8 2 ERDC/CER L TR-05- 9

2 ) Continuou s Emission s Monitorin g Systems , CE M system s ar e i n plac e t o measur e carbo n monoxid e (CO ) an doxyge n (0 2 ) i n th e exhaus t stack
. Th e C E M samplin g syste minclude s th e following : sampl e extractio n probe , hea t trace dsamplin g lines , calibratio n ports , refrigerate dcondenser , sampl e pump , filters , an dflo w meters
. Th e sampl e extractio n por t i s locate di n the exhaus t stac k approximatel y 2 0 fee t abov e grade
. Th e CE M syste minclude s automati c calibration , whic h allow s th e monitor s t o b e calibrate dperiodicall y withou t operato r intervention
. Th e C O monito r i s aNDI Ranalyze r

wit h0-20 0 pp man d 0-3,00 0 pp mdua l range capability
. Th e outpu t fro mth e C O monito r

i s correcte d t o 7 percen t

0 2(usin g dat afro mth e 0 2CEM)
. 3 ) Wast e Fee d Rat e Monitorin g System . Th e WFRM S control s th e furnac e fee drate
. Th e WFRM S consist s o f aprecisio n explosio n proo f scale , apush-of

f box , an daslid e chute
. Th e scal e report s th e measure dweigh t t o th e PL C vi aa seria l communicatio n cable
. Th e PL C verifie s tha t th e weigh t

i s les s tha n o r equa l t o th e establishe dlimi t fo r th e ite mbein g incinerated
. Onc e th e PL C ha s verifie dtha t

th e weigh t

i s acceptable , th e push-of f bo x pushe s th e ammunitio n ite monto th e slid e chute , whic h i s ove r th e primar y fee dconveyor . Th e WFRM S i s capabl e o f

cyclin g every 1 5 seconds
. 4 ) Dua l Conveyo rFee d System . Th e primar y wast e fee dconveyo r trans
port s th e munition s fro mth e WFRM S throug h th e concret e wal l int o th e barri

cade area . Th e ammunitio n i s the n fe donto the secondary fee dconveyor , whic h deposit s the ammunitio n int o th e rotar y furnac e fee dchute
. I f a n out-of

paramete r

conditio n arises , th e primar y fee dconveyo r i s stoppe dunti l the condi

tio n i s corrected
. Fo r

safet y reasons , however , th e secondary conveyo r continue s t o operate
. Thi s allow s munition s nea r th e hig h temperatur e en do f th e kil n t o continu e movin g throug h the furnac e an ddeter s possibl e explosion s outsid e the furnace
. 5 ) Rotar y Furnace . Th e rotar y furnac e i s designe dt o ignit e th e ammunitio n item s an deffectivel y incinerat e reactiv e component s fro mthe meta l shells
. Th e hea t t o ignit e th e ammunitio n i s initiall y provide db y fue l oi l formin g acounter
curren t to the movemen t

o f th e ammunitio n throug h th e rotar y furnace
. Com

bustio n gase s an dentraine das h exi t th e furnac e adjacen t

t o th e fee dchute
. Non-entraine das h an dthe meta l component s o f th e ammunitio n ar e discharge d a t th e burne r

en do f th e rotar y furnace
. Th e ammunitio n i s propelle dthroug h th e 2 0 f t long , 30. 5 inc hdiamete r retor t towar dth e burne r

en db y spira l flights
. A s th e ammunitio n approache s th e flame , the y eithe r detonat e o r

bur n freely , dependin g o n th e ammunitio n characteristics
. Th e thic k cas t stee l wall s contai n hig h orde r

detonations
. Fee drates , residenc e times , an doperatin g parameter s hav e bee n establishe dfo r eac h ammunitio n ite mb y controlle dtesting
. Th e ro 

### VES01690 0ERDC/CER L TR-05- 9 8 3

tar y furnac e i s equippe dwit haHauc k 78 3 proportionin g burne r locate da t

th e discharg e end
. Th e burne r ha s acapacit y o f

3 millio n BTU/h r

an danomina l turndow n rati o o f

4:1
. Th e fee den dtemperatur e o f the furnac e range s betwee n 350-45 0 ° Fwhil e th e discharg e en drange s fro m800-110 0 ° Fdurin g norma l op eration
. Th e rotar y furnac e i s operate dunde r asligh t negativ e pressure . 6 ) Furnac e Shroud . A meta l shrou dtha t completel y enclose s th e retor t sec tions , th e draf

t fan , an dthe retor t

combustio n ai r

fa n control s fugitiv e emission s fro mthe rotar y furnace
. Th e draft fa n i s use dt o maintai n negativ e pressur e a t the fee den do f

the furnace
. Th e retor t combustio n ai r

fa n draw s ai r

fro mth e are abeneath th e retor t shroud , creatin g anegativ e pressure . Th e combustio n ai r blowe r create s anegativ e pressur e insid e the shroud , whic h pull s an y fugi

tiv e emission s throug h th e blowe r an ddischarge s the mint o the furnac e vi ath e furnac e burner
. 7 ) Cyclone . Larg e particle s fro mth e ga s strea mar e remove db y th e cyclone
. Th e cyclon e ha s a90-9 5 percen t remova l efficienc y fo r particle s 1 0 micron s an d larger
. Th e cyclon e ha s aclock-wis e rotation , wit hinle t an doutle t

duct s a t 90 ° separation
. Particle s ar e remove dfro mthe cyclon e a t th e botto mb y adoubl e tippin g valve
. Th e valv e ha s tw o gate s tha t ar e moto r

driven
. Th e gate s ope n alternativel y s o tha t

onl y one gat e i s ope n a t an y time , thu s maintainin g the negativ e pressure . 8 ) Afterburner . Th e afterburne r i s buil t t o AE D specification s b y Souther n Technolog y Incorporated
. Th e afterburne r i s designe dt o rais e the temperatur e o f the exhaus t

gase s exitin g fro mthe kiln
. Thi s elevate dtemperature , an dthe adde dresidenc e time , enhance s th e complete combustio n o f th e explosive
. Th e afterburne r

i s capabl e o f

heatin g 400 0 scf

mo f flu e ga s fro m350-45 0 ° Ft o 1400

- 160 0 ° Fwit haminimu mflu e ga s residenc e tim e o f 2 seconds
. A diese l fue l burne r wit hapropan e pilo t

ignitio n syste mheat s th e afterburner
. Th e after

burne r i s equippe dwit haHauc k WR016 4 wid e range burne r wit h acapacit y o f

8 millio n BTU/h r

an dnomina l turndow n rati o o f 10:1
. 9 ) Discharg e Conveyor . Th e soli dwast e exit s th e furnac e b y th e discharg e conveyo r locate da t

th e discharge/burne r

end
. Th e soli dwast e i s typicall y com prise do f

th e meta l casings , melte dlea dprojectiles , an dresidua l ash
. Th e lo w en do f th e discharg e conveyo r i s locate dunderneat h the discharge/burne r en do f the rotar y furnace
. Th e hig h en do f the conveyo r

passe s throug h the concrete barricad e wal l an ddeposit s the wast e int o containers
. 10 ) Hig h Temperatur e Cas tCerami c Filter s Baghouse . Th e baghous e i s a hig h temperatur e cas t

cerami c collector , use dfo r final particulat e cleansin g fo r



### VES01690 18 4 ERDC/CER L TR-05- 9

th e ga s stream
. Th e baghous e wa s designe dan dbuil t t o AE D specification s b y J T System s Incorporated
. Th e flue gase s fro mthe afterburne r ar e transporte d to th e baghous e b y 12 0 f t o f 30-inc h diamete r

stainles s stee l ducting
. Th e duct

in g i s lon g enoug h t o produc e atemperatur e dro p fro m160 0 ° Fa t th e exi t o f the afterburne r

t o 100 0 ° Fenterin g th e baghouse
. Th e baghous e contain s 15 4 cerafi l cerami c candle s tha t

ar e 5.7 5 inche s i n diamete r an d1 0 f t

long
. Thi s result s i n a tota l filte r

are ao f 233 0 squar e fee t

wit hafiltratio n velocit y o f 4.9 7 feet/second
. Th e baghous e operate s wit h adelt apressur e range o f 0. 5 t o 6. 0 inche s o f

wate r column
. Th e particle s settl e int o th e hoppe r belo w an dar e exhauste dthroug h a doubl e tippin g gat e valv e int o aseale d55-gallo n dru mwhil e maintainin g a n ai r sea l o n th e baghous e assembly
. 11 ) Hig h Temperatur e Draf tFan . Th e ga s stea mi s pulle dthoug h th e APC S b y a n induce ddraf

t fan
. Th e fa n i s aFa n Equipmen t Compan y Mode l M-2 1 I.E
. Th e fa n i s capabl e o f

pullin g 670 0 ACF M a t adraf t (negativ e pressure ) o f 3 0 inche s o f wate r column
. 12 ) Exhaus tStack . Th e A3 6 carbo n steel , circula r exhaus t stac k i s approxi

matel y 3 0 f t

hig h (3 4 f t

wit h extension ) an dha s anomina l I D o f 2 0 inche s (Fig

ur e 3-2)
. 3.2 TEAD Emission

Limits During Testing Fo r th e verificatio n test , metal s i n th e TEA D incinerato r stac k ga s ar e regulate d unde r aTemporar y Authorizatio n permi t a s shown i n Tabl e 3-2
. O f the 1 2 regu late dmetals , 5 ar e typicall y foun di n th e feedstrea m(Pb , Sb , Ba , Cd , an dCr) ; however , P b i s th e onl y elemen t tha t i s routinel y foun di n measurabl e concentra
tion s i n the stac k

gas . Tabl e 3-2
. TEA D meta l emissio n limit s durin g verificatio n testing
. Elemen t Limi t

(g/hr ) Elemen t Limi t (g/hr ) Antimon y (Sb ) 1 4 Lea d(Pb ) 4. 3 Arseni c (As ) 0.1 1 Mercur y (Hg ) 1 4 Bariu m(Ba ) 240 0 Nicke l (Ni ) 93 0 Berylliu m(Be ) 0.20 Seleniu m(Se) 18 0 Cadmiu m(Cd ) 0.2 6 Silve r (Ag ) 140 Chromiu m(Cr ) 0.04 Thalliu m(Tl ) 1 4



### VES01690 2ERDC/CER L TR-05- 9 8 5



### 4. 0 EXPERIMENTA L DESIG N
4.1 General

Design Fo r al l tests , bot h the kil n an dth e afterburne r wil l b e fire dwit hdiese l fue l whil e incineratin g Mar k

344 fuse s (NS Nnumbe r 1325000090348 ) wit hafee drat e o f 7 9 pe r hour
. Th e chemica l compositio n o f th e fuse s i s show n i n Tabl e 4-1
. Fo r thes e fuses , lea di s the restrictiv e elemen t hmitin g th e fee drate
. Tabl e 4- 2 show s th e nin e element s tha t wil l b e measure db y th e XCE M durin g verificatio n testing
. Eigh t

o f thes e metal s wil l b e spike ddirectl y int o th e stac k downstrea m o f the controls
. Thes e metal s wil l b e spike da t th e leve l show n i n Tabl e 4-2
. Lead , however , wil l no t b e spike dsinc e th e incinerate dmunition s provid e meas urabl e concentration s o f lea dwithou t

spiking
. Spikin g wil l b e conducte db y MSE-T A usin g thre e o r fou r atomizer s to injec t

so lution s containin g th e metal s o f interes t eithe r directl y int o th e stac k o r int o a chambe r tha t drie s the solutio n prio r t o enterin g th e stack
. Th e atomize r pro vide s liqui ddroplet s that , whe n dried , yiel dfin e sal t particle s tha t

are represen tativ e o f typica l stac k

aerodynami c diameters
. Stac k ga s meta l concentration s wil l b e simultaneousl y determine db y the XCE M an dtw o Metho d2 9 (M29 ) samplin g trains
. Th e M2 9 train s wil l sampl e fo r tw o hour s whil e XCE M data , whic h i s recorde devery 2 0 minutes , wil l b e average d fo r th e M2 9 tes t

run . A tota l o f

1 2 dua l M2 9 tes t

run s wil l b e performe db y CHPPM
. Eac h ru n wil l in

clud e tw o M2 9 samplin g train s i n orde r t o determin e referenc e metho dprecision
. Metho d30 1 wil l b e applie dt o M2 9 dat at o determin e bia s betwee n th e referenc e methodsamphn g trains
. Prio r t o testing , CHPP M wil l conduc t a n EP A Metho d2 velocit y travers e to determin e arepresentativ e samplin g poin t fo r the M2 9 probes
. Th e XCE M an dM2 9 probe s wil l b e locate dapproximatel y 2 7 fee t abov e the bas e o f

the exhaus t

stack
. Th e neares t

flo w disturbance s ar e locate d9. 8 duc t diameter s upstrea m(induce ddraft fan ) an d4. 3 duc t

diameter s downstrea m(top o f th e stack ) fro mthe sampl e ports
.



### VES01690 386 ERDC/CER L TR-05- 9

Tabl e 4-1 . Compositio n o f munition s incinerate ddurin g metal s testing
. Fuze , Bomb , Tail , MK34 4 Mo d 0/ 1 Fee d Rate : 7

9 items/hr ; Loadin g (lb/item ) 0.279 1 Componen t Componen tQuan tit y (lb/item ) Componen t Fee d Rate (lb/hr) Buty l Acetat e 0.0000 1 0.000 8 Charcoa l 0.0000 2 0.001 6 Ethy l Alcoho l 0.0000 1 0.000 8 Graphit e 0.0054 1 0.427 5 Lea dAzid e 0.0002 8 0.022 1 Lea dMonoxid e 0.0000 5 0.004 0 Lea dPowde r 0.0003 1 0.024 5 Lea dStyphnat e 0.0068 3 0.539 8 Nitrocellulos e 0.0000 2 0.001 6 Nitrostarc h 0.0000 1 0.000 9 PET N 0.0003 1 0.024 5 Potassiu mNitrat e 0.0000 8 0.006 3 Seleniu mPowde r 0.0001 2 0.009 5 Sulfu r 0.0000 5 0.004 0 Tetry l 0.2655 5 20.985 5 Toluen e 0.0000 1 0.000 8 Tabl e 4-2
. Tooel e meta l emissio n limitation s an dspikin g levels
. Element s Emissio n Limits 1 Spikin g Level 1 Element s g/h r ~ fig / dsc m ~ ug

/ dsc m Element s g/h r ~ fig / dsc m Run s 1-

6 Run s 7-1

2 A s 0.1 1 1 7 1 5 1 5 B a 2,40 0 360,00 0 100 0 100 0 C d 0.2 6 3 9 3 5 3 5 C r 0.04 6. 5 5. 5 5. 5 H g 1 4 2,10 0 10 0 30 0 N i 93 0 139,50 0 20 0 50 0 P b 4. 3 64 5 N S N S S b 1 4 2,10 0 20 0 50 0 Z n N R N R 20 0 50 0 1 Th e concentratio n i n ug/dsc m assume s astac k flo w rat e o f abou t6700 dscm/h r NR : Notregulate d NS : NotSpike d



### VES01690 4ERDC/CER L TR-05- 3 8 7

CHPP M wil l conduc t

the chemica l analysi s o f recovere dsampl e fraction s fro m th e M2 9 trains
. Sampl e handling , analysis , an dal l associate dQA/Q C activitie s wil l confor mt o th e requirement s o f M29
. Accurac y dat afo r metal s analysi s wil l b e confirme dwit htw o fiel dspike s o f th e nin e measure dmetal s int o blan k sam plin g trains
. Medi ablank s o f the M2 9 solution s an dfilte r wil l als o b e analyzed
. Sampl e integrit y wil l b e maintaine db y us e o f achain-of-custod y an dadesig

nate dsampl e custodian
. Uniqu e sampl e identificatio n number s wil l b e imple

mente ds o tha t

final dat ause dfo r

verificatio n ca n b e trace dbac k throug h th e analytica l proces s t o th e origina l sample
. 4.2 Test Schedule Set-u p fo r

th e verificatio n testin g i s schedule dfo r Ma y 10
. XCE M verificatio n testin g i s tentativel y schedule dfo r Ma y 11 , 12,14 , an d15
. Thre e M2 9 tes t run s ar e planne dfo r

eac h day wit heac h ru n lastin g 2 hours
. Al l nin e metal s o f inter

es t wil l b e teste ddurin g eac h run ; however , lowe r concentration s o f

Ni , Sb , Hg , an dZ nar e schedule dfo r the first si x run s a s show n i n Tabl e 4-2
. 4.3 Test Procedures I nal l case s whe n referenc e metho ddat ai s bein g taken , the introductio n o f th e indicate dmetal s wil l b e hel dconstan t throughou t

the entir e samphn g period
. Th e inten t

o f thi s approac h i s t o allo w comparison s o f XCE M dat at o referenc e metho ddat aunde r

constan t conditions
.
4.3. 1 Spikin g approac h Spikin g wil l b e conducte db y MSE-T A o f Butte , MT
. Thre e atomizer s ar e use dto quantitativel y injec t

nitri c aci dsolution s containin g the metal s o f interest
. Th e solutio n wil l b e injecte deithe r directl y int o the stac k o r int o adryin g chamber , whic h open s t o th e stack
. Th e spike dsolutio n wil l ente r th e stac k

throug h aport locate dat

the bas e o f

the stack
. Thi s por t

wa s successfull y use di n earlie r multi

meta l CE M test s a t

Tooel e an di s directl y downstrea mo f adraf t fa n allowin g fo r goo dmixing
. Manufacture r

specification s fo r

th e atomizer s determin e drople t siz e distribu

tion s base do n pressur e an dai r flo w rate
. Fo r

thes e tests , pressur e an dflo w rat e wil l b e maintaine dto keep drople t size s les s tha n 2 8 micron s i n diameter
. Whe n dried , th e majorit y o f

the mas s i s expecte dt o b e i n th e on e t o fou r micro n range .



### VES01690 588 ERDC/CER L TR-05- 9

Eac h atomize r

ha s been gravimetricall y calibrate db y MSE-T A t o determin e mas s emissio n rate s over the rang e o f

pressur e an dai r

flo w rate s expecte dfo r th e verificatio n test
.
4.3. 2 Referenc e metho d samplin g CHPPM' s Ai r

Qualit y Surveillanc e Progra mwil l conduc t referenc e metho dsam pling
. Dua l sampl e train s wil l b e use dt o collec t metal s dat aemployin g standar d operatin g procedure s fro mM29
. Ful l sampl e custod y procedure s wil l b e em ploye ddurin g th e tes t usin g sampl e custod y sheet s an dsampl e custody seals
. Sample s wil l b e unde r eithe r direc t custod y o r

loc k an dke y a t

al l times
. Pe r M2 9 protocol , medi ablank s fro mthe sam e lo t a s use ddurin g testin g wil l b e take n an dtreate di n the same manne r a s the tes t

ru n samples
. Dr y ga s meter s ar e calibrate dbot h pre - an dpost-test s wit hawe t tes t meter
. Pito t tube s underg o ageometri c calibration , an dthermocouple s ar e calibrate d usin g standar dtw o poin t calibratio n methods
. A s aperformanc e audit , tw o blan k train s wil l b e quantitativel y spike dwit hal l nin e o f the metal s o f

interest
. Thes e spike s wil l b e conducte do n samplin g me dia , includin g th e filte r an dimpinge r

solutions , fro mth e sam e lot s use ddurin g testing
. A spik e recovery targe t o f 8 0 t o 120 percen t

o f injecte dsolutio n ha s been set
.
4.3. 3 Referenc e metho d analysi s Referenc e metho danalyse s wil l b e conducte db y CHPPM' s Directorat e o f Labora

tor y Service s (DLS)
. Analysi s wil l follo w standar dM2 9 protoco l wit hth e follow

in g exception : th e fron t hal f analysi s wil l includ e separat e reporte dvalue s fo r both the fron t

hal f rins e an dthe filter
. Blan k value s wil l b e determine dusin g M2 9 sectio n 9. 1 protocol s an dastandar dblan k subtractio n wil l b e mad e i f sig

nifican t metal s ar e foun di n the blank
. CHPP M use s ICP-M S fo r it s metal s analysis
. Th e ICP-M S i s calibrate dusin g solutio n standard s a s discusse di n sectio n 10. 2 o f M29
. 4.4 Data Comparisons Thi s sectio n describe s ho w th e referenc e an dCE M dat awil l b e use dan dcom pare dto quantif

y th e performanc e o f

th e XCEM
. Tabl e 4- 5 summarize s th e dat a tha t wil l b e use dfo r

the verificatio n comparisons
.



### VES01690 6ERDC/CER L TR-05- 9 8 9

Relativ e accurac y an dcorrelatio n wil l b e determine db y comparin g the CE M re sult s agains t

th e M2 9 results , fo r

eac h metal
. M2 9 result s fo r the probe , fron t half , an dbac k

hal f wil l b e reporte dseparatel y to evaluat e potentia l particl e los s i n th e XCE M tubing
. However , th e tota l trai n result s wil l b e combine dfo r th e relativ e accurac y an dcorrelatio n calculations
. Precisio n wil l b e determine db y analysi s o f XCE M concentration s whe n th e spik e injectio n rat e an dstac k condition s ar e hel dconstant. I t i s recognize dtha t

th e reporte dprecisio n wil l includ e variabilit y i n stac k condition s a s wel l a s XCE M variability
. Tabl e 4-5
. Summar y o f dat ato b e obtaine ddurin g XCE M verificatio n test
. Performanc

e Parameter Objectiv e Comparison

Based O n No . o

f Dat a Point s Accurac y Determin e degree of quantitativ e agreemen twit h referenc e method . Referenc e Metho d Result s 1 2

Correlatio n Determin e degre e of correlatio n wit h referenc e method . Referenc e Metho d Result s 1 2

Precisio n Determin e degre e of consistency i n XCE M measure d concentration s unde rconstan toperatin g conditions . XCE M reporte d concentration s unde rconstan t operatin g conditions . 6/ru n

Instrumen t Drif t Determin e XCE M abilit y t o measur e consistentl y ove rth e cours e of

th e test . Determin e variatio n i n palladiu m concentration s determine d wit h eac h XCE M measuremen t 3/h r

Spa n an d Zer o Determin e XCE M respons e unde r

maximu m an d minimu m condition s XCE M automate d dail y Q A routin e 4
Respons e Tim e Determin e XCE M respons e tim e a s

a batc h CEM . Continuou s monitorin g of

meta l concentration s 3/h r
Bia s Determin e i f bia s exist s betwee n M2 9 an d th e XCEM . Referenc e Metho d Result s 1 2

Lo w Leve l Meta l Respons e Determin e XCE M performanc e

whe n lo w meta l concentration s ar e presen ti n th e stack . Arseni c an d chromiu m ref

. Metho d result s 2 4



### VES01690 790 ERDC/CER L TR-05- 9

Instrumen t

drift wil l b e determine db y evaluatio n o f XCE M reporte dpalladiu m concentrations
. A s par t o f the XCE M qualit y assuranc e program , apalladiu m ro dha s been permanentl y fixe dabov e the x-ra y bea man dbelo w th e filte r tape
. Th e palladiu mro di s measure dwit heac h sample , an darunnin g recor do f th e reporte dconcentration s i s maintained
. Th e percen t relativ e standar ddeviatio n fo r palladiu mconcentration s wil l als o serv e a s adeterminatio n o f XCE M in

strumen t drift durin g testing
. XCE M respons e tim e wil l b e determine da s the tim e betwee n the star t o f one samplin g perio dan dth e beginnin g o f asecon dsamphn g period
. Th e XCE M sample s fo r

1 0 to 2 0 minutes , dependin g upo n th e desire ddetectio n limits
. Withi n afe w second s o f sampling , the expose dtap e i s move dint o th e XR Fanaly

si s region
. Analysi s require s the sam e amoun t o f tim e a s samphng
. Followin g analysis , concentration s ar e determine dan drecordedi n afractio n o f asecond
. Fo r thes e tests , th e respons e tim e wil l b e determine da s th e averag e tim e fro m the star t o f on e samplin g perio dt o th e star t o f th e nex t samplin g perio dwit ha dela y i n th e reportin g o f dat atha t

i s equivalen t

t o th e analysi s time
. Bia s betwee n th e dua l M2 9 samplin g train s fo r eac h ru n wil l b e determine db y a compariso n ofth e dua l M2 9 sampl e run s usin g a n EP A Metho d30 1 approac h fo r paire dsamplin g trains
. Fo r vali dtes t

runs , M2 9 concentration s wil l b e average d an dcompare dt o reporte dXCE M data
. Th e XCEM' s abilit y t o measur e low-leve l concentration s o f metal s wil l b e chal

lenge db y Cr , As , an dCd , whic h ar e t o b e presen t a t approximatel y 5 , 15 , an d3 5 pg/dsc mrespectively
. M2 9 result s identifie da s outlier s wil l b e reported , bu t wil l no t b e use dfo r

verifi

cation
. Th e inten t

o f thi s approac h i s t o provid e avali dse t o f referenc e dat afo r verificatio n purposes , whil e als o illustratin g the degre e o f variabilit y o f

th e ref

erenc e method
. Identificatio n o f outlier s wil l b e base dupo n analysi s o f percen t difference s i n M2 9 concentration s betwee n samplin g train s an dtrend s i n dat a throughou t

the tes t day
. I n an y case , wher e rejectio n o f areferenc e resul t

i s sug gested , effor t

wil l b e mad e t o fin da n assignabl e caus e fo r th e divergen t

result
. Accordin g to PS-10 , th e XCE M act s a s abatc h CEM
. Batc h CEM s continuousl y sampl e an dconcentrat e th e pollutan t o n acaptur e medium
. Analysi s i s per forme dafte r

sufficien t

tim e ha s elapse dt o concentrat e th e pollutan t t o level s tha t ar e detectabl e b y th e analyzer
. PS-1 0 require s tha t batc h CEM S mee t

thre e respons e tim e criteria : 1
. Th e samplin g tim e shal l b e n o longe r tha n one-thir do f

the averagin g perio dfo r the apphcabl e standard
.



### VES01690 8ERDC/CER L TR-05- 9 9 1

2
. Th e dela

y between th e en do f

the samplin g perio dan dreportin g ofth e analysi s perio dshal l be no greater tha n 1 hour
. 3
. Samphn g shal l b e continuou s excep t i ntha t th e paus e i n samplin g whe n the sampl e collectio n medi ai s change dshoul db e n o greater tha n 5 percent

ofth e averagin g perio do r

5 minutes , whicheve r

i s less
. TEA D incinerato r

emission s ar e regulate db y tw o standards : Resourc e Conser

vatio n an dRecovery Ac t (RCRA ) limit s i n gram s pe r hou r an dth e maximu m achievabl e contro l technolog y (MACT ) rule , whic h regulate s usin g a12-hour roll

in g average . Sinc e the RCR A limit s ar e mor e stringent , th e respons e tim e shal l b e limite dto 2 0 minute s fo r th e TEA D test s wit hsamphn g occurrin g at leas t 5 7 minute s pe r

hour
. Spa n an dzero determination s wil l b e conducte ddail y b y th e XCEM
. Th e auto
mate dXCE M spa n routin e extend s aplunge r containin g metal s o f

interes t int o the analysi s area . Th e plunge r i s the n analyze db y th e XCE M an dth e dat a compare dwit hthe know n meta l concentration s o n the plunger
. Zero reading s ar e determine db y analysi s o f blan k filte r tape
. Th e XCE M filte r

analysi s i s nondestructiv e an dth e expose dtap e remain s avail

abl e fo r subsequen t

analysis
. I n case s wher e unexplaine ddiscrepancie s exis t betwee n XCE M an dM2 9 data , apost-tes t filte r tap e analysi s wil l b e considered
. Setu p an dmaintenanc e need s wil l b e documente dqualitativel y b y Battelle , both throug h observatio n an dthroug h communicatio n wit hth e vendor s durin g th e test
. Factor s to b e note dinclud e th e frequenc y o f schedule dmaintenanc e activi

ties , th e downtim e o f

the CEM , an dth e numbe r o f staf f operatin g o r

maintainin g i t durin g the verificatio n test
.


### 5. 0 STATISTICA L CALCULATION S Statistica l calculation s wil l b e use dto verify the performanc e o f the XCE M a s describe dbelow
. I n al l cases , measuremen t result s fro mbot h the referenc e metho dan dth e XCE M ar e reporte di n unit s o f pg/m 3 o n adr y basi s a t 2 0 °C , 1 atmosphere pressure , an dth e actua l flu e ga s 0 2content
. 5.1 XCEM

Concentrations

During a Reference

Method

Run Averag e XCE M concentration s fo r agive n referenc e metho dru n wil l b e calcu

late da s follows :



### VES01690 99 2 ERDC/CER L TR-05- 9

[E q5.1 ] where : C j = XCE M time-weighte dconcentratio n fo r elemen t i durin g M2 9 tes t

ru n C j j = XCE M reporte dconcentratio n fo r elemen t i durin g tim e interva l j n= numbe r

o f XCE M measurement s durin g tes t ru n t , = numbe r

o f minute s XCE M measure delemen t i' s concentratio n durin g tim e interva l j
5.2 Relative

Accuracy Th e relativ e accurac y (RA ) o f th e XCE M wit hrespec t t o the referenc e metho d (M29 ) wil l b e assesse dby :

\d\ + t" RA = —^-xl00 % [E q5.2 ]
Wher e d refer s t o th e differenc e betwee n M2 9 an dth e XCE M results , an dx cor respond s t o the M2 9 result
. S d denote s th e sampl e standar ddeviatio n o f th e dif

ferences , whil e t a n li s th e t valu e fo r

th e 100(l-a) t hpercentil e o f the distributio n wit hn' ! degree s o f

freedom
. Th e R A wil l b e determine dfo r a n avalu e o f

0.02 5 (i.e. , 97. 5 percen t

confidenc e level , one-tailed)
. Th e R A calculate di n thi s wa y ca n b e interprete da s a n uppe r confidenc e boun dfo r

th e relativ e bia s o f

th e analyzer , 

# P I i.e. , wher e the superscrip t ba r indicate s th e averag e absolut e valu e o f th e x difference s o f

the referenc e values
. I f 1 2 referenc e metho dtes t run s ar e com pleted , th e R A procedure state di n PS-1 0 wil l b e followe d(i.e. , u p t o thre e result s ma y b e omitte dfro mthe R A calculation)
. Th e impac t o f the numbe r

o f dat a point s (n ) o n the R A valu e wil l b e notedi n th e verificatio n report
. Th e R A wil l b e calculate dseparatel y fo r eac h meta l measure db y the XCEM
. 5.3 Correlation

with Reference

Method Th e degre e o f

correlatio n o f

th e XCE M wit hth e referenc e methodresult s wil l b e assesse di n term s o f

th e correlatio n coefficien t (r 2 ) fo r metal s spike da t

more tha n on e concentratio n (i.e. , Hg , Ni , Zn , an dSb)
.



### VES01691 0ERDC/CER L TR-05- 9 9 3

A secon dserie s o f

intra-metho dcorrelation s wil l b e determine db y comparin g th e relativ e ratio s o f

metal s measure db y th e XCE M fo r eac h o f th e measuremen t periods
. Thi s correlatio n assume s tha t n o fractionatio n o f

th e injecte dspecie s occurre ddurin g transport
. 5.4 Precision Precisio n wil l b e calculate di n term s o f th e percen t

relativ e standar ddeviatio n (RSD ) o f aserie s o f

XCE M measurement s mad e durin g stabl e operatio n o f th e TEAD , wit hmetal s injecte da t aconstan t

level
. Thi s precisio n wil l reflec t th e variabilit y i n th e stac k conditions , spikin g rate , an dXCE M measurement s an d wil l b e identifie da s amaximu mXCE M precisio n wit hanote i n the verificatio n repor t tha t th e calculate dprecisio n i s subjec t t o th e variabilit y o f

the test , no t onl y the XCE M variabihty
. Durin g eac h M2 9 samplin g run , al l reading s fro m th e XCE M wil l b e recorde dan dth e mea n an dstandar ddeviatio n o f thos e re cording s wil l b e calculated
. Percen t precisio n (P ) wil l the n b e determine das :

o n P= ^xl0 0 [Eq5.3 ] X wher e S D i s th e standar ddeviatio n ofth e XCE M reading s an dX i s th e mea n o f th e readings
. Th e same calculatio n wil l b e performe dfo r eac h meta l measure d b y th e XCEM
. 5.5 Span, Zero, and

Instrument

Drift Th e XCE M ha s automate ddail y spa n an dzero check s an dreport s apalladiu m concentratio n wit heac h sampl e t o chec k fo r instrumen t

drift
. Span , zero , an d instrumen t

drift wil l b e reporte di n term s o f th e mean , RSD , an drang e (maxi

mu man dmimmum ) o f the reading s obtaine dfro mth e XCEM
. Th e percen t RS D wil l b e calculate das :
RSD = ~xl0 0 [Eq5.4 ] X wher e X i s the mean , an dS D i s th e standar ddeviatio n o f th e dail y reading s o f th e standard
. Thi s calculation , alon g wit hth e rang e o f data , wil l indicat e th e day-to-day variatio n i n zero an dstandar dreadings
.



### VES01691 19 4 ERDC/CER L TR-05- 9

5.6 Method

29 and XCEM Bias Bia s betwee n th e tw o M2 9 samplin g train s an dth e M29/XCE M dat awil l b e de

termine dusin g a n EP A Metho d30 1 approach
. Th e result s ar e teste dfo r statisti

call y significan t

bia s b y calculatin g the t-statisti c an ddeterminin g i f th e mea n o f the difference s betwee n th e tw o samplin g train s i s significan t a t the 80-percen t confidenc e level
. Th e t-statisti c i s calculate db y finding th e S D o f th e difference s betwee n th e tw o samplin g trains
.

E(<w„ )

Where : d j = the differenc e betwee n th e tw o sampl e trai n value s d m= mea n o f

th e d ; value s n= numbe r

o f paire dsample s Usin g th e S D determine di n equatio n 5.5 , th e t-statisti c i s the n calculate da s fol

lows :

Th e critica l valu e ofth e t-statisti c i s 0.875 5 fo r 1 2 runs . I f

th e calculate dt-valu e i s greate r

tha n the critica l value , th e bia s a s define db y M30 1 i s statisticall y sig

nificant
. A statisticall y significan t bia s i n the referenc e methodwil l b e notedi n the validatio n report
. Metho d2 9 dat apair s tha t ar e determine dt o b e unbiase drelativ e t o eac h othe r wil l b e average dan duse dfo r compariso n t o the XCEM
. Bia s betwee n th e XCE M an daverag e M2 9 dat awil l b e determine dusin g equation s 5. 5 an d5. 6 wit h ^ bein g th e differenc e betwee n th e averag e M2 9 an dXCE M data
.



### VES01691 2ERDC/CER L TR-05-9 9 5



### 6. 0 MATERIALS AN D EQUIPMEN T
6.1 Gases

and Chemicals 6.1. 1 Compresse

d ga s Th e XCE M require s abou t 1 0 scf mo f dr y compresse dga s t o provid e avacuu mi n th e extractio n system
. A smal l amoun t o f purifie dcompresse dga s i s als o use dto driv e th e XCE M pneumatics
. Th e atomizer s use dfo r spikin g wil l requir e abou t 1 0 scf mo f dr y air
. 6.1. 2 Spik e injectio n solution

s Th e spik e injectio n solution s includ e Ba(N0 3 )2 , Cd(N0 3 )2 , Cr(N0 3 )3 , As 2 O s , Hg(N0 3 )2 , Ni(N0 3 )2 , Zn(N0 3 )2 , an dSbCl 2 . Solution s wil l b e prepare don-sit e to allo w fo r flexibilit y i n respondin g t o backgroun dmeta l concentration s foun di n th e TEA D incinerator
. 6.2 Reference

Method 6.2. 1 Samplin

g train s CHPP M wil l suppl y the glassware , filters, an dassociate dequipmen t fo r M2 9 sampling
. Multipl e train s wil l b e supplie ds o tha t si x train s (i.e. , thre e samplin g run s wit h tw o train s each ) ma y b e sample di n asingl e day ; i n addition , a t leas t tw o M2 9 fieldspike s an damedi ablan k wil l b e analyzed
. Preparation , sam pling , sampl e recovery , an dcleanin g o f use dtrain s wil l b e th e responsibilit y o f CHPP M durin g thi s verificatio n test
. 6.2. 2 Analysi

s equipmen

t CHPP M wil l provid e laborator y equipmen t fo r sampl e recovery an danalysis
. Thi s wil l includ e al l chemical s an dsolution s fo r rinsin g trai n component s an d recoverin g impinge r

samples
. 6.3 TEAD Monitoring

Equipment Th e verificatio n wil l mak e us e o f monitorin g equipmen t alread y integrate dint o the TEA D facility
. Thi s equipmen t include s monitor s fo r

majo r flu e ga s constitu

ent s (0 2 , C0 2 ) , a s wel l a s sensor s fo r temperatur e an dpressure . Thes e device s ar e considere dpar t

o f th e TEA D facilit y fo r

purpose s o f

thi s test , an dwil l b e op erate ddurin g thi s verificatio n accordin g t o norma l TEA D procedures
.



### VES01691 39 6 ERDC/CER L TR-05- 9



### 7.0 QUALIT

Y ASSURANCE/QUALIT Y CONTRO L
7.1 Assessments

and Audits 7.1. 1 Technica

l system s audit s Battelle' s Qualit y Manager , wil l perfor matechnica l system s audi t (TSA ) onc e durin g th e performanc e ofthi s verificatio n test
. Th e purpos e ofth e TS A i s t o en sur e tha t the verificatio n tes t

i s bein g performe di n accordanc e wit hthi s test/Q A plan , an dtha t

al l QA/Q C procedure s ar e bein g implemented
. I n thi s audit , th e referenc e samplin g an danalysi s method s use dma y b e reviewed ; th e actua l tes t procedure s compare dt o thos e specifie di n thi s plan ; an ddat aacquisitio n an d handhn g procedure s reviewed
. Th e Quaht y Manage r wil l als o prepar e aTS A report , th e finding s o f whic h mus t

b e addresse deithe r

b y modification s o f

tes t procedure s o r

b y documentatio n i n th e tes t record s an dreport
. A t EPA' s discretion , EP A Q A staf f ma y als o conduc t

a n independen t

on-sit e TS A durin g the verificatio n test
. Th e TS A finding s wil l b e communicate dt o testin g staff a t th e tim e ofth e audit , an ddocumente di n aTS A report
. 7.1. 2 Dat aqualit y audi t Battelle' s Qualit y Manage r wil l audi t

a t leas t 1 0 percen t

o f th e verificatio n dat a acquire di n th e verificatio n test
. Th e Qualit y Manage r wil l trac e the dat afro m initia l acquisition , throug h reductio n an dstatistica l comparisons , an dt o fina l reporting
. Al l calculation s performe do n the dat aundergoin g audi t wil l b e checked
. 7.1. 3 Assessmen

treport s Eac h assessmen t

an daudi t

wil l b e documente di n accordanc e wit hsectio n 2.9. 7 o f th e QM Pfo r

th e AM S pilot
. Assessmen t report s wil l includ e th e following :
• Identificatio n o f

an y advers e finding s o r potentia l problem s
• Spac e fo r

respons e t o advers e finding s o r potentia l problem s
• Possibl e recommendation s fo r resolvin g problem s
• Citatio n o f

an y noteworth y practice s tha t ma y b e o f

us e to other s
• Confirmatio n tha t

solution s hav e bee n implemente dan dar e effective
. 7.1. 4 Correctiv

e Actio n Th e Battell e Qualit y Manager , durin g th e cours e o f an y assessmen t

o r audit , wil l notif y th e technica l staf

f performin g experimenta l activitie s o f an y immediat e



### VES01691 4ERDC/CER L TR-05- 9 9 7

corrective actio n tha t

shoul db e taken
. Onc e th e assessmen t repor t ha s bee n prepared , the Verificatio n Testin g Leade r wil l ensur e tha t

arespons e i s provide d fo r eac h advers e findin g o r potentia l problem , an dwil l implemen t an y necessary follow-u p corrective action
. Th e Qualit y Manage r wil l ensur e tha t

follow-u p cor rectiv e actio n ha s bee n taken
.


### 8. 0 DAT A ANALYSI S AN D REPORTIN G
8.1 Data Acquisition Dat aacquisitio n i n thi s verificatio n tes t include s recordin g o f

the respons e dat a fro mth e XCEM , documentatio n o f samplin g condition s an danalytica l result s fro mth e referenc e method , an drecordin g o f operationa l dat asuc h a s combustio n sourc e conditions , tes t

temperatures , th e time s o f tes t activities , etc
. Coope r Environmenta l Service s wil l perfor mdat aacquisitio n fo r th e XCE M dur

in g th e test
. Fo r

al l tests , CE S wil l b e responsibl e fo r reportin g the respons e o f th e XCE M t o the sampl e provided
. Th e XCE M dat amus t includ e the result s o f al l test s conducte deac h tes t da y an dar e t o b e provide dt o th e tes t manage r

a t th e en do f

eac h day
. Th e XCE M dat amus t includ e al l individua l reading s o f th e XCE M (i.e. , temperature , pressure , meta l concentrations , Q A data , etc. ) liste db y tim e o f day
. Average dresult s ove r the perio do f

a n M2 9 samplin g ru n wil l b e de

termine dfollowin g th e tes t an dprovide dt o the tes t manage r

prio r t o releas e o f M2 9 data
. Othe r dat awil l b e recorde di n laborator y recor dbook s maintaine db y TEAD , CHPPM , Battelle , MSE-TA , an dCE S staf f involve di n th e testing
. Thes e record s wil l b e reviewe dt o identif y an dresolv e an y inconsistencies
. Al l writte n record s mus t b e i n ink
. An y correction s t o noteboo k entries , o r

change s i n recorde ddata , mus t b e mad e wit h asingl e lin e throug h th e origina l entry
. Th e correctio n i s the n t o b e entered , initialed , an ddate db y th e perso n makin g th e correction
. I nal l cases , stric t

confidentialit y o f

dat afro mthe XCE M wil l b e maintained
. Tabl e 8- 1 summarize s the type s o f dat at o b e recorded ; how , ho w often , an db y who mthe recordin g i s made ; an dth e dispositio n o r subsequen t

processin g o f

th e data
. Th e genera l approac h i s t o recor dal l tes t informatio n immediatel y an di n aconsisten t

forma t throughou t

al l tests
. Dat arecorde db y CE S i s t o b e turne d ove r t o the CER Ldesignate dtes t manage r

immediatel y upo n completio n o f eac h tes t day
.



### VES01691 59 8 ERDC/CER L TR-05- 9

Tabl e 8-1
. Summar y o f dat arecordin g proces s fo r the verificatio n test
. Dat a T b B e Recorde d Responsibl e Part y Wher e

Recorde d Ho w Ofte n

Recorde d Dispositio n o f Dat a

Dates , time

s o f test event s CER L Laborator y recor d book s Start/end o

f test , and a teac h chang e o f ates t parameter

. Use d t

o organ ize/chec k test results ; manually incorporate

d i n dat a spread sheet s a s necessary. Tes tparameter

s (temperature, ana lyt e identitie

s and concentrations , flows , etc.) TEAD , CERL , CHPP M Laborator y recor d book s Whe

n se to r changed, o

ra s neede d t o documen tstability . Use d t

o organ ize/chec k tes t results ; incorpo rated i n dat

a spreadsheet

s a s necessary

.
XCE M reading

s in cludin g digita

l dis plays , printouts , an

d electroni c output . CE S Laborator y recor d books, dat a sheets , o

r dat a acquisi tio n system, a

s appropriate . XCE M dat a wil l b e recorde

d continuously throughou

ttest . Data sheet

s wil l b e complete

d a s required fo reac

h test . Electronically

transferred t

o spreadsheets .

Referenc e metho d sampling data. CHPP M Laborator y recor d book s A tleasta

t start/end o

f ref . test, an d a t chang e o f ates t parameter

. Use d t

o organize/chec k test results ; incorpo rate d i n dat

a spreadsheet

s a s necessary

.
Referenc e metho d sampl e analysis , chain o f custody , an d results . CHPP M Laborator y recor d books, dat a sheets , o

r dat a acquisi tio n system, a

s appropriate . Throughou tsam pl e handlin g an

d analysi s period . Transferred t o spreadsheets .

8.2 Data Review Record s generate di n th e verificatio n tes t wil l receiv e aone-over-one revie w withi n 2 week s afte r

generation
. Thes e review s ar e to b e performe dwithi n th e organizatio n generatin g th e data
. Thes e record s wil l the n b e use dt o calculate , evaluate , an dreport

verificatio n results
. Thes e record s ma y includ e laborator y recor dbooks ; operatin g dat afro mth e combustio n source ; XCE M data ; o r refer

enc e metho danalytica l results
. Th e revie w wil l b e documente db y the perso n performin g the revie w b y addin g his/he r initial s an ddat e t o ahar dcop y o f the recor dbein g reviewed
. Thi s har dcop y wil l the n b e returne dt o th e staf f wh o



### VES01691 6ERDC/CER L TR-05- 9 9 9

generate do r

wh o wil l b e storin g th e record
. Battell e wil l receiv e acop y o f al l writte n an drecorde ddat ai n th e projec t recor dbook s an dacop y o f the XCE M data
. 8.3 Reporting Coope r Environmenta l Service s wil l prepar e asummar y tes t repor t fo r CER L documentin g th e testin g results
. Th e summar y report wil l includ e adiscussio n o f the XCE M performance , testin g processes , an dacompariso n wit h M2 9 re sults
. CE S wil l provid e Battell e wit hthi s summar y tes t repor t an dcopie s o f

al l origina l ra w fiel dan dlaborator y data
. Battell e wil l prepar e a n ET V verificatio n repor t an dstatemen t

fo r th e testin g tha t include s th e tes t

dat aan dastatistica l evaluatio n ofth e dat aa s describe di n section s 4 an d5
. Th e verificatio n repor t wil l briefl y describ e the ET V progra m an dthe AM S Center , an dwil l describ e th e procedure s use di n verificatio n test
ing
. Th e result s o f

th e verificatio n tes t

wil l b e state dquantitatively , withou t commen t o n th e acceptabilit y o f th e XCEM' s performance
. Th e summar y tes t repor t prepare db y CE S wil l serv e a s th e basi s fo r th e draf t ET V verificatio n re port
. Th e ET V verificatio n repor t an dstatemen t

wil l underg o atechnica l peer review
. Fina l approva l an ddistributio n o f the ET V verificatio n repor t an d statemen t

wil l b e conducte da s state di n th e Generi c Verificatio n Protoco l fo r th e Advance dMomtorin g System s Pilot
.


### 9. 0 HEALT H AN D SAFET Y Th e verificatio n tes t

describe di n thi s test/Q A pla n wil l b e performe da t the TEA D facilit y i n Tooele , Utah
. Al l participant s i n thi s verificatio n tes t wil l ad

here to th e healt h an dsafet y requirement s o f th e facility
. Vendo r

staf f wil l b e operatin g thei r

equipmen t

onl y durin g th e verificatio n test
. The y ar e no t re sponsibl e for , no r

permitte dto , operat e th e combustio n sourc e o r perfor man y othe r verificatio n activitie s identifie di n thi s test/Q A plan
. Operatio n o f th e XCE M doe s no t

pos e an y know n chemical , fire, mechanical , electrical , noise , o r othe r potentia l hazard
. A l l visitin g staf

f a t th e TEA D wil l b e give n asite-specifi c safet y briefin g prio r t o th e installatio n an doperatio n o f th e XCEM
. Thi s briefin g wil l includ e adescrip

tio n o f emergenc y operatin g procedure s (i.e. , i n cas e o f fire , tornado , laborator y accident ) an didentificatio n an dlocatio n an doperatio n o f safet y equipmen t

(e.g
. fire alarms , fire extinguishers , ey e washes , exits
. Tes t participant s ar e require d



### VES01691 710 0 ERDC/CER L TR-05- 9

t o wear hearin g protection
. Steel-toe dsafet y shoe s an dwork glove s ar e recom mended
. Ey e wear

i s no t required
.


### 10. 0 REFERENCE S Battelle
. (1998)
. Generi c Verificatio n Protoco l fo r th e Advance dMonitorin g Sys

tem s Pilot , Battelle , Columbus , Ohio , Novembe r 1998
. Bryson , S. , C
. Whitworth , an dS
. Kujawa
. (2000)
. Fina l Repor t - Tes t an d Evaluatio n o f

a n X-Ra y Fluorescenc e Base dMulti-Elemen t Metal s Continuou s Emissio n Monitor
. Prepare dfo r U.S
. Arm y Cor p o f

Engineer s b y MSE-TA , Butte , MT
. Environmenta l Protectio n Agenc y (EPA)
. (2000)
. Qualit y Managemen t Pla n (QMP ) fo r

th e ET V Advance dMonitorin g System s Pilot , U.S
. EP A Environ

menta l Technolog y Verificatio n Program , prepare db y Battelle , Columbus , Ohio
. EPA
. (1998)
. EP A Environmenta l Technolog y Verificatio n Progra mQualit y an d Managemen t

Pla n fo r

the Pilo t

Perio d(1995-2000) , EPA-600/R-98/064 , U.S
. En

vironmenta l Protectio n Agency , Cincinnati , OH , Ma y 1998
. EPA
. (1996)
. Propose dPerformanc e Specificatio n 1 0 fo r Multi-Meta l Continuou s Emissio n Monitors , U.S
. Environmenta l Protectio n Agency , Washington , DC
. EPA
. (1991)
. U.S
. EP A Metho d30 1 Fiel dValidatio n o f Emissio n Concentration s fro mStationar y Sources
. Federa l Registe r Vol
. 56 , No
. 114
. Jun e 13,1991
. EPA
. (1990)
. U.S
. EP A Metho d2 9 Determinatio n o f Meta l Emission s fro mSta

tionar y Sources
. Fro mEPA' s technolog y transfe r websit e www.epa.gov/ttn
.ERDC/CER L TR-05- 9 10 1



# Appendi x B : Determinatio n of XCE M

Reporte d Concentration s 2001

XCE M Meta l Concentratio n Determinatio n To measur e meta l concentration s i n stac k gas , the XCE M use s a n Aalbor g mas s flo w controlle r

t o obtai n flo w rate s an daQuan X energ y dispersiv e x-ra y fluores

cenc e (XRF ) analyze r

t o determin e mas s concentrations
. Th e Quan X reporte d mas s concentration s are the n divide db y th e tota l dr y flo w t o obtai n concentra
tion s i n microgram s pe r dr y standar dcubi c mete r . Th e entir e proces s i s auto
mate db y acustomWonderWare ® softwar e interface
. Th e origina l concentration s reporte ddurin g th e 200 1 tes t ar e show n i n Tabl e Bl
. Tes t dat awer e modifie daccordin g t o afina l post-tes t calibratio n an devaluatio n o f drye r capabilitie s resultin g i n a n 8 percen t increas e i n reporte dmeta l concen trations
. Al l calibratio n adjustment s wer e complete dprio r t o receivin g M2 9 re sults
. Th e fina l reporte dconcentration s wit hth e 8 percen t correctio n ar e shown i n XCE M Reporte d Concentrations (pag e 15)
.


### Globa l Correction s t

o Reporte

d Concentration s Flow Corrections Fo r the TEA D vahdatio n testing , th e mas s flo w mete r wa s cross-checke dwit ha Sierr amas s flow mete r an dwa s determine dt o b e i n goo dagreement
. Fo r thi s reason , n

o change s were mad e t o flo w measurement s applie dt o reporte dconcen trations
. Mass Corrections Du e t o th e rapi dturn-aroun dtim e require dfo r thi s projec t

( 6 week s betwee n contrac t awar ddate an ddehver y date) , afina l XR Fcalibratio n wa s no t con ducte dunti l afte r

th e tests
. Th e XCE M i s cahbrate dwit hthin-fil mstandard s produce db y the Nationa l Institut e o f Standard s an dTestin g (NIST ) an dMicro



### VES01691 910 2 ERDC/CER L TR-05- 9

Matte r Inc
. (Dee r

Harbor , WA)
. Thes e standards , whic h ar e 47-m mi n diameter , are large r

tha n th e x-ra y bea mintensit y area . I n contrast , the expose dspo t o n th e XCE M filte r

i s abou t 7 m mi n diamete r

an di s smalle r

tha n th e x-ra y bea m intensit y area . A globa l conversio n facto r i s require dt o convert

intensitie s fro m thi n fil mto spo t

size
. Durin g th e fina l calibratio n i t wa s determine dtha t

a globa l increas e o f

4. 4 percen t

wa s require dt o bette r accoun t fo r th e thin-fil mto spo t conversio n factor
. Dryer Inefficiency

Corrections Th e XCE M use s aga s drye r buil t b y Universa l Analyze r o f Reno , NV
. Th e drye r cool s ga s t o apredefine dtemperature , whic h condense s th e wate r i n th e ga s stream
. Wate r

i s the n remove dfro mth e drye r usin g apneumati c pump . Follow

in g the test , i t

wa s determine dtha t

manufacture r

specification s wer e no t prop erl y define dfo r

the partia l vacuu mi n th e XCEM
. CE S conducte dextensiv e test
in g o n the ga s drye r

(Tabl e B2 ) an ddetermine dthat , unde r apartia l vacuum , the XCE M ha d3. 5 percen t wate r content
. Fo r

thi s reason , the XCE M concentra
tion s wer e increase duniforml y b y 3. 5 percent
.



### VES01692 0ERDC/CER L TR-05- 9 10 3

Tabl e B1 . Origina l XCE M reporte d concentration s (ug/dscm ) uncorrecte d fo r calibratio n an d drye r changes . Dat e Star

t Sto p XCNo . R M No . X C Tim e (min ) A s B a C d C r H g N i P b S b Z n 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 10:4

5 11:0 5 11:2 6 11:4 8 12:1 0 12:3 1 12:5 3 11:0

5 11:2 6 11:4 8 12.0 9 12:3 1 12:5 3 13:1 5 65 0 65 1 65 2 65 3 65 4 65 5 65 6 Ru

n 1 Ru n 1 Ru n 1 Ru n 1 Ru n 1 Ru n 1 Ru n 1 19:48.

0 21:12. 0 21:32. 0 21:42. 0 21:41. 0 21:51. 0 22:07. 0 74.

2 78. 6 76. 8 78. 8 89.1 99. 9 57. 4 15

3 15 8 17 8 15 3 17 4 20 2 18 7 25.

7 24. 0 24. 5 20. 2 26. 1 29. 5 25. 2 2. 8 2. 3 1. 7 2. 0 2. 4 2. 0 2. 2 5 5 10 1 14 5 19 2 22 4 23 8 26 2 318 40 3 43 2 41 5 43 5 47 7 42 8 1,02

0 1,04 3 1,06 4 1,10 7 1,22 1 1,48 7 65 6 31

4 34 5 33 4 32 7 34 9 36 9 35 8 27 5 29 3 29 6 29 2 31 7 34 4 32 2 Averag e SD RS D 21:24. 7 79.

2 13. 1 1 7 17

2 1 8 1 1 25.

0 2. 8 1 1 2. 2 0. 4 1 6 17 4 7 6 4 4 41 6 4 9 1 2 1,08

6 24 9 2 3 34

2 1 9 5 30

6 2 3 8 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 13:5

8 14:2 3 14:4 6 15:0 9 15:3 2 15:5 5 14:2

3 14:4 6 15:0 9 15:3 2 15:5 5 16:1 7 65 9 66 0 66 1 66 2 66 3 66 4 Ru

n 2 Ru n 2 Ru n 2 Ru n 2 Ru n 2 Ru n 2 25:09.

0 22:56. 0 22:56. 0 22:54. 0 22:36. 0 22:34. 0 177.

3 165. 0 162. 3 155. 7 146.1 25. 5 21

3 20 7 23 0 23 1 18 0 15 9 24.

8 27. 3 24.1 20. 7 27. 0 25.1 2.

2 1. 9 1. 1 1. 9 1. 1 2. 4 17 2 21 7 22 6 20 4 22 1 23 8 34 7 39 5 39 5 37 5 38 4 36 3 3,16

8 3,00 7 2,79 3 2,48 4 2,17 3 16 8 33

3 35 1 36 8 34 2 35 1 32 2 27 7 32 0 32 5 30 7 32 1 29 5 Averag e SD RS D 23:10. 8 138.

6 56. 4 41 20

3 2 9 1 4 24.

8 2. 4 1 0 1.

8 0. 5 3 0 21 3 2 3 1 1 37

7 1 9 5 2,29

9 1,10 4 48 34

5 1 6 5 30

7 1 9 6 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 5/14/01 17:0

0 17:2 3 17:4 4 18:0 5 18:2 6 18:4 7 17:2

3 17:4 4 18:0 5 18:2 6 18:4 7 19:0 7 66 7 66 8 66 9 67 0 67 1 67 2 Ru

n 3 Ru n 3 Ru n 3 Ru n 3 Ru n 3 Ru n 3 22:45.

0 21:00. 0 20:52. 0 20:58. 0 20:53. 0 20:54. 0 20.0 16. 6 15. 0 14. 9 16. 2 13. 6 11

7 13 0 14 6 16 2 15 5 13 6 23.

5 19. 7 25. 0 26. 8 19. 8 22. 2 3. 1 2. 0 2. 4 2. 6 2. 3 2. 2 24 0 24 4 24 6 24 8 23 6 23 0 36 6 35 9 38 6 37 9 38 3 38 3 11

0 8 4 5 5 5 1 5 6 6 0 30

9 310 32 9 33 6 32 6 33 3 29 7 29 5 31 5 314 30 8 32 1 Averag e SD RS D 21:13. 7 16.

0 2. 2 1 4 14

1 1 7 1 2 22.

8 2. 8 1 2 2. 4 0. 4 1 6 24 1 7 3 37

6 1 1 3 6

9 2 3 3 3 32

4 1 2 4 30

8 1 1 3 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 8:5

9 9:1 8 9:3 9 10:0 0 10:2 1 10:4 2 11:0 3 9:1 8 9:3 9 10:0 0 10:2 1 10:4 2 11:0 3 11:2 4 68 4 68 5 68 6 68 7 68 8 68 9 69 0 Ru

n 4 Ru n 4 Ru n 4 Ru n 4 Ru n 4 Ru n 4 Ru n 4 19:43.

0 20:34. 0 20:55. 0 21:00. 0 20:58. 0 20:57. 0 20:51. 0 15.

6 17. 3 17. 7 18. 2 18. 5 16. 8 18. 3 13

4 16 1 12 4 14 2 17 6 13 4 17 0 19.

9 26. 4 30. 7 28. 3 29. 7 24. 7 26. 4 4.1 5. 8 5. 0 4. 9 4. 7 4. 8 5. 1 3 1 5 0 6 4 7 4 7 8 7 9 9 0 27

3 37 1 40 0 40 0 40 1 38 7 41 2 6

3 6 4 6 1 6 0 5 9 5 1 4 1 25

1 30 8 33 5 34 3 35 0 33 4 3S 1 21 8 29 5 32 3 32 2 31 9 314 33 9 Averag e S D RS D 20:42. 6 17.

5 1. 0 6 14

9 2 0 1 4 26.

6 3. 6 1 4 4.

9 OS 1 0 6 7 2 0 3 0 37

8 4 8 1 3 5

7 8 1 4 32

5 3 6 1 1 30

4 4 0 1 3 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 12:0

6 12:2 7 12:4 8 13:0 9 13:3 0 13:5 1 12:2

7 12:4 8 13:0 9 13:3 0 13:5 1 14:1 2 69 3 69 4 69 5 69 6 69 7 69 8 Ru

n 5 Ru n 5 Ru n 5 Ru n 5 Ru n 5 Run 5 20:55.

0 20:52. 0 20:51. 0 20:48. 0 20:57. 0 20:59. 0 19.1 17. 7 17. 4 18. 4 15. 4 17. 6 16

4 15 9 14 1 16 8 17 1 16 8 29.

0 31. 2 31. 8 31. 0 33. 2 29. 8 5. 1 5. 1 5. 6 4. 9 5. 3 5. 0 8 6 9 0 9 4 10 6 11 3 12 0 40 8 39 8 38 6 416 416 41 1 4

6 5 0 4 8 4 3 4 2 3 5 35

4 34 3 33 5 35 7 36 4 36 1 32 8 32 2 314 33 3 33 8 33 1 Averag e SD RSD 20:53. 7 17.

6 1. 2 7 16

2 1 1 7 31.

0 1. 5 5 5.

2 0 3 5 10

1 1 3 1 3 40

6 1 2 3 4

4 5 1 2 35

2 1 1 3 32

8 8 3 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 5/15/01 14:5

4 15:1 5 15:3 6 15:5 7 16:1 8 16:3 9 17:0 0 15:1

5 15:3 6 15:5 7 16:1 8 16:3 9 17:0 0 17:2 1 70 1 70 2 70 3 70 4 70 5 70 6 70 7 Ru

n 6 Ru n 6 Ru n 6 Ru n 6 Ru n 6 Ru n 6 Ru n 6 20:57.

0 20:59. 0 20:58. 0 20:56. 0 20:54. 0 20:55. 0 20:58. 0 18.

4 16. 3 13. 9 14. 3 14. 8 15. 9 15. 0 15

3 14 0 15 5 15 3 17 3 17 1 15 2 29.1 29. 5 29. 1 29. 0 31. 6 30. 4 34. 0 5. 0 5. 0 5. 0 5. 5 4. 9 5. 1 5. 7 12 7 13 5 13 2 13 0 15 5 15 2 15 4 42 2 43 1 41 0 39 8 39 5 40 9 42 8 3

6 3 6 4 5 4 4 3 4 3 3 4 2 36

3 35 8 35 8 34 4 35 2 36 0 35 9 34 8 35 0 33 5 32 4 32 6 33 6 34 2 Averag e S D RS D 20:56. 7 15.

5 1. S 1 0 15

7 1 2 7 30.

4 1. 9 6 5.

2 0 J 6 14

1 1 3 9 41

3 1 4 3 3

8 5 1 3 35

6 6 2 33

7 1 0 3



### VES01692 110 4 ERDC/CER L TR-05- 9

Tabl e B l (Cont'd) . Origina l XCE M reporte d concentration s (ug/dscm ) uncorrecte d fo r calibratio n an d drye r changes . 5/15/01 18:0

3 18:2

4 710 Ru

n 7 20:55.0 17. 9 16

9 33. 0 5.

4 14 3 44 2 4

2 36

7 357 5/15/0 1 18:2

4 18:4

5 71 1 Ru

n 7 20:58.

0 19.

3 15

4 31.9 5.

9 12 4 44 3 41 37

4 36 6 5/15/01 18:4

5 19:0

6 71 2 Ru

n 7 20:58.

0 17.

5 17

7 26.

7 5. 6 11 1 45 5 4

2 34

9 34 9 5/15/01 19:0

6 19:2

7 71 3 Ru

n 7 20:59.0 16. 9 15

5 28. 6 5.

2 11 2 42 5 3

7 34

7 332 5/15/01 19:2

7 19:4

8 71 4 Ru

n 7 20:50.0 16. 6 16

2 28.4 5.

3 12 2 38 8 3

1 34

0 31 2 5/15/01 19:4

8 20:0

9 71 5 Ru

n 7 20:41.

0 15.

5 14

8 30.8 5.1 12 7 40 4 2

8 35

1 32 5 Averag e 20:S3.5 17 3 16 1 29.9 5.

4 12 3 42 6 3

7 35

5 34 0 S D 1 3 1 1 2. 4 0 3 1

2 2 6 6 1

3 2 1 RS D 7 7 8 6 1 0 6 1

6 4 6 5/16/01 8:5

8 9:1

8 72

5 Ru

n 8 20:24.

0 30.

7 10

3 30. 1 4. 8 1 5 17

8 26

8 13

0 12

4 5/16/01 9:1 8 9:3 9 72

6 Ru

n 8 20:33.0 30.8 12 8 29.

5 5. 5 1 9 20

4 22

4 12

4 139 5/16/01 9:3

9 10:0

0 72 7 Ru

n 8 20:33.

0 26. 8 13

4 29. 9 5.

0 2 0 20

5 214 11

6 14

0 5/16/0 1 10:0

0 10:2

0 72 8 Ru

n 8 20:33.0 26. 6 14 5 27,

2 4.9 2

6 18

3 18

4 12

6 137 5/16/01 10:2

0 10:4

1 72 9 Ru

n 8 20:26.

0 21.

7 16

3 33.6 4.

7 3 1 18

9 18

7 12

5 13 0 5/16/0 1 10:4

1 11:0

1 73 0 Ru

n 8 20:24.0 28. 6 14 1 30.

2 5. 3 3 3 20

0 209 12

4 139 5/16/0 1 11:0

1 11:2

2 73 1 Ru

n 8 20:30.

0 26.5 15

0 30.0 5.

3 4 0 20

9 19

9 13

0 13 9 Averag e 20:29.0 27. 4 13

8 30. 1 5. 1 2 6 19

5 212 12

5 13 5 S D 3. 1 1 9 1.

9 0. 3 9 1

2 2

9 5 6 RS D 1 1 1 4 6 6 3 4 6 1

4 4 4 5/16/01 11:4

2 12:0

3 73 3 Ru

n 9 20:28.0 29. 0 16 9 30.6 4. 1 4 5 19

5 17

6 12

6 136 5/16/01 12:0

3 12:2

3 73 4 Ru

n 9 20:26.

0 22.

2 15

7 30.

3 5. 2 4 6 18

6 15

8 12

9 13 1 5/16/0 1 12:2

3 12:4

4 73 5 Ru

n 9 20:21.

0 25.5 14

2 28.5 4. 9 4 5 18

9 15

0 13

2 136 5/16/0 1 12:4

4 13:0

4 73 6 Ru

n 9 20:18.

0 24. 9 19

1 32.8 6.

0 5 2 20

6 17

7 14

3 14 1 5/16/01 13:0

4 13:2

5 73 7 Ru

n 9 20:24.

0 23.

2 13

2 28.8 4.8 5 0 19

9 14

0 13

4 13

4 5/16/0 1 13:2

5 13:4

5 73 8 Ru

n 9 20:19.

0 24.8 12

7 26. 6 4.8 5 4 18

5 14

1 13

4 13

3 5/16/01 13:4

5 14:0

5 73 9 Ru

n 9 20:23.0 22.5 13 9 27. 0 4.8 5 6 21 1 14

4 13

7 13

2 Averag e 20:22. 7 24.6 151 29. 2 5. 0 S

O 19

6 15

5 13

3 13 5 S D 2. 3 2

3 2.

2 O.

S 4 1

0 1

6 6 3 RS D 9 1 5 7 1 1 9 5 1 0 4 2 5/16/0 1 14:4

6 15:0

7 74 2 Run 1

0 20:24.0 25. 0 14 4 32. 1 5.

5 8 5 19

4 13

5 13

7 13

5 5/16/0 1 15:0

7 15:2

7 74 3 Ru

n 1 0 20:21.0 33.

7 17

4 34.

2 5.0 8

3 20

0 24

2 14

2 139 5/16/01 15:2

7 15:4

8 74 4 Ru

n 1 0 20:23.0 21.4 13 0 30.0 5.0 7 6 17

8 10

6 12

4 12

3 5/16/01 15:4

8 16:0

8 74 5 Ru

n 1 0 20:16.

0 22.5 17

8 29.

2 5. 0 8 4 19

3 12

4 13

5 138 5/16/0 1 16:0

8 16:2

8 74 6 Ru

n 1 0 20:21.

0 21.6 14

9 33.

5 5.1 8

8 19

2 10

0 15

1 13

5 5/16/01 16:2

9 16:4

9 74 7 Ru

n 1 0 20:20.

0 21. 6 15

4 28.6 5.

2 8 8 18

8 8

8 13

0 12 7 5/16/0 1 16:4

9 17:0

9 74 8 Run 1

0 20:20.0 17. 3 12

9 27.

7 5.0 10

1 17 3 10

2 14

1 12

7 Averag e 20:20. 7 23 3 151 30. 8 5. 1 8 6 18

8 12

8 13

7 13

2 S D 5. 1 1 9 2.5 0.

2 8 1

0 5

3 9 6 RS D 2 2 1

3 8 4 9 5 4 1 6 5



### VES01692 2ERDC/CER L TR-05- 9 10 5

Tabl e B 1 (Cont'd) . Origina l XCE M reporte d concentration s (ug/dscrn ) uncorrecte d fo r calibratio n an d drye r changes . 5/16/01 17:3

2 17:5

2 75 0 Ru

n 1 1 20:21.

0 19.

9 16

5 28.

9 5. 5 9 4 19

5 10

0 13

9 13

2 5/16/01 17:5

2 18:1

2 75 1 Ru

n 1 1 20:18.

0 19.

7 13

6 28.

0 4. 8 8 9 19

3 9

4 13

6 13 0 5/16/01 18:1

2 18:3

3 75 2 Ru

n 1 1 20:20.

0 19.

5 15

7 27.

2 4. 9 8 8 18

9 9

6 13

0 13 5 5/16/01 18:3

3 18:5

3 75 3 Ru

n 1 1 20:18.

0 19.

7 16

5 27.

9 5. 0 8 8 17

8 8

4 13

6 12 8 5/16/01 18:5

3 19:1

3 75 4 Ru

n 1 1 20:12.

0 20.

4 14

1 24.

4 5. 3 8 9 17

7 8

2 13

6 13 1 5/16/01 19:1

3 19:3

4 75 5 Ru

n 1 1 20:12.

0 20.

3 15

5 30.

3 5.1 8

6 18

6 8

2 13

2 13 5 5/16/01 19:3

4 19:5

4 75 6 Ru

n 1 1 20:17.

0 18.

7 14

1 30.

7 4. 2 7 8 19

6 8

9 13

6 13 5 Average 20.16.9 19. 7 15

1 28.

2 5. 0 8 7 18

8 9

0 13

5 13 2 S D 0. 6 1

2 2.1 0.

4 5 8 7 3 3 RS D 3 8 8 8 6 4 8 2 2 5/17/01 11:1

2 11:3

2 77 0 Ru

n 1 2 20:01.

0 25.

0 16

1 24.

6 3. 8 2 2 20

8 15

7 12

7 12

3 5/17/01 11:3

2 11:5

2 77 1 Ru

n 1 2 20:08.

0 27.

4 18

1 21.

5 3. 9 3 3 221 21

5 14

7 13 5 5/17/01 11:5

2 12:1

2 77 2 Ru

n 1 2 20:14.

0 32.

6 16

1 28.

2 4. 0 5 1 20

6 25

3 15

3 14

6 5/17/01 12:1

2 12:3

2 77 3 Ru

n 1 2 20:16.

0 25.

6 21 0 22.

6 3. 7 6 8 20

5 18

9 14

6 14

9 5/17/01 12:3

2 12:5

3 77 4 Ru

n 1 2 20:12.

0 25.1 14

1 29.

3 4. 4 7 3 19

0 14

9 14

6 14

0 5/17/01 12:5

3 13:1

3 77 5 Ru

n 1 2 20:12.

0 18.

2 16

4 25.

9 4.1 7

7 18

9 12

7 14

4 13 3 5/17/01 13:1

3 13:3

3 77 6 Ru

n 1 2 20:07.

0 20.

0 13

8 26.1 3.

8 8 0 17

7 12

9 14

4 14

0 Average 20:10. 0 24.

9 16

5 25.

4 4.0 5

8 19

9 17

4 14

4 138 S D 4. 7 2

4 2.

8 0. 2 2 3 1

5 4

7 8 9 RS D 1 9 1

5 1

1 6 4

0 7 2

7 6 6 5/17/01 14:1

4 14:3

4 77 9 Ru

n 1 3 20:15.

0 23.

6 15

0 33.

3 4. 7 7 4 18

6 11

0 15

8 13

6 5/17/01 14:3

4 14:5

4 78 0 Ru

n 1 3 20:10.

0 24.

5 19

4 31.

3 4. 9 7 4 19

7 11

3 15

7 13

5 5/17/01 14:5

4 15:1

4 78 1 Ru

n 1 3 20:09.

0 21.

9 14

7 33.

4 5. 6 7 6 21

7 10

9 15

5 13

8 5/17/01 15:1

4 15:3

4 78 2 Ru

n 1 3 20:10.

0 24.

3 12

9 31.

3 5. 4 7 7 19

7 10

3 15

7 13

8 5/17/01 15:3

5 15:5

5 78 3 Ru

n 1 3 20:12.

0 26.

2 18

2 37.

6 5. 4 7 7 16

0 11

9 15

7 10

9 5/17/01 15:5

5 16:1

5 78 4 Ru

n 1 3 20:02.

0 23.

8 15

3 36.

2 5. 6 6 9 15

7 11

2 15

4 7 6 5/17/01 16:1

5 16:3

5 78 5 Ru

n 1 3 19:57.

0 12.

0 8

7 17.

3 3. 7 4 2 6

5 7

9 7

1 2 0 Average 20:07. 9 22.

3 14

9 31.

S 5. 0 7 0 16

8 10

7 14

4 10 7 S D 4. 7 3

5 6.

7 0. 7 1 2 5

0 1

3 3

2 45 RS D 2 1 2

4 2

1 1 4 1 8 3 0 1

2 2

2 4 2

Tabl e B2 . Result s o f drye r tests .

Da y Tim e

(min ) Flo wactua l

(sLpm ) Pressur e

i n lin e (psia ) We b Bul b

Tem p <°F ) Vo l o f

air/water (L ) Mas s o f

Wate r Collecte d (a ) Vo l o f

Wate r (L ) Impinge r

% wate r b y vo l
1 27 0 0.8 2 7. 3 15 0 220. 4 7. 9 9. 8 4. 5 2 20 0 0.8 2 7. 3 15 0 163. 3 4.7 5. 8 3. 6 3 7 8 0.8 4 7. 3 12 0 65. 5 1. 8 2. 2 3. 4 4 126 0.8 3 7. 3 16 8 104. 6 2. 8 3. 5 3. 3



### VES01692 310 6 ERDC/CER L TR-05- 9



# Appendi x C : Transpor t an d Calibratio n Evaluation s

Quantitativ

e Spik e Injectio n b

y CE S
CES Spiking

Test Design Followin g calibration , aserie s o f 1 1 test s wer e conducte da t TEA D t o certif

y the calibratio n an dchec k

th e abilit y o f

th e XCE M t o transpor t particulate s fro mthe to p o f th e she dto the filte r

tape
. Th e test s include dquantitativ e spikin g o f vari

ou s aerosohze dmetal s int o th e XCE M transpor t lin e immediatel y prio r t o enter
in g th e shed
. Th e metal s were the n sample db y the XCEM
. Th e res t o f the spike daerosol , abou t

9 9 percen t

o f th e volume , wa s sample db y tw o filter s down

strea mofth e stillin g chambe r a s illustrate di n Figur e Cl
. CE S use daQuantitativ e Spik e Injectio n Syste m(QSIS ) t o conduc t the tests
. Th e QSI S include s a n atomize r an dadryin g chambe r

tha t generat e asimulate d stac k ga s containin g the metal s o f interes t i n -10 0 pp mo f

nitri c acid
. Tw o pump s pulle d80-10 0 sLp mo f the simulate dstac k

ga s throug h the atomizatio n syste man dXCE M stillin g chamber
. Approximatel y 1 percen t o f th e simulate d stac k ga s wa s sample dan danalyze db y the XCEM
. Th e remainin g ga s wa s transporte dou t

o f th e XCE M stillin g chambe r int o amanifol dcontainin g tw o filte r holders
. Th e upstrea mfilte r holde r containe da47-mm-diamete r mem brane filte r

(MF ) whil e th e downstrea mholde r hel da47-mm-diamete r quart z fibe r filte r (QFF)
. Afte r

eac h test , the meta l concentration s o n the tw o filter s were determine dusin g aQuan X XRF , an dthei r tota l mass , identifie da s the "To

ta l Capture " concentration , wa s compare dto the theoretica l atomizatio n concen tratio n an dreporte dXCE M concentrations
.



### VES01692 4ERDC/CER L TR-05- 9 10 7

ATOMIZATIO N CONCENTRATIO N XCE M CONC . TOTA L CAPTUR E

CONCENTRATIO N

Dryin g Chambe r

Atomize

r

Figur e Cl . Experimenta l desig n fo r atomizatio n tests . Mas s Flo w Mete r Pump

s

Tes tdesig n fo ratomizatio

n o f P b an d C r(Test s 1-3 ) Thre e test s wer e conducte dusin g asolutio n o f P b an dC r

nitrate s i n 5 percen t nitri c acid
. Th e injecte dsolutio n ha daconcentratio n o f 25. 4 pg/m L o f

P b an d 25. 1 pg/m L o f

Cr
. Atomize r

concentration s wer e determine db y weighin g the so lutio n before an dafte r testin g an dmultiplyin g the ne t atomize dmas s b y th e concentratio n t o determin e tota l microgram s o f meta l emitte ddurin g th e test
. Thi s mas s wa s compare dt o the tota l mas s o n th e resin-impregnate dan dquart z fibe r filter s (RI Fan dQFF ) locate ddownstrea mofth e XCEM
. Durin g thes e tests , th e XCE M reporte dvalue s ever y 2 0 minute s an dcomplete d 3 0 runs . Atomizatio n chambe r an dtota l captur e filte r temperature s wer e main

taine da t abou t 14 0 ° Fwhil e the stillin g chambe r an dcassett e wer e maintaine d a t abou t 22 5 °F
. Th e mainlin e flo w varie dbetwee n 88-9 7 sLp man dthe XCE M sample d0. 8 sLpm
. Followin g the firs t

test , alea k

wa s discovere di n th e system , s o th e firs t tes t wa s disregarde dan dathir dtes t wa s conducted
. Dat afro mth e firs t tes t ar e include d i n Appendi x C , bu t

were no t

use dt o evaluat e th e calibration
. Tes tdesig n fo ratomizatio

n o f As , Cd, Cr

, Ba , Hg , Pb , Se , an d A g (Test s 4-7 ) A secon dserie s o f

fou r test s wa s conducte dusin g aNIS T traceabl e stoc k solutio n o f As , Cd , Cr , Ba , Hg , Pb , Se , an dA g (VH GLabs , Inc. , Manchester , NH)
. Al l eigh t element s wer e a

t the sam e concentratio n i n the stoc k solution
. Tw o set s o f



### VES01692 510 8 ERDC/CER L TR-05- 9
duplicat e run s wer e conducte dwit h nomina l concentration s a t abou t 25 0 pg/m 3 fo r test s 4 an d5 an d12 5 pg/m 3 fo r test s 6 an d7
. Atomizatio n an dXCE M tem
peratur e an dflo w condition s wer e th e same a s fo r th e P b an dC r

tests
. Th e XCE M reporte dvalue s every 2 0 minute s an dcomplete da n additiona l 3 0 runs . Tes tdesig n foratomizatio

n o f Cd , Ba , Hg , Ni , Pb , an d Z n (Test s 8-11 ) Th e thir dserie s o f

test s use daNIS T traceabl e VH Gstoc k solutio n o f

Cd , Ba , Hg , Ni , Pb , an dZn
. Tw o set s o f duplicat e run s wer e conducte dwit h concentration s fro mrun s 8 an d9 cu t

i n hal f fo r run s 1 0 an d11
. Atomizatio n an dXCE M tem
peratur e an dflo w condition s wer e th e same a s fo r th e P b an dC r

test
. Th e XCE M reporte dvalue s every 2 0 minute s an dcomplete da n additiona l 3 5 run s durin g thes e tests
. CES Spiking

Test Results Atomizatio

n vs . XCE M Befor e an dafte r

atomization , the spik e injectio n solutio n wa s weighe dt o deter

min e ne t chang e i n mass . Thi s mas s wa s divide db y th e tim e an dflo w t o deter

min e atomizatio n rat e i n microgram s pe r dr y standar dcubi c mete r a s show n i n equatio n 6 : (m, -m r)-a t C t = K ' S J k -10 6[Eq6 ] d-f- t
where : C k = Ga s concentratio n fo r elemen t "k " durin g ates t i n = Initia l mas s o f

atomize dsolutio n (g

) m f = Fina l mas s o f

atomize dsolutio n (g) d= Densit y o f

solutio n (g/mL ) a t = Concentratio n o f

elemen t "k " i n solutio n ( g o f

elemen t k/m Lo f solution ) t = Tim e (min ) f = Ga s flo w rat e (dscm/min ) Dat ause dt o calculat e predicte dmetal s concentration s base do n atomizatio n rate s are shown i n Tabl e Cl
. Atomizatio n rat e prediction s vs . XCE M measure d concentration s ar e show n i n Tabl e C2
.



### VES01692 6ERDC/CER L TR-05- 9 10 9

Tabl e C1 . Flo wrate s an d concentration s use d t o calculat e atomizatio n concentrations . Tes t Atom , vo l

(ml ) A s C d F e C r B a H g N i P b S b S e A g Z n T i

m l ug/m l ug/m l ug/m l ug/m l us/m l ug/m l ug/m l ug/m l ug/m l ug/m l ug/m l ug/m l us/m l 1 2 3 4 5 6 7 8 9 1 0 1 1 56. 1

31. 9 41. 8 30. 3 37. 8 35. 5 32. 9 32. 1 31. 3 36. 2 33. 2 50. 6

50. 6 25. 1 25. 1 50. 6 50. 6 25. 1 25. 1 17. 4 17. 4 8. 6 8. 6 25. 1

25. 1 25. 1 50. 6 50. 6 25. 1 25. 1 50. 6

50. 6 25. 1 25. 1 497. 7 497. 7 246. 9 246. 9 50. 6 50. 6 25. 1 25. 1 99. 6

99. 6 49. 4 49. 4 25. 4

25. 4 25. 4 50. 6 50. 6 25. 1 25. 1 29. 9 29. 9 14. 8 14. 8 50. 6

50. 6 25. 1 25. 1 50. 6

50. 6 25. 1 25. 1 99. 6

99. 6 49. 4 49. 4

Tabl e C2 . Atomizatio n vs . XCE M concentrations .

A S C D C R B A H G TES T X C A T XC/A T X C A T XC/A T X C I A T XC/A T X C | A T XC/A T X C A T XC/A T

ug/DSC M XC/A T ug/DSC M XC/A T Ug/DSC M XC/A T ug/DSC M XC/A T ug/DSC M XC/A T 2 12 2 10 6 1.1 5 3 126 11 2 1.1 2 4 24 5 23 0 1.07 20 1 23 0 0.8 7 26 0 23 0 1.1 3 24 7 23 0 1.0 7 22 6 23 0 0.9 8 5 23 0 23 4 0.9 8 192 23 4 0.8 2 24 3 23 4 1.0 4 24 7 23 4 1.0 6 21 8 23 4 0.9 3 6 12

6 12 6 1.00 10

5 126 0.8 3 137 12 6 1.0 9 158 12

6 1.26 120 12 6 0.95 7 12

3 12 2 1.00 9 7 12 2 0.7 9 12

6 12 2 1.0

3 15

3 12 2 1.2

5 11 2 12

2 0.9 2 8 63 7 6 0.8 2 238 4 218 3 1.0 9 5 0 87 0.5 7 9 5 4 6 6 0.8 1 202 2 190 1 1.06 4 1 7 6 0.5 4 1 0 3 2 3 8 0.8 4 126 5 110 1 1.1 5 2 0 4 4 0.4 5 1 1 33 4 0 0.8 2 121 4 1152 1.0 5 2 8 4 6 0.6 1 AVG . 18 1 17 8 1.0 1 9 7 11 7 0.8 3 16 9 15 5 1.0 9 96 1 88 1 1.1 2 102 12 1 0.75

N I P B S E A G Z N TES T X C A T XC/A T X C A T XC/A T X C A T XC/A T X C A T XC/A T X C A T XC/A T

ug/DSC M XC/A T ug/DSC M XC/A T ug/DSC M XC/A T ug/DSC M XC/A T ug/DSC M XC/A T 2 11 1 10 7 1.04 3 11 7 11 3 1.0 3 4 26 6 23 0 1.1 6 23 6 23 0 1.0 3 21 7 23 0 0.9 4 5 24 7 23 4 1.0 6 22 1 23 4 0.9 4 20 4 23 4 0.8 7 6 137 12 6 1.0 9 12 2 126 0.9 7 11 3 126 0.9 0 7 12 1 12 2 0.9 9 11 7 12 2 0.9 6 10

2 12 2 0.8 4 8 45 0 43 7 1.0 3 13

3 13 1 1.0 1 46 3 43 7 1.0 6 9 38 3 38 0 1.0 1 11 4 11 4 1.00 39 4 38 0 1.04 1 0 24 3 22 0 1.1 0 7 3 6 6 1.1 0 24 9 22 0 1.1 3 1 1 22 6 23 0 0.9 8 6 7 6 9 0.9 6 23 3 23 0 1.0 1 AVG . 32 6 31 7 1.03 13 8 13 1 1.0 4 174 17 8 0.9 7 15 9 17 8 0.8 9 33 5 31 7 1.0 6 Reporte dXCE M concentration s matche dexpecte datomizatio n value s fo r A s (10 1 percent) , C r

(10 9 percent) , N i (10 3 percent) , P b (10 4 percent) , B a(11 2 percent) , S e (9 7 percent) , an dZ n (10 6 percent)
. Mercur y XCE M concentration s matche d atomizatio n rate s fo r

run s 4- 7 (9 5 percent) , bu t wer e lo w fo r

run s 8-1 1 (5 4 per cent)
. Durin g run s 8-11 , th e outsid e ai r temperatur e droppe ddramaticall y an d



### VES01692 711 0 ERDC/CER L TR-05- 9

sno w wa s o n the transpor t line
. Fo r

thi s reason , th e H g number s fo r run s 8-1 1 wer e considere dles s reliable
. Bot hC dan dA g wer e lo w b y 10-1 5 percen t relativ e t o the expecte dconcentra
tions
. Thi s differenc e wa s eithe r cause db y transpor t

inefficienc y o r

cahbratio n error . To determin e whic h sourc e create dthe discrepancy , acompariso n wa s mad e o f th e Cd/A g concentration s relativ e to othe r element s capture ddown

strea mo f

the XCEM
. Th e result s o f thes e comparison s ar e discusse di n the nex t section
. Tota l captur e vs . XCE M Th e tota l flo w use dfo r atomizatio n wa s capture ddownstrea mo f the XCE M o n a n M Fan dQFF
. Thes e filter s wer e the n analyze da t CE S an dcompare dto th e atomize dconcentrations
. Th e tota l capture syste mi s downstrea mo f a90 ° elbo w an di s no t

expecte dt o b e quantitative ; however , th e relativ e concentration s o f th e element s shoul dsta y constant
. Tabl e B 3 show s th e tota l microgram s atomize d vs . th e tota l capture ddownstrea mo f th e XCEM
. Reporte dC r concentration s hav e no t bee n correcte dfo r

filter absorption , whic h ca n b e significan t o n aQFF
. I n thi s table , i t

ca n b e see n tha t

the transpor t

efficienc y t o th e filter s wa s de

penden t o n the injectio n solution
. Fo r test s 2 an d3 , th e transpor t wa s abou t

9 0 percen t fo r Pb
. Th e secon dsolutio n wa s use dfo r test s 4 throug h 7 , wit haresult

in g transpor t

efficienc y o f

abou t 8 5 percen t

fo r As , Cd , Ni , Pb , an dSe
. Excep t fo r Hg , whic h ca n for mavapor , the atomizatio n proces s result s i n parti

cle s tha t contai n metal s i n proportio n t o thei r concentratio n i n th e origina l solu

tion
. Becaus e th e element s associate dwit hparticle s shoul db e i n proportio n t o the solution , th e result s i n Tabl e C 3 wer e normalize dt o P b to determin e relativ e transpor t

efficiencies
. Thes e result s ar e shown i n Tabl e C4
. Bot hC dan dA g i n Tabl e C 4 sho w goo dagreemen t wit hPb , arsenic , an dth e othe r elements
. Thus , i t appear s tha t

C dan dA g wer e transporte dwit hth e othe r elements
. Fro mthes e data , i t wa s conclude dtha t

th e significan t

differenc e betwee n Cd/A g an dth e othe r element s i n Tabl e C 2 wa s no t du e t o transpor t

inefficienc y bu t

rathe r th e resul t o f calibratio n error .



### VES01692 8ERDC/CER L TR-05- 9 11 1

Tabl e C3 . Tota l captur e mas s (TC ) vs . atomizatio n mas s (AT) .

A s C d C r B a H g Tes t T C A T FIL/T C T C A T FIL/T C T C A T FIL/T C T C A T FIL/T C T C A T FIL/T C

u g FIL/T C u g FIL/T C u g FIL/T C u g FIL/T C u g FIL/T C 2 700 82 1 0.85 3 79 1 107 7 0.7 3 4 119

2 157 4 0.7 6 119

2 157 4 0.76 91 7 157 4 0.58 1461 1574 0.93 101 3 157 4 0.6 4 5 153

5 196 3 0.78 1530 196 3 0.78 114

5 196 3 0.58 188

4 196 3 0.9 6 140

2 196 3 0.7 1 6 80 7 91 4 0.8 8 78 1 91 4 0.8 5 662 91 4 0.7 2 948 91 4 1.0 4 68 9 91 4 0.75 7 70 2 84 8 0.8 3 68 2 84 8 0.8 0 57 1 848 0.6 7 83

2 84 8 0.9 8 64 2 848 0.76 8 45 4 572 0.7 9 14746 1637 4 0.9 0 9 44 6 55 9 0.8 0 1463 1 15976 0.92 10 28 6 32 0 0.8 9 914 2 915 8 1.0 0 1 1 21 8 29 4 0.7 4 7263 841 8 0.8 6 AVG . 105

9 132 5 0.8 1 69 9 88 1 0.8 0 85 0 123 5 0.7 1 636

3 6903 0.9 5 93 7 132 5 0.7 2
N i P b S e A g Z n Tes t T C I A T FIL/T C T C A T FIL/T C T C 1 A T FIL/T C T C A T FIL/T C T C A T FIL/T C

n g FIL/T C fi g FIL/T C FIL/T C u g FIL/T C f g FIL/T C 2 76 0 83 1 0.9 1 3 97 0 1090 0.89 4 1258 157 4 0.8 0 119

6 157 4 0.7 6 129

5 157 4 0.82 5 162 2 196 3 0.8 3 155

0 196 3 0.79 166

7 196 3 0.8 5 6 83 7 91 4 0.9 2 80 6 91 4 0.8 8 84 7 91 4 0.9

3 7 72 8 848 0.86 702 848 0.8 3 74 1 84 8 0.87 8 195

2 3277 0.6 0 72 4 98 4 0.7 4 197 9 3277 0.6 0 9 190

6 319 7 0.6 0 71 3 96 0 0.74 193 3 3197 0.60 1 0 1421 183

3 0.7 8 463 55 0 0.84 139 4 183 3 0.7 6 1 1 113 9 168 5 0.6 8 36 9 50 6 0.7 3 114 0 168 5 0.6 8 AVG . 160

4 249 8 0.6 6 887 106 2 0.8 3 106

4 132 5 0.8 1 113

8 132 5 0.87 161 1 249 8 0.6 6

Tabl e C4 . Lea d normalize d atomizatio n mas s (AT ) vs . tota l captur e (TC) .

A s C d C r B a H g I est T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T 2 0.9 2 0.99 0.93 3 0.8 2 0.99 0.8

3 4 0.95 1.0

0 0.9 5 0.9 5 1.0 0 0.9 5 0.7 3 1.0 0 0.7 3 1.1

6 1.0 0 1.1 6 0.8 0 1.0 0 0.8 0 5 0.95 1.0

0 0.9 5 0.94 1.0 0 0.94 0.7 1 1.0 0 0.7 1 1.16 1.0 0 1.1 6 0.8 6 1.0 0 0.8 6 6 0.9 6 1.0

0 0.9 6 0.93 1.0 0 0.9 3 0.79 1.0

0 0.7 9 1.1

3 1.0 0 1.1

3 0.8 2 1.0

0 0.82 7 0.9 6 1.0

0 0.9 6 0.94 1.0 0 0.94 0.7

8 1.0 0 0.78 1.1

4 1.0 0 1.1 4 0.8 8 1.0 0 0.8 8 8 0.63 0.58 1.0 8 20. 4 16. 6 1.2 2 9 0.63 0.5 8 1.0 8 20. 5 16. 6 1.2 3 1 0 0.62 0.5 8 1.0 6 19. 7 16. 6 1.1 9 1 1 0.5 9 0.5 8 1.0 2 19. 7 16. 6 1.1 8 AVG . 0.9 6 1.0

0 0.9 6 0.7 8 0.7 9 1.0 0 0.79 1.0

0 0.7 9 10. 6 8. 8 1.1 8 0.8 4 1.0 0 0.8 4

Tes t N i P b S e A g Z n Tes t T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T 2 1.0 0 1.0 0 1.0 0 3 1.0 0 1.0 0 1.0 0 4 1.0 0 1.0 0 1.0 0 0.95 1.0

0 0.95 1.0

3 1.0 0 1.0

3 5 1.0 0 1.0 0 1.0 0 0.9 6 1.0

0 0.96 1.0

3 1.0 0 1.0

3 6 1.0 0 1.0 0 1.0 0 0.9 6 1.0

0 0.96 1.0

1 1.0 0 1.01 7 1.0 0 1.0 0 1.0 0 0.9 6 1.0

0 0.9 6 1.0

2 1.0 0 1.0

2 8 2.70 3.3

3 0.8 1 1.0

0 1.0 0 1.0 0 2.7 3 3.3 3 0.82 9 2.6 7 3.3 3 0.8 0 1.0

0 1.0 0 1.0 0 2.7 1 3.3 3 0.8 1 10 3.0

7 3.3 3 0.92 1.0

0 1.0 0 1.0 0 3.0 1 3.3 3 0.9 0 1 1 3.0 9 3.3

3 0.93 1.0

0 1.0 0 1.0 0 3.0 9 3.3 3 0.9 3 AVG . 2.8 8 3.3 3 0.8 7 1.0 0 1.0 0 1.0 0 0.9 6 1.0

0 0.9 6 1.0

2 1.00 1.0

2 2.8 9 3.33 0.8 7



### VES01692 911 2 ERDC/CER L TR-05- 9



### Evaluatio n o

f Stac k Transpor

t
Test Design Th e QSI S test s jus t

discusse di n th e previou s sectio n were abl e to effectivel y evaluat e the XCE M calibration
. Sinc e th e QSI S wa s injecte da t th e to p o f

the shed , however , mor e dat awere neede dt o determin e the transpor t efficienc y o f th e sampl e lin e fro mth e stac k t o th e shed
. T

o evaluat e th e entir e transpor t sys te man dth e responsivenes s o f th e XCE M t o munition s burning , asecon dserie s of test s were conducte dfro m3 0 Apri l t o 2 Ma y i n whic h th e TEA D stac k wa s spike db y MSE-T A fo r

metal s o f

interes t whil e munition s wer e incinerated
. A n EP A Referenc e Metho d1 7 (M17 ) typ e trai n wa s use dt o capture arepresentativ e stac k sampl e o f

P M near the inle t

o f the XCE M stac k

probe
. Result s o f

the M1 7 test s were the n compare dwit hth e concurren t XCE M concentrations
. XCEM Responsiveness

to Munitions

Destruction Durin g the stac k

spiking , TEA D conducte dnorma l burnin g operation s i n whic h the y were destroyin g 2 0 m mbullet s an dtracers
. Th e bullet s wer e observe db y th e XCE M t o hav e significan t quantitie s o f

Pb , Cd , an dti n (Sn) , whil e onl y S n wa s observe di n significan t quantitie s durin g trace r incineration
. Thes e ele

ment s were no t

spike db y MSE-TA
. A s show n i n Figur e 38 , th e XCE M displaye d goo dresponsivenes s to variou s type s o f ammunition s burnin g an dstac k opera tio n approaches
. Figur e C 2 show s the XCE M relationshi p betwee n S n an dC dwhe n bullet s wer e bein g destroyed
. Th e hig h correlatio n (r 2= 0.94 ) indicate s tha t th e tw o element s were fro mth e same source . A 7 5 t o 9 0 percen t decreas e i s see n i n C dan dP b whe n tracer s ar e bein g burne dwhil e S n remain s unchanged
. Follo w u p conver sation s wit hTEA D personne l indicate dtha t the tracer s di dno t

contai n C dan d Pb , bu t di dcontai n Sn
. Figur e C 2 als o show s the impac t o f openin g an dclosin g the bypas s valv e eac h day , wit hconcentration s exhibitin g spike s durin g the shor t perio dtha t

th e bypas s valv e wa s open . On e o f the intende duse s o f

th e XCE M i s a s amonito r to bette r

understan dcon tro l efficiencies
. Th e dat ai n Figur e 3 8 wer e use dto hel p TEA D personne l iden

tif y th e source s o f

metal s i n th e stac k

ga s an dbette r

contro l th e emissions
. Fol

lowin g M2 9 testing , TEA D stac k operator s conducte dtest s i n whic h the y use d th e XCE M t o determin e tha t th e metal s emission s coul db e significantl y reduce d b y completel y cuttin g of f th e bypas s syste mdurin g operation
.



### VES01693 0ERDC/CER L TR-05- 9 11 3

XCE M Ru n No . j j XCE M Ru n No . Figur e C2 . XCE M reporte d concentration s fo r nonspike d elements . XCEM Response

vs. MSE-TA Spiking
Fro m3 0 Apri l t o 2 May , MSE-T A spike dknow n concentration s o f Ba , Hg , Ni , Sb , an dZn
. Th e XCE M relativ e respons e t o thes e concentration s i s show n i n Figur e B3
. Othe r tha n Zn , whic h i s associate dwit h th e incineratio n feed , th e XCE M re porte dconcentration s wer e slightl y les s tha n th e MSE-T A predicte dconcentra
tion s o n 3 0 Apri l an dth e mornin g o f 1 Ma y (run s 795-837)
. Followin g thes e runs , however , th e transpor t lin e hea t

tracin g wa s complete dan dth e XCE M concentration s wer e withi n 5 t o 1 5 percen t o f MSE-T A estimate dconcentrations
.



### VES01693 111 4 ERDC/CER L TR-05- 9

78 0 SO

O 82 0 84 0 86 0 88 0 XCK M Ru n No . Figur e C3 . XCE M reporte d concentration s an d MSE-projecte d concentration s fo r spike d elements . XCEM Comparisons

to Method 17 Results
T o obtai n adequat e flow s an dmee t stac k temperatur e requirements , quart z fibe r filter s (QFF ) wer e use dfo r th e in-stac k

filte r holde r fo r M1 7 testing
. Th e QFF s canno t adequatel y tra p Hg , bu t wer e analyze dfo r

th e spike delement s Ba , Ni , Zn , an dS b a s wel l a s th e element s C dan dPb , whic h wer e bot h foun di n th e mu nitions
. A tota l o f

1 5 vali drun s wer e conducted
. Tabl e C 5 show s th e results
. Bot hN i an dZ n wer e spike dtogethe r b y MSE-TA
. Fo r

thes e tw o metals , th e XCE M t o M1 7 ratio s wer e 1.1 8 an d1.09 , respectively
. Sinc e th e XCE M wa s highe r tha n M17 , n o indicatio n o f los s i n th e transpor t lin e wa s believe dt o hav e occurred
. Th e uncertaint y o f th e ratio s wa s abou t 20-2 5 percent , whic h wa s



### VES01693 2ERDC/CER L TR-05- 9 11 5
primaril y the resul t

o f variabilit y i n th e M1 7 flo w measuremen t an duncertain

tie s i n M1 7 absorptio n corrections
. A secon dsolutio n spike db y MSE-T A containe dB aan dSb
. Th e tw o element s ha drespectiv e XCE M t o M1 7 ratio s o f 0.9 9 an d1.03 , whic h indicate dgoo d transpor t efficiencie s fo r

element s i n thi s spike dsolution
. Althoug h neithe r

P b no r C dwa s spike db y MSE-TA , significan t concentration s o f bot h were foun di n th e stac k whe n bullet s were bein g burned
. Th e concentra
tion s change ddramaticall y whe n tracer s were burne dinstea do f bullet s fo r

par t o f ru n 4
. Th e XCE M an dM1 7 wer e i n goo dagreemen t fo r Pb , bu t the XCE M wa s significantl y highe r tha n M1 7 fo r

Cd
. Th e C dresult s indicate dapotentia l XCE M calibratio n erro r fo r Cd
. Durin g th e 3 day s o f

testing , th e P dconcentration , whic h i s measure dwit h every sampl e b y th e XCE M an dindicate s stability , varie dfro m9 0 t o 10 5 percent
. Th e highe r tha n norma l variabilit y wa s determine dt o b e associate dwit hhig h ambi

en t temperature s i n th e sampl e she ddu e to afault y ai r conditioner
. Installatio n o f a n improve dtemperatur e contro l syste mwoul dhel p remed y thi s proble mi n the future
.



### VES01693 311 6 ERDC/CER L TR-05- 9|WWC| 

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# Appendi x D : Mercur y Calibratio n an d Los s Discussio n 200

2

Introductio n Mercur y (Hg ) represent s adistinctl y differen t hazardou s elemen t

fro mth e oth

er s include di n thes e test s i n tha t i t i s mor e likel y t o exis t

i n the vapo r

phas e an d ha s bee n shown t o exhibi t distinctl y differen t

transpor t

properties
. Thes e prop ertie s appear

t o hav e contribute dt o difference s i n the H g concentration s meas ure db y the differen t

method s compare di n th e 200 2 test
. Thi s appendi x dis

cusse s the detail s associate dwit hbot h th e adjustment s tha t wer e mad e t o th e XCE M calibratio n factor s an dlosse s o f H g fro mparticulat e deposit s afte r sampl e collection
. 

### Calibratio n Adjustment s Tw o adjustment s wer e mad e t o th e H g result s afte r th e firs t

M2 9 tes t

ru n wa s started
. Th e firs t

adjustmen t

wa s a7 percen t

increas e i n the H g sensitivit y fac

to r betwee n M2 9 ru n 1 an dru n 2
. Th e secon dwa s a4 percen t increas e i n the sensitivit y facto r

shortl y afte r

the completio n ofth e test s an dbefor e th e M2 9 an d XCE M result s wer e submitted
. Th e necessity fo r thes e adjustment s wa s du e i n par t t o the volatilit y o f

th e Hg , whic h make s i t difficul t t o mak e stabl e thin-fil m H g standards
. A s such , thi n filmH g standard s are no t availabl e fro mNIST
. Th e standard s tha t

are availabl e ar e relativel y unstabl e an dnee dt o b e fre

quentl y validated
. Thi s metho dlimitatio n i s generall y minimize db y the fac t tha t energ y dispersiv e X-ra y fluorescenc e (XRF ) sensitivit y factor s ar e a smoothl y varyin g functio n o f atomi c number
. Thi s allow s H g sensitivit y factor s t o b e estimate db y interpolatio n usin g well-define dsensitivit y factor s fo r ele

ment s wit hsimila r

atomi c numbe r

suc h a s platinum , gold , thallium , lea d(Pb) , an dbismuth
. Th e followin g tw o adjustment s were base do n thi s interpolatio n proces s an dare-evaluatio n ofth e best-estimate dcalibratio n factor
.



### VES01693 511 8 ERDC/CER L TR-05- 9

Adjustments

During First Day of Testing Th e XCE M underwen t mercur y calibratio n durin g preliminar y spikin g tests , prio r to the M2 9 tests
. Durin g thes e spikin g tests , the NIS T thin-fil mstandar d fo r P b wa s no t

available , an dth e H g sensitivit y wa s estimate dbase do n aprevi

ou s measuremen t

o f th e P b NIS T standard
. Thi s fac t wa s no t realize dunti l afte r th e preliminar y spikin g testin g starte dan darevie w o f th e preliminar y H g re sult s indicate dapotentia l bia s relativ e t o the NIS T P b results
. A s aresult , th e H g calibratio n wa s adjuste db y 7 percen t a t th e earlies t

possibl e time , whic h wa s afte r M2 9 ru n 1 an dbefore ru n 2
. Post-Tes t

Adjustments Th e secon dadjustmen t t o th e H g result s o f

4 percen t

wa s apphe dwhe n the cali

bratio n factor s wer e reviewe dfollowin g th e M2 9 tests
. A compariso n wit hth e rati o o f H g to P b sensitivit y factor s develope dfro mamor e extensiv e stud y i n th e laborator y indicate dtha t th e 0.83 8 rati o use ddurin g th e test s shoul dhav e bee n 0.873
. Thi s 4 percen t

correctio n wa s apphe dt o th e XCE M result s prio r t o th e submissio n o f

eithe r the M2 9 o r

th e XCE M results
.


### Losse s Fro m P M Fractio n Th e XCE M H g result s were , o n average , 1 8 percen t greate r tha n the predicte d concentration , 2 7 percen t greate r tha n th e M2 9 results , 3 7 percen t greate r tha n th e laborator y XR Fmeasurement s o f th e XCE M deposi t

spots , an d4 5 percen t greate r tha n col dvapo r

atomi c absorptio n (CVAA ) measurement s o n the XCE M deposi t spots
. Subsequen t

investigation s o f

thes e difference s strongl y sugges t tha t th e XCE M result s ar e the bes t estimat e o f

th e actua l H g concentration s i n th e stack
. I t

i s hypothesize dtha t

the larg e difference s betwee n th e XCE M H g result s an dthe result s fro mth e othe r method s i s du e t o th e los s o f H g fromthe filte r deposit s afte r

th e M2 9 an dXCE M sample s wer e collecte dan dafte r th e XCE M origina l measurement s wer e made
. Model A mode l ha s been develope dto explai n the apparen t hig h XCE M H g concentra
tion s relativ e t o M29
. I n thi s model , H g i s los t fro mth e particulat e fractio n o f the M2 9 an dXCE M filter s afte r the initia l XCE M measurement s were made
. Tha t is , asubstantia l fractio n o f H g wa s associate dwit hth e particulat e fraction , an dthe H g i n thi s particulat e wa s unstable
. Sinc e al l o f th e othe r

analytica l method s relie do n age dsamples , the H g concentratio n result s wer e lo w du e t oERDC/CER L TR-05- 9 11 9
vaporizatio n o f

particulat e H g prio r t o laborator y analysis
. A substantia l amoun t o f experimenta l dat ai s available , al l o f whic h i s supportiv e o f thi s hy

pothesize dmodel
. Mos t o f thi s experimenta l dat awa s develope donl y becaus e o f the uniqu e characteristic s o f th e XCE M an dth e fac t tha t th e XCE M elementa l measuremen t

i s nondestructiv e an dth e spectr afro meac h o f th e origina l meas urement s wer e archived
. Experimental Th e initia l XCE M measurement s were base do n th e analysi s o f filte r deposits , whic h wer e acombinatio n o f bot h absorbe dvapo r

phas e H g specie s an dsurfac e deposit s o f

particulat e H g species
. Eac h deposi t wa s analyze dusin g thre e differ

en t X-ra y excitatio n conditions , resultin g i n spectr atha t wer e use dt o determin e concentration
. Al l spectr awer e archive di n th e XCE M computer
. A s such , the deposi t wa s availabl e fo r

furthe r analysi s an dtesting , an dthe origina l spectr a wer e availabl e fo r

compariso n wit hsubsequentl y develope dspectra
. Followin g th e vahdatio n testin g a t TEAD , CE S conducte dsevera l test s t o bette r understan dth e H g concentratio n difference s betwee n M2 9 an dth e XCEM
. • Al l ofth e XCE M deposi t spot s correspondin g to al l o f the M2 9 run s wer e re analyze db y CES' s laborator y Quan X XR Fanalyze r 6 week s afte r

th e initia l vali

datio n test
. I n addition , 1 0 XCE M filter deposi t spot s wer e analyze dover a2

- mont h perio dt o evaluat e H g stability
. Spectr afro mthes e test s were compare d wit h archive dspectr afro mth e origina l validatio n test
. • Th e XCE M deposi t

spot s correspondin g t o M2 9 run s 5 an d6 were analyze d firs t b y laborator y XR Fan dthe n b y CVA A b y a n independen t laborator y (Columbi aAnalytica l Services)
. • Th e elementa l concentration s i n th e MSE-T A spikin g solution s correspondin g t o M2 9 run s 5 an d6 wer e analyticall y determine db y HK M Lab s (Butte , MT)
. Results and Discussion Th e H g result s fo r

th e origina l validatio n tes t ar e summarize di n Tabl e Dl
. Ther e i s aclea r

bia s o f abou t 2 6 percen t

betwee n th e XCE M result s an dth e M2 9 results
. Normally , th e M2 9 result s woul db e accepte da s th e bes t estimat e o f stac k H g concentratio n an di t woul db e assume dtha t th e candidat e metho d (XCEM ) wa s i n error . However , becaus e o f th e tota l Q A associate dwit hthe XCE M an dthe fac t

tha t the XR Fanalysi s i s nondestructive , i t i s possibl e t o con duc t furthe r analyse s to evaluat e the potentia l caus e o f thi s difference
. Addi

tionally , the laborator y analysi s result s fo r eac h componen t

o f th e M2 9 samplin g train s (i.e. , probe , filter, an dbac k half) wer e determine dseparately , an dar e availabl e fo r

interpretation
.



### VES01693 712 0 ERDC/CER L TR-05- 9

Tabl e D1 . Mercur y reporte d concentration s durin g Yea r 200 2 M2 9 validatio n testing . RU N PRD M29 X C Q N C A PR D X C Q N C A RU N g/DSC M Normalize d t o M2 9 1 32

4 33 2 36 7 25 7 0.9

8 1.1 0 0.7 7 2 32

5 33 4 38 1 25 1 0.9

7 1.1 4 0.7 5 3 33

3 29 4 36 5 26 2 1.1

3 1.2 4 0.8 9 4 32

2 32 7 36 8 30 1 0.9

8 1.1 3 0.9 2 5 32

3 31 8 37 9 30 8 27 4 1.0 2 1.1 9 0.9 7 0.8 6 6 32

9 28 0 37 8 28 8 25 4 1.1 8 1.3 5 1.0 3 0.9 1 7 32

7 28 5 39 2 30 2 1.1

5 1.3 7 1.0 6 8 32

5 30 6 40 6 29 4 1.0

6 1.3 3 0.9 6 9 32

4 30 9 40 5 28 7 1.0

5 1.3 1 0.9 3 1 0 32

8 29 2 39 5 28 2 1.1

3 1.3 5 0.9 7 1 1 32

6 29 5 39 7 28 6 1.11 1.3

5 0.9 7 1 2 32

2 29 3 38 9 26 7 1.1

0 1.3 3 0.91 AVG . 32

6 30 5 38 5 28 2 26 4 1.0 7 1.2 7 0.9 3 0.8 8 S D 3.

3 1 9 1 4 1 9 13.8 0.0

7 0.10 0.0

9 0.0 3 Loss o f mercur y fro m th e XCE M filte r Laboratory XRF

measurements (QN). Tw o month s afte r th e validatio n testing , CES' s laborator y Quan X XR Fanalyze r reanalyze dth e origina l XCE M deposi t sample s wit hgoo dreplicatio n fo r al l element s excep t

H g (se e Tabl e 3 1 i n mai n body o f text)
. A serie s o f

1 0 spot s o n the XCE M filte r tap e wer e reanalyze dbetwee n 2 1 Jun e 200 2 an d1 1 Jul y 2002
. Th e spots , whic h represen t 1 0 XCE M runs , showe da consisten t

H g los s o f

abou t 3 0 percen t

ove r the 3-week

period
. Othe r

source s o f erro r suc h a s shift s i n geometry o r instrumen t

instabilit y were eliminate da s possibl e systemati c source s o f erro r b y notin g tha t

the othe r

element s wer e repli

cate dwithi n experimenta l erro r t o afe w percent
. XCEM measurements (XCEM). T o confir mthi s los s o f Hg , fiv e XCE M deposi t spot s were re-analyze db y the TEA D XCEM , whic h wa s stil l operatin g wit hth e same condition s an dcalibratio n factor s a s use ddurin g th e M2 9 test s abou t 2 month s earlier
. Th e X-ra y spectr afro mth e origina l analysi s o f XCE M run s 93 9 t o 94 3 (M2 9 ru n 4

) ar e compare di n Figur e Dl
. Thi s compariso n clearl y show s tha t agreemen t

i s goo dfo r

the tw o closes t

analyt e peak s fo r

Z n an dPb , bu t

re ductio n i s substantia l i n the peak intensit y fo r

th e H g L-alph aanalyt e line
. A compariso n o f

th e XCE M H g concentration s measure ddurin g th e M2 9 testin g (1 4 Ma y 2002 ) wit h thos e measure dwit hthe XCE M o n 2 5 Jul y 200 2 indicat e a 31. 4 ± 0. 4 pg/m 3 reductio n i n measure dconcentration
. Althoug h thi s reductio n migh t be associate dwit hpossibl e systemati c error s suc h a s sampl e positioning , thi s possibl e sourc e o f

erro r wa s eliminate db y comparin g othe r element s suc h a s



### VES01693 8ERDC/CER L TR-05- 9 12 1

Z nan dP b a s wel l a s th e rati o o f H g t o thes e elements
. Th e reductio n i n H g t o Z nratio , fo r

example , wa s 29. 1 percent , whic h i s i n goo dagreemen t wit h th e Hg

measure dreduction
. Clearly , H g wa s los t

fro mth e XCE M deposi t afte r th e sampl e wa s collecte dan d analyze db y th e XCEM
. A s discusse di n th e followin g subsection , th e availabl e dat astrongl y sugges t tha t asubstantia l portio n o f th e M2 9 H g wa s als o los t fro m th e M2 9 P M filte r

deposit s prio r

t o analysis
. 

### 1400 0 1200 0 1000 0 | 800 0 o 600 0 400 0 200 0 0

•XCE M 05140 2 B XCE M 07250 2 Figur e D1 . Compariso n o f XCE M x-ra y spectr a measure d durin g M2 9 testin g an d 7 1 day s later .
Instabilit y o f M2 9 H g P M deposi t highl y likel y Althoug h ther e i s n o direc t evidenc e o f

th e los s o f

H g fro mth e M2 9 samples , ther e i s ampl e indirec t evidenc e tha t

asimila r

los s t o tha t

o f th e XCE M deposi t woul db e expected
. Thi s indirec t evidenc e i s discusse di n th e followin g thre e subsections
. Train location ofHg deposits. Th e recover y an danalysi s o f th e M2 9 probe , filter , nitri c aci dimpingers , sulfuri c aci dimpingers , an dth e hydrochlori c aci drins e wer e kep t

separat e fo r

bot h th e Ma y 200 1 an dMa y 200 2 M2 9 tests
. Th e result s ar e summarize dan dcompare di n Tabl e D2
. I t i s interestin g t o not e that , durin g th e 200 1 testing , onl y abou t 1 percen t

ofth e H g wa s deposite do n th e quart z fi

be r filter. Thi s i s typica l o f mos t stac k measurement s o f

Hg , s o ther e i s littl e concer n fo r

tb e stabilit y o f

th e P M deposite do n th e filter
. Thi s i s no t th e case , however , fo r

th e 200 2 H g measurements
. Durin g thes e latte r tests , 1 8 percen t

o f th e H g wa s deposite do n th e filte r durin g run s 1 throug h 5 , wit h n o P b i n th e Hg

Ni-Z n spikin g solution
. Afte r addin g P b t o th e spikin g solution , th e percen t o f H g depositin g o n th e filte r increase dt o 2 9 percen t fo r th e remainin g M2 9 runs . 

### Zin c Mercur y

VES01693 912 2 ERDC/CER L TR-05- 9

Tabl e D2 . Compariso n o f th e locatio n i n M2 9 samplin g train s wher e th e H g wa s deposite d durin g th e 200 1 an d 200 2 tests .

YEA R RUN

S FILT . PROB E M2

B M3 A M3 B M3 C TOTA L Percen to n Filte r 200

1 1-1 3 1.

1 0. 1 9

3 0. 4 0. 3 5. 2 10 0 Percen to n Filte r 200

2 1-1 2 24. 7 0. 1 7 1 0. 2 0. 1 4. 1 10 0 Percen to n Filte r 200

2 1- 5 18. 2 0. 2 7 7 0. 3 0. 1 4.7 10 0 Percen to n Filte r 200

2 6-1 2 29. 4 0. 1 6 7 0.2 0. 0 3.

7 10 0 Mas s o n Filte r(ng ) 200 1 1-1 3 6.0 0. 2 41 4 2.

2 1. 0 2 6 45 0 Mas s o n Filte r(ng ) 200 2 1-1 2 16

6 0. 8 48

4 1. 6 0. 4 2 8 68

1 Mas s o n Filte r(ng ) 200 2 1- 5 12 9 1. 1 55

1 1. 9 0.7 3

4 71 8 Mas s o n Filte r(ng ) 200 2 6-1 2 19

1 0. 6 43

7 1. 4 0.2 2

4 65

4
I t i s interestin g t o note tha t durin g th e 200 1 M2 9 tests , th e reporte dM2 9 H g concentration s were 1 2 percen t greate r tha n th e predicte dconcentrations ; simi

la r t o the 1 8 percen t

(1 2 percen t

wit hcorrecte dsolutio n concentrations ) meas ure di n 200 2 wit h th e XCEM
. O n th e othe r hand , the 200 2 M2 9 result s are 6 percen t les s tha n the predicte dconcentration s rathe r tha n 1 2 percen t

greate r a s i n2001
. Thes e result s ar e certainl y consisten t wit hth e hypothesi s tha t M2 9 H g result s are lo w becaus e ther e wa s alos s o f H g fro mthe M2 9 quart z fibe r filte r betwee n the tim e i t

wa s collecte do n the filte r an dthe tim e i t

wa s analyzed
. I t

i s als o consisten t

wit hthe fac t

tha t man y ofth e H g compound s an damalgam s o f H g are relativel y unstabl e an dhav e relativel y hig h vapo r pressures . Thus , i t

shoul dno t b e surprisin g tha t

i f ther e i s asubstantia l portio n o f the H g o n the filte r

a s ther e wa s durin g the 200 2 tests , ther e migh t b e apotentia l fo r

significan t

los s du e t o volatilization
. I t

als o need s t o b e note dtha t the filter s wer e no t

store di n acon trolle denvironmen t

fro mth e tim e the y wer e collecte dunti l the y were delivere d t o th e analytica l laborator y severa l day s later
. Durin g thi s time , the y ma y hav e bee n expose dt o relativel y hig h ambien t temperature s whil e bein g transporte d throug h th e wester n deser t fro mTooele , U T t o Californi ai n the bac k o f aclose d pane l truck
. Correlation with percent Hg on M29filter. Th e percen t differenc e betwee n th e M2 9 H g result s an dth e XCE M result s i s significantl y correlate dwit h the per cent H g o n th e M2 9 filter s a s i s illustrate di n Figur e D2
. Tha t is , th e percen t differenc e betwee n th e tw o method s (percen t los s fro mthe M2 9 filter ) i s depend

en t o n th e fractio n ofth e tota l H g measure di n th e M2 9 trai n tha t i s o n the filter
. Thi s observatio n i s consisten t wit hth e propose dhypothesi s fo r th e differenc e betwee n th e variou s methods , tha t is , los s o f

H g fro mthe M2 9 filter
.



### VES01694 0ERDC/CER L TR-05- 9 12 3

e 5 0 oneeBetvXCEM 4 o ' y 3 0 i - 1.25

x - 4.322

3 R 2= 0.805

5 T S 

## £ C S 2 0 • 5 s I O

I H 0 _

0 1

0 2

0 3

0 4

0 Percento

f H g o n M2 9 Filte r Figur e D2 . Percen t differenc e betwee n M2 9 an d th e XCE M vs . percen t o f H g o n th e M2 9 filter .
Precisio n Th e differenc e i n th e H g concentration s wa s no t likel y du e t o imprecisio n i n ei

the r o f th e tw o measurements
. Mercur y wa s on e o f tw o element s spike db y MSE-T A tha t

wer e clearl y no t

presen t i n th e backgroun dstac k emissions
. Thus , th e variabilit y i n th e H g concentratio n wa s du e primaril y t o variabilit y i n th e spikin g an dstac k

flo w rates
. Th e H g precisio n a s measure db y th e XCE M wa s 3. 8 percen t

an d6. 1 percen t

fo r M29 , whic h include s th e variabilit y i n th e tw o parameter s abov e a s wel l a s th e measuremen t metho dvariability
.
Mercur y t o nicke l rati o Nicke l wa s anothe r

elemen t

tha t clearl y wa s no t

presen t i n th e background , an d i t wa s i n th e sam e spikin g solutio n a s th e Hg
. Thus , th e rati o o f H g shoul dno t var y significantl y sinc e th e concentration s fo r thes e tw o element s wa s kep t con stan t fo r thes e lates t

tests
. Th e XCE M measure dH g t o N i rati o wa s 1.3 7 ± 0.01 5 (1. 1 percen t

relative ) an dclos e t o bot h th e M2 9 ratio , 1.4 1 ± 0.11 6 (8. 3 percen t relative) , an dth e predicte dconcentratio n rati o base do n th e measure dsolutio n concentratio n rati o o f 1.33
. I t i s interestin g t o not e tha t th e XCE M precisio n i s significantl y bette r

tha n th e M2 9 rati o precision , bot h o f whic h shoul db e rela

tivel y independen t

o f factor s othe r

tha n th e individua l method
.
Lo wColumbi a Analytica l Service s result s Th e XCE M deposi t

sample s submitte dt o Columbi aAnalytica l Service s fo r CVA A analysi s wer e extracte d4 1 day s afte r the y wer e analyze db y CES
. Base do n a n assume dlinea r

los s rate , th e expecte dH g concentration s a t th e tim e o f

extrac


### VES01694 112 4 ERDC/CER L TR-05- 9

tio n woul db e abou t

1 0 percen t

lowe r tha n measure db y the CE S XR Fanalyzer
. Th e observe ddifferenc e wa s 1 4 percent
. 

### Conclusio n Th e weigh t

o f evidenc e clearl y indicate s tha t th e XCE M H g deposi t wa s unstabl e a s wa s th e M2 9 P M deposi t o n th e quart z fibe r

filter
. Thi s instabilit y mos t likel y cause dthe differenc e betwee n th e H g measure db y thes e tw o method s an dthe othe r methods
. I t

i s highl y likel y that , i f thes e losse s ha dno t

occurred , th e XCE M woul dhav e passe dthe PS-1 0 R A tests
. I t i s recommende dthat , i n futur e M2 9 testing , th e filter s b e immediatel y seale d an dcoole dt

o at leas t 0 °C , store da t

belo w freezin g temperature s an ddigeste da s soo n a s possibl e afte r

sampling
.ERDC/CER L TR-05- 9 12 5



# Abbreviation s an d Acronym s
A E C Arm y Environmenta l Cente r A E D Ammunitio n Equipmen t Directorat e A M P Alternativ e Monitorin g Pla n AM S Advance dMonitorin g System s (Center ) A P E ammunitio n peculia r equipmen t CAA A Clea n Ai r Ac t Amendment s (o f

1990 ) C E M continuou s emissio n monito r CER L Constructio n Engineerin g Researc h Laborator y CE S Coope r

Environmenta l Service s CHPP M U.S
. Arm y Cente r fo r Healt h Promotio n an dPreventiv e Medicin e CVA A col dvapo r atomi c absorptio n EP A U.S
. Environmenta l Protectio n Agenc y EQ T Environmenta l Qualit y Technolog y ERD C U.S
. Arm y Enginee r Researc h an dDevelopmen t Cente r ET V Environmenta l Technolog y Verificatio n (program ) HA P Hazardou s Ai r Pollutant s HW C hazardou s wast e combustor s IC P inductivel y couple dplasm a LIB S laser-induce dbreakdow n spectroscop y L V M lo w volatil e metal s MAC T Maximu mAchievabl e Contro l Technolog y M1 7 EP A Referenc e Metho d1 7 M2 9 EP A Referenc e Metho d2 9 M F membran e filte r NESHA P Nationa l Emission s Standar dfo r Hazardou s Ai r

Pollutant s NIS T Nationa l Institut e o f Standard s an dTechnolog y P M particulat e matte r PS-1 0 EP A Propose dPerformanc e Specificatio n 1 0 QA/Q C qualit y assurance/qualit y contro l



### VES01694 312 6 ERDC/CER L TR-05- 9

QF Fquart z fibe r filte r QSI S Quantitativ e Spik e Injectio n Syste m R A relativ e accurac y RCR A Resourc e Conservatio n an dRecovery Ac t RI Fresin-impregnate dfilte r RS D relativ e standar ddeviatio n SCF M standar dcubi c fee t pe r minut e TEA D Tooel e Arm y Depo t XCE M XRF-base dcontinuou s emissio n monito r XR Fx-ra y fluorescenc e

Chemica l element s

A g silve r

P b lea d A s arseni c P dpalladiu m B abariu mS b antimon y B e berylliu mS e seleniu m C dcadmiu mS n ti n C r chromiu mT l thalliu m H g mercur y Z n zin c N i nicke l



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s wil l nee

d t o compl y wit h th e Hazardou

s Wast e Combusto

rNationa

l Emission Standar

d fo rHazardou

s Ai rPollutant

s tha twil l regulat

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s liste d unde rth e Clea n Ai rAc tAmendments . A larg e proble m forthes

e in cinerato roperation

s i s limite d knowledg

e o f th e typ e an d quantit y o f emitte d metals , s o tha tcomplianc

e ma y b e determine

d onl y throug h tria l bur n emissio

n tests . A continuou

s emissio n monito r(CEM ) fo rmulti-metal s wil l provid

e th e emissio n data , atoo l t o help mee

t complianc

e requirements

, an d th e opportunit

y t o adjus tbum strategie

s forincrease

d production. A user-friendl y multi-meta

l CE M tha

t use s x-ra y fluorescenc

e (XRF ) a

s th e analytica

l metho d an d a n automate

d samplin

g syste m tha tprovide s extractiv

e batc h samplin

g ont o a filtertap

e (XCEM ) wa

s demonstrate

d a tth e 123 6 Deactivatio

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e uni twa s compare

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d 2002) . Th

e secon d tes twa s performe

d afte rimprovement

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d Performanc

e Specificatio n 1

0 fo r multi-meta

l CEM s excep

tfo rsom

e ofth e relativ

e accurac

y requirements

. It s failure s ar e attribute

d t o inadequacie

s i n th e referenc

e method. Th

e monito ri s provin g usefu l a tTooel e an d is read y fo rimplementatio

n a tothe rArm y demilitarizatio

n incinerators . 15 . SUBJEC TTERM S emission s ai rpollutio n hazardou

s ai rpollutant

s (HAPs ) continuou s emissio

n monito r(CEM ) 16 . SECURIT Y CLASSIFICATIO N OF : 17 . LIMITATIO N O F ABSTRAC T SA R 18 . NUMBE R O F PAGE S 13 7 19a . NAM E O F RESPONSIBL E PERSO N

K . Jame s Ha y a . REPOR T Unclassified b . ABSTRAC T

Unclassified c . THI S PAG E

Unclassified 17 . LIMITATIO N O F ABSTRAC T SA R 18 . NUMBE R O F PAGE S 13 7 19D.TELEPHON E NUMBE R (includ e are a code ) (217 ) 373-348

5 NS N 7540-0 1 -280-550 0 Standar d For m 29 8 (Rev . 8-98) Prescribed b

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VES01694 5

# VES016946-016949.pd fEnviron. Sci. Technol. 1888 , 20 , 735-73 8 (20 ) Schwarzenbach , R . P. ; Giger , W. j Schaffnei , C ; Wanner , O . Environ. Sci. Technol. 1985, 19 , 322-327 . (21 ) Schweiier , C ; Tarradellas , J . Chimin 1980, 34, 609r619 . (22 ) Olle , K. | Vermeulen , P . L. ; Huteinger , 0 . Chemosphere 1977, 6 , 455-469 . (23) Buser , H . R. ; Bosshardt , H . P. ; Rappe , C . Chemosphere 1978 , 7, 165-172. (24 ) BaUachmiter , K . Universit y o f Ulm , Ulm , Federa l Republi c o f Germany , persona l communication , 1985 . (25) Harlesa , R , L. ; Oswald , E . 0. ; Wilkinson , M . K. ; Dupuy , A . E „ Jr., McDaniel , D . D. ; Han , T . Anal. Chem. 1980,52 , 1239-1245 .
Received forreview October21,1985. Accepted February 18, 1986. 

### Adsorptio n o

f Mercur y Vapo r o n Particle s YosW o Otanl, " Chlka o Kanaoka , Chlyok l Usui , Sabur o Matsul, Tan d Hltosh l Em I Departmen t o f Chemica l Engineering , Kanazaw a University , 2-40-2 0 Kodatsuno , Kanazaw a 920 , Japa n

• Th e adsorptio

n o f mercur y vapo ro n particle

s wa s studie d b y usin g soo tparticle s generate

d b y incineratio

n o f sewag e sludg e (EP-ash

) an d activate

d carbo n particles. Throug h th e experiments

, i twa s foun d that , a t29 8 K , th e EP-as h ha s afairl y hig h adsorptio

n capacit y fo rmercur y vapo ri n th e orde ro f 10" * g/g , whic

h i s betwee n tha to f th e ordinar y soil s an d tha to f activate d carbo n particles . Furthermore

, itwa s foun d tha tphysica

l adsorptio

n o f mercui y vapo ro n th e studie d particle s a thig h temperatur

e i s describe

d b y Dubinin' s equation

. O n th e basi s o f th e equation , itwa s show n tha ttli e EP-as h physicall

y adsorb s ver y littl e mercur

y vapo ra thig h temperature

, an d therefore , mos tmercur y i n th e EP-as h i

s chemicall

y ad sorbe d o rcontaine

d i n a for

m o f mercur y compounds

. Nevertheless

, th e tota l amoun to f mercur y containe

d i n th e particle

s is ver y little compare

d t o th e tota l mercur y inth e exhaus

tgase s s o tha tmos tmercur y behave s a s a vapo reve n i n th e presenc

e o f particulat

e matter . Introduction I tha s bee n reporte d tha tmercur y a ta lo w concentratio

n i s release d int o th e atmospher

e togethe rwit h combustio

n product s resultin g fro m th e incineratio

n o f sewag e sludg e o rmunicipa

l garbage . Th e mercur

y conten ti n sewag e sludg e is usuall

y 0.2-1. 8 mg/kg dr

y matter , an d mos to f th e mercur

y i s volatilize

d b y th e incineratio

n t o giv e mercur y concentration

s i n th e emissio

n o f abou t0. 3 mf/m 9 (N-m 3 ) (i , 2). Althoug h ther e i s n o regulatio

n fo r th e mercur y emissio n in wast e gases , i ti s urgen tt o instal l effectiv e collector

s fo rmercur y sinc e itma y caus e seriou s disease s b y accumulatin

g i n th e huma n body . I n incinerator

s wher e a larg e numbe ro f soo tparticle s an d reactiv e gase s ar e generate

d a ta hig h temperature

, i ti s expecte

d tha tther e ar e stron g interaction

s betwee n mercur y vapo ran d thes e substances

. I n orde rt o develo p a n effectiv

e mercur y contro l technique

, iti s necessar

y t o conduc tquantitativ

e studie s o n th e interactio

n o f mercur y vapo rwit h particulat

e matte ra s wel l a s reactiv e gases . In th e previou s pape r(3) , w e investigate

d th e existenc

e o f particulat

e mercur y i n adust-fre

e atmospher

e a tvariou s mercur y concentration

s an d foun d tha tmercur y mostl y exist s a s avapo reve n a taconcentratio

n 20 0 time s highe r tha n th e saturatio

n a t27 3 K . I n a dust y atmosphere

, however , th e situatio n woul d b e mor e complicate

d becaus e o f mercury-particl

e interaction. I n th e presen twork , th e interactio

n o f mercur y vapo r an d particles, i.e. , th

e adsorptio

n o f mercur y o n particles, wa s studie d wit h soo tparticle s obtaine d fro m a n electrostati c precipitato

ri n a sewag

e sludg e incineratio

n plan t

• Presen taddress : Departmen to f Sanitar y Engineering , Kyot o University , Voshida-Honmachi , Sakyoku , Kyot o 606, Japan . Tabl e I . Chemica l Composition s an d Physica l Propertie s o f th e Particle s
ra w heate d activate d EP-as h EP-as h carbo n ignitio n loss , % 35.2 1 33.3 7 chemical component C, % 15.3 5 16.0

5



## - H , % 0.5 9 0.3

6



### - N , % 0.2 3 0,15 - SiC V % 6.6 8 7.4

9



## - CaO, « % 16,2 0 7.6

0



## - KjO , % 1.6 9 2.0

6



## - MgO , % 0.9 7 1.0

6



### - Al 2 Oj , % 2.8 3 3.1 6



## - Fe , pp m 5.1 4 5.4 1 

### - Cd , pp m 53 1



## - - Pb , pp m 347 0



### - 

## - geometric mea n particl e 1. 6 1.

6 6

2 diameter , jt

m geometri c standar d deviatio n 1. 8 1.

8 1.

2 particl e density , g/cm 3 2.4 7



### - 

## - specifi c surface area (BE T



## - 17. 8 716 method) , m s / g "Determine d b y th e metho d specifie d b y JIS-R-2212 . 6 (-) , no t measured . (EP-ash ) an d als o wit h activate

d carbo n particles. Experimental

Procedures Adsorptio

n characteristic

s o f mercur y o n particle s wer e studie d by th e followin

g experiments : (i

) determinatio

n o f mercur y i n soli d particle

s (desorptio

n method) ; (ii

) determinatio

n o f equilibriu

m adsorbe

d mas s o f mercur y wit h packe d be d o f particle s (adsorptio

n method). I n th e experiments

, EP-ash sample

d fro m a n electrostati c precipitato

ri n a sewag

e sludg e incineratio

n plan t (ra w EP-ash

) an d th e EP-ash heate

d a t77 3 Kfo r8 min i n nitroge n atmospher

e (heate d EP-ash

) wer e use d wit h activate d carbo n particle s a s a referenc

e adsorbent

. Th e result s o f chemica l compositio

n analyse

s o f th e ra w an d heate d EP-ashe

s an d thei rphysica l propertie

s ar e show n in Tabl e I wit h thos e o f th e activate

d carbo n particles . The detail

s o f experiment

s i an d i i ar e describe

d here , (i) Desorptio n Method . Th e mercur y conten ti n particle s wa s measure

d b y trappin

g thermall

y desorbe

d mercur y i n liquid absorbent

. Particle

s wer e heate d i n nitroge n atmospher

e b y a n infrare d imag e furnac e (Shinku-rik o Co. Ltd. , Mode

l RHL-E25) . Th

e desorbe d mercur y wa s entraine

d b y nitroge n ga s an d collecte

d i n a ga

s washin g bottl e containin

g 20 0 cm 8o f 0. 2 w t% KMn0 4+ 2 N H 2 S0 4(4)

, Th e collecte

d mercur

y wa s the n determine d b y aflameless atomi

c absorptio

n spectrophotomete

r (Shimadzu

, Mode l AA-640-13) . Th e desorptio n metho d wa s examine

d b y usin g activate

d carbo n particle

s con0013-936X/86/0920-0735$01.50/ 0 © 198 6 America n Chemica l Society Environ , Sci . Technol. , Vol . 20 , No . 7 , 1986 73 5



### VES01694 6H g hollo wabsorptio n colho d lam p len s cal l | e n . I=SM-I==H - amplifie r Tabl e III . Mercur y Conten tI n th e Ha w EP-ash »

dilution l gas washin g cel l bo i li e

Figur e 1 . Experimenta l setu p fo r th e measuremen t o f breakthroug h curves . Tabl e II , Experimenta l Condition s fo rth e Measuremen to f Breakthroug h Curve s

packed mas

s of particles , g averag e particl e size , Ji

m flow velocit

y of air , cm/ s le d depth , cm be d diameter , c m bed, temperature , K mercur y vapo rconcentration , mg/(N-m s ) EP -Bshe s 0.0 7 1. 6 7. 4 0. 3 activate d

carbo n 0.0 5 5 2 10. 4 0. 2 0. 8 29 6 0.14-1. 6 tainin g know n amount

s of mercur y sinc e th e desorptio

n efficienc y o f mercur y from particle

s depend s upo n th e heatin g tim e an d temperature

. Th e mercury-containin g activate d carbo n particle

s wer e prepare

d i n th e followin

g manner . On e gra m o f activate d carbo n particle

s wa s packe d i n a 8 m m diamete

ran d 4 c m lon g bed, throug

h whic h know n volum e o f ai rcontainin

g mercur y wa s passed . Th e tota l amoun to f mercur y adsorbe

d i n th e particle s wa s calculate d b y th e tota l ai rvolum e passin g throug h th e be d an d it s mercur y vapo rconcentration

, Whe n th e temperatur e o f particle s wa s kepta t77 3 Kfor8 mi

n durin g desorption

, th e accurac

y o f th e metho d wa s withi n 5 % (standar d deviation

) ove rmercur y content s fro m 3 x lflr 6 t o 4. 4 X IO"

8g/g . (ii ) Adsorptio n Method . Th e equilibriu m adsorbe

d mas s o f mercur y in particle

s wa s determine

d b y measurin

g breakthroug

h curve s o f th e packe d beds . The experimenta l setu p i s show n i n Figur e 1 . Ai rcontainin

g a know n concentratio

n o f mercur y vapo rwa s passe d throug h th e packe d be d o f particles, an

d th e outle tconcentratio

n o f mercur y wa s continuousl

y measure

d b y introducin

g th e exi tga s directl y t o th e flameles

s atomi c absorptio

n spectrophotometer

. The equilibriu

m adsorbe

d mas s o f mercury , q, wa s obtaine d b y usin g th e followin

g relationship. < j = fVo-OdlQ. ) (1 ) wher e C 0an d C ar e th e inle tan d outle tconcentration

s o f mercury , an d Q ti s th e tota l ai rvolum e flowin g int o th e bed . Th e mercur y conten twa s als o determine

d b y th e desorptio n method

. Th e experimenta

l condition

s fo rth e measuremen

to f th e breakthroug

h curve s ar e show n i n Tabl e II . Results and

Discussion Th e mercur

y content

s i n th e EP-ash sample

s measure

d b y th e desorptio

n metho d ar e show n i n Tabl

e III . Th e averag e mercur y conten tin th e particle s i s 2.4 2 X IO"

8g/ g wit h a standar

d deviatio

n o f 0.7 5 x 10"

4g/g. Th e averag e mercury mercury mercury

content , content , content , sampl e PP m sampl e pp m sample pp m 1 3.7

3 1

6 2.7

5 3 1 1.41 2 1.1

3 1

7 3.6

0 3

2 2.4

4 3 1.5

7 18 3.3 6 3

3 1.8

0 4 1.7

4 19 3.4 8 3

4 2.8

3 5 6.8

4 2

0 2.7

0 3

5 1.7

3 6 1.9

6 2 1 2.0 0 3

6 1.7

3 7 2.1 9 2 2 2.7

6 3

7 2.6

7 6 2.2

6 2

3 2.7

7 3

8 2.5

4 9 2.5

0 2

4 2.0

0 3

9 2.6

7 10 2.4

0 2

5 1.2

0 4

0 1.9

3 1 1 2.5

0 2

6 3.4

7 4 1 1.2 8 1 2 1.41 2 7 1.8

7 4

2 2.8

3 13 1.7

0 2

8 1.4

7 4

3 1.5

6 14 3.3

0 2

9 2.9

3 4

4 . 2.9

0 15 3.6

0 3

0 2.13 4 5 3.3

4 "pp m = 10*8g/g .

ro. a > I 0. 6 S 0. 2 HeaJa d EP-as h

activate d carbo n 1 C «l. O mg/m- N 1 0.8 2 r / r / !

/ / / 0.4 9

•0.4 4 0.2 5

O O. I 0. 2 0. 3 0. 4

toto l ai r volum e flowin g int o bed , O t tnv^-N J Figure 2 , Breakthroug h curve s fo r th e heate d EP-as h an d activate d carbo n particles . conten tagree s wit h th e previousl

y reporte d mercur y content s i n EP-ashe

s o f sewag e sludg e incinerator

s (5 , 6) . The breakthroug

h curve s o f th e heate d EP-ash ar

e show n i n Figur

e 2 wit h thos e o f th e activate

d carbo n particles . Th e perio d o f zer o outle tconcentratio

n decrease

s i n th e followin

g order : activate

d carbon , heate d EP-ash , an d ra w EP-ash . Fo rth

e sam e particles, breakthroug h occur s mor e rapidl y a s th e mercur

y concentratio

n in creases . Th e equilibriu

m adsorbe

d masse s o f mercur y i n th e EP-ashe s an d th e activate

d carbo n particle

s measure

d b y th e adsorptio

n metho d ar e plotte d b y hollo w symbol

s i n Figur e 3, togethe

rwit h thos e o f variou s soil s measure

d b y Fan g (7). First, whe

n th e orde ro f thes e sorbent s i s compared , iti s note d tha tth e EP-ashes

, havin g a n adsorptio

n capacit y o f abou t10"

6g/g , ar e betwee n activate

d carbo n particle s an d ordinar

y soils . I n th e sam e figure, th

e ad sorbe d masse s o n th e ra w an d heate d EP-ashe

s measure

d b y th e desorptio

n metho d ar e show n b y soli d symbols

. Th e adsorbe d masse s o n th e heate d EP-as h measure

d b y bot h adsorptio n an d desorptio

n method s agre e wit h eac h othe r withi n experimenta

l error , wherea s th e adsorbe

d mas s o n th e ra w EP-ash measure

d b y th e adsorptio

n metho d i s lowe rtha n tha tmeasure

d b y th e desorptio

n metho d sinc e th e ra w EP-as h alread y containe

d a n averag e o f abou t2.4 2 X 10"

6g/ g mercury

. Th e adsorbe

d mas s o n th e heate d EP-ash i s highe rtha n tha tofth e ra

w EP-ash , indicatin

g tha tth e sample d ra w EP-ash i

s no tthermall

y stabl e an d it s adsorptio

n capacit

y ma y b e change d b y th e hea t treatment

. Second , lookin g a tconcentratio

n dependenc

e o fth e isotherms

, iti s foun d tha tth e heate d EP-as h an d th e ra w 7) 0 Environ . Sci . Technol. , Vol . 20 , No . 7 , 198 6



### VES01694 7mercur y concentration

, C- Cmg/rrt'-N

l Fljiir s 3 . Compariso n of adsorptio n Isotherm s o t variou s adsorbents , EP-as h measure

d b y th e adsorptio

n metho d hav e almos t th e sam e slop e a s tha tof th e activate

d carbon

. Th e agreemen

to f th e slope s probabl

y indicate

s tha tmercur y vapo ri s adsorbe

d o n thes e particle

s b y th e sam e mechanism , i.e., physica

l adsorptio

n whic h i s th e mai n adsorptio

n mechanis m o n th e activate

d carbon . O n th e othe rhand, th e slop e o f di e ra w EP-as h measure

d b y th e desorptio

n metho d i s smalle rtha n tha to f th e othe radsorbents

. The possibl e explanatio

n fo rth e wea k concentratio

n dependenc e o f th e ra w EP-ash ma

y b e th e resul to f mercur y conten to f th e ra w EP-ash , whic

h i s mos tprobabl y presen t inth e for

m o f mercur y compounds

. When, th e abov e consideration

s ar e take n int o accoun t an d th e Freundlic

h isother

m i s applie d t o th e data , physica l adsorptio

n o f mercur y vapo ro n th e studie d particle s ca n b e expresse

d b y th e followin

g equations

. Fo r th e ra w EP-ash (b

y adsorptio

n method ) (2

) (3 ) q = (3. 5 X lO^Co 0 8 7 Fo rth e heate d EP-as h q = (5. 4 X W W Fo rth e activate

d carbo n q = (1. 8 X lO-^C/ 3 7(4 ) wher e q i s th e adsorbe

d mas s i n g/ g an d C 0i s th e equilibriu m mercur

y concentratio

n i n g/(N-m s ) . W e hav e obtaine d th e adsorptio

n isotherm

s o f mercur y vapo ro n th e ra w EP-ashe

s a troo m temperatur

e (29 8 K) . I n orde rt o predic tth e adsorbe

d mas s o f mercur y a televate d temperatures

, w e appl y Dubinin' s equatio

n t o th e obtaine d isotherms

, confinin

g ou rconsideratio

n t o th e physica l adsorptio

n o f mercur y vapor . I n addition, sinc

e th e adsorptio

n capacit

y o f th e ra w EP-as h wa

s foun d t o b e change d b y th e hea ttreatment

, w e assum e tha tisother m ofth e ra

w EP-as h a

thig h temperatur

e varie s betwee n tha to f th e ra w EP-as h a

troo m temperatur

e an d tha to f th e heate d EP-ash , followin

g th e sam e concentra

tio n dependence

, i.e . 1 2 3 4 adsorption potential , AxlO" 4 5 tJ/mot l Figure 4 . Adsorbe d masse s of mercur

y o n th e activate

d carbo n particle s an d EP-ashe s a s a functio n o f th a adsorptio

n potential

. wher e 3. 5 X IO" 5< a

< 5. 4 X 10" * an d p = 0.37 . Th e Freundlic

h for m o f e q 5 i s rewritte

n i n th e for m o f Du binin' s equatio

n a s q - g o exp(-A/.E ) (6 ) I n thi s equation

, q 0is a constant

, E th e characteristi

c energ y o f adsorption

, an d A th e Polanyi' s potentia

l give n b y A = RT l n (P,/Po) (? ) wher e R i s th e ga s content , T i s th e temperature

, an d P, an d P 0ar e th e saturate

d vapo rpressur e an d th e adsorptio

n equilibriu

m pressure

, respectively

. ? 0an d E ar e relate d t o a an d / J i n e q 5 b y th e followin

g equations :

> = 0! \rt ) E = RT/0 (8 )

(5 ) (9 ) Substitutio

n o f a an d 0 int o e q 8 an d 9 yield s th e constant

s o f e q 6 a s 8. 2 x icr < < 9 o< 1. 3 x irr * (g/g

) J S = 6. 7 X 10

3(J/mol ) fo rra

w EP-as h (10

) T o tes tth e applicabilit

y o f Dubinin' s equation

, th e equilibriu

m adsorbe

d mas s wa s measure

d a televate d temperatures

. I n th e experiment

, activate d carbo n particle s wer e use d becaus e mercur y vapo ri s physicall

y ad sorbe d o n bot h ra w EP-ash an

d activate

d carbo n particle

s an d th e equilibriu

m adsorbe

d mas s o f th e ra w EP-ash i

s change d b y hea ttreatment

. The experimen

twit h th e activate d carbo n ca n provid e informatio

n o n th e temperatur e dependenc

e o f th e mercur y adsorptio

n i n cas e o f physica l adsorption

. Th e equilibriu

m adsorbe

d mas s measure d a tvariou s temperatur

e i s plotte d i n Figur e 4 a s a functio n o f th e adsorptio

n potential

. The dat

a fo rbot h ra w an d heate d EP-ashe

s contai n onl y thos e obtaine d a t roo m temperature

. I n th e figure, th

e curve B ar e predicte

d line s b y e q 6 . Th e dat

a obtaine d a tvariou s temperature

s forth e activate

d carbo n particle

s ar e i n fairly goo

d agreemen twit h th e predicte

d line, showin

g tha tth e for m o f e q 6 i s applicabl

e t o th e physica l adsorptio

n o f mercur y vapor . I f w e tak e representativ

e value s o f th e temperature

, th e concentratio

n o f mercur y vapor , an d th e dus tconcentra

tio n a tth e outle to f th e electrostati

c precipitato

ra s 47 3 K , 0. 3 mg/(N-m s ) , an d 0. 2 g/(N-m 3 ) , respectively

, the n th e Environ . Sci . Technol. , Vol . 20 , No . 7 , 1986 73 7



### VES01694 8adsorptio n potentia

l is A ~ 5.

3 X 10

4J/mol . B y substitutio n o f thi s valu e int o e q 6 wit h th e constant

s give n i n e q 10 , th e equilibriu

m adsorbe

d mas s o f mercur y vapo ri s betwee n 3. 0 X IO"

8an d 4. 8 X 10" * g/g . Thus , th

e quantit y o f mercur y i n th e particle s leavin g th e precipitato

ri s onl y betwee n 6. 0 X IO" 1 0an d 9. 6 X 10" 1 0g fo reac h N-m 3ga

s generate d compare

d wit h th e averag e mercur

y concentratio n 0. 3 mg/(N-m 8) . Thi s calculatio

n resul tindicate

s tha tth e ra w EP-as h woul

d contai n ver y littl e mercur

y vapo ra thig h temperature

s if th e mercur y is onl y physi call y adsorbe

d o n th e particles

. However

, sinc e abou t2.4 2 X Kr 6g/ g o f mercur y wa s detecte d i n th e ra w EP-ash i

n average , i tca n b e sai d tha tmercur y i s no tadsorbe d physicall y o n th e EP-ash bu

titi s chemicall

y adsorbe

d o r containe d i n th e for m o f chemica l compounds

. Therefore

, if w e assum e tha tth e averag e mercur

y conten to f th e EP-as h doe s no tchang e wit h temperatur

e sinc e th e mercur y compound

s ar e mor e stabl e thermall

y tha n meta l mercury , th e amoun to f mercur y a tth e representativ

e conditio n o f th e incinerato

remissio n i s 4. 8 X 10" ' g/CN-m 3 ) . Althoug h thi s predicte

d valu e i s abou t10 0 time s highe r tha n th e amoun to f physicall y adsorbe

d mercury

, i ti s still onl y y 6 o o o f th e tota l mercur y conten tin th e incinerato

r emission . Therefore, w

e ma y conclud

e tha tmos tmercur y i s i n th e vapo rstat e eve n i n th e presenc e o f soo tparticles

. Conclusions Th e adsorptio

n experiment

s lea d t o th e followin

g conclusions : (1 ) Th e mercur

y conten tin th e EP-ash sample

d fro m a n incineratio

n plan ti s abou t2.4 2 x IO"

6g/ g whic h agree s wit h th e previousl

y reporte d value s fo rth e sewag e sludg e incineratio

n dus tcollecte d b y a n electrostati

c precipitator

. (2 ) Th e EP-as h ha s a fairl y hig h mercur

y adsorptio

n capacit y o n th e orde ro f 10" 8g/ g compare

d wit h th e ordinar y soils. (3 ) Physica

l adsorptio

n o f mercur y vapo ra ta n elevate d temperatur

e ca n b e predicte

d b y Dubinin' s equation

. (4 ) Ver y little physicall

y adsorbe

d mercur y o n th e ra w EP-as h occur

s a tahig h temperature,-an

d mos tmercur y i s chemicall

y adsorbe

d o rcontaine

d a s chemica

l compound s i n th e EP-ash . Acknowledgments W e expres s ou rappreciatio

n fo rth e financial suppor

t an d usefu l discussion

s b y T . Kasakura

, Assistan

tt o th e Genera l Manager

, Environmenta

l Syste m an d Equipmen

t Division, NG KInsulators , Ltd .

. Registr y No. Hg

, 7439-97-6 ; C , 7440-44-0 . Literature Cited (1 ) Suzuki , M. ; Kubota , H. ; Kanaya , K . Kougai to Taisaku 1985 , 21 , 69-76 . (2 ) Kato , T . Nibo n Gaish i Researc h Report-Kanky o Souch i Tokushu , NG KInsulator s Ltd. , Japan , 1976 . (3 ) Otani , Y. ; Emi , H. ; Kanaoka , C ; Matsui , S . Environ. Sci. Technol. 1984, 18

, 793-796 . (4 ) Kitamura , S. ; Kondo , M. ; Takizawa , Y. ; Fujii , M ; Fujiki , M . Suigin; Koudansh a Press : Tokyo , 1976 ; p 84 . (6) Hayashi , S . Sangyo Kougai 1980, 16 , 714-717 . (6) Kurihara , S . Kagaku Kogyo 1980 , 1, 83-88 . (7) Fang , S . C . Environ. Sci. Technol, 1978, 12 , 285-288 . (8 ) Astakhov , V . A. ; Dubinin , M . M. ; Romankov , P . G . Theor. Osn. Khim. Tekhn. 1969 , 3 , 292-295 . Received forreview April

IB, 1985. Revised

manuscript

received February 20,1986. Accepted April 8,1986.

738 Environ . Sci . Technol. , Vol . 20 , No . 7 , 1986



### VES01694 9

# VES016950-016960.pd fThi s articl e wa s downloade d by : [70.88.2.29 ]

On : 3 0 Octobe r 2014 , At : 13:5 9 Publisher : Taylo r & Franci s Inform a Lt

d Registere d i n Englan d an d Wales Registere d Number : 107295 4 Registere d office : Mortime r House , 37-4 1 Mortime r Street , Londo n WI T 3JH , U K



## Journa l o

f th e Ai r 8

t Wast e Managemen t Associatio n Publicatio n details , includin g instruction s fo r author s and subscriptio n information : http://www.tandfonline.com/loi/uawm2 0 

## Validatio n of Thre e Ne wMethod s fo r Determinatio n of Meta l Emission s Usin g a Modifie d Environmenta l Protectio n Agenc y Metho d 30 1 Catherin e A . Yanc

a a, Dougla

s C . Barth a , Kra

g A . Petterso n a, Michae l P . Nakanishi a

, Joh n A . Cooper a , Bruc e E . Johnsen b, Richar

d H . Lambert c& Danie l G . Bivins d

aCooper Environmenta l Services , LL C , Portlan d , O

R , US A

bSAIF Co . , Portlan d , O R , US A

cEngineerin g Tec h Center , El i Lill y and C o , Indianapoli s , I

N , US A

d U.S . Environmenta l Protectio n Agenc y , Research Triangl e Par k , N C , US A Publishe d online : 2

7 Fe b 2012 .
T o cit e thi s article : Catherin e A . Yanc a , Dougla

s C . Barth , Kra

g A . Petterso n , Michae l P . Nakanish i , Joh n A . Cooper , Bruc e E . Johnse

n , Richar

d H . Lamber

t & Danie l G . Bivin s (2006 ) Validatio n o

f Three Ne

wMethods fo r Determinatio n o f Meta l Emission

s Using a Modifie

d Environmenta l Protectio n Agenc y Metho d 301 , Journa l o

f th e Ai r & Wast

e Managemen

t Association , 56:12 , 1733-1742 , DOI : 10.1080/10473289.2006.1046457 8 T o lin k t o thi s article : http://dx.doi.org/10.1080/10473289.2006.10464578

PLEAS E SCROL L DOW N FO R ARTICL E Taylo r & Franci s make s every effort to ensure th e accurac y o f al l th e informatio n (th e "Content" ) containe d i n th e publication s o n ou r platform . However , Taylo r & . Francis , ou r agents , an d ou r licensor s mak e n o representation s o r warrantie s whatsoeve r a s t o th e accuracy , completeness , o r suitability fo r an y purpos e o

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### VES01695 0TECHMICA L PAPE R ISSN 1047-328 9 J. Air& Waste Manage. Assoc. 56:1733-174 2 Copyrigh t 200 6 Ai r & Waste Managemen t Associatio n 

# Validatio n o f Thre e Ne wMethod s forDeterminatio n o f Meta l Emission s Usin g a Modifie d Environmenta l Protectio n Agenc y Metho d 30 1 Catherin e A . Yanca

, Dougla s C . Barth

, Kra g A . Petterson

, Michae l P . Nakanishi

, an d Joh n A . Coope

r Cooper Environmental

Services, LLC, Portland, OR Bruc e E . Johnse

n SAIF Co., Portland, OR Richar d H. Lamber

t Engineering

Tech Center, Eli

Lilly and Co., Indianapolis, IN Danie l G . Bivin

s U.S. Environmental

Protection

Agency, Research

Triangle Park, NC

ABSTRAC T Thre e ne

w method s applicabl e to th e determinatio n of hazardous meta l concentration s i n stationar y source emissions wer

e develope d an d evaluated fo rus e i n U.S . Environmenta l Protectio n Agency (EPA ) complianc e applications . Tw o of

th e thre e independen tmethods , a continuou s emission s monitor-base d metho d (Xact ) an d a n X-ray-base d filtermetho d (XFM) , ar e use d to measur e metal emissions . Th e thir d metho d involve s a quantitativ e aeroso l generato r(QAG) , whic h produce s a reference aeroso l used t o evaluat

e th e measurement methods . A modificatio n of EP A Metho d 30 1 wa

s use d t o validat

e th e three method s fo rAs , Cd , Cr , Pb , an d Hg , representin g three hazardous wast e combusto rMaxi mu m Achievabl e Contro l Technolog y (MACT ) metal categorie

s (lo w volatile , semivolatile , an d volatile) . Th e modifie d procedure teste d th e method s usin g mor e stringentcriteri a tha n EP A Metho d 301 ; these criteri a include d accuracy , precision , an d linearity . Th e aeroso l generatio n metho d wa s evaluated i n the laborator y b y comparin g actua l wit h theoretical aeroso l concentra tions . Th e measurementmethod s wer e evaluate d a

ta hazardou s wast

e combusto r(HWC ) b y comparin g mea sured with referenc e aerosol concentrations . Th e QAG , Xact , an d XF M metth e modifie d Metho d 30 1 valida tio n criteria . Al l three of th e method s demonstrate d precision s an d accuracies o n th e ordero f 5% . In addi tion , correlatio n coefficients fo reac h metho d were o n th e orde ro f

0.99 , confirmin g th e methods ' linea rre spons e an d hig h precisio n overa wide range of concen trations . Th e measurementmethod s shoul d be applica bl e to emission s fro m a wide range o f sources , an d th e reference aerosol.generato rshoul d be applicabl e t o ad ditiona l analytes . EP

A recentl y approve d a n alternativ e monitorin g petitio n fo ran HW C a tEl i Lilly' s Tippeca no e sit e i n Lafayette , IN , i n whic h th e Xac tis use d fo r demonstratin g complianc e with th e HW C MAC T meta l emissions (low volatile , semivolatile , an d volatile) . Th e QA G reference aerosol generatorwa s approve d a

s a metho d fo rprovidin g a quantitativ e reference aerosol , whic h is require d fo rcertificatio n an d continuin g qual ity assuranc

e o f th e Xact . INTRODUCTIO N Ai rtoxi c metal s hav e been associated wit h a wid e rang e of environmenta l an d huma n healt h effects , includin g respirator

y disorders , pulmonar y disorders , an d can cer. 1 ' 2EP

A regulates th e emissions o f toxi c metal s fro m stationar

y sources unde rth e Nationa l Emissio n Stan dard s fo rHazardou s Ai rPollutant s (NESHAP

) o rMaxi mu m Achievabl e Contro l Technolog y rule. 3Currently , emissions ar

e estimate d base

d o n contro l efficiencie s establishe d durin g performance test s an d estimate d fee d rate

s durin g normal operations . Whe n actua l emis sions ar e measured , EP

A Referenc

e Metho d 2

9 (Metho d 29) i s used. 4However , Metho d 29 is base d o n 30-yr-ol d IMPLICATION S Th e tw o measuremen t method s fo r

determinin g meta l emission s validate dI

n thi s stud y (the Xac t

an dth e XFM ) includ e significan t

improvement s i n measuremen t technol

ogy . Withthes e tw o ne w methods , plan t operator s ca n mak e mor e precise , accurate , an dfrequen t measurements , leadin g t o abette r

understandin g o f

emissions
. Withth e ne w referenc e aeroso l generato r validate di n thi s stud y (the QAG) , developmen t

an devaluatio n o f

ne w measuremen t method s ar e no w mor e practical
. Th e measuremen t meth

od s are applicabl e t o awid e rang e o f element s an dma y b e applicabl e t o othe r

sources . Th e aeroso l generato r ma y b e applicabl e t o bot h organi c an dinorgani c analytes
.

Volume 5

6 Decembe r200

6 Journal of the Air & Waste Management

Association

1733Yanca et al. impinge rtechnolog y wit h accuracies an d precision s o n th e ordero f

15%. 5 - 7Th e metho d also involve s hazard ou s chemicals , an d itrequires lon g turnaroun d times . I t i s clea rthatthere ar

e opportunitie s fo rimprovemen ti n th e currentmonitorin g technology . There have bee n attempt s overth e pastdecade t o improv e metal s measurementtechnolog y b y develop in g multimeta l continuou s emissions monitorin g sys tem s (CEMS). 8 - 1 0Non e o f th e proposed technologie s hav e been approve d fo rcomplianc e demonstratio n othe rtha n thos e discussed i n thi s paper. Th e ne w tech nolog y presente d her e include s three new method s ap plicabl e t

o th e determinatio n of hazardous metal con centration s i n emissions : a multimeta l CEMS-base d metho d (Xact) , a samplin g an d analysi s measurement metho d (X-ray-based filte rmetho d [XFM]) , an d a Na tiona l Institut

e fo rStandards an d Technolog y (NIST- - traceable reference aerosol generatin g metho d (QAG) . Th e method s an d th e instrument s use d to perfor m th e method s wer

e develope d to provid e mor e precise , accu rate , an d frequen tmeasurementcapabilitie s tha n ar e offere d b y Metho d 29 . Th e Xac tmetho d use

s a CEMS based o n X-ra y fluorescenc e (XRF ) analysis o

f aeroso l deposit s (particulat

e an d vapo rphase

) o n reactive filter tape. 111 2XF M is comparabl e t o Metho d 2

9 bu tuse

s reactiv e filters (soli d sorbants) 11 ' 1 2instead of impinger s t o tra p bot h particulat

e an d vapo rphas e metals , fol lowe d b y nondestructiv e XRF analysi s of th e filters. Th e quantitativ e aerosol generato r(QAG ) i s base d o n neb ulizatio n o f

ametal-containin g solutio n an d produce s a referenc e aerosol thatca n b e use d t o validat

e measure men tmethods , such a s th e Xactan d XFM . T o evaluat

e the performance o

f the ne w methods , a tes tplan 1 3base

d o n th e requirement s o f EP A Metho d 301 1 4wa

s developed . Metho d 30 1 is a define d procedur e fo rvalidatin g ne

w pollutantmeasuremen tmethods that coul d potentially b

e use d to demonstrat

e complianc e with permit

s o rotherEP

A applications . A mor e stringen

t modificatio n o f

thi s procedur

e wa s use d t o validat

e th e thre e methods base

d o n accuracy, precision , an d linearit

y criteria . Thi s pape

rpresents : (1

) a n overvie

w of th e thre

e methods , (2

) th e procedur

e use d fo rvalidatin g these methods , an d (3

) th e result

s of the validatio n tests. Detail s abou tthes e instrument

s an d methods , performanc e specifications , an d standar d operating procedure s ar e pre sented elsewhere. 15 - 2 0 EXPERIMENTA LWOR K Quantitativ e Referenc e Aeroso l Generatio n Th e metho d fo rgeneratin g a quantitativ e reference aerosol involve s th e operatio n of th e QA G instru ment. 1 5 ' 2 1 Usin g th e QAG , a n aerosol of analyt e solu tio n droplet

s is create

d usin g a nebulizer. 21 - 2 2Th e drop let s ar e the n passe

d int o a settlin g chamberwher e th e larg e droplet

s ar e remove d an d liqui d an d vapo rphases ar e equilibrated . Droplets <3 0 \x.m i n diameterar e al lowe d t o pass into a dryin g chamberwher e the y ar

e drie d befor

e bein g emitted . Th e aeroso l exitin g th e dry in g chamberconsist

s o f th e transpor

tgas, wate

ran d metal vapor , an d drie d saltparticles . Th e aerosol emis sio n concentratio n (Q ) is calculate d fro m th e analyte concentratio n i n th e nebulize d solutio n (C s ) , th e solu tio n emissio n rat

e (R m ) correcte d fo rvapo rlos s (R v ), an d th e total volum e o f nebulizing , drying , an d dilu tio n ga s use d t o creat e th e aerosol (Ft

).
C a = y(R m -R v

) (1 ) Quantitatio n of

th e emitte

d aeroso l is mad e possibl e by : (1 ) usin g a larg

e reservoiro

f NIST-traceabl

e analyt e solu tio n t o minimiz e th e impac tof evaporation o n solutio n concentration , (2

) continuousl y measuring th e solutio n emissio n rat

e (R^) with aNIST-traceabl e balance , (3 ) pre cis e contro l of

nebulize rconditions , an d (4 ) stabl e contro l o f th e maximu m drople tsiz e introduce d into th e gener ator' s dryin g chambersuc h tha tonl y aerosol

s wit h hig h transpor tefficiencie s ar

e generated . Th e referenc e aeroso l produce d b y th e QA G is proces s NIS T traceabl

e an d ca n be use d i n additio n t

o it s otherapplications to challeng e and evaluat e the accuracy , precision , an d linearit y o f th e measuremen tmethods . I

ti s applicabl e t

o both meta l and nonmetal species . Meta l Concentratio n Measuremen t Xact. Th e Xac tmetho d of metal s measurementuses a CEMS , calle d th e Xac tCEMS , thatcollects an d analyze s asampl e of

emission s usin g filter-based technolog y an d nondestructiv e XRF. 1 5 - 2 3Durin g sample collection , th e Xac tCEM S direct

s a continuou s flow o f stack ga

s throug h a stillin g chamberwher e it s velocity is reduce d (i.e. , stilled) . A continuou s subsampl e is taken fro m th e stillin g chambe ran d drawn throug h chemically-reac tive filtertape , whic h traps both particulate an d vapor phas e metals. 11 - 12 ' 2 3 Th e volum e of th e sample flo w i

s measured , an d th e filtertape deposit s ar e advance d t

o a positio n wher

e the y ar

e analyze d fo rmeta l mas s usin g XR F analytica l procedures simila rt o thos e liste d i n EPA' s Compendiu m Metho d IO-3.3. 2 4Th e Xac tCEM S the n divide s th e XRF-determine d mas s persampl e b y th e volum e persample an d simultaneousl y report s con centration s fo r=s2

0 analyt e metals ever

y 1 5 min . Dur in g analysi s o f

th e currentsample , th e nex tsampl e is automaticall y collected . In th e Xac tCEMS , samplin g an d analysi s i s performe d continuousl y i n th e sam e instrumen texcep tfo rth e tim e require d to advanc e th e tap e (~ 3 sec

) an d th e tim e require d fo rautomate d quality assurance check s (~ 1 hr , onc e pe rday) . Detec tio n limit s fo rth e Xac tCEM S ar e liste d i n Tabl e 1 an d range fro m 0. 1 (xg/dr y standard cubi c meter(dscm) t o

~ 6 fj,g/dsc

m wit h 15-mi n samplin g times . Thes e limit s can b e lowere d significantl y b y varyin g samplin g an d analysi s conditions . Bot h th e XF M an d Xac tmethod s ar e generall y applicabl e t o element

s wit h atomi c num ber s rangin g fro m 1

3 (Al ) t o 9 2 (U) . XFM. Like th e Xact , th e XF M use

s filter-based technolog y t o collecta representativ e sampl e o f emission

s followe d by nondestructiv e XR F analysis o

f the sample. 15 ' 2 3 Fo

r sampl e collection , the XF M samplin g trai n connect s t o a stillin g chamber , suc

h a s the one use

d fo rth e Xac

tCEMS . A representativ

e sampl e of stac k ga s i s continuousl y di recte d int o th e stillin g chambe r(a t—30-10

0 L/min) , an d
173 4 Journal

of the Air & Waste Management

Association Volum e 5 6 December

2006Yanca etal.
Tabl e 1 . Xac t

an dXF M detectio

n limits
. Xact " XFM " Elemen t (ug /dscm ) ((j.g /dscm )
C r 0. 3 0,0 8 A s 0. 1 0.0 8 C d 2. 4 0. 8 H g 0. 3 0.1 4 P b 0. 6 0.1 2 M n 0. 2 0.0 8 C o 0. 3 0.0 8 N I 0. 3 0.0 6 S e 0. 1 0.0 8 A8 4. 2 0. 6 Sb 6. 2 1.6 C u 0. 5 0.0 8 F e 0. 9 0,1 2 Z n 0. 2 0.06 B r 0. 4 0. 2 Sr 0. 3 0.1 8 T l 0. 3 0.1 4 La b Ai r o r Stac k Gas Xac t Stillin g XF M

Chambe r Sampl e Trai n

Quantitative Aeroso l Generato r (QAG) Exhaus t

Figur e 1

. Experimenta l arrangemen t fo r laboratory an dfiel dtests
.
NIS T traceabilit

y o f th e generation an d measurement methods , inductivel y couple d plasma (ICP ) analysi s con ducted a

ta n independentlaborator y (Cheste

rLabNet , Tigard , OR

) confirme d th e standar d solutio n concentra tions use

d i n th e QA G an d th e filte rdeposi tmeasure ment s made b y th e XF M method . Notes: "95 % Confidence , interference free , 15-mln sample
. "95 % confidence , Interferenc e free , 30-mi n sample
.

th e XF M pull s a subsampl e of — 1 L/mi n int o it

s samplin g train . Th e subsample i s dilute d an d cooled befor e bein g draw n through a stacke d filte rcassett

e containin g a poly tetrafiuoroethylene filte rfollowe d b y a chemically reactiv e niter. 11 - 12 - 2 3Particulate-phase metal s ar e trapped o n th e nonreactive polytetrafluoroethylene filter , wherea s vapor-phas e metals , includin g Hg , ar e collecte d o n th e chemicall y reactiv

e filtero

rsoli d sorbent

. Aftersample collection , the filtercassette s ar e removed fro m th

e sam plin g train , an d th e resulting filter deposit s ar e analyzed fo rmetal mas

s usin g nondestructiv

e XR F procedure

s sim ila rto thos e liste d i n EPA' s Compendiu m Metho d IO 3.3. 2 4The filters d o no trequir e handlin g durin g any par t o f th e XF M procedure , and they ca n be readily shippe d to a laborator

y fo ranalysis o

ranalyzed i n th e field. Th e emissions concentratio n i s calculated b y dividin g th e XRF-determined meta l mas s b y th e volum e of

emission

s thatpasse

d through the filters. Typical sampl e time s ar e 30 min , an d analysis turnaround time s ca n be o n th e ordero f a fe w hours wit

h a field-portable XR

F analyzer. Detectio n limits typicall y rang e fro m 0.0

6 ug/dsc

m t o 1. 6 u-g/dsc m wit h 30-mi n sampl

e time s (Tabl e 1) . Substan tiall y lowe

rdetection limit

s ca n b e attained b y varyin g samplin g an d analysis conditions .

Metho dIndependenc e Th e QAG-generated aeroso l concentratio n i

s independent o f th e aeroso

l concentrations measure d b y the Xactan d XFM . Metho d independence i s confirme d usin g NIS T traceabilit

y an d additional procedures . Th e concentratio n o f th e aeroso

l produce d b y the QA G is procedurally traceable t o NIS T throug h nebulize d solutio n standard s an d QA G operating parameters . Th e XFM - an d Xact-measure d concentrations ar

e bot h analytically NIS T traceabl e through thi n film standard s an d NIS T Standar

d Referenc

e Materials 183

2 an d 1833. I

n additio n t

o th e independent Validatio n Methodolog y Th e procedure

s use d t o validat

e th e QAG , XFM , an d Xac t wer e base d o n EP

A Metho d 301 . Thi s EP A metho d is required when new methods o f measuring analyte

s ar e to be use d o n a sourc

e i n lie u o

f the standar

d reference method . Metho d 30 1 establishe s accurac

y an d precisio n capabilities o

f ane w metho d b y comparin g it s determine d concentrations with those o f an accepte

d reference method . Th e resulting bia s betwee n concentration s fro m th e tw o methods i

s use d a s a n indicato ro

f accuracy . Simultaneous metho d measurement s ar e use d t o determin e precision . Followin g normal Metho d 30 1 proce dures , th e Xac

tan d XF M measuremen tmethods woul d b e teste d agains tReferenc

e Metho d 29 . However , th e preci sio n an d accurac

y o f Metho d 29 , whic h ar e o n th e order of 15%, s - 7wer

e insufficien tfo rverifyin g the precision s an d accuracie

s believed t

o be attainable wit

h th e Xac tan d th e XF M (i.e. , potential precisio n <5 % an d accurac

y <5%) . Th e validatio n procedur e presente

d i n thi s sectio n is a modifie d Metho d 30 1 i n whic h Metho d 2 9 compari son s wer e replace

d wit h QA G referenc

e aeroso l compari sons. 1 3 Thi s modifie d metho d wa s mor e stringenttha n Metho d 301 , becaus

e itinclude d mor

e replicat

e runs , sequentia

l measurement

s instead o

f simultaneous mea surements , additional validatio n criteria (e.g. , linearity) , an d independentNIS T traceabilit y of results . Th e firstste

p i n the modifie d Metho d 301 procedure required laborator

y validatio n o f

th e QA G emissions , an d th e secon

d ste p wa s a field validatio n o

f th e XF M an d Xact measurements . Th e genera l experimenta

l arrangement use d fo rboth laborator

y an d field test

s i s schematicall y illustrate d i n Figur

e 1 . First , th e QA G generate

d a n aero sol , whic h wa

s blended with laborator y ai rfo rlaboratory test s an d stac

k ga s fo rfield tests. The aeroso l flow wa

s the n directed int o th

e XactCEM S stillin g chamber 15 ' 17 - 1 9fro m whic h th e Xac tCEM S an d XF M simultaneousl y withdre w representativ

e samples . Afte rsampling , th e XF M filters wer e removed an d analyzed , wherea s th e Xac

tautomati call y reported metal concentrations ever y 1 5 mi n fo rth e duratio n o

f th e test . I tshoul d b e note d tha

ta n Xac tCEM S locate d a

tth e Coope rEnvironmental Service s facilit y wa

s
Volum e 5 6 December

200 6 Journal ot the Air & Waste Management

Association

173SYanca et al.

use d i n th e laborator

y tests , an d an Xac

tCEM S located a

t El i Lill y an d Company' s Tippecanoe facilit y i n Lafayette, IN , wa s used i n th e field. QA G Laboratory Validation. Th e QA G wa s evaluate

d i n a serie s o f laborator

y tests 1 5 i n whic h a QAG-generated aeroso l wa s combine d wit

h ambien

tlaborator

y airan d simultaneously sample d by th e Xac

tCEM S an d XF M sam plin g train . Th e theoretica l QA G concentratio n calculated usin g ec [ 1 wa s the n compare

d wit h the actua

l concentra tions measure

d wit h th e Xactand XF M t o determin

e th e accuracy , precision , an d linearit

y o f the QA G method . Al l o f th e QAG-generated aerosol s contained As , Cd , Cr , Pb , an d Hg, representing the volatile , semivolatile , an d low volatility metal categorie s a s define d i n the NESHAPHW C rule. 3Test

s wer e conducted a

tfou rconcentratio n levels (high , mid , low , and blank ) rangin g fro m 0 t

o >13 0 u,g/dscm . In thes

e laborator

y tests , th e QA G aeroso

l con centrations wer

e compare

d wit h result s fro m a tota

l of 2 2 XF M an d 13

5 Xac truns . Onl y Xactruns tha tcorre sponde d wit

h simultaneou

s XF M runs wer

e use d fo raccurac y an d precision determinations . Al l of the runs fo r both method s wer

e use d i n the linearregressio n analysis . Th e XF M sample time wa s 30 mi n pe

rru n an d th e Xac t wa s 1 5 min ; concentrations fro m tw o Xactrun

s wer e average d t o represen

ta30-min sampl

e perio d fo rcompar iso n wit h th e XFM . Al l o

f the methods wer

e performed accordin g to specifications se tforth b y thei rtes

tmetho d an d standar

d operating procedures. 15 - 2 0
Xact and XFM Field Validation. Th e Xac tan d the XF M wer e evaluated i n a serie s of field test

s conducte d a

ta hazardous Wast

e incinerator, wher

e a n Xac tCEM S wa

s i n operation. 1 5Fo reac

h field test

, th e validated QA G wa s use d to generat

e a referenc

e aerosol of

known concentra tion , whic h wa

s spike d int o th e hazardou

s wast e inciner atorflu e gas. Thi s dynamically-spiked flue ga s wa s trans porte d t o th e Xac tCEM S stillin g chambe rwher e i twa s simultaneously sample d b y th e Xac tCEM S and XF M sam plin g train . Measure

d concentrations fro m eac h metho d wer e compared wit

h the QAG-spike d stac k ga s concentra tio n t o determine th

e accurac

y an d precisio n o

f th e Xac t an d XF M methods . Al l o f th e QAG-generate

d aerosol

s containe d As , Cd , Cr , Pb , an d Hg , an d test s wer e con ducte d a

tfou rconcentration levels (high , mid , low , an d blank) rangin g fro m 0 t o >130 p-g/dscm

. Durin g these field tests , a tota l of

2 4 XF M an d 19

2 Xac trun s wer e compared with th

e QA G aeroso

l concentrations . Again , onl y correspondin g Xact/XF M run s wer e use d fo raccu rac y an d precisio n determinations , butal l o f th e runs wer e use d fo rlinearregressio n analysis . Durin g these tests , th e background concentrations of the stac k ga s wer e negligibl e relativ

e t o the spike

d stac k ga s concentrations . Al l of th e methods wer

e performed accordin g t o specifi cations se

tforth by thei rtes

tmetho d and standar d oper atin g procedures. 15 - 2 0

Validatio n Criteri a Criteri afo rmetho d validatio n wer e base d o n Metho d 30 1 bia s and precision requirement s an d wer

e eithe requa l t o those listed i n Metho d 301 o rwer e mor e stringent

. A genera l criterio n fo rall o

f the vahdatio n test

s wa s tha ta 9
1736 Journal

of the Air & Waste Management

Association run s ha d t o b e used t o demonstrat

e acceptabl

e value s fo r accuracy , precision , an d linearity. 2 S Accuracy , precision , an d linearit

y criteria ar

e define d an d discusse d below . Accuracy. Accurac

y fo rth e ith elemen

t04, ) is define d a

s bia s (JB V ug/dscm

) divide d b y th e theoretica l o rreference concentratio n o

f th e QA G generate

d aeroso l (CP 4 0 , u.g

/ dscm) , expresse

d a s a percent.
A , = 7^-10 0 (2 )
Bia s i s th e difference betwee n the mea

n measure

d aeroso l concentratio n (Cf , >g/dscm ) an d th e theoretica

l o rrefer enc e concentratio n (Cp* 0 , (j-g/dscm) .

B , = Cr * - CP A G(3 ) Forth e QAG , accurac y value s <20 % wer e define d a

s acceptable fo rvalidation . Fo rthe measuremen tmethods , thi s sam e criterio n wa

s required fo raccurac

y value s determine d a tconcentrations a

to rnea rthe emission limi ta s required b y Metho d 301 . I n additio n t

o meetin g th e abov e accurac

y criterion , th e bia

s wa s required t

o b e in significantrelativ

e t o th e uncertaint

y i n the bias . I n thi s case , th e uncertaint

y i n the bia

s fo rth e it h elemen

t(Uf ) i s the squar

e rooto f the su m of the uncertaint

y i n th e QA G aeroso l concentratio n (Up AG ) square d an d th e standard deviatio n of

th e mean o f

th e measuremen

tmetho d concentratio n (SDMf ) squared , a

s show n i n followin g equation ; Uf

= 7(UP AG ) 2+ (SDMf 1 ) 2 (4

) wher e the QA G propagate

d uncertaint

y wa s estimate d t

o be ~5 % durin g th e laborator y an d field tests. 1 5 Bias wa s considered significanta tth e 95 % confidence level i f

B , > 2Uf. I f B , wa s foun d t

o be significant, a correctio n facto r wa s required . Th e correctio n factor(CF, ) is calculate d b y dividin g the concentratio n o f the QA G aeroso

l (CP A G ) b y th e concentratio n of

the measuremen

tmetho d (Cf) . CF,=-gM - (5 )
Precision. Tota l precisio n fo rth e it h elemen

t(P\) i s defined a s percen trelative standar

d deviatio n (PJ?SD,)

, o rthe standar d deviatio n (5D,

) divide d b y th

e mean concentra tio n (C, ) o f a give n metho d determined fro m sequentia l measurements .
P | = -^-10 0 (6 )
Becaus e ther e is rando m variabilit y associate

d with both the QA G aeroso

l concentration , a

s well a s th e measured aerosol concentration , th e total precisio n (Pf ) is a n in dicato ro

f th e combine d variability introduce d b y al l
Volum e 5 6 Decembe r

200 6Yanca etal.
Tabl e 2 . QA

Gaccuracy determine

ddurin g laborator

y tests
. Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n (-2 0 ng/tlscm ) (-6 5 ug/dscm ) (-13 0 ug/dscm ) Averag e Al l Run s Measuremen t Metho d Elemen t N Accurac y A , % S D N Accurac y A , % S D N Accurac y A , % S O N Accurac y A , % S D
Xac t

XF M C

r A s H g P b C d C r A s H g P b C d 1.7

1. 9 2. 3 2. 9 2. 8 2. 5 2. 5 6. 3 2. 2 6. 2 1.

0 1. 7 1. 4 2. 1 1. 8 1. 9 1. 2 1. 1 2. 2 3. 4 2 4 2 4 2 4 2 4 2 4 1 2 1 2 1 2 1 2 1 2 1.

4 4. 1 1. 3 1. 5 1. 7 2. 7 3. 0 3. 5 2. 3 2. 0 1.

4 1. 7 1. 0 0. 8 0. 9 2. 7 3. 0 3. 0 2. 6 1. 4 2.4

4. 9 0. 6 1. 6 2. 0 1.5 2. 6 6. 7 2. 3 1. 1 0. 3

1. 0 0. 5 1. 1 1.5 1. 4 1. 5 5. 1 1. 5 0. 8 4 0 4 0 4 0 4 0 40 2 0 2 0 2 0 2 0 2 0 1.6

3. 8 1. 3 1. 8 2. 0 2.4 2. 8 4. 7 2. 3 2. 6 1.

2 1. 9 1. 1 1. 2 1. 2 2. 3 2. 4 3. 5 2. 2 2. 5
Mores : SD = standar

ddeviation
. components of

th e generation-measuremen tsystem ; that is , QA G an d measuremen tmethod . Fo

rthi s serie

s o f tests , th e magnitud e o

f the QA G precisio n is considered t o b e th e sam e a s the measuremen

tmethod . Therefore , th e individua l precision o

f the QA G o rmeasuremen tmetho d (P, ) i s define d a

s the combined , o

rtotal , precisio n (Pf

) divide d b y th e squar

e rootof 2 .
P^PRSD^^ (7 )
A precisio n =£10 % wa

s require d fo rth e metho d t

o satisf y established validatio n requirements . Linearity. Evaluatio n o f linearit y wa s base d o n parameter

s derive d fro m a linearleas tsquare s regressio

n analysis of th e theoretica

l o rreferenc

e concentrations an d the mea sure d concentrations . Althoug h slope an d intercep to f th e regression lin e wer

e considered , th e ke

y linearit

y criterio n wa s th e correlation coefficient(r) . Th e QA G an d bot h Tabl e 3 . QA

Gprecision determine

ddurin g laborator

y tests
. measuremen tmethod s musthav

e a correlatio n coeffi cien t(r ) tha ti s 3=0.8 5 fo rmetho d validation . RESULT S AN D DISCUSSIO N

QA GValidatio n Accuracy. QA G accurac y result s fo reac h o f th e fiv e metals teste d ar e listed i n Table 2 . Thi s tabl e includes result

s fro m a compariso n o

f theoretica

l QA G concentrations wit h 4 0 Xactan d 2

0 correspondin g XF M measurements . Concen trations range

d fro m a lo w of

—2 0 |xg/dsc m t o a hig h of -13 0 (Ag/dscm

. Th e QA G demonstrate d accuracie

s <7 % fo ral l o f th e element

s a teac h concentratio n level , well below th

e 20 % validatio n threshold . These result s sho w tha taverag e QA G accurac

y fo ral l run

s range d fro m a lo w o f 1.3 % fo rH g a

s measure

d wit h the Xac tt

o a hig h o

f 4.7% fo rH g a

s measure

d wit h th e XFM . Th e overal l averag e accurac

y includin g all five elements , al l thre e concen tratio n levels , an d bot h methods i s 2.5 ± 2.3% . Non e of th e biase

s wer e determined to b

e significant, I

n addition , independentICPanalysis of a nebulize d solutio n an d

Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n (-2 0 pg/dscm ) (-6 5 ug/dscm ) (-13 0 ug/dscm ) Averag e Al l Run s Measuremen t — Metho d Elemen t N Precisio n P , % N Precisio n P, % H Precisio n P , % n Precisio n P, %
Xac t C

r 8 1. 7 2

4 1. 1 8 1. 7 4

0 1. 0 As 8 2. 0 2 4 1.0 8 2. 0 4 0 1. 2 H g 8 2. 0 24 0. 7 8 2. 0 4 0 1. 1 P b 8 2. 0 24 0. 8 8 2. 0 40 1. 3 C d 8 2. 5 24 1. 5 8 2. 5 4 0 1. 7 XF M C

r 4 1. 3 1 2 2. 3 4 1.3 2 0 1. 5 As 4 1. 8 1 2 2. 2 4 1. 8 2 0 1. 7 H g 4 0. 8 1 2 2. 8 4 0. 8 2 0 2. 4 P b 4 1. 7 1 2 2. 2 4 1. 7 2

0 1. 6 C d 4 2. 3 1 2 1.9 4 2. 3 2 0 1. 7

Volum e 5 6 Decembe

r 2006 Journal of the Air S Waste Management

Association

1737Yanca et al,
Tabl e 4 . QA

Glinearit y determine

ddurin g laborator

y tests
.

o O o

©
X ) o
o O Metho

d Elemen t n R Slop e S D Intercep t S D
XF M C

r 2 2 0.999 1.0

2 0.005 -0.5 4 0.3 5 A s 2 2 0.999 1.0

5 0.005 -0.7 1 0.3 8 H g 2 2 0.999 0.9 9 0.00 4 -0.0 1 0.3 2 P b 2 2 0.99 9 1.0 2 0.00

7 -1.1 3 0.5 1 C d 2 2 0.999 0.9 8 0.00 8 07 2 0.5 6 Xact C

r 13 5 0.999 1.0 1 0.00 4 -0.4 2 0.25 A s 13 5 0.999 0.9 8 0.00 4 0.3 1 0.2 6 H g 13 5 0.999 1.0 4 0.00

4 -0.6 7 0.25 P b 13 5 0.999 1.0 0 0.005 -0.4 1 0.3 0 C d 13 5 0.99 8 0.9 8 0.005 0.2 7 0.3 5 Notes: SD = standar

ddeviation
. selecte d filte rsample

s wer e supportiv

e of th e XF M mea sure d concentrations . Clearly , thes e result s demonstrat

e tha tth e QA G is an accurat e metho d fo rgenerating a referenc e aeroso l containin g meta

l concentrations i n th e rang e from 2 0 t o 13 0 |i.g/dscm . Precision. Precisio n fo rth e QA G an d the measuremen t methods teste

d i n th e field wa

s determined fro m sequen tial measurement

s take n durin g a perio d of

~ 4 hr . Th e result s from these test

s ar e presente

d i n Table 3 . Th e QA G demonstrated precisions wel l below th e 10 % validatio n threshold ; averag

e precision

s wer e bette rtha n 3 % fo ral l of th e element

s a teac h concentratio n level . Th e averag e QA G precisio n fo ral l of the run s range d fro m a low o

f 1 % fo rC ra s measure

d wit h the Xactt

o a hig h of

2.4 % fo rH g a s measure

d with XFM . Includin g al l five o f the elements , al l thre e o f th e concentratio n levels , an d both measure men tmethods , th e averag e QA G precisio n wa

s 2.2% . Thes e result

s show tha

tth e QA G i

s a precise metho d fo r generating aerosol

s i n the concentratio n rang e fro m 20 t

o 130 u-g/dscm

. Linearltf. Linearit

y o f th e QA G wa

s analyzed wit

h linea r least-square

s regression

s o f the measure

d aeroso l concen trations compared wit h th e theoretica

l concentrations overal l o f th e concentratio n levels . Correlatio n coeffi cient s (r), slopes , an d intercept s fro m these regression s ar e presented fo reac

h elemen

ti n Table 4 . Th e correlation coefficient

s fo ral l o

f the element

s a s determined wit h each measuremen

tmetho d wer

e >0.99 , well abov

e th e acceptabilit

y requiremen

to f 0.85 . Slope

s range d fro m a lo w o f 0.9 8 t o a hig h o

f 1.05 , al l withi n 5

% of unit y (i.e. , 1.00) . Intercept

s range d fro m -0.0 1 t

o -1.1 3 and wer

e al l <1 % o f th e concentratio n range . Plot s o f the regressio

n analyse s usin g al l 5 o

f th e metal s combine d ar

e presente

d fo rth e Xac

ti n Figur

e 2 an d fo rth

e XF M i n Figur

e 3 . Th e QA G agai

n demonstrate

d correlation coefficient s o f 0.99 , an d slope

s wer e withi n 0.4

% o f 1.00. Intercept

s wer e <0.3 % ofth e concentratio n range . A final regressio n anal ysi s o f al l o f th e measure

d versu s theoretica

l QA G dat

a yielde d a 0.99

8 correlation coefficient, a slope withi n 0.2 % o f unit y (0.99

8 ± 0.002) , an d a

n intercept<0.1 % o

f 14

0 I 120 1 10 0 i 1 8 0 I 6 0 c o S 4 0 £ 3 2 0 ' 0.999

X - 0.10 3 r = 0.99 8 n = 67 5 0 C r A A s • H g Pb !
+ C d
2 0 4 0 6 0 8 0 100 12 0 Theoretica

l Concentratio n (pgldscm ) 140 Figur e 2 . QA Glinearit y a s determine db y th e Xac t usin g al l fiv e elements
. th e concentratio n rang e (-0.0 4 ± 0.16) . Thi s stron g lin ea rrelationship betwee

n the theoretica

l QA G aerosol con centrations an d th e independentl y measure d concentra tion s demonstrate

s the abilit

y o f th e QA G t

o produc e aerosol s quantitativel

y ove ra wid e rang e o f concentrations . Xac t Metho dValidatio n Accuracy. Th e Xac tme tthe 20 % validatio n criterio n fo r accuracie

s demonstrated a

tth e hig h concentratio n level (Tabl e 5) . Fo rth e measuremen

tmethods , thi s leve l is expecte d t o be mos trepresentativ e o f concentration s nea

r th e emission limi ta

s required b y Metho d 301 . Forth e 2 4 high-concentratio n runs , th e Xac taccuracie

s range d fro m 1.8 % fo rA

s t o a hig h o

f 13 % fo rHg . Th e Xactaverag e accuracie

s fo ral l 4 0 run

s range d fro m a low o

f 4.9 % fo rA

s t o a hig h of

16 % fo rHg . Th e averag e Xac taccurac

y cal culated usin g al l five of th e element

s wa s 4. 7 ± 4.3 % fo r th e hig h concentratio n an d 8. 3 ± 7.2 % fo ral l three o f

th e concentratio n levels . Bia s wa s insignifican tfo rfou ro f the five metal s but wa s significantfo rH g a

tall o f th e concentratio n levels . A post-tes tinvestigatio n of

thi s bia s reveale

d a 6 % calibra tio n error

, althoug h thes

e runs wer

e retained i n th e data se twithoutcorrection . Assuming correc tcalibration , th e H g accuracie

s woul d hav

e been o n the sam

e ordera

s th e accuracie

s of th e othe rfou relements ; fo rexample , th e H g accurac y a tth e hig h concentration leve l woul d be —7

% (i.e. , 14 0 120 10 0 8 0 60 4 0 20 0 y = 0.996

x - 0.28 6 r = 0.99 7 n = 11 0

2 0 4 0 6 0 8 0 100 12 0 Theoretica

l Concentratio n (ug/dscm ) 14 0 Figur e 3 . QA Glinearit y a s determine db y th e XF M usin g al l fiv e elements
. 173 8 Journal

oi the Air& Waste Management

Association Volum e 5 6 Decembe r 2006



### VES01695 6Yanca etal.
Tabl e 5 . Xact

accuracy determine

ddurin g fiel dtests
. Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n (-2 0 pg/dscm ) (-4 5 ug/dscm ) (-11 0 pg/dscm ) Averag e Al l Run s Elemen t N Accurac y A , % S D N Accurac y A , % S D N Accurac y A , % S D N Accurac y A , % S D C r 8 7. 4 2. 9 8 2 0 1. 6 2

4 4. 5 1. 7 4 0 8. 2 6. 5 A s 8 3. 3 2.4 8 1 6 1. 9 2 4 1. 8 0. 7 4 0 4. 9 5. 7 H g 8 14 " 2. 1 8 25 a1. 7 2 4 13 a1. 0 4 0 16 " 5. 2 P b 8 1 3 1. 4 8 2

0 1.

4 2 4 2. 4 1.5 40 7. 9 7. 4 C d8 3. 6 2. 6 8 1 6 1. 7 2 4 2. 1 0. 8 40 5. 2 5. 7 fVotes.

- SD = standar

ddeviation ; a Bla s wa

s determine

dt o b e significant

fo r thi s value
.

6 % o f th e 13 % accurac

y ca n b e attribute

d t o th e calibration error) . Thi

s identified erro

rca n be readil

y correcte

d an d futur e Mas , thus , eliminated . A

s aresult , a correction factor wa s no trequired. In addition t o th e calibratio

n error , the averag e accuracie

s fo rbot

h th e Xac tand XF M (discusse

d below ) wer e somewha

timpacte

d b y biase

s i n the middl e concentratio

n runs . Thes

e biase s appea rt o b e the resul

to f a n increase

d difficult

y i n maintaining prope rQA G operat

in g condition

s i n th e field compare d wit h the laboratory. Th e biase

s wer e notsignificant, an

d thes e run s wer e retaine d i n the dataset

. The result

s presente

d i n Tabl

e 5 demonstrat

e a hig h accurac

y fo rth e Xac tmeasuremen

tmetho d eve

n wit h th e H g calibratio

n erro rand midconcentxatio n biases. Furthermore

, thes e result s sugges teve n bette raccuracie

s wit h correc tHg calibrations .
Precision. Th e Xac

tdemonstrate

d bette rthan 4 % fo ral l of th e concentration levels , wel l belo w the 10

% validatio n threshol d (Tabl

e 6) . Th e averag

e precision fo ral l o

f th e Xactrun

s range d fro m a low o

f 1.4 % fo rH g t

o a hig h o

f 1.9 % forCd . Ove

ral l five ofth e element s an d al l three o

f th e concentratio n levels , th e tota l averag e precisio n fo r the Xactwa

s calculated a

s 1.6% . Thes e result

s demon strat e th e hig h precisio n o

f th e Xac tove ra wide rang

e of concentrations . Linearity. Xactlinearit y wa s evaluate

d wit h linearleast

square s regressio

n analysis o f

th e Xact-measure

d concen tration s compare

d with the QAG-spiked stac k ga s referenc e concentrations ove

rall o f th e concentratio n levels . Regressio

n parameter

s fo reac h elemen

tar e presented i n Tabl e 7 . Xactcorrelatio n coefficient s fo ral l o

f th e element s wer e >0.99 , easil

y surpassin

g the 0.8

5 require ment. Slope

s fo ral l of

th e metal

s ranged fro m 0.8

7 fo rH g t o a hig h o f

1.0 2 fo rPb . Intercept

s ranged fro m -0.7 9 t o -1.09 , al l <1 % of

th e concentratio n range . A plotte d regressio n analysis fo ral l 5 o

f th e metals combine d (Figur e 4 ) produce d a correlation coefficien to f 0.995 , a slop

e withi n 5 % of unit y (0.95

2 ± 0.003) , an d an intercep t<2 % o f th e concentratio n rang e (-1.1 0 ± 0.18) . Th e stron g linea rrelationshi p betwee n th e Xac tconcentration s and the referenc

e concentrations confirm s th e Xac tlinea rrespons e an d hig h precisio n ove ra wide rang

e o f concen tration s an d demonstrate

s it s abilit y t o accuratel

y measur e metal s overthi s range . XF M Validatio n Accuracy. Th e XF M accurac y result s fo reac h elementar

e presente d i n Tabl e 8. A tthe hig h concentratio n level , th e XF M accuracie

s ranged fro m 3.5 % fo rH g t o 5.8 % fo rPb , all well below th e 20

% validatio n requirement. Non e of th e biase s wer e significantrelativ

e t o thei runcertainty . Th e averag

e XF M accurac

y fo ral l o

f th e runs range d fro m a low o f 6 % fo rC d an d A

s t o a hig h of

7.9 % fo rPb . Combinin g dat

a fro m al l five o

f th e elements , the averag e XF M accurac

y wa s calculated a

s 4.7 ± 3.1 % fo rth e hig h concentratio n leve l and 6. 5 ± 4.5 % fo ral l thre e o f the concentratio n levels . These result s clearly demonstrat

e the hig h accurac

y of th e XF M measuremen tmethod . Precision. Th e XF M precisions (Tabl e 9 ) al l me tth e 10 % validatio n criterio n and wer e bette rtha n 7 % a tal l o f th e concentratio n levels . Th e averag e XF M precisio n fo ral l o f
Tabl e 6 . Xac

t precisio n determine

ddurin g fiel dtests
. Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n (-2 0 ^g/dscm ) (-4 5 pg/dscm ) (-11 0 pg/dscm ) Averag e Al l Run s Elemen t H Precisio n P , % N Precisio n P , % N Precisio n P , % N Precisia n P , % C r 8 2. 2 f ! 1. 4 2

4 1. 3 40 1. 6 A s 8

I 2.4 f i1.6 2 4 1.0 4 0 1.

7 H g 8

I 1.

7 f i1.6 2 4 0.8 3 4 0 1.

4 P b 8

I 1.

2 f i1. 3 2

4 2. 0 4 0 1. 5 C d8

i3.4 i i1.

4 2

4 0.8 3 4 0 1.9

Volum e 5 6 Decembe r 200 6 Journal of the Air & Waste Management

Association

1739Yanca et al.
Table 7 . Xac t

linearit y determine

ddurin g fiel dtests
. Tabl e 10 . XF M linearit y determine

ddurin g fiel dtests
. Elemen t N R Slope S D Intercept S D Elemen t N R Slop e S D Intercept S D C r 19 2 0.99 7 0.95 1 0.0050 5 -1.0 8 0.297 C r 2

4 0.997 1.0

4 0.0174 -1.6 1 1.3 9 A s 19 2 0.99 8 0.982 0.00487 -0.99 4 0.287 A s 2 4 0.997 1.0

7 0.0180 -2.7 2 1.4 3 H g 19 2 0.99 8 0.86 9 0.0041 2 -0.78 8 0.24 3 H g 2

4 ' 0.99 6 1.0

4 0.0209 -1.8 0 1.6 7 P b 19 2 0.99 9 1.0 2 0.00387 -1.0 9 0.22 0 P

b 2

4 0.99 5 1.0

7 0.022 1 -2.0 8 1.8 1 C d 19 2 0.99 7 0.970 0.0057 3 -0.80 2 0.33 7 C d 24 0.997 1.0 5 0.017 1 -1.6 1 1.3 6 Notes: SD = standar

ddeviation
. Notes: SO = standar ddeviation
.

• 8

C S < s 0 0 0 0 o

o I Q the run

s range d fro m a lo

w of 1.8 % fo rC ran d A

s an d t o ahig h of

3.7 % fo rPb . The total averag e XF M precisio n wa s calculated a

s 2.6% ove

ral l fiv e ofth e element s an d al l thre e o f th e concentratio n levels . These result s demon strat e tha tth e XF M me

tthis acceptanc

e criterio n an d i

s precise overa wid e rang e o f concentrations . 14 0 12 0 10 0 8 0 c 

# ! 6 0 c a u c 0 4 0 8 1 3 2 0 X y - 0.952 X -1.1 0 r = 0.99 5 r t= 96 0
0 C r A
. A s D H g X P b
+ C d O 2 0 4 0 6 0 8 0 10 0 12 0

QA G Reference Concentratio n (ug/dscm ) Figur e 4 . Xac t

linearit y usin g al l fiv e elements
. Tabl e 8 . XF

M accuracy determine

ddurin g fiel dtests
. Linearity. Th e result s of th e XF M linearit

y evaluatio n ar

e presente d o n Table 10. These parameter s wer e determine d wit h linearleast-square s regressio

n analysi

s of th e XFM measure d concentrations compared wit h th e QAG-spike d stac k ga s concentrations ove

ral l of th e concentratio n levels . XF M correlatio n coefficient s fo ral l element

s wer e a0.99 , wel l abov

e th e 0.8 5 acceptanc

e value . Slope

s fo ral l of th e metal

s range d fro m 1.0

4 t o 1.07, al l withi n 7

% o f unity . Intercept

s wer e al l <3 % of th e linearit

y tes tcon centratio n rang

e an d range

d fro m -1.6 1 t

o —2.72

. A plotte d regressio

n analysis fo ral l 5 o f the metals com bine d is presente

d fo rth e XF M i n Figur

e 5. Th e combine d metal regressio

n yielde d acorrelatio n coefficientof 0.996 , aslope withi n 5

% o f 1.0 0 (1.0 5 ± 0.01) , an

d an intercep t <2 % o f th e ful l concentratio n rang e (-1.9 6 ± 0.6) . Th e strong correlatio n of

the XF M concentrations wit h th e referenc e concentrations demonstrate s the abilit

y o f th e XF M t o accuratel

y measur

e a wid e rang

e o f concentra tion s an d confirm s it

s precisio n overthi s range. Summar y A summar

y o f eac h method' s perfonnanc e i n reference t o th e validatio n criteria is presente d i n Table 11 . Thi s table

Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n 1 —2 0 pg/dscm ) (-4 5 pg/dscm ) (-11 0 pg/dscm ) Averag e Al l Run s Elemen t N Accurac y A , % S D N Accurac y A , % S D N Accurac y A , % S D N Accurac y A , % S D C r 4 6. 0 3. 4 4 1 2 1.3 1 2 4. 0 2.4 2 0 6. 0 3. 9 A s 4 1.

7 1.0 4 1 3 2. 5 1 2 5. 0 2. 9 2 0 6. 0 4. 7 H g 4 5. 5 3. 4 4 1 5 3. 8 1 2 3. 5 3. 4 2 0 6. 1 5. 5 P b 4 8. 0 6. 4 4 1 4 2. 3 1 2 5. 8 4. 0 2 0 7. 9 5. 2 C d4 6. 7 2. 0 4 9. 0 2, 5 1 2 5. 1 2. 5 2 0 6. 2 2. 8 Notes: S D = standar

ddeviation
. Tabl e S . XF

M precision determine

ddurin g fiel dtests
. Lo wConcentratio n Mi d Concentratio n Hig h Concentratio n (-2 0 pg/dscm ) ( ~ 4 5 pg/dscm ) -110 pg/dscm ) Averag e Al l Run s Elemen t N Precisio n P , % N Precisia n P , % N Precisia n P , % N Precisio n P , % C r 4 2, 3 4 1.0 1 2 2. 2 2 0 1. 8 A s 4 1.5 4 2. 0 1 2 1. 9 2

0 1. 8 H g 4 2, 3 4 3. 2 1 2 2. 9 2 0 2. 8 P b 4 6. 5 4 1. 9 1 2 2. 7 20 3. 7 C d4 4. 7 4 2. 0 1 2 2. 4 20 3. 0

1740 Journal

of the Air & Waste Management

Association Volume 5 6 Decembe

r 200 6


### VES01695 8Yanca et al.

© C N S 3

o

O s C N c s o o 0 0 d

• s o o Q 14

0 12 0 10 0 8 0 60 4 0 2 0 y1.05x-1.9 6

r = 0.99 6 n = 12 0

12 0 2 0 40 60 8 0 10 0 QAO Referenc

e Concentratio n (ug/dscm ) Figur e S . XF M linearit y usin g al l fiv e elements
.

clearly show

s tha tth e thre e methods easil

y passe d al l o f th e required criteria fo ral l fiv e o f th e metals . CONCLUSION S Th e thre

e independen tmethod s discusse

d i n thi s paper me tEP A Metho d 30 1 requirement s fo rcompliance appli cations an d ar

e precise, accurate

, an d lineartool s applica bl e t o th e determinatio n o

f hazardou

s meta l concentra tion s i n emissions . Th e QA G and th e Xac ttechnologies have currently bee

n approve

d b y EP

A fo rcomplianc e demonstratio n a

ta HWC. 2 6I

n additio n t

o th e five ele ment s measure

d wit h thes e tests , th e methods ar

e expected t o b e applicable t

o mosthazardou

s element

s i n stac k an d fugitiv e emission s fro m stationar

y sources, a

s wel l a s i n th e ambientenvironment. Th e QA G referenc e aeroso l generato rcould , thus , be use d a s a generall

y ap plicable reference aeroso l generato

rfo rresearch, metho d certification , an d audits . The XF M measuremen tmethod s coul d b e used fo rperformanc e testing , initia l certification , an d continuin g qualit y assuranc

e audit s of multimetal CEMS . Finally , the Xac tcoul d b

e use d to demonstrat

e ongoing complianc e through it s us e a s a CEMS , an d it

s technology coul d b

e extende

d t o a n instrumenta

l analysis procedur

e with applications similarto th e XFM . I n additio n t

o the result

s presente

d i n thi s paper

, al l thre e methods hav

e demonstrate

d hig h precisions an d accurade

s i n otherfiel d an

d laborator

y tests. 27 - 3 0Th e measuremen

tmethods hav

e als o consistently demon Table 11 . Summar

y o f validatio n results
. Parameter s Criteri a QA G Metho d XF M Metho d Xac t Metho d
No
. o f run s (n) a 9 2

0 1 2 2 4 Accurac y (A ) s20 % <5 % <6% a <7% a ' b Precisio n (P ) £10 % <3 % <4% <4 % Linearit y (i ) >0.8 5 0,99 0.9 9 0.9 9 Notes: "Results fro mhig

h concentratio

n level ; "Assumin

g correct calibration o f Hg
. strate d frequen

tsamplin g times , rapi d analysi s turn aroun d time

s (1 5 mi n fo rthe Xactan d 2 h rfo rth e XF M i f a field-portable analyzeris used) , an d lo w detectio n limits . Analysis is nondestructive , an d the method s ca n b e independentl y audite d with the QAG . I n additio n t o metals , the QA G ca

n potentiall y generat e aerosol

s o f bot h organic and inorgani c analytes . REFERENCE S 1 . Prieditis , H. ; Adamson , I.Y . Comparativ e Pulmonar y Toxicity o f Vari ou s Solubl e Metal s Foun d i n Urba n Particulat e Dust ; Exp. Lung. Res. 2002 , 28, 563-576 . 2 . Monn , C ; Becker

, S . Cytotoxicit y an d Inductio n o f Proinflammator y Cytokine s fro m Huma n Monocyte s Expose d to Fin e (PM2.5 ) an d Coars e Particles (PM10-2.S ) i n Outdoo ran d Indoo rAir ; Toxicol. Appl. Pharmacol

1999, ISS, 245-252 . 3 . U.S . Environmenta l Protectio n Agency . Nationa l Emissions Standard s fo rHazardous Ai rPollutants fo rSourc e Categories . I

n Code of

Federal Regulations, 40 CFR 63 ; U.S . Governmen tPrintin g Office : Washington , DC , 2005 . 4 . U.S . Environmenta l Protectio n Agency . Metho d 29 , Determinatio n o f Metal s Emission s fro m Stationar y Sources . I

n Code of

FederalRegulations, 40 CFR 60 ; U.S . Governmen tPrintin g Office : Washington , DC , 2005 . 5 . U.S . Environmenta l Protectio n Agency . Evaluation of Two Methods for the Measurement

of Mercury Emissions in Exhaust Gases from a Mumcipal Waste Combustor; EPA 450/4-92-013 . U.S . Governmen tPrintin g Office : Washington , DC , 1991 . 6. Rigo , H.G. ; Chandle rA.J . Quantitatio n Limit s fo rReferenc e Method s 23 , 26 , an d 29 ; / . Air& Waste Manage. Assoc. 1999 , 49, 399-411 , 7. America n Societ

y o f Mechanica l Engineers , Researc h Committe e o n Industria

l an d Municipa l Waste . Reference Method Accuracy and

Precision (ReMAP): Phase 1, Precision of Manual Stack Emission Measurements; Repor tNo . CRTD-60 ; America n Societ y of Mechanica l Engineer s In ternational : Washington , DC , 2001 . 8 . Zhang , H. ; Yuen , F.Y. ; Singh , J.P . Evaluatio n o f th e Potential o f

Laser Induce d Breakdown Spectroscop y fo rDetectio n of Trac e Elemen ti n Liquid ; / . Air& Waste Manage. Assoc. 2002 , 51, 681-687 . 9 . Seltzer

, M.D . Performance Testin g of a Multimetal s Continuou s Emis sion s Monitor . / . Air& Waste Manage. Assoc. 2000 , 50 , 6 . 10 . Sk y + , Inc . 1997

Performance Testing of Multi-Metal

Continuous Emissions Monitors; DOE/ID-10665 . U.S . Departmento f Energy , Idah o Op erations Office : Idah o Falls , ID , 1998 . 11 . Cooper , J.A ; Fry , S.C ; Johnsen , B.E . Apparatus and Methods forRemoving Mercury from Fluid Stream. U.S . Patent6,770,25 0 B2 , 2004 . 12 . Cooper , J.A ; Fry , S.C ; Johnsen , B.E . Apparatus and Methods forRemoving Mercury from Fluid Stream. U.S . Paten

t6,872,370 B2 , 2005 . 13 . Draft

Test Plan forValidating a Reference Procedure forMeasuring the Concentration of

Metals in Eli Lilly and Company's Hazardous Waste IncineratorStack Gas; Coope rEnvironmenta l Services : Portland , OR , 2004 . 14 . U.S . Environmenta l Protectio n Agency . Metho d 301 , Fiel d Validatio n o f Pollutio n MeasurementMethod s fo rVariou s Media . I n Code of Federal Regulations, 40 CFR 56 ; U.S . Governmen tPrintin g Office : Washington , DC , 2005 . 15 . Method

301 Evaluation of

Three Methods forMulti-Metals Measurement and Validation; Coope rEnvironmenta l Services : Portland , OR , 2006 . 16 . Barth , D.C ; Yanca , C.A. ; Petterson , K.A. , Nakanishi , M.P. ; Cooper , J.A. ; Johnsen , B.J. ; Lambert , R . H . Aerosol

Sci. Tech., submitte d fo r publication . 17 . Determination of

Metal Concentration in CES'XactCEMS Stilling Chamber Using the CES XFM; Coope rEnvironmenta l Services : Portland , OR , 2006 . 18 . Determination of

Metal Concentrations from Stationary Sources Using the CES XFM; Coope rEnvironmenta l Services : Portland , OR , 2006 . 19 . Specifications and Test Procedure forX-Ray Fluorescence BasedMultiMetals Continuous Emissions Monitoring Systems at Stationary Sources; Coope rEnvironmenta l Services : Portland , OR , 2006 . 20 . Quality Assurance Requirements forX-Ray Fluorescence Based Multi-Metals Continuous Emissions Monitoring Systems at Stationary Sources; Coope r Environmenta l Services : Portland , OR , 2006 . 21 . Cooper , J.A. ; Barth , D.B. ; Nakanishi , M.P. ; Petterson , K.A. ; Yanca , CA . A Quantitative , Traceable-to-NIST , Reference Aeroso l Generato rfo r Evaluatin g Aeroso l Speciatio n Monitor s an d MeasurementMethods . I n Proceedings ofthe Air& Waste Management Association's Symposium on AirQuality Measurement Methods and

Technology, Durham , NC , Ma y 9-11 , 2006 ; A&WMA : Pittsburgh , PA , i n press . 22 . May , K.R. Th e Colliso n Nebulizer . Description , Performance & Appli cation . / . Aerosol. Sci. 1973 , 4, 235-243 . 23 . Cooper , J.A. ; Barth , D.B. ; Nakanishi , M.P. ; Petterson , K.A. ; Yanca , CA . New Filter-Based Method s fo rPrecise , Accurate , an d Timelie rMeasure men to f Meta l Emissions . I

n Proceedings of

the Air& Waste Management
Volum e 5

6 Decembe r 200

6 Journal of the Air & Waste Management

Association

174 1


### VES01695 9Yanca et al.

t o O o

O S t s c s o o o o Association's Symposium on MrQuality Measurement Methods and

Technology, Durham, NC , Ma y 9-11 , 2006 ; A&WMA : Pittsburgh , PA , i n press . 24 . U.S . Environmenta l Protectio n Agency . Compendiu m Metho d 10-3.3 : Determinatio n of

Metal s i n AmbientParticulat e Matte rUsin g X-Ra y Fluorescenc

e (XRF ) Spectroscopy . I n Compendium of

Methods forthe Determination of

Inorganic Compounds in Ambient Air; EPA/625/R-96 / 010a . U.S . Governmen tPrintin g Office : Washington , DC , 1999 . 25 . Watson , J.G. ; Lioy , P.J. ; Mueller , P.K . Th e MeasurementProcess : Pre cision , Accurac y an d Validity . I n AirSampling Instruments forEvaluation of Atmospheric Contaminants, 6t h ed. ; Lioy , PJ ; Lioy , M.J.Y ; Eds. ; Amer ica n Conferenc e o f

Governmenta l Industria l Hygienists : Cincinnati , OH , 1983 ; p p 2-7 . 26 . Oldham , C.B . Ai rMeasurement s an d Qualit y Group , Offic e of Ai r Quality Plannin g an d Standards , U.S . Environmenta l Protectio n Agency , Researc

h Triangl e Park, NC . Writte n communicatio n wit h E U Lill y and Company : Lafayette , IN . 2006 . 27 . Hay , KJ. ; Boddu , V.M. ; Johnsen ; B.E. ; Cooper , J.A . X-Ray FluorescenceBased Multi-Metal

Continuous Emission MonitorTechnology Demonstration; ERDC/CERL-TR-05-3 ; U.S . Arm y Corp s of Engineers Enginee r Researc h an d Developmen tCenter : Champaign , IL , 2005 . 28 . Installation and

Use of an X-Ray Based

Continuous Emissions Monitorfor AED Treatability Study; Coope rEnvironmenta l Services : Portland , OR , 2003 . 29 . Re-design and

Field Testing of

an X-Ray Fluorescence Multi-Metals Monitor at the Iowa Army Ammunition Plant, Middleton, Iowa Coal Fired Boiler; Coope rEnvironmenta l Services : Portland , OR , 2005 . 30 . Hay , K.J. ; Johnsen , B.E, ; Ginochio , P.R. ; Cooper , J.A . Relative Accurac y Testin g of

a n X-Ray Fluorescence-Based Mercur y Monito ra tCoal Fire d Boilers ; / . Ai r& Waste Manage. Assoc. 2006 , 56 , 657-665 .

Abou tth e Author s Catherin e Yanca , Dougla s Barth , Kra g Petterson , an dMi

chae l Nakanish i ar e environmenta l scientist s at Coope r

En

vironmenta l Services , LLC
. Joh n Coope r i s th e presiden t

o f Coope r Environmenta l Services , LLC
. Bruc e Johnse n i s a claim s adjuste r

at SAI FCo
. Richar dLamber t i s a n engi

neerin g consultan t

at th e Engineerin g Tec h Center , El i Lill y an dCo
. Danie l Bivin s i s th e work assignmen t

manage r

fo r th e Emissio n Measuremen t Cente r o f th e Offic e o f

Ai r Qual

it y Plannin g an dStandards , U.S
. Environmenta l Protectio n Agency
. Addres s correspondenc e to : Joh n Cooper , Coope r Environmental Services , LLC , 1018 0 S W Nimbu s Ave. , Suit e J6 , Portland , O R97223 ; phone : +1-503-624-5750 ; fa x +1

- 503-624-2120 ; e-mail : Jacooper@cooperenviranmental.com
.

o O

174 2 Journal of the Air & Waste Management

Association Volum e 5 6 Decembe r200

6


### VESO1696 0

# VES016961-016974.pd f

# CR(» I

CoaWo nlor ResponsiblB Wast

eIrcnerafo n

MEMBE RCOMPANIE S Clea n Harbor

s Environmenta

l Service s Do w Chemica l U.S.A . E . I . D u Pon

td e Nemour

s Eastma n Chemical Compan y INVIST A S.&r.l . 3 M Ros s Incineration Services , Inc . Veoli a E S Technica

l Services , LL C GENERATO RMEMBER S El i Lill y an

d Compan

y ASSOCIAT E MEMBER S AECO M B 3 Systems Complianc e Strategie s & Solution s Coteri e Environmental , LL C Focu s Environmental , Inc . Foste rWheele rUS A Franklin Engineerin g Group , Inc . METC O Environmental , Inc. SAI C SG S Analytica l Perspectives , LL C Strata-G , LL C TestAmeric a Laboratories , Inc . TR C Environmenta

l Corporatio n UR S Corporatio n INDIVIDUA L MEMBER S Ronal d E . Bastian , P E Ronal d 0 . Kagel , Ph D ACADEMI C MEMBER S (Includes facult

y from: ) Clarkso n Universit

y Colorad o Schoo l o

f Mine s Lama rUniversity Louisian a Stat

e Universit

y Mississipp i Stat

e Universit

y Ne w Jerse

y Institut

e o f Technolog y University o f

Californi a- Berkeley University o f

Dayto n University o f

Kentuck

y University o f

Marylan d University o f

Uta h Apri l 1,201 3
Georg e Czernia k U.S

. EP A 7 7 W

. Jackso n Blvd

. (A-18J ) Chicago , I L 60604

. Attn : Docke t I D No

. EPA-R05-OAR-2012-064 9 Th e Coalitio n fo rResponsibl e Wast e Incineratio n (CRWI ) appreciate s th e opportunit yt o submi t comment s o n Veoli a E S Technica l Solution s draf t Titl e V Permit

. CRW I i s a trad e associatio n comprise d o f 2 3 members

. Veoli a E S Technica l Solution s i s a membe ro f CRWI

. E P Ai s proposin g t o mak e majo rchange s t o Veolia' s permit

. CRW I ha s concern s abou t the followin g fou rissue s associate d wit h th e draf t permit

. 1

. EP Ashoul d no t remov e th e ter m "NESHAP " i n sectio n 2.1(C)(1)

. 2

. Regio n 5 shoul d correc t the discrepancie s betwee n th e draf t permi t an d th e Statemen t o f Basis , shoul d allo wfo r upwar d extrapolatio n o f mercur yfee d rates , an d calculat e th e mercur yfee d rat e o n actua l analytica l dat a rathe rtha n theoretica l calculations

. 3

. Regio n 5 shoul d no t requir e th e facilit yt o install , calibrate , operate , an d maintai n a multi-metal s CEMS

. 4

. Regio n 5 shoul d modif yth e samplin g an d analysi s requirements

.

4412 1 Harr

y Byr d Highway , Suit e 22 5 Ashburn , V A 2014

7 Phone : 703-431-734 3 E-mail : mel@crwi.or g We b Page : http://www.crwi.or g



### VES01696 1Docke t I D No

. EPA-R05-OAR-2012-064 9

Specifi ccomment s o n eac h o f th e issue s liste d abov e ar e attached

. Than k yo u fo rth e opportunit yt o commen t o n thi s draf t Titl e V permit

. I f yo u hav e an yquestions , pleas e contac t m e a t (703-431-734 3 o rmel@crwi.org)

. Sincerel yyours ,
Melvi n E

. Keener , Ph.D

. Executiv e Directo rDocke t I D No

. EPA-R05-OAR-2012-064 9 3



### Specifi c Comment

s 1

. EP Ashoul d no t remov e the ter m "NESHAP " i n sectio n 2. 1 (C)(1)

. O n pag e 1 1 ofth e draf t permit , Regio n 5 propose d t o delet e the ter m "NESHAP " i n sectio n 2.1(C)(1)

. W e sugges t tha t Regio n 5 reconside rdeletin g tha t ter m becaus e i f finalize d a s proposed , thi s provisio n wil l eliminat e th e abilit yt o bur n an ywast e containin g beryllium

. Sinc e th e Regio n talk s abou t fee d rate s o f berylliu m i n othe r section s o f th e draf t permi t an d i n th e Statemen t o f Basis , w e d o no t believ e thi s wa s intended

. I n thi s cas e "berylliu m NESHA P containin g waste " refer s t o wast e tha t wa s generate d whe n complyin g wit h th e berylliu m NESHAP

. Th e languag e i n the origina l permi t wa s intentiona l an d shoul d b e retained

. 2

. Regio n 5 shoul d correc t th e discrepancie s betwee n th e draf t permi t an d the Statemen t o f Basis , shoul d allo wfo rupwar d extrapolatio n o f mercur yfee d rates , an d calculat e th e mercur yfee d rat e base d o n actua l analytica l dat a rathe rtha n theoretica l calculations

. I n th e Statemen t o f Basi s (se e pag e 14) , EP Apropose s t o allo wupwar d extrapolatio n o f th e SV M an d LV M fee d rat e use d durin g th e tes t t o th e historica l highes t 12-hou rrollin g average . EPA' s decisio n wa s base d o n guidanc e provide d i n th e preambl e o f th e firs t hazardou s wast e combusto rMAC Tfina l rul e (6 4 Fed

. Reg

. 52,946-47 , Septembe r30,1999)

. CRW I support s the decisio n b yRegio n 5 t o allo w upwar d extrapolatio n fo rSVM s an d LVMs

. W e woul d lik e t o poin t ou t tha t ther e ar e tw o discrepancie s o n fee d rat e limit s betwee n the Statemen t o f Basis , Tabl e 2 (pag e 17 ) an d the draf t permi t (pag e 1 2 o f 134)

. Fo rUni t 2 , th e Statemen t o f Basi s show s a fee d rat e limi t fo rLV M a s 68. 5 Ib/h rwhil e th e draf t permi t ha s a valu e o f 8 4 Ib/hr

. Fo rUnit 4 , the Statemen t o f Basi s ha s a fee d rat e limi t fo rSV M o f 98. 1 Ib/h rwhil e the draf t permi t ha s a valu e o f 6 4 Ib/hr

. CRW I believe s tha t thi s i s a simpl e translatio n erro ran d suggest s tha t th e Agenc ydetermin e whic h on e i s correct
. Whil e Regio n 5 i s allowin g upwar d extrapolatio n o f SV M an d LVM , the yar e no t usin g upwar d extrapolatio n fo rmercury . Th e state d reason s fo rthi s ar e tha t Unit 4 use s carbo n injectio n an d tha t the facilit yspike d mercur ydurin g th e tes t runs . However , Unit s 2 an d 3 d o no t hav e carbo n injection

. S o th e onl yreaso n Regio n 5 use s fo rno t allowin g extrapolatio n fo rUnit s 2 an d 3 i s o n pag e 1 8 ofth e Statemen t o f Basis

. Mercur ywa s spike d a s par t o f th e comprehensiv e performanc e test
. Th e intende d purpos e o f meta l spikin g whe n conductin g comprehensiv e test s i s t o enabl e a facilit yt o verif ycomplianc e wit h MAC Tlimit s unde rworst-cas e conditions

. T o protec t workers , EP Adoe s no t encourag e unnecessar yspikin g o f metal s durin g comprehensiv e tests
. Therefore , i f a facilit yspike s metal s whe n conductin g comprehensiv e tests , th e meta l spik e rate s an d the nativ e mercur y conten t o f th e wast e shoul d b e use d t o se t the feedrat e limi t with littl e o rn o



### VESO1696 3Docke t I D No

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extrapolation , provide d th e correspondin g stac k emission s assur e complianc e wit h al l MAC Tlimit s wit h a n ampl e margi n o f safety

. (Statemen t o f Basi s a t 18 , footnote s omitted ) Whil e par t o f thi s statemen t i s correc t (regardin g th e protectio n o f workers) , th e statemen t tha t i f a facilit yspike s metal s durin g a test , th e meta l spik e rate s shoul d b e use d i s incorrect

. I f the Agenc ywoul d g o bac k t o the sam e documen t the yquot e i n justifyin g th e upwar d extrapolatio n fo rSV M an d LV M (th e 199 9 fina l rule ) an d loo k a t footnot e 240 , the ywoul d fin d tha t EP AHeadquarter s full yintende d fo rthi s metho d t o appl yt o mercur ya s well : Footnot e 240

. Althoug h thi s extrapolatio n discussio n i s presente d i n contex t o f semivolatil e an d lo wvolatil e meta l feedrates , simila rprovision s coul d b e implemente d fo rmercur yfeedrates

. (6 4 Fed

. Reg

. 52,946 ) I n addition , Regio n 5 contradict s EP AHeadquarter s guidanc e whe n the ystat e tha t the spike d rat e shoul d b e use d i n settin g the fee d rat e limits

. I n th e sam e quot e fro m th e 199 9 rul e tha t i s i n th e Statemen t o f Basis , EP AHeadquarter s states : Further , w e expec t tha t som e spikin g woul d b e desire d t o increas e confidenc e i n th e measured , performanc e tes t feedrat e level s tha t wil l b e use d t o projec t feedrat e limit s (i.e. , the error s associate d with samplin g an d analyzin g heterogeneou s feedstream s ca n b e minimize d b yspikin g know n quantities)

. (Statemen t o f Basi s a t 1 4 an d 6 4 Fed

. Reg

. 52,946 ) Thus , unde rcertai n circumstances , spikin g i s desire d t o increas e the confidenc e o f the measurement s an d th e extrapolate d values

. Regio n 5 ha s n o basi s fo rno t allowin g upwar d extrapolatio n o f mercur yfee d rate s an d i n fact , no t allowin g extrapolatio n fo rmercur yi s contrar yt o the guidanc e quote d b yth e Agency

. Also , Regio n 5' s curren t positio n tha t upwar d extrapolatio n o f mercur yi s no t allowe d ma y hav e unintende d consequences . I f facilitie s canno t us e upwar d extrapolation , the y wil l b e force d t o spik e mercur ya t highe rrate s tha n neede d t o ge t the operationa l flexibilit yrequire d t o operate
. Thi s wil l nullif yal l o f the benefit s (reductio n o f mercur y emissions , protection s o f workers , purchas e o f exces s mercur ytha t mus t b e dispose d o f later , etc. ) fro m allowin g upwar d extrapolation

. Th e technica l basi s fo rupwar d extrapolatio n i s lai d ou t i n th e Technica l Suppor t Documen t (Volum e 4 , Chapte r6.3 , pag e 6-7 ) ofth e 199 9 hazardou s combusto rfina l rule

. Ther e i s nothin g i n the technica l suppor t documen t tha t set s a n uppe rlimi t o n extrapolation

. I n fact , EPA' s grap h (Figur e 6.1 ) show s tha t upwar d extrapolatio n wil l b e a conservativ e estimato ro f actua l emission s a t an yleve l abov e wher e i t i s



### VES01696 4Docke t I D No

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measured

. Thus , th e emissio n level s predicte d a t highe rfee d rate s base d o n linea r extrapolatio n ar e greate rtha n o requa l t o the actua l emissions

. Obviously , th e uppe r limi t ha s t o b e th e promulgate d emissio n limit

. I n the initia l hazardou s wast e combusto rfina l rul e (6 4 F R 52,828 , Septembe r30,1999) , EP Amad e a polic y decisio n t o limi t extrapolatio n t o th e highes t historica l fee d rate s (64 , F R 52,946-7)

. Ther e i s a n extensiv e discussio n o n thi s i n th e preambl e o f tha t rule

. I t shoul d b e emphasize d tha t the decisio n t o limi t t o historica l level s i s a polic ydecision , no t a decisio n base d o n technica l information

. I n th e sam e paragrap h wher e th e Agenc y mad e the polic ydecision , the ylef t som e flexibilit yi n thi s decisio n b yaddin g a sentenc e tha t say s "Extrapolatio n approache s tha t reques t feedrat e limit s tha t ar e significantl yhighe rtha n the historica l rang e o f feedrate s shoul d no t b e approved. " (6 4 F R 52,946-7)

. I t i s ou runderstandin g tha t othe rstate s an d region s allo w upwar d extrapolatio n u p t o 3 time s th e historica l maximu m fee d rate
. W e sugges t tha t Regio n 5 shoul d no t limi t the upwar d extrapolatio n t o th e historica l limit s i f othe r informatio n ca n b e use d t o sho wtha t suc h emission s rate s ar e belo wthe emissio n limit s an d ar e protectiv e o f huma n healt h an d th e environment

. I n addition , Regio n 5 modifie d the calculatio n ofth e spik e rate s t o matc h the minimu m purit yofth e reagen t instea d o f usin g the actua l laborator yanalysi s o f th e spike d material s (se e footnot e 2 , Tabl e 2 , Statemen t o f Basis , pag e 17)

. Thi s i s surprisin g sinc e bot h Regio n 5 an d th e facilit ytoo k sample s o f th e spikin g solutions

. Th e facilit yanalyze d thes e sample s an d use d th e analytica l dat a t o propos e mercur y fee d rates
. Surel yactua l analytica l dat a o n the amoun t o f mercur yfe d i s superio rt o a theoretica l analysis

. W e se e n o reaso n t o us e theoretica l calculatio n whe n actua l analysi s fro m eithe rVeoli a o rEP Ai s available

. CRW I strongl ysuggest s tha t Regio n 5 recalculat e th e fee d rate s base d o n th e analytica l dat a fro m th e tes t an d allo w upwar d extrapolatio n wher e appropriat e (Unit s 2 an d 3 ) t o se t th e fee d rat e limit s fo r mercury . 3

. Regio n 5 shoul d no t requir e the facilit yt o install , calibrate , operate , an d maintai n a multi-metal s CEMS

. Regio n 5 i s proposin g tha t Veoli a instal l an d operat e a multi-metal s CEM S fo ra t leas t on e year . CRW I ha s severa l concern s abou t thi s requirement

. I t i s inappropriat e t o us e a Titl e V permi t t o forc e Veoli a t o instal l a multi-metal s CEMS

. ATitl e V permi t i s suppose d t o b e a compilatio n o f emission s limits , monitorin g requirements , an d reportin g requirement s tha t ar e develope d a s a part ofth e regulation s fo rtha t sourc e category
. Thi s facilit yi s regulate d unde rSubpar t EEE

. A multi-meta l CEM S i s no t require d unde rSubpar t EEE

. W e d o no t fee l i t i s prope rt o us e the Titl e V proces s t o ad d entirel yne wan d unteste d requirements , especiall y whe n th e Agenc yha s no t provide d adequat e justification

. Th e Agenc yha s th e authorit yt o requir e a facilit yt o instal l instrument s an d gathe rdat a fo reithe r



### VES01696 5Docke t I D No

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rulemakin g o renforcemen t bu t no t throug h th e Titl e V permittin g process . Thi s doe s no t appea rt o b e eithe ra rulemakin g o ra n enforcemen t action

. Rathe ri t seem s t o b e a thinl ydisguise d researc h projec t tha t Regio n 5 want s th e facilit yt o run . EP Aha s mad e a numbe ro f statement s o n multi-meta l CEM S tha t ar e incorrect , misleadin g o runsubstantiated

. I n the Statemen t o f Basis , th e Agenc ymake s severa l statement s fo rwhic h the y hav e no t provide d an ydocumentatio n t o sho wtha t the yar e correct
. I n addition , ther e ar e a numbe ro f statement s tha t ar e eithe rincorrec t o rmisleading

. Th e statement s tha t hav e n o supportin g documentatio n ar e liste d below

. a . "Th e uncertaintie s cause d byfeedstrea m analysi s ar e largel ysolve d whe n a n EPA
approve d CEM S i s use d t o directl ymeasur e emissions. " (Statemen t of Basi s a t 21 ) b

. "Second , moder n multi-metal s CEM S hav e bee n show n t o b e mor e accurat e an d reliabl e tha n feedstrea m analysi s fo rmonitorin g mercuryan d othe rhazardou s meta l emission s fro m combustio n of heterogeneou s feedstreams. " (Statemen t o f Basi s a t 22)

. c . "Withou t a CEMS , mos t emissio n excursion s fro m combustio n of suc h heterogeneou s feedstream s woul d g o undetected. " (Statemen t o f Basi s at 22)

. Th e Agenc yha s not provide d an ydocumentatio n o rcitation s t o sho wthes e statement s t o b e correct
. Th e court s hav e state d (Northeast Maryland, 35 8 F.3 d a t 954 ) that EP A mus t provid e proo f of it s statements , no t jus t mak e unsupporte d assertions

. I f everythin g th e Agenc ysai d abov e wer e correct , on e woul d assum e tha t multi-metal s CEM S woul d b e require d i n a numbe ro f the recen t combustio n MAC Trules

. However , i t i s no t require d i n an yof them

. I n addition , th e Agenc ymake s a numbe ro f statement s tha t ar e eithe rincorrec t o r misleading

. a . "Multi-metal s CEM S ar e commerciall yavailabl e an d hav e bee n demonstrate d t o b e reliabl e fo rmeasurin g mercur yan d othe rmeta l emission s fro m hazardou s wast e combustors. " (Statemen t of Basi s a t 22)

. Whe n th e Statemen t of Basi s wa s written , th e Xac t wa s offere d b yPal l Corporation

. Thi s i s n o longe rcorrect
. Pal l n o longe rmanufacture s an d sell s th e Xac t unit

. Th e marketin g right s t o th e Xac t hav e reverte d t o Coope rEnvironmenta l Services

. I t shoul d als o b e note d that thi s instrumen t i s not a n instrumen t tha t i s carrie d i n inventory

. I f a facilitywante d t o purchas e a n Xac t unit , Coope rEnvironmenta l Service s ha s indicate d that i t woul d tak e the m a t leas t si xmonth s t o buil d it

. Thi s i s th e tim e t o buil d th e instrumen t itsel f an d doe s not includ e tim e t o develo p th e site
specifi csamplin g trai n o rth e tim e t o develo p th e softwar e interfac e betwee n th e instrumen t an d th e facility' s contro l systems
. Th e softwar e developmen t proces s (custo m softwar e fo rthat site ) woul d tak e severa l month s afte rthe instrumen t wa s installed

. Onl yon e Xac t uni t ha s bee n installe d an d operate d fo ra n extende d perio d



### VES01696 6Docke t I D No

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o f tim e a t onl yon e hazardou s wast e combustor , the combusto ra t Evonik s Tippecano e Laboratories

. Du e t o frequen t maintenanc e issue s an d equipmen t failure , tha t Xac t uni t i s n o longe roperating

. b

. "EP Aha s approve d th e us e o f multi-metal s CEM S a s alternativ e monitorin g methodologie s at hazardou s wast e combustors. " (Statemen t of Basi s at 22)

. Th e Agenc yha s approve d alternativ e monitorin g requirement s fo ron e hazardou s wast e combusto r- no t hazardou s wast e combustor s a s stated

. Thi s proces s too k thre e year s forth e facilit yt o ge t approval

. Whil e th e Arm yallowe d th e CEM S compan yt o instal l an d tes t a n Xac t uni t o n the Tooel e Arm yDepo t researc h an d developmen t furnace , i t i s not include d a s a par t o f th e facility' s permi t no rha s i t bee n include d a s a par

t o f HW C MAC Ttestin g (CRW I obtaine d thi s informatio n fro m persona l communication s wit h th e operatin g facility)

. c . "EP Aha s performe d side-by-sid e evaluation s of multi-metal s CEM S wit h EP A Metho d 2 9 o f Appendi xA- 8 t o 4 0 C.F.R

. Part 6 0 a t industria l wast e incinerator s an d foun d goo d correlatio n betwee n the tw o methods

. 7 5 Fed

. Reg

. 3196 2 (Jun e 4 , 2010). " (Statemen t of Basi s at 22-23)

. Thi s referenc e i s fro m th e propose d CISW I rule

. Th e preambl e o f thi s propose d rul e states
. EP Abelieve s multi-metal s CEM S ca n b e use d i n man yapplications , includin g CISWI

. EP Aha s monitore d side-by-sid e evaluation s o f multi-metal s CEM S wit h EP AMetho d 2 9 o f appendi xA- 8 o f 4 0 CF R par t 6 0 a t industria l wast e incinerator s an d foun d goo d correlation

. EP Aals o approve d the us e o f multimetal s CEM S a s a n alternativ e monitorin g metho d a t hazardou s wast e combustors

. EP Abelieve s i t i s possibl e t o adap t propose d PS-1 0 (Specification s an d Tes t Procedure s fo rMulti-metal s Continuou s Monitorin g System s i n Stationar ySources ) o f appendi xB o f 4 0 CF R par t 6 0 o rothe r EP Aperformanc e specification s t o allo wth e us e o f multimetal s CEM S a t CISWI

. W e reques t commen t o n th e appropriatenes s o f usin g multi-metal s CEM S instea d o f initia l performanc e test s couple d wit h P M CEM S an d othe r surrogates
. Th e procedure s use d i n propose d PS-1 0 fo rth e initia l accurac y determinatio n us e the relativ e accurac ytest , a compariso n agains t a referenc e method

. EP Ai s takin g commen t o n a n alternat e initia l accurac y determinatio n procedure , simila rt o the on e i n sectio n 1 1 o f PS-1 5 usin g the dynami co ranalyt e spikin g procedure

. Whil e the statemen t abov e i s i n th e propose d rule , the fina l rul e di d no t requir e multi-metal s CEMS

. I n th e preambl e o f the fina l rule , EP Amad e the followin g statement s i n respons e t o comment s o n includin g multi-meta l CEMS

. [EPA] Response:

Fo rthe operation s an d facilitie s subjec t t o th e rule , w e believ e tha t th e combinatio n o f periodi ccomplianc e emission s testin g an d



### VES01696 7Docke t I D No

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continuou s monitorin g o f operationa l an d parametri ccontro l measur e condition s i s appropriat e fo rassurin g ongoin g compliance

. Th e rul e allow s a sourc e owne ro roperato rt o instal l an d operat e CEM S i n lie u o f som e testin g an d parametri cmonitorin g requirements

. Thi s proces s require s sourc e owner s t o propos e site-specifi cmonitorin g plan s fo rapproval

. Thes e plan s woul d includ e CEM S P S an d periodi cQA/Q C step s t o assur e the qualit yo f th e alternativ e monitorin g data

. Currently , EP Aha s th e requisit e CEM S P S fo rH g monitorin g system s an d no t fo rmultipl e metal s CEMS

. (7 6 F R 15,736 , Marc h 21 , 2011 ) Joh n Coope r(th e develope ro f th e Xac t technology ) submitte d extensiv e comment s supportin g the us e o f th e Xac t multi-metal s CEMS

. EPA' s response s t o comment s documen t i s EPA-HQ-OAR-0119-2494

. EPA' s response s t o Mr

. Cooper' s comment s with pag e number s ar e below

. [EPA ] Respons e 5 [pag e 1074]

. A t thi s time , EP Adoe s no t hav e promulgate d performanc e specification s fo rmultimeta l CEM S an d thu s th e fina l rul e doe s no t contemplat e a requiremen t t o us e suc h monitorin g o raddres s thes e monitor s directly

. Se e preambl e Sectio n III.C

. fo ra discussio n o n th e testin g an d monitorin g requirement s i n the fina l rule

. Se e als o respons e t o EPA-HQ
OAR-2003-0119-1133.2 , excerp t 12

. [EPA ] Respons e 1 2 [pag e 1072]

. W e recogniz e an d agre e tha t a n integratin g multipl e metal s CEM S operate s i n a manne rfundamentall ydifferen t tha n th e instrumenta l metal s CEM S fo rwhic h draf t Performanc e Specificatio n 1 0 wa s developed

. Sinc e EP Adoe s no t hav e a publishe d performanc e specificatio n fo rmetal s CEMS , instrumenta l o rintegrating , the sourc e owne rmus t prepar e a site-specifi cmonitorin g pla n i n orde rt o appl yth e metal s CEM S option

. Th e monitorin g pla n nee d no t imitat e existin g CEM S performanc e specification s (e.g. , samplin g frequency ) bu t shoul d b e structure d t o addres s thos e characteristi coperation s ofth e CEM S relectin g (sic ) th e operatin g principl e an d associate d QA/Q C procedures

. I n addition , th e Ne wYor k Departmen t o f Environmenta l Conservatio n (DEC ) submitte d a shor t commen t opposin g th e us e o f multi-metal s CEMS

. The ystate , "Th e DE C believe s tha t multi-metal s an d P M CEM S ar e inadequat e t o indicat e the comple xnatur e o f incinerato remissions. " [pag e 1078]

. EP Aresponded : Fo rth e operation s an d facilitie s subjec t t o th e rule , w e believ e tha t the combinatio n o f periodi ccomplianc e emission s testin g an d continuou s monitorin g o f operationa l an d parametri ccontro l measur e condition s i s appropriat e fo rassurin g ongoin g compliance

. Th e rul e allow s fo rthe sourc e owne ro roperato rt o instal l an d operat e continuou s emission s monitorin g system s i n lie u o f som e testin g an d parametri cmonitoring

. Thi s proces s



### VES01696 8Docke t I D No

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require s sourc e owner s t o propos e site-specifi cmonitorin g plan s fo rapproval

. Thes e plan s woul d includ e CEM S performanc e specification s an d periodi c qualit yassuranc e an d qualit ycontro l step s t o assur e the qualit yofth e alternativ e monitorin g data

. Currently , EP Aha s th e requisit e CEM S performanc e specification s fo rmercur ymonitorin g system s an d no t fo r multipl e metal s CEMS

. Whil e th e statemen t a t the beginnin g o f thi s sectio n i s a n accurat e quot e fro m th e propose d rule , tha t propose d rul e di d no t documen t tha t thi s statemen t i s correct
. I n fact , i n th e fina l rule , EP Adecline d t o requir e multi-metal s CEM S i n spit e o f extensiv e comment s submitte d b yth e develope rofth e Xac t system
. Th e rational e th e EP Aprovide d wa s tha t th e Agenc yha d no t promulgate d a performanc e standard

. I t shoul d b e pointe d ou t tha t OT M 1 6 an d OT M 2 0 alread yexiste d a t th e tim e EP Amad e the decisio n no t t o requir e multi-meta l CEM S a s a requiremen t i n th e CISW I rule

. Sinc e th e Agenc ydi d no t recogniz e OT M 1 6 an d OT M 2 0 a s vali d performanc e specification s whe n the yresponde d t o Mr

. Cooper' s comment s o n th e CISW I Rule , the ycanno t no wus e the m i n Veolia' s circumstance

. d

. "I n addition , performanc e specification s an d qualit yassuranc e (QA ) procedure s ar e no wavailabl e fo rbot h mercur yan d multi-metal s CEMS. 2 4EP Aha s publishe d performanc e specification s an d Q Aprocedure s fo rmulti-meta l CEM S a s OT M 1 6 (Specification s an d Tes t Procedure s fo rX-ra yFluorescenc e Base d Multi-Metal s Continuou s Emissio n Monitorin g System s a t Stationar ySources ) an d OT M 2 0 (Qualit yAssuranc e Requirement s fo rX-Ray-Fluorescenc e Base d Multi-Metal s Continuou s Emissio n Monitorin g System s a t Stationar ySources). 2 5 Moreover , multi-metal s CEM S ar e a n accepte d optio n fo rmetal s emissio n complianc e i n th e recentl ypromulgate d mercur yan d ai rtoxic s (MATS ) rule

. 7 7 Fed

. Reg

. 930 3 (Februar y16 , 2012)

. Therefore , th e multi-metal s CEM S ha s bee n prove n t o b e reliabl e fo rmeasurin g actua l emission s o f HA P metal s fro m a hazardou s wast e combusto rsuc h a s Veolia. " (Statemen t o f Basi s a t 23 ) Further , Footnote s 2 4 an d 2 5 o f th e Statemen t o f Basi s state : Footnot e 24.Performanc e Specificatio n 1 0 (fo rmulti-metal s CEMS ) an d Performanc e Specificatio n 1 2 fo rmercur yCEM S wer e propose d i n 199 6 i n conjunctio n with th e origina l HW C MACT

. However , becaus e th e multi
metal s an d mercur yCEM S measuremen t technologie s ha d no t bee n full y develope d an d demonstrated , neithe rperformanc e specificatio n wa s promulgated

. Betwee n 200 3 an d 2005 , Performanc e Specificatio n 12 Afo r mercur yCEM S wa s propose d an d promulgate d i n conjunctio n with th e Clea n Ai rMercur yRul e (CAMR ) afte rextensiv e demonstratio n o f mercur yCEM S an d identificatio n o f appropriat e performanc e parameters
. I n 2007 , CAM R wa s vacate d b ythe U.S

. Cour t o f Appeal s fo rth e Distric t o f Columbia , whic h calle d int o questio n th e legalit yo f usin g Performanc e Specificatio n 12A

. I t



### VES01696 9

### Docke t I D No

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ha s sinc e bee n re-propose d i n conjunctio n wit h amendment s t o th e Portlan d Cemen t NESHAP

. Se e http://www.epa .g0v /ttn/emc /m0nit0r .html#metal s Footnot e 25.Se e http://www.epa.gov/ttn/emc/prelim/otm16.pdfan d http://www.epa.gov/ttn/emc/prelim/otm20.pdf

. OT M 1 6 an d 2 0 ar e no t promulgate d performanc e specifications

. Whe n CRW I suggeste d EP Aus e publishe d OTM s fo rHC I monitor s i n th e Portlan d Cemen t MAC Treconsideratio n rule , th e Agenc ydecline d t o us e thes e specification s givin g the followin g reason s (EPA-HQ-OAR-2011-0817-0846 , pag e 78) : Othe rTes t Method s (OT M 2 2 an d 23 ) wer e provide d o n ou rwebsit e fo r evaluatio n and/o rus e b yth e stakeholde rcommunit yan d t o encourag e developmen t o f fiel d tes t dat a supportin g th e procedure s describe d i n thes e methods

. Significan t improvement s an d addition s t o thes e OT M procedure s ar e necessar ybefor e the ywil l mee t EPA' s HC I CEM S performanc e specificatio n requirements

. EPA' s effort s t o prepar e an d distribut e a technolog yneutra l Performanc e Specificatio n embrace s the ke ycomponent s o f OT M 2 2 an d 23

. I f a facilit ymanage rbelieve s tha t ther e i s a n alternativ e procedur e tha t ca n bette rmee t th e HC I complianc e monitorin g requirement s i n thi s rule , the yalway s hav e th e optio n t o submi t i t a s a n alternativ e tes t metho d unde r63.7(f ) a s previousl ymentioned

. I n a t leas t tw o rulemakings , EP AHeadquarter s ha s decline d t o us e OT M durin g th e rulemakin g o rdecline d t o requir e CEM S becaus e ther e wa s n o promulgate d performanc e specificatio n fo rthat instrument

. I n addition , Regio n 5 states i n th e Statemen t of Basi s (pag e 21 ) tha t "th e HW C MAC Tdoe s no t mandat e th e us e of CEM S t o documen t complianc e wit h the HW C MAC Tlimit s fo rmercury , LVM , SVM , o rchlorin e base d i n par t o n EPA' s determinatio n tha t performanc e specification s fo r mercuryo rmulti-metal s CEM S wer e no t ye t availabl e a t the tim e o f finalizatio n o f tha t rule. " W e believ e tha t i t i s disingenuou s at bes t fo rRegio n 5 t o sa ythat performanc e specification s an d qualit yassuranc e procedure s ar e no wavailabl e fo r multi-meta l CEMS

. I f a facilit yha d aske d t o pu t suc h a CEM S on , the Agenc ywoul d requir e the m t o submi t a n alternativ e monitorin g applicatio n an d th e proces s of approvin g tha t applicatio n woul d hav e take n severa l years . e . EP Ase t fort h i n it s Statemen t of Basi s (a t footnot e 33 ) that : "Th e U.S

. Arm yha s als o successfull yinstalle d an d evaluate d a multi-metal s CEM S o n on e o f it s hazardou s wast e incinerators

. Ha yet al. (2005)

. EP A als o understand s tha t the U.S

. Departmen t o f Defens e ha s purchase d thre e Xact TM unit s fo rus e a t arm ymunition s incinerators

. Finally , multi-metal s CEM S ar e a n accepte d optio n fo rmetal s emissio n complianc e i n the utility mercur yan d ai rtoxic s (MATS ) rul e tha t wa s recentl ypromulgate d b yEPA. " (Statemen t o f Basi s a t 24)

.



### VES01697 0Docke t I D No

. EPA-R05-OAR-2012-064 9 1 1

Ahypertex t searc h ofth e MAT S rul e di d no t sho wan yreferenc e t o a multi
metal s CEMS

. Thus , th e statemen t tha t a multi-metal s CEM S i s a n acceptabl e optio n i n the MAT S rul e i s no t correct
.

, Whil e i t i s correc t tha t th e Arm ypurchase d an d installe d thre e Xac t units , non e hav e eve ruse d fo rcomplianc e wit h Subpar t EEE

. CRW I aske d Arm ypersonne l the curren t statu s o f th e multi-metal s CEM S a t thei rfacilities

. Thei rresponse s ar e below

. Tooel e Arm yDepo t researc h an d developmen t furnace : Thi s uni t onl y operate s fro m tim e t o tim e t o establis h ne w"recipes " fo rne wfee d items

. It' s actuall yno t covere d b yan yofth e sit e permits , a s lon g a s i t stay s unde ra certai n numbe ro f hour s o f operation

. We'v e neve rteste d i t fo rHW C MAC T an d i t isn' t include d i n th e NOC

. I woul d no t conside rthi s a realisti cexampl e o f multi-meta l CEM S operatin g o n a dail ybasis

. Tooel e Arm yDepo t productio n furnace : Thi s uni t wa s operationa l o n th e furnac e fo ra perio d o f time

. The yn o longe roperat e the CEM S o n th e unit

. I thin k onc e the yfinishe d u p th e prove-ou t fo rCooper , i t wa s shu t down

. Cran e Arm yAmmunitio n Activit yproductio n furnace : I t wa s installed , ha s bee n starte d u p fo ra n initia l qualification , the n shu t down , an d ha s neve r bee n used

. CRW I encourage s Regio n 5 t o contac t thes e facilitie s t o verif ytha t thes e statement s ar e correct
. f . "Yanc a e f al. evaluate d bot h th e Xact TM an d th e QA G usin g a modifie d EP A Metho d 30 1 a t a hazardou s wast e combusto rb ycomparin g measure d an d referenc e aeroso l concentrations

. Th e author s foun d tha t bot h the Xact TM an d th e QA G me t the Metho d 30 1 validatio n criteri a wit h precision s an d accuracie s o n th e orde ro f 5 percen t ove ra wid e rang e o f concentrations. " (Statemen t o f Basi s a t 24)

. Thi s statemen t i s accurat e forth e operatin g condition s an d th e flu e ga s condition s a t th e Evonik s hazardou s wast e combustor

. However , thi s ha s no t bee n verifie d a t an yothe rfacility

. g . "I n 2010-201 1 , EM C deploye d th e Xact TM 62 5 fenc e lin e multi-metal s monito ra t tw o site s i n Ohi o i n coordinatio n wit h EP ARegio n 5 , EP AOffic e of Researc h an d Developmen t (ORD ) an d Ohi o EPA

. Th e XactTM62 5 report s hourl yambien t ai r metal s concentration s i n nea rreal-time , whic h allow s fo rfaste rdat a acquisitio n an d decisio n makin g ove rconventiona l filter-base d monitorin g methods

. EPA' s Ohi o studie s sho wexcellen t comparabilit ybetwee n th e Xact TM 62 5 an d conventional , filter-based , metal s monitorin g methods. " (Statemen t o f Basi s at 25)

.Docke t I D No

. EPA-R05-OAR-2012-064 9 1 2

Thi s i s no t a vali d comparison

. Ambien t ai rmonitorin g i s relativel ysimpl e du e t o th e ambien t ai rmatrix

. Flu e ga s samplin g a t hig h temperatur e an d moistur e conten t i s a totall ydifferen t problem

. It i s muc h mor e difficul t t o ge t a consisten t flu e ga s sampl e t o the instrument

. Thus , an ycompariso n o f samplin g th e flu e ga s o f a hazardou s wast e combusto rt o ambien t ai rmonitorin g ignore s too man y variable s t o b e valid

. h

. "Th e us e o

f a multi-metal s CEM S i s the onl ysur e wa yt o verif ytha t Veolia' s feedstrea m analysi s procedure s an d th e propose d feedrat e limit s ar e sufficien t t o assur e continuou s complianc e wit h th e HW C MAC Tlimits. " (Statemen t o f Basi s at 25)

. A s alread ydiscussed , du e t o the lac k o f performanc e specification s fo rmulti-metal s CEMS , ther e i s n o wa yo f determinin g whethe rdat a fro m th e CEM S i s accurate
. Therefore , thi s statemen t i s inaccurate

. Th e vas t majorit yo f the statement s Regio n 5 ha s place d i n th e Statemen t o f Basi s ar e no t supporte d b yanythin g i n the officia l recor d o ri n th e publi crecord

. Th e fact s ar e tha t a n Xac t uni t wa s intermittentl yoperate d o n on e hazardou s wast e combusto r fo ra numbe ro f years . Du e t o frequen t maintenanc e issue s an d equipmen t failure , th e facilit yremove d the CEM S fro m servic e permanentl yi n 2011

. Whil e a n Xac t uni t wa s installe d o n thre e othe rfacilities , i t wa s neve ruse d o n thos e thre e unit s t o compl ywit h Subpar t EEE

. ACEM S canno t b e use d fo rcomplianc e unles s i t ha s a promulgate d performanc e specificatio n o runles s th e facilit ysubmit s an d the Agenc yapprove s a n alternativ e monitorin g application

. EP Aha s no t promulgate d a performanc e specificatio n fo ra multi-metal s CEMS

. Withou t a performanc e specification , th e Agenc ycanno t us e thi s instrumen t fo r complianc e unles s the yapprov e a n alternativ e monitorin g application

. I t shoul d b e note d tha t th e facilit yha s no t submitte d a n application

. I n addition , the court s (Portland Cement Association

v. Ruckelshaus, 48 0 F.2 d 375,39 6 (D.C

. Cir

. 1973) , cert, denied, 41 7 U.S

. 92 1 (1974) ) hav e mad e i t clea rtha t complianc e ca n onl yb e show n usin g the sam e method s use d t o develo p the standards

. Sinc e Metho d 2 9 wa s use d t o develo p the dat a use d t o se t the standard s i n Subpar t EEE , Metho d 2 9 i s the onl ywa ya facilit yca n sho wcomplianc e unles s th e Agenc yapprove s a n alternativ e monitorin g application

. OT M 1 6 an d 2 0 ar e site-specifi cmethod s an d ar e no t applicabl e t o Veolia' s operations

. OT M 1 6 an d 2 0 wer e writte n specificall yfo rEl i Lill yan d Co.' s (Lilly ) sourc e an d instrument

. Whil e the ywoul d provid e a startin g plac e fo ranothe rfacilit yt o develo p



### VES01697 2Docke t I D No

. EPA-R05-OAR-2012-064 9 1 3

thei row n site-specifi cmethod , on e canno t assum e tha t eithe rcoul d b e use d a t anothe rfacilit ywithou t significan t modification

. Fo rexample , th e sampl e transpor t syste m i n OT M 1 6 provide s fo ra protoco l fo rincludin g th e sampl e transpor t syste m int o th e instrumen t validatio n usin g eithe rdynami cspikin g o f know n gase s o r compariso n t o anothe rmetho d (instrumenta l o rreference , M29 , filters/tube s an d Ohi o Luminex , etc.)

. Thi s wa s writte n specificall yfo rthe Lill ysyste m usin g a Sigris t samplin g system
. I t i s no t a t al l clea rtha t a n appropriat e sampl e transpor t syste m coul d b e designe d an d develope d fo rVeolia' s stac k ga s conditions

. Lill yspen t considerabl e tim e an d resource s i n developin g bot h the laborator yan d stac k dat a underlyin g thes e methods

. I t i s als o no t clea rwhethe rthi s instrumen t woul d ti e int o Veolia' s dail yoperations , alarms , an d QA/Q C procedures

. I t i s likel ytha t thes e tw o OTM s woul d nee d extensiv e wor k befor e the ywoul d b e usabl e forth e condition s i n Veolia' s stack

. I n addition , ther e i s a goo d chanc e tha t th e curren t QA G wil l no t b e abl e t o produc e quantitativ e mas s o f metal s i n the range s require d t o calibrate/tes t th e Xact

. Th e QA G operate s a s a dynami cspikin g int o the probe/sampl e loo p o f the Xac t system
. Operatio n o f thi s uni t i s dependen t o n th e typ e o f prob e used , the flo wi n th e sampl e loop , an d ga s conditions

. Lill yspen t a yea rdevelopin g thi s devic e t o presen t the mas s o f metal s specifi ct o it s sampl e loo p (flow/moisture , etc.)

. I n summary , a Titl e V permi t i s no t th e appropriat e plac e t o ad d entirel yne wan d unprove n monitorin g requirement s t o a EE E source . Th e Agenc yha s mad e a numbe ro f statement s tha t ar e unsubstantiated , incorrect , o rmisleadin g i n a n effort t o sho wtha t multi-metal s CEM S ar e off-the-shel f instrument s tha t ca n simpl yb e purchase d an d easil yplace d o n a stack

. Thes e instrument s ar e expensive , custo m built , requir e a grea t amoun t o f resource s t o install , calibrate , maintain , an d operate , an d ultimatel yafte rspendin g considerabl e amount s o f money , ma yfai l t o provid e th e dat a expected

. Installin g an d operatin g a multi-metal s CEM S woul d tak e severa l year s t o accomplish

. I t woul d tak e severa l mor e year s t o gathe rdat a an d t o determin e whethe rtha t dat a i s a n accurat e representatio n o f wha t i s emitte d fro m th e stack

. EP Aha s no t promulgate d a performanc e standar d fo rmulti-metal s CEM S an d unti l the yd o so , thes e instrument s canno t b e use d fo rcomplianc e purpose s withou t a n approve d alternativ e monitorin g application

. CRW I doe s no t se e ho w Regio n 5 ca n justif yth e expenditur e o f resource s fo ra "researc h project " whe n i t ha s bee n establishe d tha t othe rmethod s - namel ythos e require d i n th e existin g EE E regulation s - shoul d b e use d t o sho wcompliance

. 4

. Regio n 5 shoul d modif ythe samplin g an d analysi s requirements

. CRW I ha s safet yan d publi chealt h concern s regardin g thi s requiremen t tha t wast e b e sample d withi n 2 4 hour s o f receipt

. Wast e arrive s a t facilitie s a t al l hour s an d i n al l conditions

. I t i s no t alway s feasibl e t o accep t an d safel yanalyz e wast e withi n 2 4 hour s o f receipt

. I f thi s requiremen t wer e imposed , facilitie s coul d b e force d t o choos e betwee n acceptin g th e wast e an d ris k violatin g thei rpermi t b yno t samplin g



### VES01697 3Docke t I D No

. EPA-R05-OAR-2012-064 9 1 4

th e wast e withi n 2 4 hours , o rrefusin g th e wast e an d forcin g carrier s with load s o f hazardou s wast e t o wai t i n area s tha t ar e fa rles s saf e tha n insid e the gate s o f the facility

. W e believ e tha t th e timetabl e fo rsamplin g wast e an d an ysupplementa l analysi s requirement s ar e mor e appropriatel yhandle d unde rRCR Aan d th e facility' s Par t B permit

. Further , CRW I i s concerne d tha t EP Ai s requirin g analysi s simpl yfo r th e sak e o f doin g analysis

. A s written , th e draf t permi t require s th e analysi s o f wast e tha t ha s littl e o rn o chanc e o f containin g metals

. CRW I find s i t highl yironi ctha t Regio n 5 i s requirin g th e facilit yt o repor t non-detect s a t th e reportin g limit

. CRW I ha s bee n tryin g (unsuccessfully ) fo rman yyear s t o ge t th e Agenc yt o recogniz e tha t the reportin g limi t i s the onl ydefensibl e numbe rtha t ca n b e used

. However , sinc e the Agenc yrejecte d thi s ide a whe n finalizin g Subpar t EEE , Regio n 5 canno t no wchang e th e rul e an d requir e tha t al l non-detect s b e reporte d a t th e reportin g limit

. W e agre e wit h Regio n 5 tha t the reportin g limi t i s th e onl ydefensibl e numbe rbu t th e Agenc yha s t o b e consistent

. Whateve rmetho d wa s use d t o se t th e standard s ha s t o b e th e on e tha t i s use d t o sho wcompliance

. Thus , Regio n 5 canno t requir e non-detect s t o b e reporte d a t th e reportin g limit

. Thi s woul d inflat e th e value s an d potentiall ycreat e complianc e issue s wher e non e actuall y exist

. Further , i t place s th e facilit yi n the untenabl e positio n o f certifyin g th e accurac yo f EPCR A(Emergenc yPlannin g an d Communit yRight-to-Kno wAct ) reports
. Finally , w e woul d not e tha t EP AHeadquarter s i s currentl ytakin g comment s o n a revise d wast e analysi s pla n guidanc e document

. W e believ e tha t i t i s prematur e t o includ e an ychange s i n wast e analysi s plan s unti l EP Afinalize s tha t document

. CRW I suggest s tha t thes e provision s b e removed

.



### VES01697 4

# VES016975-016983.pd fUnle dState s Soli dWast e andEPA-530-R-92-01 1 EnvbonmentalPnteeSon

- Emergenc y Respons e FB92-15494 7 Agenc y (OS-322V^ March1992 

# Technica l p 

# **2*i

5ub , . 

# Implementatio

n Documen t fo r EPA' s Boiler an d Industrial Furnac e Regulations

# TECHNICA L IMPLEMENTATIO N DOCUMEN T FO REPA' s BOILE RAN D INDUSTRIA L FURNAC E

REGULATION S

U.S . Environmenta

l Protectio

n Agenc y Offic e o f Soli d Wast e 40 1 M Street

, S.W. Washington

, D.C . 2046

0

Marc h 199 2compound

s i n orde ro f destructio n difficulty

. Th e tw o method s tha tar e commonl

y use d i n permittin

g ar e th e hea to f combustio

n inde x an d th e therma l stabilit y inde x (TSLo02) , I n th e hea to f combustio n index , th e compound

s whic h hav e th e lowes thea to f combustio

n ar e ranke d a s mos tdifficul tt b destroy . Thi s inde x i s liste d i n

. Guidanc e Manua l fo rHazardou

s Wast e Incinerato

r Permit s (11 ) an d othe rdocuments

. Th e TSL0O 2 inde

x wa s develope

d b y th e Universit y o f Dayto n Researc h Institut e (UDR1 ) unde r contrac tt o EPA . I n th e TSLo0 2 index , compound

s ar e ranke d accordin g t o thei rtherma l stabilit y unde rlo w oxyge n conditions

. Th e compound

s tha trequir e th e highes ttemperature

s t o achiev e destructio

n ar e ranke d a s mos tdifficul tt o destroy . Th e TSLo0 2 rankin g relie s o n te&t & tha : ' ' i«ri»»'» ifi tfa "^T"V." ,n r f t c temperature

s u i up i

_aui~ b :.z ^Luwipuer e an d measur e thei rdegre e o f destructio n afte r2 seconds

. Representativ

e compound

s from al l majo rgroupiog

s o f 4 0 CF RPar

i 261 , Appendi

x VII I compound

s hav e bee n tested , an d th e inde x fo rth e remainde

rhave bee

n estimated . Th e TSL0O 2 inde

x i s stil l bein g refine d a s a resul to f ongoin g experimenta

l studies . A cop y o f th e ranking , whic h include s experimenta

l result s throug h tb e en d o f th e 199 0 fisca l year , i s include d i n Appendi

x H . Applicant

s shoul d us e th e mos tcurren tinde x availabl e whe n developin

g a tria l bur n plan . Whe n thi s rankin g i s used , i ti s recommende

d tha tPOHC s b e selecte d fro m thos e compound s b rwhic h actua l experimenta

l dat a exist . Guideline s b rth e us e o f th e TSL0O2 inde

x ar e include d i n Appendi x D o f Guidanc e o n Settin g Permi t Condition s aa d Reportin

g Tria l Bur n Result s (23) . Th e BI F Rul e allow s th e selectio n o f surrogat e POHCs , i.e., compound

s whic h ar e no tpresen ti n th e wast e and/o rar e no tliste d i n Appendi x V M o f 4 0 CF R 261 . Th e us e o f surrogat e POHC s ma y b e propose d i f th e compound

s presen ti n th e wast e ar e impractica

l fo r POH C selectio n becaus e o f th e consideration

s liste d above , o rbecaus e o f hig h cost , hig h toxicity , samplin g an d analysi s problem

s o ri f th e facilit y believe s i ti s mor e appropriat

e t o selec tPOHC s fo rwhic h experimenta

l dat a exist . A permi tappUcan tseekin g th e us e o f surrogat e POHC s mus tsubmit , i n th e tria l bur n plan , adequat e documentatio

n o f th e relationshi

p betwee n th e DRE o f th e surrogat e POHC an

d th e DRE s o f th e Appendi

x VH I compound

s i n th e waste . Tw o surrogat e POH C concept s tha thav e bee n advance d ar e th e us e o f SF, and/o rth e us e o f POH C "soups. * Th e pro s an d con s o f SF B hav e bee n discusse d i n th e BI F preambl e (5 6 F R7147 , Februar y 21,1991)

. 1Q£ Extrapolation/Interpolatio n o f Metal s Emission s Dat a Extrapouuion/uuerpolatio

n o f tes tdat a ca n b e use d t o develo p operatin g Emit s (e^» metal

s fee d rat e Emits ) from tes tdat a obtaine d a toperatin g condition

s tha tar e differen tfrom th e limits . Extrapolatio

n mean s settin g limit s outsid e th e bound s (abov e o rbelow ) o f tes tresults, an

d interpolatio

n mean s settin g operatin g limit s betwee n th e bound s o f th e tes tresults . . Thi s subsectio

n discusse

s th e specific

, circumstance

s i n whic h extrapolation/interpolatio n ma y •b * 'siwl ; «o rsettin g prtmi tqrxratin g limits . Becaus e £«iapoi«u'.'a/I.iter^>;-.iti

i o f dat a i s vali d onl y i n certai n cicumstances

, an d becaus e EP A i s abl e t o provid e onh / limite d oversigh tdurin g interi m status , i t shoul d no tb e use d fo rcomplianc

e certification

. Operatin g condition

s demonstrate

d durin g . th e complianc e tes tprovid e th e basi s fo rlimit s establishe

d i n th e complianc

e certification

, a s discusse d i n Sectio n 5.0 . 105. 1 Theoretica

l Backgroun

d ExtrapoIation

/iDterpoIatio n o

f tes tdat a mus t conside rth e relationshi

p betwee n th e emission s rat e o f ameta l fro m a BI F an d th e fee d rat e o f th e metal . Becaus e thi s relationshi

p i s no

tlinear , extrapolation/interpolatio n ma y resul t i n nonconservativ

e Emits , an d i s therefor e inappropriat

e i n som e cases . Th e emissio n rat e o f a meta l depend s o n numerou s operatin g r^rameters

, includin g th e fee d rat e o f th e metal , APC S parameters

, ga s velocity , operatin g temperatures

, etc . Th e fee d rat e o f ameta l t o aBI F varie s a s aresul to f (1 ) change s i n th e concentratio

n o f metal s i n th e fee d material

s t o th e BI F (wastes , fuels , an d ra w materials); an

d (2 ) change s i n th e fee d rate s o f th e variou s material s t o th e BIF. Conside

ra simpl e eas e wher e metal s ar e bein g fe d t o aBI F fro m a singl e -nonpumpabl

e feed stream

. Th e expecte d effec to f increasin g th e metal s fee d rat e o n metal s emission s fro m aBIF , wher e th e othe roperatin g parameter

s ar e hel d constant , i s show n i n Figur e 10-1 .

BJF\SECT10.B1 F 10-14 '

## 1 

# 1

- Zone I | (Viponzfttioa

) J 

# I Zone S



# ^ 1 FisarelO-l(a ) Meta l Fee dRat e i n Liqui d

i 

# I Zone I ] (Vaporization

) j (Botraioineat )



# 1 Figur e 10 -l(b ) Meta l Fee dRat e i n Soli d (LiquidFee

dRat e i t Coutaat )

i I 

# 1 1 Zone I | Zon

e II l Zon

e I U 

# 1 1

^ \ 

# 1 l i • 

# 1 Figr a104(c). Meta l Fee dRat e i aLiqui d (Soli dFee dRat e fcCooatant) Figur e 10

- L Typica l Relatioaalrt

p Betwee n Meta b Fee dBaf r an dFmtmdnni

- Rat e
10-1 5 

# I

! I I I i 1 

# ti

VES01697 8Fo rlo w metal s feed rates

, metal s behavio ri s controlle d mainl y b y vaporizatio

n (Zon e I), a s show n i n Figur e 10-l(a) . Metal s ten d t o vaporiz e unti l th e combustio n ga s become

s saturate

d wit h meta l compounds

. Th e quantit y e f a give n meta l tha twil l saturat e th e ga s i s detennine

d b y th e effectiv e vapo r pressur e o f th e metal , whic h depend s o n th e temperature

, an d ma y depen d o n th e concentratio

n o f cMcrine , oxygen , and/o rsulfu ri n th e gas . I f tiie vapo r pressur e i s hig h enoug h t o completel

y vaporiz e th e meta l withou tsaturatin

g th e ga s (Le. , a trelativel y lo w meta l fee d rates) , a n increas e i n th e metal s fee d rat e result s i n a n equivalen

t( 1 t o I ) increas e i n th e amoun t o i metal s emitted . Eventually

, a s th e metal s fee d rat e continue s t o increase

, th e ga s become s saturate d wit h meta l compounds

. Afte rth e saturatio

n leve l i s reached , th e metal s fcisir .non rat

e become

s a functio

n o f th e particl e Ci'-uusic w race , oui i mtuit

- :,.iictui4ti&i

i c u tLos e particle s (Zon e IT) . Th e tota l metal s emission s rat e continue s t o increas e wit h increasin

g metal s fee d rate s becaus e o f increase d meta l concentration

s i n th e entraine d as h particles

. However

, becaus e n o additiona

l amoun to f meta l ca n vaporize

, di e metal s emission s rat e i n Zon e I I doe s no tincreas e a s rapidl y a s i n Zon e I . A mor e comple x cas e i s on e i n whic h metal s ar e bein g fe d t o a BI F fro m bot h liqui d an d soli d fee d streams , Tn e cxr^ae d effet to f a n maeas e i n th e fee d rat e o f metal s i n th e solid s feed strea

m whe n Ih e othe r operatin g parameter

s ar e hel d constan tis show n i n Figur e 10- 1 (b) . Thi s i s simila rt o th e simpl e singl e fee d sourc e cas e o f Figur e 10-l(a ) excep ttha tther e b a n obse ti n metal s emission

s a s th e fee d rat e o f metal s i n tb e soli d fee d strea m approache

s zer o becaus e o f th e emission s fro m th e liqui d fee d stream . Tb e expecte d effec to f increasin g th e fee d rat e o f metal s fro m th e hqui d fee d strea m o n meta l emissions , wher e th e othe roperatin g parameter

s ar c hel d constant

, i s show n i n Figur e 10-l(c) . Fo rlo w meta l fee l rates , meta l behavio ri s controlle

d mainl y b y vaporizatio

n (Zon e I}. . Metal s fro m bot h fee d stream s ten d t o completel

y vaporiz e unti l th e combustio

n ga s bc^me s saturate d wit h meta l compounds

. A s th e fee d rat e o f metal s fro m th e liqui d strea m become

s highe r tha n th e saturatio

n poin t(Zon e II) , al l o f th e metal s fe d wit h th e liqui d fee d strea m wil l vaporize ; however , onl y a portio n o f th e metal s fe d wit h th e soli d fee d strea m wil l vaporize , aa d th e remainde

rwil l remai n i n th e ash . I

n tins example

, furthe rincrease s i n meta l fee d rate s resul tin a sligh

tincreas e i n meta l emissio n rate s becaus e o f th e increas e i n di e metal s concentratio

n o f th e entraine d particles

. Frnally , a poin ti s reache d wher e th e metal s i n th e Squi d feed strea

m alon e air e sufficien t t o saturat e th e gas . A s meta l fee d rate s increas e beyon d thi s poin t(Zon e IU), furthe

rincrease s i n th e fee d rat e o f metal s i n hqui d fee d stream s resul ti n a direc t increas e i n th e amoun to f entraine d metals . Th e relationshi

p betwee n meta l fee d rate s an d men d emission

s i s fin ea rwithi n eac h o f thes e thre e zones . Furthermore

, th e contribution

s o f th e liqui d an d th e soli d fee d stream s ar e expecte d t o b e additive

. Thus , a s lon g a s tiie extrapolation/interpolatio n i s conducte d ove ra limite d rang e (Le, no tove reithe ro f th e breakpoint

s o f Figur e 104(c))

, extrapolation

/ interpolatio

n i s appropriate

, fo rsituation

s wher e th e meta l fee d rat e change s i n bot h th e soli d an d th e liqui d fee d streams , an d th e Mowin g equation

s apply :
SF . - SF, +

LF L- LF 4* E L- E ,

Et-JE * (SF

, - SFj)

(LF , - LFj )

where : S F - feed-rate o

f th e meta l i n th e soli d fee d strea m L F * fee

d rat e .o f th e meta l i n th e liqui d feed strea m E emissio

n rat e o f th e meta l
» " tes

tconditio n 1 tes tconditio n 2 t th

e extrapolate

d o rinterpolate

d limi t conditio n Th e abov e theoretica

l treatmen

tassume s tha t ther e i s a singl e stabl e soli d for m o f th e meta l ove rth e rang e o f extrapolation

. I n situation

s wher e th e meta l ha s a n affinit y fo rth e cuhker/aggregate/sla

g (e.g , arsenic) , ther e ma y b e a numbe

ro f stabl e complexes

, an d th e saturate d vapo rpressur e ma y chang e wit h th e

BIF\$ECT10.BI F 10-1 6



### VES01697 9concentratio n o f metal s i n th e solids . - in thi s case , Figur e 10- 1 woul d b e expecte d t o chang e a s follows :

• Zon

e I woul d b e unaffected

. Th e meta l emission s rat e i n th e ^porization " zon

e woul d b e linea rwit h th e metal s fee d rate .

• A shar

p brea k a tth e saturatio n point , woul d stil l b e eviden t

• A n increase d meta l fee d rat e i n Zone s T X an d i n woul d resul ti n a n increas e (probabl

y aoalinear ) i n vaporizatio

n wit h a conespondingl

y nonlinea rincreas e i n th e meta l emissio n rate . Th e nonlinea rimpac twoul d b e greate ri n Zon e I I tha n i n Zon e li t However , becaus e th e nonlinea rrelationshi

p i s likel y t o b e approximatel

y linea rove r as&u £migc, tl h -l'.-.-..-. . necessaril y preclud e th e us e o f th e abov e extrapolation

/ interpolatio

n equation

s ove rasmal l rang e o f meta l fee d rates . - 10.5. 2 Extrapolatio

n t o Differen

tFee d Rate s Figure s 10-2(a ) an d (b ) illustrat e example s o f extrapolation/interpolatio

n o f tes tdat a t o establis h meta l fee d rates , usin g th e abov e theoretica

l backgroun

d o n meta l emissions

. I n Figur e 10-2(a) , tb e measure d meta l emission s (Poin t1 } ar e greate rtha n th e allowabl e emissions , determine

d fro m dispersio

n modeling

, A linea rextrapolatio

n bac k t o tb e allowabl

e maximu m emission s leve l (Poin t2 ) provide s apropose

d meta l fee d rat e limi t(Poin t3) . However

, becaus e o f th e nonlinearic y o f th e metal s emissio n curve , th e actua l emission s produce d a tth e propose d fee d rat e limi t (Poin t4 ) ar e stil l highe rtha n th e maximu m allowabl

e leve L Th e larges tallowabl e meta l fee d rat e shoul d b e smalle r/Poin t5). Becaus

e o f thi s typ e o f noncouservaov

e result , adownwar

d linea rextrapolatio

n o f dat a i s no trecommended

; actua l dat a shoul d b e use d i n thi s situation . I n Figur e 10-2(b)

, th e measure

d meta l emission s (Poin t1 ) ar e belo w th e allowabl e emissions

. I n thi s case , th e extrapolatio

n t o Poin t2 woul d produc e alowe rpropose d tee d rat e limi t(Poin t3 ) tha n tha t winc h shoul d actuall y b e allowe d (Poin t5). Therefore

, upwar d extrapolatio

n woul d b e theoreticall

y conservativ

e i athi s case. ' Suc

h upwar d extrapolatio

n ma y b e reasonabl e fo rjustificatio

n o f limite d (e.g ^ 72 0 hours ) testin g a thighe rmetal s fee d rates; however

, i ti s no t generall

y recommende

d fo rlettin g permi tlimit * becaus e o f th e lac k o f validatio n data . On e situatio n whic h ma y warran tth e us e o f upwar d extrapolatio

n i s whe n th e projecte d emission

s a t th e extrapolate

d fee d rate s ar e fa rbelo w th e Tie rD I (o r Tie rD ) emissio n limits . Fo rexample , suppos e afacilit y run s a tria l bur n usin g typica l wast e wuhou tspiking , an d th e meta l emission s ar e 2 0 times lowe

rtha n th e Tie rff l limits. . I n thi s case , th e permi twrite rcoul d reasonabl

y allo w upwar d extrapolatio

n t o se ta metal s fee d rat e limi tsomewha

thighe r(e« , doubl

e th e fee d rat e base d o n th e tria l burn) . Thi s woul d theoreticall

y resul ti n meta l emission s whic h ar e 1 0 times lowe

rtha n th e Tie r H I limit . Allowin g extrapolatio

n i n suc h ease s woul d eliminat e th e nee d fo rexpensiv e metal s spikin g t o achiev e flexible , bu tstil l conservative

, metal s fee d rat e limits . 10.5 3 Interpolatio

n t o Differen

tFee d Rate s A n approac

h tha ti s subjec tt o fewe r uncertainties

, i s interpolatio

n betwee n dat a points . Thi s approac h i s illustrate d i n Figur e 10-3 . Suppos e tw o test s wer e conducte

d i n a tria l burn , eac h a ta differen

t metal s fee d rate . On e tes t(Poin t1 ) resulte d i n emission s abov e th e limit , an d on e tes t(Poin t2 ) resulte d i n emission s belo w th e limit . Thes e tw o point s defin e th e actua l emission s curv e observe d durin g th e tes tove rth e rang e o f meta l fee d rates ' tha twer e examined . I f th e rang e o f feed rate s wa s small , linea r interpolatio

n ca n b e use d a s show n i n th e figur e t o detennin e th e meta l fee d rat e tha tjus tmeet s th e limi t (Poin t3) , an d th e theoretica

l meta l fee d rat e limi ttha t correspond

s t o th e maximu m pernrissibt

e emissio n rat e ca n b e establishe

d (Poin t4). I n considerin

g thi s approach

, th e owner/operato

ran d penni twrite rshoul d carefull

y revie w th e overal l rang e in meta l fee d rate s represented b y th e availabl e tes tdata , a s wel l a s th e variatio n i n othe roperatin g parameters

, t o ensur e tha tth e linea r bterpolatio

n i s applicable

. Fo rexample , i n asituatio

n wher e on e tes twa s conducte

d a tmeta l fee d rate s abov e th e saturatio n poin tan d on e tes tbelo w th e saturatio n point , interpolatio

n coul d resul ti n error . Becaus e i ti s no tpffmnW e t o determin

e whethe rth e dat a point s straddl e th e saturatio

n point , EP A recommend

s ?jtfjifr»fflyjnf

c th e feed rate l"T"t

s a tth e demonstrate

d level s (Poin t2 ) m thes e situation

s an d doe s no t recommen d th e us e o f interpolation

. BIF\SECn0.BI

F 10-1 7

### FfgoxelO-2(a )

Figur e 10-2(b )



## Figur e 10-2 , i^nffp f ^f^ft f flf Kttrapftlitfwi q

f Tra f ftrrn Daf t
10-1 8

### VES01698 2wher e availabl e dat a sho w the y pos e ntinhna i ris k t o huma n healt h an d th e environment

. Thes e include :

• BIF

s burnin g lo w ris k wastes ; an d
• Specifi

c type s o f bouer s burnin g certai n classe s o f waste . Th e facilit y mus tsubmi tdocumentatio

n tha t demonstrate

s tha tth e BI F meet s th e requirement

s o f th e lo w ris k wast e exemptio

n o rspecia l operatin g requirement

s (SOR ) a s specifie d i n 1270.22(a)

. I n addition , unde r§270.22(a)(6) , i

ti s possibl e t o submi t dat a i n lie u o f atria l bur n i f th e dat a demonstrat

e a unit' s complianc

e wit h th e BI F Rule . 10.6. 1 Lo w Ris k Wast e Exemptio

n Sectio n 266.10 9 allow s EP A t o waiv e th e DR E tria l bu m standar d fo rcertai n boiler s an d industria

l furnaces , an d i f th e BI F i s exemp tiro m th e DR E Lis t bum , possibl y th e tria l bur n fo rparticulat

e matte r (PM).

3 1 Thes e facilitie s ar e no texemp tfrom othe

r portion s o f RCR A regulations

, suc h a s notificatio

n o f hazardou s wast e activities

, th e nee d t o obta m permit s forstorag

e o f hazardou s wastes , o rothe rBlF emission

s standards . T o qualif y fo rth e lo w riskwast

e exemption

, th e devic e mus tfirstsatisfy

, th e foUowin

g operatin g requirement

s o f 5266.109(a)(1)

: 1 . A tleas t50 % o f th e fue l (th e prunar y fuel ) i s a fossi l fue l fue l derive d fro m a fossi l fuel , tal l oil, or , i f approve d o n a casc-by-cas

e basi s b y th e appropriat

e regulator

y authority

, othe r nonhazardou

s fue l wit h combustio

n characteristic

s simila rt o fossi l fue l Th e percentag e o f primar y fue l i s determine

d o n th e basi s o f eithe rth e hea tinpu t(le , Btu/h

rfro m th e primai y versu s al l fuels ) o rth e mas s fee d rat e (Le , lb/h ro f th e primar y fue l versu s th e wast e fuel) , dependin g o n whic h metho d result s i n th e lowe rmas s liazardou

s wast e fee d rate . % Th

e primar y an d hazardou

s wast e fuel s hav e a minimu m as-fire d heatin g valu e of8,00 0 Btu/lb. 4

. Th e stac k ga s eoncenrratio

n o f C O i s £10 0 ppm v houri y rollm g averag e (o n a dr y basi s correcte d t o 7%Oj). Th

e devic e i s no teligibl e forth e alternativ

e standar d fo rH C emission

s (<2 0 ppm v hourl y rolling average

, reporte d a s propane , o n adr y basi s correcte d t o 7%,O

a ) i f th e BI F fall s unde rth e lo w risk waste

exemption . 5 . Th e wast e doe s no tcontai n no ri s i tderive d fro m acutel y hazardou

s (dicodn-listed

) waste s fisted unde

r$2613 1 (specifically

, th e wast e stream s F020 , P021 , F022 , F023 , F026 , an d F027 , whic h ar e relate d t o the . manufacture

, disposal , an d us e o f chlorophenols

, chlorobenzenes, cblorobexanes, an d hexachlorophene)

. I n addition

, th e foUowin g action s mus tb e implemente

d t o ismoustrai

e los tu* e Ul l w3 > so tpos e unacceptabl

e advers e risks t o huma n health :

. • Identif

y an d quantif y th e nonmeta l compound

s hste d i n 4 0 CF RPar t%% , Appendi x VH I tha t coul d b e presen ti n tb e hazardou

s waste ;

• Calculat

e reasonable

, worst-cas e emissio n rate s fo reac h constituen

tidentifie d above ;

• Us

e ai rdispersio

n modelin g t o predic tth e maximum

. annua l averag e ground-leve

l concentratio

n o f th e constituent

s identifie d above ; an d

• Ensur

e tha tground-leve

l concentration

s o f th e constituent

s predicte d abov e d o no texcee d level s establishe

d i n J266.106(a)(2)(iv)

. Thes e procedure

s requir e calculatio

n o f th e worst-cas e emission

s o f th e Appendi x V m organic

s whic h ma y b e fe d t o th e BIF , avalu e tha tca n b e use d i n a maximu

m expose d mdividua

l (MET ) exposur e calculatio n fo rtb e system . Th e hazar d level s ar e determine d followin g th e procedure

s fo rdispersio n

3 . . Th e hazardou

s wast e i s fired directl

y int o tiie

. primar y fue l flame zone

.

" A wnve rfro m th e P M compline s te n required unde rinteri m ttatu s a ro tmilabl e unde

rth e Um rttkw«t e ettmptkw. BIF\SECno.BI

F 10-2 0



### VES01698 3

# VES016984-016988.pd f

## Technica l Suppor tDocumen

tforHW C MAC T Standard s

Volum e IV : Complianc

e wit h th e HW C MAC T Standard s

U.S . Environmenta

l Protectio

n Agenc y Offic e o f Soli d Wast e an d Emergenc

y Respons

e (5305 ) 120 0 Pennsylvani

a Avenue

, N W Washington

, D.C . 2046

0
Septembe

r200 5maximu mlimit s a s determine db y the PCDD/PCD Fandmetal s testin g i n case s wher e complianc e wit h thes e standard s ar e conducte dunde

r separat e performanc e tes t

conditions
. Meta l capturin g sorbents ~ Sorbent s suc h as kaolin , bauxite , silica , alumina , an dclays , ar e currentl y bein g develope dt o contro l semivolatil e metal s emissions
. N o hazardou s wast e burnin g facilitie s ar

e currentl y intentionall y usin g thes e contro l techniques , however the y ma y i n th e future
. Th e sorbents ca

n b e adde ddirectl y t o th e feed , or injecte dseparately downstrea mo f th e combustor
. Operatin g paramete r requirement s ma

y b e analogou s t o carbo n injectio n anddr y scrubbin g technologie s discusse di n othe r Sections
. I n site-specifi c case s wher e wast e andothe

r feedstrea mmaterial s ma

y potentiall y contai n thes e type s o f meta l capturin g ingredients , monitorin g o f

wast e compositio n durin g th

e comprehensiv e performanc e testin g (anddurin g subsequen

t regula r operation ) ma

y be appropriat

e i n case s wher

e i t might b e expecte dtha

t compositio n o f

waste s and/or

fee dmaterial s ar

e likel y t o significantl y change
. 

### 6. 3 Extrapolatio

n Th e "upward " extrapolatio n o f SV M andLV M feedrate s an dassociate demission s rate s fro mlevel s demonstrateddurin g th e comprehensiv e performanc e tes t t o higher allowabl e feedrate an demission s rate s ca n b e requeste do n asite-specifi c basis
. Linear upwar d extrapolatio n fro mth

e "origin " (a

t ametal fee dan demission s rat e o f zero ) ca n b e conservativel y use dt o allo w fo r

highe r metal s feedrat

e limit s whil e continuin g to ensur e tha t th e facilit y i s withi n th e MAC T emission s limits. 1 0Thi s i s becaus e metal s systemremoval efficiencie s tendt o sta y th e sam e o r increas e a

s th e feedrat e increases
. Thi s has been show n base do n theor y and statistica l analysi s o f

experimental tes t

results
. Thi s applie s to al l metal s type s an dvolatilit y groupings
. Th e conservativ e natur

e o f th e "upward " extrapolatio n procedur e i s show n i n Figur e 6-1
. Tli e emission s leve l predicte da t ahigher feedrat e basedo n linea

r extrapolatio n through th e origi n an dfro mmeasuredemission s level s a t alowe r feedrat e i s greate

r tha n o r equa l t o th e actual emission s level s a t the highe r

feedrat e (base do n the expecte drelationshi p between metal s fee dan demission s rates)
. Alternatively , becaus e "downward " extrapolatio n ma y no t alway s be conservative , a

s als o show n i n Figur e 6-1 , i t i s generall y no t

allowed
. Downwar dextrapolatio n i s permitte dfo r normal emissions-base dstandard s (se e Sectio n 2 an dAppendi x B ) A reques t

fo r th e us e o f extrapolatio n fo r

settin g allowabl e metal s feedrat e limit s must

b e containe di n the comprehensiv e performanc e tes t plan , whic h i s submitte dt o EP A a t leas t 1 yea r
W e not e tha tallowin g upwar d extrapolatio

n o f performanc

e tes tfeedrate

s t o establis

h feedrat

e limit s (whil e ensurin g tha tth e emissio

n standar

d woul d no tb e exceeded

) preclude

s th e nee d fo rsource

s t o spik e toxi c metal s excessivel

y durin g performanc

e testin g t o achiev e feedrate

s a tth e high-en

d o f norma l operations. Spikin

g toxi c metal s pose s ahealt h ris k t o workers

, increase

s th e environmenta

l loadin g o f toxi c metals, an

d increase

s th e cos to f performanc

e testing . 6- 9



### VES01698 5prior to the actua

l testing
. Th e extrapolatio n methodolog y wil l b e reviewe dandapprove db y th e Agency
. Th e extrapolatio n submitta l mus t discuss :

• Rational e fo r

th e selectio n o f

the comprehensiv e performanc e tes t metal s feedrates , and desire dextrapolate dfeedrates
. In particular , the feedrat e level s mus t

a t aminimu m represen t thos e i n typica l "normal " wast e streams
. I

t shoul dals o reflec t

th e potentia

l variabilit y an dfluctuatio n i n normal wast e metal s levels , whic h wil l dependo n th e heterogeneit

y andothe

r characteristic s ofth e waste
. Th e discussio n shoul dinclud e a listin g ofth e variou s wast e streams tha

t ar e treated , an dresult s o f

historica l metal s characterizatio n efforts
. Thi s i s t o ensur e tha t the amoun

t o f extrapolatio n tha

t i s neede d i s minimized
.

• Rational e fo r

th e selectio n o f

the physica l for mandspecie s o f th e metal s used , als o base d o nexpecte dwast

e characteristics
.

• A maximu mextrapolate dfeedrat e tha t woul db e desired , agai n considerin g the historica l metal feedrat

e data
. Specifically , EP A doe s no t want source s to extrapolat

e to allowabl e feedrate s tha

t ar e significantl y highe r

tha n thei r historica l rang e o f

feedrates
. Th e requeste dextrapolate dfeedrate s shoul dbe limite dto the upper endo f historica l metal s feedrat e range s tha

t asourc e ha

s actuall y fed , unles s the sourc e document s tha t future operation s wil l necessitat e higher metal s feedrat

e limits
.

6-1 0



### VES01698 6Downwar d Extrapolatio n

Meta l Fee d Rat e
Upwar d Extrapolatio n Actua l metal s

Meta l Fee d Rat e Figur e 6-1

. Basi s fo rmeta l feedrat e extrapolatio n guidance

. 6-1 1



### VES01698 7• Discussio n o f characterizatio n procedure s to be use dto ensur e tha t metal s feedratesan demission s rate s documente di nth e comprehensiv e performanc e tes t plan ar e highl y accurate
. Som

e spikin g wil l likel y b e require dt o increas e confidenc e i n th e measure dfeedrat

e level s usedto projec t

higher allowabl e feedrate limits
. Error s associate dwit hsamplin g andanalyzin g heterogeneou s wast e streams ca

n be minimize d b y spikin g know n quantities
. Also , after

th e performanc e testing , th e Agenc y wil l revie w the testin g andextrapolatio n result s t o confir mtha

t the y have been interprete dproperl y andtha t the extrapolatio n procedur e i s appropriat

e fo r th e source . Th e extrapolatio n procedur e tha t i s t o b e use dwil l dependo n the exten t andqualit

y ofth e metal s feedrate andemission s data
. T o ensur e tha t the extrapolatio n i s "conservative " i n natur e (i.e. , produce s projecte demission s level s a t the projecte dfeedrat

e tha t ar e uppe r bound s o n tha

t expected) , i t

i s recommende dtha

t th e extrapolatio n b e base do n either th e lowes t SR Ewithi n a test condition , or

som e statisticall y basedanalysi s procedure
. Thi s migh t include :

• Fo r case s wher

e alarg e amoun

t o f dat ahas bee

n compile dfro mdifferen t feedrat e level s (fo r example , throug h man

y tests ove r

th e years) , extrapolatio n fro mastatisticall y base d analysi s ofth e specifi c facilit y dat ama y b e appropriate , suc h as fro mawors t cas e tes t conditio n averag e considerin g typica l statistical variabilit y o f the within-tes t

conditio n runs , o r alinea r regressio n ofth e conditio n average (or individua l run ) feedrat

e and emission s rat

e data , considerin g som

e uppe r confidenc e limi t

bound
.

• Fo r case s where mor

e limite dand/or

widel y sprea

ddataar e available , extrapolatio n fro m th e wors t cas e lowes t

observe dSR Etha

t i s not a n outlier
.

• Extrapolatio n fromasingl e tes t bur n conditio n basedo n determinatio n ofth e "Uppe r Confidenc e Limit"
. Specifically , thi s involve s usin g asingl e tes t conditio n average , an d a"withi n tes t

condition " standar

ddeviatio n basedo n either site specifi c dat

aor th e demonstratedvariatio n observe di n other similar typ e tests
.

• Fo r smal l extrapolation s to feedrate s relativel y clos e t o demonstratio n testin g levels , more aggressiv e extrapolation s ma y b e warranted , suc h a

s thos e fro mates t

conditio n median o r average . Alternately , fo r large r extrapolations , amor

e conservativ e procedur

e i s generall y appropriate
.

6-1 2

# VES016989-016996.pd fUNITE D STATE S ENVIRONMENTA L PROTECTIO N AGENC Y



# *§2L\ REGION S V ^ Z Z ? 7 7 WES TJACKSO N BOULEVAR D S ^*T ^ CHICAGO , I L 60604-359 0



## FE B 2 7 7.00

4 REPL Y T O TH E ATTENTION ) O F

Bet h Brock , Tea m Leade r (AE-17J )

Environmenta l Service s E l i Lill y an d Compan y

# ISO F l i Tippecano e Laboratorie s " L65 0 Lill y Roa d Lafayette , Indian a 47909-920 1 R e : El i Lill y an d Company , Tippecano e Laboratorie s Alternativ e Monitorin g Petitio n fo rT14 9 Solid-Liquid . Incinerato rUnde rHazardou s Wast e Combusto rMAC T Dea rMs . Brock : Th e Nationa l Emis s io n Standard s fo rHazardou s Ai rPollutant s fro m Hazardou s Wast e Combustors , 4 0 C.F.R . Par t63 , Subpar tEEE , (HW C MACT ) require s th e owne ro roperato ro f a hazardou s wast e incinerato rt o submi tt o th e Unite d State s Environmenta l Protectio n Agenc y (U.S . EPA ) a comprehensiv e performanc e tes t (CPT ) pla n an d continuou s monitorin g syste m (CMS ) performanc e evaluatio n tes tplan . Th e CP T Pla n mus tinclud e th e informatio n specifie d i n 4 0 C.F.R . § 63.1207(f ) (1 ) (i ) throug h (xxvii) . Th e CN S performanc e evaluatio n tes tpla n mus tinclud e th e informatio n specifie d i n th e Appendi x t o th e HW C MACT . Pursuan tt o 4 0 C.F.R . § 63.1209(g) , regulate d entitie s ma y als o submi ta n applicatio n t o U.S . EP A fo rapprova l o f alternativ e monitorin g requirement s t o documen tcomplianc e wit h th e emissio n standard s o f th e HW C MACT . O n Septembe r30 , 2003 , El i Lill y an d Compan y (El i Lilly ) submitte d t o U.S . EP A severa l document s require d unde rth e HW C MAC T fo rit s solid-liqui d hazardou s wast e incinerato rlocate d a t t h e Tippecano e Laboratorie s i n Shadeland , Indiana . Thi s lette r serve s t o respon d t o you rAlternativ e Monitorin g Application . E l i Lill y operate s a Solid-liqui d Incineratio n Syste m a tth e Tippecano e Lab s facility , referre d t o a s Therma l Oxidize r14 9

Recycled/Recyclabl e . Printe d wit h Vegetabl e Oi l Base d Ink s o n 100 % Recycle d Pape r (50 % Postconsumer )2 (T149 ) . Th e T14 9 incinerato ri s equippe d wit h a n ai rpollutio n contro l syste m (APCS ) tha tinclude s a quenc h system , condenser/absorber , an d a Hydro-Soni c scrubber . Th e alternativ e monitorin g petition s submitte d b y El i Lill y pertai n t o th e condenser/absorbe ran d th e Hydro-Soni c scrubber . Specifically , E l i Lill y i s seekin g approva l fo rth e following : 1 . A waive ro f th e requiremen tt o establis h a n operatin g paramete rlimi t(OPL ) o n th e maximu m solid s conten to f th e scrubbe rsolution , o rth e minimu m blowdow n rat e an d eithe r t h e minimu m scrubbe rtan k volum e o rleve l a tth e condenser/absorber . 2 . A waive ro f th e requiremen tt o establis h a n OP L o n th e minimu m pressur e dro p acros s th e condenser/absorber . 3 . A waive ro f th e requiremen tt o establis h a n OP L o n th e minimu m liqui d fee d pressur e a tth e condenser/absorber . 4 . A waive ro f th e requiremen tt o establis h a n OP L o n th e minimu m scrubbe rwate rp H a tth e condenser/absorber . 5 . A waive ro f th e requiremen tt o establis h a n OP L o n th e minimu m liqui d t o ga s rati o o rminimu m liqui d an d maximu m flu e ga s flo w rate s a tth e condenser/absorber . 6 . A n alternativ e OP L fo rth e minimu m pressur e dro p acros s th e Hydro-Soni c scrubber . El i Lill y propose s t o establis h a n alternativ e OP L base d o n a n equivalen tdifferentia l pressur e tha twoul d b e calculate d base d o n a n equatio n develope d b y t h e manufacture ro f th e Hydro-Soni c scrubber .

Pursuan tt o 4 0 C.F.R . § 63.8(f)(2) , afte rreceip tan d consideratio n o f writte n application , th e Administrato rma y approv e alternative s t o an y monitorin g method s o rprocedure s o f thi s part . Pursuan tt o 4 0 C.F.R . § 63.1209(g ) (1 ) (ii) , i f th e owne ro roperato rdocument s tha tneithe ra n operatin g paramete r limi ti n 4 0 C.F.R . § 63.120 9 no ra n alternativ e operatin g paramete rlimi ti s neede d t o ensur e complianc e wit h a n emissio n standar d i n th e HW C MACT , th e owne ro roperato rma y reques ttha t t h e Administrato rwaiv e th e requiremen tfo rth e operatin g



### VES01699 03 paramete r limit
. Base d o n th e informatio n yo u provide d i n you r reques t an d o n additiona l informatio n supplie d b yMik e Foste r o f E l i Lilly , U.S . EP Ai s approvin g you r request s 1 an d 6 an d disapprovin g request s 2 throug h 5
. Detail s o f th e approvals/disapprovals/comment s fo r eac h reques t ar e provide d below . Condenser/Absorbe r Th e APC S servin g th e T1 4 9 incinerato r include s a s a secon d stage , a condenser/absorber . Th e condenser/absorbe r consist s o f spra y nozzles , packin g an d a liqui d collector . Causti c an d make-u p wate r ar e introduce d i n th e condenser/absorber . Th e condenser/absorbe r provide s additiona l conditionin g o f th e combustio n gase s fro m th e quenc h syste m prio r t o routin g the mt o t h e Hydro-Soni c scrubber . Accordin g t o Mik e Foster , th e primar y functio n o f th e condenser/absorbe r i s t o provid e som e residenc e tim e an d cooling.fo r th e combustio n gase s s o tha t th e combustio n gase s ar e a t a n optima l velocit yan d th e entraine d particle s ar e o f a n optima l siz e fo r remova l a t th e Hydro-Soni c scrubber ; ther e i s n o significan t particulat e contro l a t th e condenser/absorber . I n term s o f th e HW C MACT , th e condenser/absorbe r meet s th e definitio n o f a lo w energ ywe t scrubber . Th e followin g fiv e alternativ e monitorin g request s pertai n t o th e condenser/absorbe r specifically
. 1 . A waive r o f th e requiremen t t o establish , a noperatin g paramete r limi t (OPL ) o n th e maximu m solid s conten t o f th e scrubbe r solution , o r th e minimu m blowdow n rat e an d eithe r t h e minimu m

scrubbe r tan k volum e o r leve l a t th e condenser/absorber . Th e regulatio n a t 4 0 C.F.R . § 63.120 9 (m ) (1 ) (i ) (B ) (l j require s source s equippe d wit h a we t scrubbe r t o establis ha n OP L t o ensur e tha t th e solid s conten t o f th e scrubbe r liqui d doe s no t excee d level s durin g th e performanc e test . Afacilit ymus t establis hon e o f th e followin g OPLs : a ) a limi t o n th e solid s conten t o f th e scrubbe r liqui d usin g a CM S o r b ymanua l samplin g an d analysis ; o r b ) establis ha minimu mblowdow n rat e usin g a CM S an d eithe r a minimu mscrubbe r tan k volum e o r liqui d leve l usin g a CM S .



### VES01699 14 E l i Lill yi s requestin g tha t th e requiremen t fo r thi s OP L b e waive d fo r th e condenser/absorber . El i Lill yprovide s th e followin g reaso n fo r waivin g thi s OPL . El i Lill ystate s tha t 4 0 C.F.R . § 63.1209 (m ) applie s onl yt o particulat e contro l device s an d th e condenser/absorbe r doe s no t serv e a s a particulat e contro l device ; th e Hydro-Soni c scrubbe r i s th e particulat e contro l device
. Base d o n ou r revie wo f th e bloc k flo wdiagra m o f th e APC S provide d i n th e reques t an d discussion s wit h Mr . Foste r o f El i Lilly , U.S . EP Aapprove s El i Lilly' s request . U.S . EP Aha s determine d tha t sinc e th e maximu msolid s conten t o f th e scrubbe r solution , o r th e minimu mblowdow n rat e an d eithe r th e minimu m scrubbe r tan k volum e o r liqui d leve l ar e bein g measure d a t th e Hydro-Soni c scrubber , thi s OP L doe s no t nee d t o b e measure d a t t h e condenser/absorber .

2 . A waive r o f th e requiremen t t o establis ha nOP L o nth e minimu m

pressur e dro p acros s th e condenser/absorber . Th e regulatio n a t 4 0 C.F.R . § 63.120 9 (o ) (3 ) (ii ) require s source s equippe d wit h a lo wenerg ywe t scrubbe r t o establis ha minimu m pressur e dro p acros s th e scrubbe r base d o n manufacturer' s specifications
. Facilitie s mus t compl ywit h th e OP L o n a n hourl y rollin g average . E l i Lill yi s requestin g tha t th e requiremen t fo r thi s OP L b e waived
. Th e justificatio n provide d simpl ystate s tha t th e condenser/absorbe r i s no t th e HC1/C1 2 contro l device ; th e Hydro

Soni c scrubbe r is
. U.S . EP Ai s denyin g thi s request . Base d o n th e bloc k flo w diagra mo f th e APC S an d furthe r discussion s wit h Mr . Foste r a t E l i Lilly , U.S . EP Abelieve s i t i s likel ytha t ther e i s som e HC L remova l occurrin g a t th e condenser/absorber . Th e HC L i s remove d throug h th e liqui d t o ga s interface
. Therefor e i t i s appropriat e t o establis ha n OP L o n th e o n th e minimu mpressur e dro p acros s t h e condenser/absorber .

3 . A waive r o f th e requiremen t t o establis ha nOP L o nth e



### VES01699 25 minimu m

liqui dfee d pressur e a t th e condenser/absorber . Th e regulatio n a t 4 0 C.F.R . § 63.1209(o ) (3 ) (iii ) require s source s equippe d wit h a lo w energ ywe t scrubbe r t o establis ha n OP L o n t h e minimu m

liqui d fee d pressur e t o th e we t scrubbe r base d o n th e manufacturer' s specifications
. Facilitie s mus t compl ywit h th e OP L o n a n hourl yrollin g average . E l i Lill yi s requestin g tha t th e requiremen t fo r th e OP L o n th e minimu m

liqui d fee d pressur e b e waive d a t th e condenser/absorber . Th e justificatio n provide d simpl ystate s tha t th e condenser/absorbe r i s no t th e HC1/C1 2 contro l device ; th e polishin g scrubbe r is
. U.S . EP Ai s denyin g thi s request . Base d o n th e bloc k flo w diagra m

o f th e APC S an d furthe r discussion s wit h Mr . Foste r a t E l i Lilly , U.S . EP Abelieve s i t i s likel ytha t ther e i s som e HC L remova l occurrin g a t th e condenser/absorber . Th e HC L i s remove d throug h th e liqui d t o ga s interface
. Therefor e i t i s appropriat e t o establis ha n OP L o n th e o n th e minimu mliqui d fee d pressur e a t t h e condenser/absorbe r t o ensur e a minimu mliqui d fee d i s a t leas t th e amoun t a s durin g th e performanc e test . 4 . A

waive r o f th e requiremen t t o establis ha n OP L o n th e minimu m

scrubbe r wate r p H a t th e condenser/absorber . Th e regulatio n a t 4 0 C.F.R . § 63.1209(o ) (3 ) (iv ) require s tha t fo r we t scrubbers , a n OP L mus t b e establishe d o n th e minimu mp H o n a n hourl yrollin g averag e a s th e averag e p H durin g th e performanc e tes t runs . El i Lill yi s requestin g tha t thi s OP L fo r th e condenser/absorbe r b e waive d becaus e th e Hydro-Soni c scrubbe r i s t h e fina l aci d ga s contro l device , no t th e condenser/absorber . U.S . EP Ai s denyin g thi s request . Base d o n th e bloc k flo w diagra mo f th e APC S tha t wa s submitted , El i Lill yadd s a mixtur e o f causti c an d make-u p wate r t o th e APC S a t th e condenser/absorber , no t a t th e Hydro-Soni c scrubber . Therefore , i t i s appropriat e t o establis ha n OP L o n th e p H o f th e caustic/wate r solutio n a s i t enter s th e condenser/absorbe r t o ensur e tha t th e p H o f thi s solutio n i s a t leas t tha t o f th e solutio n use d durin g th e performanc e test .



### VES01699 36 5 . A

waive r o f th e requiremen t t o establis ha n OP L o n th e minimum

liqui dt o ga s rati o oa r th e minimu m liqui dan d maximu

m flu e ga s flo w

rates . Th e regulatio n a t 4 0 C.F.R . § 6 3 .120 9 (o ) (3 ) (v ) require s source s equippe d wit h a we t scrubbe r t o establis ha n OP L o n eithe r th e minimu mliqui d t o ga s ratio , o r th e minimu mscrubbe r wate r flowrat e an d th e maximu mflu e ga s flowrat e a s a n hourl yrollin g averag e base d o n th e averag e o f th e tes t runs . E l i Lill yi s requestin g tha t th e requiremen t fo r thi s OP L b e waive d fo r th e condenser/absorber . Th e justificatio n provide d simpl ystate s tha t th e condenser/absorbe r i s no t th e HC1/C1 2 contro l device ; th e polishin g scrubbe r is
. U.S . EP Ai s denyin g t h e reques t t o waiv e thi s OPL . Afte r discussio n wit h Mr . Foster , El i Lill yi s no w requestin g t o s e t th e minimu m

ga s flo wrat e t o the.manufacturer s recommende d flo wrat e o f 93 7 gp mo r lowe r i f demonstrate d durin g th e CPT . U.S . EP Aapprove s El i Lilly' s reques t t o se t th e minimu mliqui d fee d rat e t o th e recommende d minimu mb yth e manufacture r o r lowe r i f demonstrate d durin g th e CPT . Hydro-Soni c Scrubbe r Th e coole d an d saturate d combustio n gase s exitin g th e condenser/absorbe r ente r th e Hydro-Soni c scrubbe r wher e particulate , includin g metal s an d organi c compound s boun d t o th e particulate , an d aci d gases , includin g HCI , ar e removed . A s a venturi-typ e scrubber , th e Hydro-Soni c scrubbe r meet s th e definitio n o f a high-energ ywe t scrubbe r unde r th e HW C MACT . Th e followin g alternativ e monitorin g reques t pertain s t o th e Hydro-Soni c scrubbe r specifically
. 6 . A n alternativ e OP L fo r th e minimu m pressur e dro p acros s th e Hydro-Soni c scrubber . El i Lill y propose s t o establis ha n alternativ e OP L base d o n a n equivalen t differentia l pressur e tha t woul d b e calculate dbase d o n a n equatio ndevelope d b y t h e manufacture r o f th e Hydro-Soni c scrubber . Th e regulatio n a t 4 0 C.F.R . § 63.120 9 (m ) (1 ) (i ) (A ) require s tha t Eo r source s equippe d wit h hig h energ ywe t scrubbers , a n OP L o n



### VES01699 47 t h e minimu mpressur e dro p acros s th e scrubbe r o n a n hourl y averag e b e establishe d base d o n th e averag e o f th e tes t run s However , i n th e cas e o f El i Lilly' s Hydro-Soni c scrubber , stea m i s injecte d i n orde r t o enhanc e scrubbin g efficiency , bu t thi s cause s a reductio n i n th e measure d pressur e dro p acros s th e scrubber . T o tak e thi s int o account , El i Lill yi s proposin g a n alternativ e OP L base d o n th e equivalen t differentia l pressur e acros s th e Hydro-Soni c scrubber . Th e equivalen t differentia l pressur e woul d b e calculate d base d o n measure d differentia l pressur e an d th e stea mfee d rate . El i Lill ypropose s t o initiat e a n automati c wast e fee d cutof f whe n th e rollin g hou r averag e equivalen t differentia l pressur e i s les s tha n th e OP L minimu m equivalen t differentia l pressure . E l i Lilly' s experienc e a t it s facilit yi n Kinsale , Ireland , suggest s tha t th e equatio n develope d b yHydro-Soni c System s fo r equivalen t differentia l pressur e i s ver yconservative , an d woul d lea d t o excessiv e stea musage . U.S . EP Aha s evaluate d th e mode l fro mth e Kinsale , Irelan d an d th e additiona l informatio n provide d b yMr . Foste r i n th e Octobe r 1 , 200 3 e-mail
. U.S . EP Ai s approvin g you r reques t t o us e th e mode l wit h th e conditio n tha t E l i Lill ymaintain s a minimu mequivalen t differentia l pressur e o f 2 5 inches
. Thi s equivalen t differentia l pressur e wa s provide d i n t h e supportin g informatio n provide d i n th e supportin g dat a fro m Hydro-Soni c System s an d submitte d t o U.S . EP Ab yMr . Foster . I f E l i Lill yi s stil l intereste d i n lookin g int o developin g a site

- specifi c model , U.S.

- EP Awil l conside r th e model , provide d tha t E l i Lill ysubmit s al l th e supportin g dat a t o U.S . EPA . El i Lill y mus t involv e U.S . EP Ai n th e developmen t o f th e mode l tha t El i Lill yshoul d submi t fo r U.S . EPA' s approva l withi n 24 0 day s fro m t h e CPT .



### VES01699 58
I f yo u hav e an yquestion s abou t thi s letter , pleas e contac t Sara h Marshall , o f m

ystaff , 312-886-6797 . Sincerel yyours ,
George\T
. Cze-fitiak , Chie f Air^Enforce^ien t ar^ d Complianc e Assuranc e Branc h

c c : Phi l Perry , Chie f A i r Complianc e Branc h Indian a Departmen t o f Environmenta l Managemen t Raymon d Schic k A i r Complianc e Sectio n Indian a Departmen t o f Environmenta l Managemen t



### VES01699 6

# VES016997-017002.pd f