd concluded that soil vol atiliz ation is unlikely to be a sig nificant contributor to emissions. Th e likelihood that these estimates were hig h was

a ttr ibute d to the f a c t tha t a ssumptions we r e ma de tha t the c onc e n tr a tions of CDDs/CDF s in a i r

we r e ze r o a nd the mode l doe s not c onside r the r e sista n c e of CDDs/CDF s to vola tilize f r o m soil. Harner et al. (1995) developed a model to predict the long -t erm fate of PCB s in soils,
with e m pha sis on soil- to- a ir e x c h a n g e s. Using da ta on levels of PCB s in a i r , soil, a nd ve g e ta tion
in the U.K., the inve stig a t or s de ve lope d a ma ss ba la nc e mode l to simula te the f a te of PCB s in
U.K. soils from 1935 to 1994. Specifically , monito ring data and phy sica l/chemical property data were compiled to calculate fug acities for PCB cong eners 28, 52, 138, and 153. The model was
desi g n ed t o provi de an order-of-m ag ni t ude l e vel of accuracy , due i n part t o t h e i nherent variability in the input data. The mass balance equations in the model included a bell-shaped
function for rates of emissions of PCB s , with the max imum emission rate occurring in 1967.
F r om the se e missions r a te s, f l ux e s be twe e n a i r a nd soil ove r se ve r a l de c a d e s we r e e stima te d.
Table 11-4 summariz e s the calculated flux es.

Table 11-4. P C B 138 f l uxes predicted by Harner et al. (1995)

Ye ar C o n cen tra tio n in a ir (p g /m 3 

### ) Fugac i t y in a ir ( Pas c a l s × 10 -9 

### ) Fugac i t y in so il ( Pas c a l s × 10 -9 

### ) C o n cen tra tio n in so il (n g /g ) N e t f lu x /d irectio n
1950 4 0 .24 1 .1

- ­ a i r 6 s o i l ( 444 k g / y r )

1965 280 1.5 12

- ­ a i r 6 s o i l ( 1 ,000 k g / y r )

1975

- ­ - ­ 16

- ­ 1980 49

- ­ - ­ - ­ s o i l 6 a i r ( 820 k g / y r )

1994 6

- ­ 8 .3

- ­ s o i l 6 a i r ( 700 k g / y r )

-- = N o i n fo r m a t i o n gi ve n



### During the 1960s and 1970s, levels of total P C B s in U.K. soils reached averag e levels of

approx imately 300 : 

### g / kg as a result of atmospheric depos ition. B ecause of restrictions on P C B

11-16

### use duri n g t h e l a st t w o decades, ai r concent r at i ons have fal l e n, and t h e pri m a ry source t o t h e

a tmosphe r e is now be lie ve d to be vola tiliza tion f r o m soils. The ma ss ba la nc e mode l e stima te d a
net flux of 700 kg /y r of total PCB s from soils to the atmosphere in 1994. However, this estimate is presented with the caveat that the model tends to underestimate the ra te of reduction of PCB

concent r at i ons i n recent y ears, whi c h coul d be at t r i but ed t o ot her m echani s m s such as biodeg r adation, photoly s is, and other deg r adation processes.

11.2.2. Water
11.2.2.1. Potential Mass of Dioxin-Like Com pounds Present
The surface area of i n l a nd wat e rs (i ncl udi ng t h e Great L a kes) i n t h e Uni t e d S t at es i s about 359,000 km 2 

### (U.S. DOC, 1995b). Assuming that the mean depth of inland water is 10 m (Duarte-Davidson et al., 1997), the total inla nd water volume is appr ox imately 3,600 billion m 3



### . No com p i l a t i on of C DD/ C D F m easurem ent s i n i n l a nd surface wat e rs was m a de for t h i s report ; however, i f i t i s assum e d t h at t h e “t y p i cal ” val u e us ed by Duarte-Davidson et al. for rivers in the U.K., 38 pg I

- TEQ DF 

### /m 3 

### , is representative of U.S. waters, th en the burden is calculated to be 137

g I

- TEQ DF 

### .

11.2.2.2. Mechanism s Responsible for Suppl y to and Releases from Water
As discussed in S ection 11.2.1.2, diox in- like compounds enter surface water from atmospheric deposition, stormwater runoff erosi on, and discharg es of anthropog enic wastes.
Volatiliz ation is the primary mechanism for re lease of diox in-like compounds from the water

c o lumn to the a tmosphe r e

. Se ve ral studies have addressed the wa ter-air ex chang e of diox in-like
PCB s throug h volatiliz ation in the Great L a ke s (Achman et al., 1993; Hornbuckle et al., 1993; Swackhamer and Armstrong , 1986; B a ker and Eisenreich, 1990). No similar body of literature
ha s be e n de ve lope d to a ddr e ss vola tiliza tion of CDDs/CDF s f r o m wa te r

. Most studie s tha t ha ve a ddr e sse d PCB wa te r

- a ir e x c h a n g e ha ve use d the two- f ilm mode l developed by W hitman (1927) and made popular by L i ss and Slat er (1974). W h en assessing g a s

ex chang e bet ween ai r and wat e r, t h e i n t e rface bet ween t h e t wo phases can be consi d ered as a two-lay e r (film) sy stem consistin g of well-mix ed g a s and liquid films adjacent to the interface; the rate of transfer is controlled by molecu lar diffusion throug h the stag nant boundary lay e r (Achman et al., 1993). L i ss and Slater (1974) a pplied the model to assess the flux of various

g a se s, spe c i f i c a lly in the a i r

- se a sy ste m s, a nd indic a t e d the possibility of its use a t a n y a i r

- w a t e r interface in the environment if the necessary data are available. Hornbuckle et al. (1993)

c onc lude d tha t the two- f ilm mode l is the be st a v a ila ble tool f o r

e stima ting r e g i ona l a nd loc a l f l ux of PCB s from natural waters. The following parag r aph, from Achman et al. (1993), succinctly

summa r ize s the mode l.

11-17

### The basi c equat i on used t o descri be t h e rat e of t r ansfer across t h e i n t e rface i s

F = K ol 

### (C
w 

### – C*) ( 11-1)

whe r e F is the f l ux ( m ol/m 2 

### -day ), C
w 

### ( m ol/m 3 

### ) is the dissolve d PCB c onc e n tr a tion in the bulk

wa te r , a nd C* is the a i r c onc e n tr a tion e x pr e sse d a s a wa te r c onc e n tr a tion in e quilibr i um with the

a i r ( P /H, mol/m 3 

### ). The variable P is the vapor-pha se ai r concent r at i on m easured (m ol / m 3 

### ) and converted to units of pressure using the ideal g a s law; H is Henry ’ s L a w constant (atm-m 3 

### /mol)

. The overal l m a ss-t r ansfer coeffi ci ent , K ol 

### , has units of velocity ( m / d ay ). The concent r at i o n
g r adient determines the direction of flux and dri v es t h e m a ss t r ansfer, whereas K ol 

### is a kinetic

pa r a me te r tha t qua ntif ie s the r a te of transfer. The value of K ol 

### is dependent on the phy sical and chemical properties of the compound as well as e nvironmental conditions. The reciprocal of K ol 

### i s t h e t o t a l resi st ance t o t r ansfer ex pressed on a g a s (R T/ Hk
a 

### )- and liquid (1/k
w 

### )-phase basis:

1/K ol 

### = 1/k
w 

### + R T / Hk
a 

### (11-2)

where k
w 

### is the wa te r

- side ma ss tr a n sf e r

c o e f f i c i e n t ( m/da y ) a nd k
a 

### is the a i r

- side ma ss tr a n sf e r coefficient (m/day ). R is the universal g a s constant (8.2057 × 10 -5 

### a tm- m 3 

### /mol K) , T is the
absol u t e t e m p erat ure, and H is Henry ’ s L a w constant. Achman et al. (1993) and Hornbuckle et al. (1993) calculated the volatilization rates of
PCB s from Green B a y on L a ke Michig an on the ba sis of a i r a nd wa te r sa mple s simulta ne ously collected over a 14-day period a bove and below the air-water in terphase and analy z ed for 85
P C B cong eners. Ai r sam p l e s col l ect ed over nearby l a nd were al so anal y z ed for t h e 85 P C B

cong eners. The di rect i on and m a g n i t ude of fl ux for each cong ener were t h en cal cul a t e d usi n g He nr y ’ s L a w a nd me te or olog ic a l a nd hy dr olog ic a l pa r a me te r s in the “ t wo- f ilm” mode l ( se e e q 11-1).
The net total PCB transfer rate (i.e., the sum of all cong ener transfer rates) was found to
be f r o m wa te r to a i r ( i .e ., vola tiliza tion)

. Howe ve r , dur ing c ool wa te r te mpe r a t ur e pe r i ods (October), the direction of transfer reversed for many cong eners. C a l c ul at ed t r ansfer rat e s t o ai r
rang ed from 15 to 300 ng /m 2 

### /day at low wind speeds (1 to 3 m/sec) to 50 to 1,300 ng /m 2 

### /da y a t hig h er wind speeds (4 to 6 m/sec). On a cong ener basi s, t h e l o wer-chl ori n at ed cong eners dominated total flux es. The summary of flux cal culations is presented in Table 11-5. The most impor ta nt f a c t or s inf l ue nc ing the ma g n itude of vola tiliza tion we r e the wa te r c onc e n tr a tion of
PCB s , wind speed, and water temperature. I n addition, Achman et al. (1993) and Hornbuckle et al. (1993) found that atmospheric PCB concentrations were hig h er over contaminated water than over nearby land, atmospheric PC B s over water tended to increas e with increasing dissolved

11-18

### T a b l e 11-5. S u m m a ry of f

l u x cal c u l ati o n s f o r total P C B s i n Green B a y

Date S i te Fl u x a 

### (ng/m 2 

### -day)
6-4 1 8 4 0
6-5 1 8 4 0
6-6 1 0 9 5
6-7 1 0 155
6-10 4 325
6-11 10 13
7-28 18 330
7-29 21 70
7-30 14 225
7-31 10 90
8-1 4 800
10-21 14 555
10-22 10 1,300
10-23 4 3 0

a Nu m b ers in d i cate w a ter- to

- a ir tran sf er o f to tal P C B s

. T h ey repres en t th e s u m of in div i du al P C B con g e n e r f l u x e s

an d are des c ribed as “ d aily ” f l u x e s becau s e th ey corres pon d to air s a m p les collected ov er 5–10 h r an d w a ter s a m p les collected ov er ~1 h r

.

S o u r ce: A c h m an et al . (1993).



### PCB concentrations, and the cong ener distribution in the a tmosphe r e c o r r e la te d line a r ly with the

cong ener di st ri but i ons i n t h e adj acent wat e r. Achman et al. (1993) also summariz e d the PCB volatiliz ation rate s reported by other researchers (B aker and Eisenreich, 1990; Sw ackhamer and Armstrong , 1986; Strachan and Eisenreich, 1988; Swackhamer et al., 1988) for Great L a kes water bodies. The results of these other studies, presented below, also show net flux of PCB s from water to air.

Tota l PCB vola tiliza tion r a te W a ter body (ng / m 2 

### /da y ) R e ference L a ke Superior 141 B a ker and Eisenreich (1990) L a ke Mi chi g an 240 Strachan and Eisenreich (1988) L a ke Superior 63 Strachan and Eisenreich (1988) Siskiwit L a ke 23 Swackhamer et al. (1988) L a ke Mi chi g an 15 Swackhamer and Armstrong (1986)

11-19

### 11.2.3. Sedim e nt 11.2.3.1. Potential Mass of Dioxin-Like Com pounds Present EPA conducted cong ener-specifi c measurements of CDDs/C DF s in the sediments from 11 U.S. lakes located in areas relatively unimp acted by nearby industrial activity

. The mean TEQ concentration in the uppe rmost sediment lay e rs from these 11 lakes was 5.3 ng TEQ DF 

### WH O 98 

### /kg (5.3 ng I

- TEQ DF 

### /kg ) dry weig ht. F or most of the lakes, the uppermost lay e r represents about 10 y ears worth of sedimenta tion. CDD/CDF concentrations in lakes impacted by industrial activity ma y have hig h er concentrations. F o r ex ample, Duarte-Davidson et al. (1997) reported a TEQ con centration of 54 ng I

- TEQ DF 

### /kg for urban sediments in the U.K. As noted above, the surface area of inland wate rs in the United S t ates is approx imately 359,000 km 2 

### (U.S. DOC, 1995b). I n their calculations ofsediment burdens in the U.K., DuarteDavidson et al. (1997) assumed that (1) the se diment surface area equals the water surface area, ( 2 ) the ma jor ity of CDDs/CDF s we r e loc a t e d in the top 5 cm of sediment, and (3) sediment density was 0.13 g dry weig ht/cm 3



### . Appl y i ng t h ese assum p t i ons t o t h e wat e r surface area and backg r ound TEQ concentration for U.S. sedime nts y i elds a burden of at least 120 kg TEQ DF 

### WH O 98 

### (120 kg I

- TEQ DF 

### ).

11.2.3.2. Mechanism s Responsibl e for Supply to and Releases from Sedim e nt
B ecause sediment is closely connected to the water column above it, evaluating the potential for sediment to act as a reservoir of diox in-like compounds is complex and likely to be more difficult than study ing diox in-like compounds in a sing le medium, such as water or soil.
Vola tiliza tion a nd se dime nta tion a r e two me c h a n isms whe r e b y pe r siste nt c h e mic a l s suc h a s CDDs/CDF s and PCB s are lost from water bodies /columns. Numerous authors (Swackhamer and Armstrong , 1986; Muir et al., 1985; L i ng et al ., 1993) have noted that sediments are a likely sink for persistent hy drophobic org a nic compounds because these compounds are likely to be strong ly bound to org a nic pa rticles in the sediment.
F o r ex ample, Muir et al. (1985) radiol abeled 2,3,7,8-TCDD and studied its dissipation from sediments (collected from a farm pond and a lake) to the water column in laboratory
studies under static aerobic conditions at 10EC. After 675 day s , more than 80% of the labeled TCDD was still present in the pond sediment and 87% was still present in the lake sediment.
Ae r a tion ha d little e f f

e c t on the dissipa tion r a te s. The c onc e p t of f

u g a c ity is a use f ul wa y to e stima te the be ha vior of diox in- like compounds in sediments. F ug acity is ex pressed in units of pressu re (pascals, or Pa) and is the partial pressure ex erted by the chemical in each medium. F u g a city models estimate equilibrium

concent r at i ons i n speci fi c m e di a at g i ven chem i cal concent r at i ons i n t h e envi ronm ent

. C l ark et al. (1988) sug g e sted evaluating contaminant con centrations in multiple environmental media by

c o mpa r ing f u g a c ity of a d joining me dia ( e .g ., c o mpa r ing se dime nt f u g a c ity with wa te r c o lumn

11-20

### f u g a c ity to de te r mine a c h e mic a l ’ s te nde nc y to move from one to the other). The authors evaluated fug acities of certain org a nochlorine compounds, including PCB s , in air, water,

se dime nt, f i sh, a nd f i sh- e a ting bir d s a nd the i r e g g s. The a u thor s pr e se n te d PCB s f u g a c itie s developed from data collected in a study of the L a ke Ontario reg i on. The fug acities of PCB s in
various media can be ranked as bir d s> f i sh> w a t e r > bottom se dime nt, indicating that PCB s and
othe r simila r c h e mic a l s a r e like l y to r e ma in in bottom se dime nt a nd a r e le ss like l y to r e

- e nte r the

wa te r c o lumn.

11.2.3.3. Releases from Sedim e nt to Water Given the lack of data, no qua ntitative estimates of annual releases can be made. L i ng et al. (1993) evaluated the fate of various chemicals, including PCB s , in Hamilton Harbour, located
in Onta r i o, Ca na da , using a modif i e d ve r sion of the Qua n tita tive Wa te r Air Se dime nt I n te r a c tion (QW A SI ) fug acity model. Among the processes evaluated were diffusion between air and water and sediment and water; sediment deposition, resuspen sion, and burial; and sediment
transformation. Three primary co mpartments were studied: air, water, and bottom sediments.
The sedi m e nt was t r eat ed as a si m p l e , wel l

- m i x ed surface l a y e r of act i v e sedi m e nt and t h e buri e d
sediment underneath. Chemicals in the active sed iment were assumed to be able to ex chang e with the ove r l y i ng wa te r ; c h e mic a l s in the bur ie d sediment were assumed to be isolated from the
sediment-water ex chang e

. Sed iment was assumed to be homog e nous rather than heterog e nous. The e p i- a nd hy polimne tic c o mpa r tme nts of the wa te r c o lumn we r e de f i ne d on the ba sis of a the r moc line

, a nd the a tmosphe r e was defined as a semi-infinite medium of constant, defined composition.
L i ng et al. estimated rates of PCB movement on the basis of 1987 loading s using two models: one with a thermoclin e and one without a thermocline. The results for the waterse dime nt tr a n sf e r

using the mode l with a the r moc line we r e ~32 kg /y r e n te r i ng the hy polimnion from the epilimnion, ~27 kg /y r entering the surface sediment from the hy polimnion, and ~18 kg /y r ( > 50% ) g o ing to bur ia l. F o r se dime nt- t o- wa te r tr a n sf e r , ~7 kg /y r tr a n sf e r

r e d to the hy polimnion and then 12.5 kg /y r transferred to the epilimnion. Similar numbers were found in the sing le water column model (t he model without a thermocline).
B oth the model with a thermocline and th e model without a thermocline predicted
volatiliz ation from the water to the atmos phere—1.6 kg /y r and 1.8 kg /y r, respectively

. However, the actual contribution of PCB s fro m se dime nt to a i r wa s not determined. A

c o mpa r ison of e stima te d c onc e n tr a tions with obse r ve d va lue s a r e pr e se n te d in Ta ble 11- 6. F o r PCB s , 68% were buried in the se diment, 20% were ex ported to L a ke Ontario, 5.4% deg r aded in
the wa te r a nd se dime nt, a nd 6% vola tilize d. The a u thor s note d tha t the se pe r c e n ta g e s we r e
uncert a i n. At t h e sedi m e nt -wat er ex chang e , m o re t h an 90% of each chem i cal was cont ai ned i n the sediment because of particle deposition and the hig h affinity of the chemical for sediment.

11-21

### Table 11-6. Com p arison of m odel- esti m a ted P CB con c en trati o n s w i th observed values

Var i abl e PCBs

O b served con cen tration Se di m e nt Wa te r 0.23–1.04 : g/g

< 20 : g/m 3



### E s tim ated con cen tration from m o d el with ou t th erm o clin e Se di m e nt Wa te r Am o unt i n s e di m e nt A m ou n t in water T o tal m a ss 0.518 : g/g 8.33 : g/m 3 

### 74.9 k g 2.33 k g 77.2 k g
E s tim ated con cen tration from m o d e l with th erm o clin e Se di m e nt Hy po l i m ni o n E p ilim n i on Am o unt i n s e di m e nt Am o unt i n hy po l i m ni o n A m ou n t in ep ilim n i on T o tal m a ss 0.527 : g/g 8.48 : g/m 3 

### 7.93 : g/m 3 

### 76.3 k g 1.28 k g 1.02 k g 78.6 k g

S o u r ce: L i n g et al . (1993).



### The r e wa s no indic a tion tha t c onta mina n ts bur ie d in the bottom se dime nts a r e tr a n sf e r

r e d

t h roug h di ffusi on m echani s m s back t o t h e surface sedi m e nt s; however, epi s odi c rel ease of t h ese chem i cal s from surface sedi m e nt s can occur t h r oug h m echani s m s such as resuspensi on duri n g flooding or lake inversions and uptake/ing e stion by benthic biota.

11.2.4. Biota
11.2.4.1. Potential Mass of Dioxin-Like Com pounds Present
The ma ss of CDDs/CDF s in biota in the Unite d Sta t e s wa s not e stima te d a s pa r t of this report

. However, t o pl ace perspect i v e on t h e pot ent i a l m a g n i t ude of t h i s reservoi r, 82 g I

- TEQ DF 

### ha ve be e n e stima te d to be pr e se n t in biota in the U.K. ( 50 g in huma n s a nd 32 g in ve g e ta tion)

, which is about three orders of mag nitude less than the mass es timated to be present in U.K. surface soils (Duarte-Davidson et al., 1997; Edulj ee and Dy ke, 1996). No data are available to

e stima te the biota bur de n in the Unite d Sta t e s.

11.2.4.2. Mechanism s Responsible for Suppl y to and Releases from Biota Apparently , very little of th e diox in-like compounds contained in contaminated soil is ultimately taken up by the veg e tation g r owing in the soil. Kjeller et al. (1991) analy z ed

11-22

### concentrations of CDDs/CDF s in archived so il and g r ass samples collected from the mid-1840s to 1989 at an Eng lish ex perimental station a nd found that only 0.006 to 0.02% of the soil burden
of CDDs/CDF s was taken up by the g r ass. I n a ddition, scientists g e nerally ag ree that, once taken up by plant tissue, CDDs/CDF s ar e not translocated to other pa rts of the plant (e.g ., fruits or shoots) (B acci and Gag g i , 1985; Hülster and Marschner, 1993, 1994; Na kamura et al., 1994).
Researchers have found that th e concentration of diox in-like compounds in a plant should reach equilibrium with the va por phase concentrations of diox in-like compounds in the surrounding air (B acci et al ., 1990a, b; Frank and Frank, 1989; Horstmann and McL achlan, 1992; McCrady and Mag g a rd, 1993; McL achlan et al., 1995; Paters on et al., 1991; Simonich and Hites, 1994; Tolls and McL achlan, 1994; W e lsch-Pausch et al., 1995). Horstmann and
McL achlan (1992) stated that the leaf-air transf er of volatile compounds is a reversible process

g overned by concentration g r adients. I f CDD/ CDF concentrations are hig h er in the surrounding air than they are in the air spaces within plant tissue, CDDs/CDFs should diffuse into the plant. Once equilibrium is reached and CDD/CDF concentr ations in the plant equal that of surrounding air, no more CDDs/CDF s should be taken into the plant. W hen CDD/CDF concentrations in surrounding air beg i n to decrease, CDDs/CDF s s hould diffuse (probably at a slow rate) out of
the pla n t tissue

. Appa r e ntly , CDDs/CDF s a r e not bioc onc e n tr a t e d to a sig n if ic a n t e x te nt in the lipid portion of the leaf cuticle (Gag g i et al., 1985). The CDDs/CDF s present in the leaf tissue are predom i n ant l y rel eased from t h e pl ant t h roug h leaf fall onto soil. Therefore, veg e tation is not likely to be a long -term re servoir of diox in-like compounds. Research sug g e sts that diox in-like compounds in animal tissue, unlike in veg e tation, seldom, if ever, reach equilibrium with va por phase concentrations in the surrounding

a tmosphe r e ( o r wa te r c o lumn c onc e n tr a tions in the c a se of a qua tic lif e )

. Ra the r , a n ima ls

ex posed to diox in-like compounds are known to bioaccumulate these compounds, primarily in body fat (U.S. EPA, 1993g , h). Nonetheless, animals, unlike plants, can metaboliz e certain chlorinated hy drocarbons after they enter th e body (Carlberg et al., 1983). Diox in-like compounds can be released from an animal’s body (at cong ener-specific rates) throug h metabolic processes or throug h weig ht loss, breast-feed ing

, or sweating

. McL achlan (1996) reported the half-life for the clearance of 2,3,7,8- TCDD from humans to be 7 y r

. As a result,

a n ima l lif e ha s a g r e a t e r pote n tia l tha n doe s ve g e tation for being a long -term reservoir source of
CDDs/CDF s. The majority of the diox in-like compounds released by animals in the form of
waste materials will be releas ed to water or soil. Similarly , upon death, the diox in-like compounds remaining in the body will be deposite d onto soil or aquatic sediments or will be ing e sted by other animals.

11-23

### 11.2.4.3

. Approaches for Measuring and Estim ating Releases from Biota
R e searchers have i nvest i g at ed t h e upt ake and release of CDDs/CDF s by veg e tation throug h measurement of actual concentrations during uptake and release by veg e tation g r own in closed sy stems (g reenhouses). B acci et al. (1992) conducted uptake and release studies of 1,2,3,4-TCDD by plant foliag e in a closed sy st em (a specially c onstructed g r eenhouse). Concentrations of TCDD vapor in the g r eenhouse air were maintained during the 370-hr uptake phase at a mean concentration of 0.0062 ng /L (a ir concentration varied slig htly from 0.005 to 0.0075 ng /L ). To beg i n the release phase, the TC DD vapor source (amended sand) as well as the

g r eenhouse walls were removed, a nd release of CDDs/CDF s from th e leaves was measured for
500 hr. The authors concluded that, during uptake, TCDD concentration in th e leaves varied as a
f unc tion of time a nd wa s de pe nde nt on the c onc e ntr a tion of va por

- pha se TCDD in the surrounding air. They estimated the release of TCDD from the veg e tation to be relatively slow, with a half-life of TCDD of 3,300 hr. McCrady and Mag g a rd (1993) conducted a mass balance study of uptake and release of
diox in in g r ass foliag e

. The results indicated a half-life of diox in in g r ass of 128 hr. These researchers also noted that, in addition to volatiliz ation, photodeg r adation of diox ins on the foliag e appeared to be a sig n ificant removal mechanism. They calculated the photodeg r adation
half-life to be 44 hr.
I n te r p r e ta tion of upta k e a nd r e le a se da ta ove r va r i a b le e x posur e time s a nd c onta mina n t

c onc e n tr a tions ha s le d to the de ve lopme n t of mode ls de sc r i bing a i r

- t o- ve g e ta tion e quilibr i um and kinetics controlling th e behavior of diox in in veg e tati on. Some earlier fug acity modeling attempts described the leaf of a plant as behaving as a sing le c o mpa r tme nt. One

- c o mpa r tme nt models were described by B acci et al. (1990a, b), Trapp et al. (1990), S c hramm et al. (1987), and
Tolls and McL achlan (1994). Re searchers presenting most of the recently developed models
claim that the available data be tter support the concept of a leaf behaving as two compartments (Riederer, 1990; Paterson et al., 1991; Ho rstmann and McL achlan, 1992; McCrady and Mag g a rd, 1993; Tolls and McL achlan, 1994; Mc L achlan et al., 1995). I nput parameters consi d ered by m o st m odel s i n cl ude cri t i cal chem i cal charact e ri st i c s of t h e cont am i n ant ,

c h a r a c t e r istic s of the pla n t, e x posur e time s, a nd c onta mina n t c onc e n tr a tions me a sur e d within the plant. Riederer (1990) sug g e sted treating a leaf as multiple compar tments having different accessibilities to the atmosphere a nd different diffu sion resistances.
I nput parameters for the two- compartment model are octanol-w ater coefficients, cuticlewa te r pa r tition c o e f f i c i e n ts, a que ous solubility , a nd sa tur a tion va por pr e ssur e of the c h e mic a l of

c onc e r n. Outputs of the mode l a r e pr e d ic tion of e quilibr i um c onc e n tr a tion in dif f

e r e nt le a f
tissue s, e stima te s of a i r

- t o- ve g e ta tion bioc onc e n tr a tion e quilibr i a , a nd ide n tif ic a tion of le a f compartments in which compounds are likely to accu mulate. Riederer (1990) also presented an

11-24

### a ppr oa c h f o r

using the mode l to se miqua ntita tive l y a sse ss the pote n tia l f o r

r e vola tiliza tion of
diox ins from veg e tation. One advantag e of the model presented by Ri ederer (1990) is that it considers critical plant characteristics in the release of diox ins. A plant is an active org a nism, responding to chang e s i n i t s envi ronm ent and act i n g accordi n g l y t o ensure i t s survi v al

. C e rt ai n pl ant charact eri s t i c s, such as t h e act i on of st om at a (s pe c i a lize d c e lls usua lly on the lowe r le a f sur f a c e that open and close to control pa ssag e of vapors into and out of the le a f inte r i or ) a nd tota l le a f
vol um e, are i m port a nt fact ors t h at affect t h e release rates of vapor phase contaminants from

veg e tation. Paterson et al. (1991) also presented a two-co mpartment model for release of diox in-like compounds from veg e tation. This model describes a plant as be ing made up of compartments in terms of volume fractions of air, water, a nd nonpolar (lipid-soluble, or octanol-equivalent)

or g a nic ma tte r

. Pa te r son e t a l . a tte mpte d to show tha t le a f

- a ir e quilibr i um a nd kine tic s c a n be

c o rr e la te d with c h e mic a l pr ope r tie s of the contaminant and proper ties of the leaf. The authors

sug g e st ed t h at t h e cl earance rat e const a nt ( k 2 

### ) c a n be c o r r e la te d with th e bioconcentration factor.
Thi s m odel does not consi d er cri t i cal pl ant charact er istics, such as action of the stomata, and for
this r e a son it ma y be le ss r e lia ble tha n mode ls tha t do c onside r pla n t c h a r a c t e r istic s, suc h a s the model presented by Riederer (1990).
Horstmann and McL achlan (1992) developed a fug acity mode l to describe release of semivolatile org a nic compounds from the surface of a solid (spruce needles). Their approach was slig htly different in that their g oal wa s instrument/method development, but their data supported the behavior of a leaf as a two-compartment sy stem. McCrady and Mag g a rd (1993) also collected data supporting the importance of viewing a le a f a s a two- c o mpa r tme nt sy ste m

. The y use d a two- c o mpa r tme nt mode l simila r to the one described by Paterson et al. (1991) that also does not consider critical plant characteristics and thus may be less reliable than m odels that do (e.g ., Reiderer, 1990).
Tolls and McL achlan (1994) ex posed g r a ss cultures for up to 240 hr to several semivolatile org a nic compounds and then measured the release of contaminants from the g r ass. The y de ve lope d a two- c o mpa r tme nt pa r titioning mode l ba se d on the da ta the y c o lle c t e d. The

m odel consi s t s of a sm al l surface com p art m e nt (t he l eaf cut i c l e ) and a l a rg e i n t e ri or reservoi r (ai r spaces within the leaf). Their model assumes that the flux of a chemical is the product of the fug acity difference (surface fug acity minus rese rvoir fug acity ) and the conductance between the
l eaf com p art m e nt s. I n an attempt to validate this model, McL ach lan et al. (1995) compared concentrations of semivolatile org a nic compounds measured in g r ass g r own under field conditions with concentrations predicted by their previous la boratory work with a fug acity meter. The

11-25

### c onc e n tr a tions me a sur e d in the g r a ss c u ltur e s a g r e e d with r e sults pr e d ic te d by the ma the m a tic a l
model described by To lls and McL achlan (1994).

11.3. SUMMARY AND CONCLUSIONS As depicted in F i g u re 11-1 a set of comple x relationships ex ists among reservoirs and between reservoirs and contempor ary formation sources. The si g n ificance of reservoirs for
huma n e x posur e is mor e de pe nde nt on the i r a b ility to a f f

e c t the c onc e n tr a tion of diox in- like compounds in other media than on their siz e or ne t release rate. This section first summariz e s

a nd dr a w s c onc lusions f r o m the limite d inf o r m a tion a v a ila ble r e g a r d ing the c h a r a c te r a n d

mag n itude of reservoir sources. This inf o r m a tion is the n use d to disc uss the implic a tions of
reservoir sources to human ex posure.

11.3.1. Reservoir S o u rces The following are summary statemen ts about soil reservoir sources.

C 

### Soil is like l y to be the r e se r voir sour c e with the g r e a t e st pote n tia l f o r

r e le a se of CDDs/CDF s to other environmental media, par tic ula r ly to wa te r

. This is due in pa r t to its r e la tive l y la r g e ma ss of stor e d CDDs/CDF s, but mor e impor ta ntly , it is due to the e x iste nc e of de monstr a t e d tr a n spor t m echani s m s for i n t e rm edi a ex chang e , e.g

. , soi l erosi on t o surface wat e rs and part i c l e resuspensi on t o ai r.

C 

### The preliminary estimates of CDD/CDF r unoff from urban areas to waterway s is comparable to known industrial point sour ce releases, and runoff from ag ricultural areas to surface waters is more than 100 times g r eater. I t is unclear how much of the soi l erosi on and runoff represent s recent l y deposi t e d C DDs/ C DFs from pri m a ry sources or long er-term accumulation. Mu ch of the eroded soil comes from tilled ag ricultural lands, which would incl ude a mix of CDDs/CDF s from various deposition times. The ag e of CDDs/C DF s in urban runoff is less clear.

C 

### B a se d on the limite d inf o r m a tion c u r r e ntly a v a ila ble ( i .e ., pr ima r ily f

u g a c ity mode ling ) , vola tiliza tion of CDDs/CDF s f r o m soils is not be lie ve d to sig n if ic a n tly

a lte r a m bie n t a i r c onc e n tr a tions. Howe ve r , vola tiliza tion of PCB s f r o m soil ma y be a sig n if ic a n t pr oc e ss.

C 

### B a se d on the limite d inf o r m a tion c u r r e ntly a v a ila ble

, r e suspe n sion of soil ma y account for a small fraction (~4%) of C DD/CDF concentrations in air. This

r e suspe nde d soil ma y , howe v e r , c onstitute a mor e sig n if ic a n t por tion of dr y deposition.

The following are summary statemen ts about water reservoir sources.

11-26

### C 

### I t is unc le a r whe t he r vola tiliza tion of CDDs/CDF s f r o m wa te r c a n sig n if ic a n tly a lte r ai r concent r at i ons. For P C Bs, however, t h e wat e r-ai r ex chang e appears t o be sig n ificant, and for some water bodies resu lts in a net transfer from water to air.

C 

### Wa te r is the ma jor me dia c ontr i buting CDDs/CDF s a nd PCB s to se dime nt. Note tha t most of the CDDs/CDF s in se dime nts or ig ina lly c a m e f r o m soils. F o r spe c i f i c wa te r bodies, however, the CDDs/CDF s and PCB s in sediments may have been dominated by local industrial discharg es to water.

The following are summary statements about sediment reservoir sources.

C 

### I t i s i m port a nt t o di st i n g u i s h bet w een surface and deep sedi m e nt s. S u rface sedi m e nt s are commonly resuspended and introduced b a c k into the wa te r ; de e p se dime nts g e neral l y do not i n t e ract wi t h t h e wat e r col u m n. S u rface sedi m e nt s can cont ri but e si g n i f i cant l y t o t h e C DD/ C DF and P C B concent r at i ons i n wat e r, whereas deep sediments do not.

C 

### There is little, if any , movement of diox in -like compounds once they are buried in the bottom se dime nts. B o ttom se dime nt s may be considered as sinks.

The following are summary statemen ts about biota reservoir sources.

C 

### The ma ss of CDDs/CDF s in ve g e ta tion a t a n y g i ve n time is like l y to be sma ll whe n

c o mpa r e d with the ma ss in soil. Ve g e ta tion doe s pla y a n impor ta nt r o le in
t r ansferri ng C DDs/ C DFs from t h e ai r t o t h e soi l vi a t h e decay of pl ant bi om ass.

C 

### Re le a se by vola tiliza tion f r o m ve g e ta tion ha s be e n studie d a nd mode le d using the f u g a c ity a ppr oa c h, a nd ha lf

- live s ha ve be e n e stima te d. B a se d on the se r e sults, vola tiliza tion is not be lie ve d to be a sig n if ic a n t me c h a n ism f o r

r e le a se of C DDs/ C DFs and P C Bs ex cept possi bl y duri n g forest / b rush fi res.

C 

### The ma ss of CDDs/CDF s in a n ima ls a t a n y g i ve n time is like l y to be sma ll whe n

c o mpa r e d with the ma ss in soil. Simila r l y , r e le a se s a r e sma ll a nd oc c u r pr ima r ily by

ex cretion and decomposition of dead biomass.

11.3.2. Im plications f o r Hum a n Exposure Althoug h, the ability to make quantitative estima tes of releases from reservoir sources is
limite d a t pr e se n t, it is r e a sona ble to c onc lude tha t the c ontr i bution of r e se r voir sour c e s to huma n

ex posure may be sig n ificant. Diet accounts for more than 95% of human ex posure. Althoug h
the siz e of the biota reservoir is small when co mpa r e d with the soil a nd se dime nt r e se r voir s, it is clearly the key contributor to human ex posure. The potential contribution of the other reservoirs
to human ex posure is discussed below.

11-27

### P CB reservoi r rel eases. Because current sources of newl y form ed P C Bs are m o st l i k el y
neg lig ible, human ex posure to the diox in-like PCB s is thoug ht to be de rived almost completely
from current releases of old PCB s stored in reservoir sources. Key pathway s involve releases
from both soils and sediments to both aquatic and terrest rial food chains. One-third of g e neral population TEQ DF P 

### ex posure is due to PCB s

. Thus, at l east one-third of the overall risk to the

g e neral population from diox in-like co mpounds comes from reservoir sources.
CDD/CDF releases f r om soil an d sed i m e n t s to w a ter an d exp o su re via th e aq u a tic pathw ay. The earlier discussion has shown that soils can have sig n ificant inputs to waterway s via soil e r osion a nd r unof f

. Simila r l y , the se dime nt r e se r voir c ontr i bute s sig n if ic a n tly to C DD/ C DF concent r at i ons i n wat e r. These rel eas es appear t o be g r eat er t h an t hose from t h e pri m a ry sources i n cl uded i n t h e i nvent ory

. Di ox i n s i n wat e rway s bi oaccum u l a t e i n fi sh, and fi sh consumption causes human ex posure. F i sh cons umption makes up about one -third of the total

g e neral population CDD/CDF TEQ ex posure. This sug g e sts that a sig nificant portion of the
CDD/CDF TEQ ex posure could be due to releas es from the soil and sediment reservoir.
CDD/ CDF rel eases f r om soi l to ai r an d exp o su re vi a th e terrestri a l p a th w ay. Pote ntia lly , soil r e se r voir s could have vapor and part i c ul at e rel eases t h at deposit on plants and
enter the terrestrial food chain. The mag n itude of this contribution, however, is unknown. EPA pla n s f u tur e studie s in a g r i c u ltur a l a r e a s tha t will c o mpa r e mode le d a i r c onc e n tr a tions f r o m
pr ima r y sour c e s with me a sur e d le ve ls a s a wa y to g a in f u r t he r insig h t into this issue

.

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