Xac textracte d a sample o f

effluentdownstrea

m o f al l controls . Th e extracte d effluentwa

s dynamicall y spike d with five differentmetals (As , Cd , Cr , Pb , Hg ) a tthre e different concentration level s (27 , 9 2 an d 250 pg/dscm ) usin g th e QAG . Th e Xac treported concentration was plotted agains

tth e referenc

e aeroso l concentration an

d a linea rleastsquare s regressio n fit was performed . Th e accurac y ofth e Xac twas evaluated o n th e basi s o f

slope , correlatio n coefficien tan d intercept . 

## Measuremen

to f Mercur y wit h tb e Xac to n Coal Fire d Powe

rPlant s Thi s pape

rals o summarizes th

e result s o f two distinctstudie

s evaluatin g th

e accurac

y ofth e Xact' s mercui y measuremen to n coa l fired powe rplants . Durin g both studie s th e accuracy o f

the Xac twa s detennine d b y comparing i tt o Metho d 30B 20 , a sorben ttrap approac

h t o measuring mercuiy . Th e firststudy wa s performed o n a 58

5 M W facihty , burnin g subbituminou s coa l an

d operating wit

h ES Pcontrols . The Xac twa s deploye d a tthis facilit y fo rthre

e week s and comparison testing too k place o n on e o f thos e days . Th e second stud

y was performed a

ta 750M W sourc

e burnin g tw

o separat

e blends o f

lignite an

d PowderRive rBasi n (PRB ) coal (60/4 0 and 80/2 0 blends o f

lignite/PRB) . Th e facihty wa s equipped with a n ES Pan d we tscrubber, butal l o f

th e Xac tsamplin g wa

s don e downstrea

m o f a singl e ES Pmodul e an d upstrea m o f th e wetscrubber. In addition , the facility wa s testing tw

o separat e mercui y contro l option s - activated powdered carbo n an d EMO , a bromin e based additive . Durin g the course o f th e approximately tw

o wee k tes tth e Xac treported mercur y concentration wa

s compared t

o Metho d 30 B measure d concentration a

tsevera l times eac

h day . 

## RESULT S AND DISCUSSION Metho d 30 1 Validation Result

s Diirin g th

e Metho d 30 1 validatio n ofth e Xac tth e bias , precisio n an d linearit y o f th e Xac twer

e detennined b y comparin g th e Xact' s reported concentration wit h reference aerosol concentration ove rthre e differentconcentration level s (nominall y 20,4 5 and 11 0 ug/dscm) and a zer o concentration . Th e bias wa s calculated fo reac h elemen ta teac h dat a poin tusin g Equatio n 2

Bi = • 10 0 Equatio n 2

where : Bi— Th e Xact' s bias fo rth e i * elemen

trelativ e to th

e QA G expresse d a

s a percentag

e Cf 1 = Th e concentratio n ofth e i * elemen ta s measured b y th

e Xac t Cf AG = Th e concentration o f tiie r * elemen

ti n the QA G aerosol Th e precisio n o f

th e Xac twa

s calculating b y firs tdetermining th e relative percen

tstandar d deviation a

s shown i n equation 3 .



### VES01680 0Equatio n 3
where : V-=the total variabilit y o f th e r * elemen

t SD(= th e standar

d deviatio n o f

th e r * elemen

t C{= th e averag e concentration o f

th e i * elemen

t

Becaus e ther

e i s random variabilit

y associated wit

h bot h the QA G aerosol concentration a s wel l th e Xac tmeasurement

, th e tota l variabilit

y (V?) i s a

n indicato rofth e overal l variabilit y o f bot h th e QA G aerosol generatio n an d th e Xac tmeasurement

. Th e individua l variabilit y o f jus tth e Xac tmeasured concentration the n i s determined b y dividin g the tota l variabilit

y b y th e squar e roo to f 2 a s show n i n equatio

n 4. vf Vi~-fl Equatio n 4 where : 7i=th e precisio n ofth e Xac tmeasuremen tfo rth e i * elemen

t V?=th e total precisio n ofth e r * elemen t Tabl e 1 summarizes the result s fo rbot h th e averag e bia s and averag

e precisio n fo rth

e Xac tfo r eac h o f the five teste

d element

s overal l thre

e concentration levels . I n general , ther e wa s les s tha n 10 % differenc e betwee

n th e Xac treported concentration s an d th e known concentration o f th e reference aerosol . Onl y th e bias fo rmercur

y wa s determined t

o b e statistically significan tan d 6 % o f th e bia s wa

s late rdetermine

d t o b e due t

o a calibratio n errorfo rmercury . Th e averag e variabilit

y o f the Xac twa

s als o les s tha

n 2% fo reac

h elemen

tindicatin g tha

tth e Xact' s measurement

s were extremely precis e an d consistent. Tabl e 1 . Xac tMetho d 30 1 Results fo rMeasuremen tBia s an d Variabilit y Elemen t N Averag e Bia s (% ) Averag e Variabilit y (% ) Cr 4 0 8. 2 1.6 A s 4 0 4. 9 1. 7 H g 4 0 1 6 1.4 P b 4 0 7. 9 1.5 C d 4 0 5.2 1. 9 Figure 1 show

s th e overal l linea

rregression fo ral l o f

th e metals teste

d overal l thre

e concentration level s an d azer o concentration . Th e slop e ofth e linea rregressio n fitwa s 0.9 5 indicatin g excellentagreemen tbetwee

n the Xac tmeasure

d concentration an d th e QA G referenc

e aerosol . Th e interceptwa s slightly greate

rthan 1 pg/dscm indicatin g ver y littl e background bias

6



### VES01680 1and th e correlation coefficien twa s greate rtha n 0.99 indicatin g ver y littl e scatte ri n th e dat a an d goo d precision. 1 2
Figur e 1 . Xac tLinearit y Durin g Metho d 30 1 Validatio n 14 0



### QA G Referenc e Concentratio n (pg/dscm )


## Operatio n ofth e Xac

tOve rSevera l Year s Th e Xac toperate

d fo rsevera

l year s a tE h Lilly' s hazardous wast e incinerato rand during tha t tin e me tal l ofth e daily , quarterl y and annua

l qualit y assuranc

e requirements . Some sampl e upscal e cahbration check result s from Marc h o f

2006 t o Marc h of200 7 ar

e show n i n Figure 2 . Darin g tha

tentir e 1 2 mont h perio d th

e Xac tupscal e drif

texceeded its upscal e calibratio n drif t criteria o n onl y tw

o occasions . Tabl e 2 show s al l th e quarterl

y XR F and flow audi

tresult s fo r the entir e compliance operation perio d fro m 200 7 t o 2010 . Durin g tha

tfou ryearspa

n th e Xac t passed al l o f

it s quarterl

y audi trequ h ements . Finally , table thre e show s the result

s fro m six separat e relative accurac

y tes taudit s (RATA ) ove ra spa

n o f five years . Th e Xac tme tth e RAT A criteri a i n al l cases , however , i n 2006 and 2008 a smal l correctio n facto rneeded t o b e applied t

o ti e instnunen

tdat a fo rarsenic .
Figur e 2 . Dail y Upscal e Result s fro m Marc h 2006 t o Marc h 200 7



### VES01680 28



### VES01680 3Tabl e 2 . Quarterl y Flo w an d XR F Audi tResult s fro m 2007 to 201 0 Audi t Yea r Quarte r Flo w Erro r {%) XR

F Audi tErro r(%

) Audi t Yea r Quarte r Flo w Erro r {%) C r A s C d H g Pb 2O0 7 1 3.0 4 1.46 2.1 8 2.8 4 1.7 5 2.3 4 2 3.1 3 3.3 2 0.1 3 4.2 3 2.6 0 2.9 6 2O0 7 3 0.6 8 -3.7 4 2.1 8 -4.1 3 2.3 6 2.7 6 2O0 7

4 1.4 2 6.5 0 0.3 6 7.3 6 4.1 8 0.4 0 2O0 8 1 N A 0.22 .1 1 1.2 0 -0.9 9 0.8 7 2 1.0

7 1.9

3 .6 6 1.8 2 2.1 6 2.3 4 2O0 8
3 0.5 3 2.9 6 2.6 1 3.3 0 2.53 0.6 8 2O0 8

4 1.37 1.7 7 0.7

2 1.48 0.5 6 1.06 200 9 1 2.1 0 0.6 0 2.9 4 1.5 2 3.4 5 0.4 6 2 3.6 7 1.49 4.0 9 1.0 7 1.78 0.3 0 200 9
3 0.8 4 2.0 0 5.4 3 2.7 8 0.72 0.22 200 9

4 N A N A NA N A NA N A 201 0 1 NA 1.60 5.1 3 0.45 0.7 1 2.1 1

2 NA 1.6 1 5.92 1.1 2 4.0 0 0.9 6 201 0
3 1.6 8 -3.47 -0.9 2 -2.8 2 -2.42 -2.1 1 201 0

4 NA 2.0 0 0.82 2.7 0 1.8 3 2.9 1 Averag e 1.7 7 1.35 2.1 6 1.66 1.6 8 1.2

2 N A - Dat a no tavailabl e

Tabl e 3 . Annua l QA G RAT A Results Yea r Slop e

C r A s C d H g P b Annua l Averag e 2006 0.8

3 0.9

0 0.85 0.8 2 0.8

5 0.8

5 2006 (Quarterly

) 0.9 1 0.7

7 0.9

5 0.9

2 0.9

3 0.8 9 200 7 0.8

4 0.8

2 0.88 0.8 4 0.8 1 0.84 200 8 0.9

6 0.7 1 0.9 8 0.9 9 0.9

7 0.92 2O0 9 0.9

6 0.9

9 0.9 9 1.10 1.0 0 1.01 201 0 0.9

7 1.0

6 1.1 1 1.0 2 1.0

4 1.0

4 Averag e fo rEac h Elemen t 0.9 1 0.8 7 0.9 6 0.9 5 0.9

3 0.9

3



## Result s ofth e Evaluatio

n ofth e Xac

to n a Coa l Fire d Sourc

e Tabl e 4 show

s th e result s o f th e evaluatio

n ofth e Xact' s accuracy o n a coal fired source . Durin g tli e stud y th e Xac twa

s challenged wit

h thre e concentration level s usin g CES ' quantitativ e aerosol generator

. A s wit h th e Metho d 30 1 testin g th e Xac teffluentwa

s dynamically spike d t o tes tfo ran y potentia

l interference

s from th

e coa l fired effluent . Fo reac h element

, th e Xac t 9



### VES01680 4reported concentiations wer e plotted agains

tth e know n referenc

e aeroso l concenhatio n an d a leastsquare

s regression analysi s wa s performed . I n al l cases , th e Xac tslop e wa

s betwee n 1.0 0 an d 1.1 5 wit h correlatio n coefficient s greate rtha n 0.99 . Thi s indicate d tha tther e wer e n o measuremen

tmatri x effects associate

d emissions fro m a coa l fire d sourc e an d tha tth e Xac ti s able t o accuratel

y measur

e many o f

th e ke y metals o f

mteres to n such a source. 2 1 Tabl e 4 . Result s fro m Accurac y Testin g o n a Coa l Fire d Sourc e Elemen t N Slop e Correlatio n Coefficien t C r 28 1.0 9 >0.99 A s 2 8 1.14 >0.99 C d 2 8 1.1 1 >0.99 H g 2 8 1.14 >0.99 Pb 2 8 1.0 0 >0.99 

## Mercur y Measuremen

twit h th e Xac to n a Coal Fire d Powe

rPlan t Darin g testing o n a 58 5 M W coal fire d facilit y equippe d wit h ES Pcontrol s th

e mercur

y concentration a

s reported b y th

e Xac twas compared agains tmetho d 30B . Th e percen t differenc e betwee

n th e Xac tan

d Metho d 30 B wa

s 3.53%. 22Thes e result s ar e show n graphicall y i n Figur e 3 . Figur e 3 . Xac tCompariso n wit h Metho d 30 B

§
• 8 1 0 9 8

li c o u > » 

### 2 

# • •

• CE S Xac t

• Metho d 30 B

0 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 RAT A Numbe r



### 1 0



### VES01680 5Additiona l comparisons hav e bee n mad e betwee

n Metho d 30 B and the Xac ta tanothe rcoa l fired powerplant. Thi s 750 M W facility wa s burnin g lignite-PR B coa l blend s an d testing tw o differentmercur

y contro l technologie

s (powderactivated carbo n and EMO) . Ove rth e entir e tw o wee k perio d 2 1 comparison s wer e made betwee

n th e Xac tand Metho d 30 B unde ra variet

y o f stac k effluen tconditions . Th e averag e percen tdifferenc e between th e Xac tand Metho d 30 B wa s 6.0 % demonstrating th e accurac

y ofth e Xact' s mercur y measurements . Th e result s ar e summarized i n Tabl e 5 . Tabl e 5 . Xac tMercur y Measurements Wit h an d Withou tMercur y Contro l Fue l Condition s Date Tim e H g Control s Metho d

30 B (ug/dscm ) Xac t

(pg/dscm ) Percen t

Differenc e 60 % 10/3/1 2 11:4 5 Baselin e 24.57 22.59 -8. 1 Lignite 10/3/1 2 14:4 5 EM O 14.8 5 15.3

3 3.

2 40 % PR B 10/3/1 2 16:4 5 EM O 16.30 15.8 3 -2. 9 10/5/1 2 12:15 EMO & PA C 9.2

5 10.0

9 9.0 10/5/1 2 16:4

5 EMO &

PA C 11.5

2 12.7

4 10.6 10/5/1 2 17:4

5 EMO &

PA C 4.0

5 5.8

8 45.2 10/6/1 2 10:4

5 Baselin e 24.0 3 24.55 2. 2 10/6/1 2 13:4

5 EMO &

PA C 11.1 4 12.3 4 10.

8 10/6/1 2 15:4

5 EMO &

P A C 5.7

4 7.9

7 38. 8 10/6/1 2 18:4

5 EMO &

PA C 13.9

2 15.7

2 13.0 80 % 10/9/1 2 10:15 Baselin e 28.1 4 25.07 -10. 9 Lignite 10/9/1 2 12:15 PA C 19.0 1 19.2 6 1.

3 20 % PR B 10/9/1 2 16:15 PA C 7.00 7.3 4 4. 9 10/10/1 2 10:3

0 Baselin e 23.1 9 23.98 3.4 10/10/1 2 13:4

5 E M O 18.7 3 20.2

2 8.0 10/10/1 2 16:4

5 E M O 20.1 0 22.1 0 10.0 10/10/1 2 19:4

5 E M O 18.60 22.1 1 18.8 10/10/1 2 9:0

0 Baselin e 21.57 18.6 9 -13. 4 10/11/1 2 9:0

0 Baselin e 24.0 0 23.5 3 -1. 9 10/11/1 2 10:4

5 E M O 20.52 18.9 0 -7. 9 10/11/1 2 11:3

0 E M O 21.3 8 19.5 5 -8. 6 Averag e Percen tDifferenc e Unde rBaselin e Condition s -4. 8 Averag e Percen tDifferenc e wit h H g Control s 7.6 Overal l Percen tDifferenc e 6.0

1 1



### VES01680 6

## CONCLUSIO N Tk e Xac tha

s demonstrate

d metal s measuremen

taccurac

y o n a variet

y o f sourc e type s an d wit

h a variet y o f differentcontrols . Thes e source s hav e include d ga

s fire d and coa l fire d source s wit h ES Pan d we tscmbbin g controls . I n addition , th e Xac tdemonstrate

d accurac

y measuring mercxu y with a tleas ttw o differentapproache

s t o mercur

y contro l - powde ractivated carbon an d EMO . I n th e futur e th e accurac

y an d precisio n ofth e Xac twil l b e teste d o n tw o secondar

y lea d smelter s i n the Lo s Angele s Basi n area. Thes e test s wil l includ e bot

h dynami c spikin g test s wit h a reference aerosol a

s wel l a s comparisons t

o stac k metals measuremen tmethod

s such a s Metho d 29 . REFERENCE S 1 . El i Lill y and Co . (2005) , Alternativ e Momtorin g Petitio n fo rth e Solid-Liqui d Incinerator, Tippecano e Laboratories , Lafayette , I N 47909 2 . Oldham , C3. Ai rMeasurement s and Quality Group , Offic e o f Ai rPlannin g an d Standards , U.S . Environmental Protectio n Agency , Research Triangl e Park , NC . Writte n communicatio n wit

h El i Lill y and Company : Lafayette , IN . 200 6 3 . U . S . Envhonmental Protectio n Agency . Metho d 301 , Fiel d Vahdatio n o f Pollutio n Measuremen

tMethod s fo rVariou s Media . In Code of Federal Regulations, 40 CFR Part 56. U.S . Governmen

tPrintin g Office : Washington , DC , 2005 4 . "National Emission s Standard s Fro m Coal - Oil-fire d Electri c Stea m Generatin g Units an d Standard

s o f Performance fo rFossil-Fuel-Fire d Electri c Utility , mdusuial-Commercial Institutiona

l Stea m Generatin g Units , Fina l Rule. " Federal Register7

7 (Februar

y 16 , 2012) : 9403-9513 . 5 . "Nationa

l Emission s Standard

s fo rHazardous Ai rPollutant s fo rHazardous Wast e Combustors (Phas

e I Fina l Replacemen

tStandard

s an d Phas e II); " Fina l Rule . Federal Register70 , No . 19

6 (October12,2005) : 5940 2 - 59450) httD.//ww.epa.gov/fed^gsh/CTA-AIR/2005/October/Dav - 12/al 8824a.pdf . Accesse d July24,2014 . 6. "Standard

s o f Perfonnance fo rNe w Stationar y Sources and Emission s Guideline s fo r Existin g Sources : Hospital/Medical/Infection s Wast e Incinerators; " Fina l Rule . Federal Register74, No. 192 (October6,2009) . http://ww.gpo.gov/fQSVs/pkg/FR-2Q09-10 - Q6/pdf/E9-22928.pdf

Accesse d Jul y 24.2014 . 7 . "National Emissio n Standard s fo rHazardous Ai rPollutant s from th

e Portland Cemen

t Manufacturin g Industr y an d Standard

s o f Performance fo rPortland Cemen tPlants; " Fina l Rule . Federal

Register75, No. 174 (Septembe

r9 , 2010) . htto://www.epa.gov/ttn/atw/pcem/fr09sel0.pdf . Accesse d Jul y 24 , 201 4 8 . U.S . Envhonmental Protectio n Agency . Metho d 29 , Detenrunatio n o f Metal s Emission s from Stationar

y Sources . I n Code of Federal Regulations, 40 CFR 60\ U.S . Governmen t Printin g Office : Washington , DC , 2005 . 1 2



### VES01680 79. "Revise d Standard s fo rHazardous Wast

e Combustors " Propose d Rule . Federal Register 61, No. 77

(Apri l 19,19961 . http://ww.gro.gov/fdsv ^ 7872.pdf

Accesse d M v 24.2014 . 10. U.S . Environmenta l Protectio n Agency , Regio n 5 . Ai rPollutio n Contro l Titl e V Permi tt o Operate . Permi

tNo . V-IL-1716300103-08-01 . http://ww.regulatioiis.gov/#!documentDetail;D==EPA-R05-OAR-20r2-0649-000 1 Accesse d Jul y 24,2014 . 11 . "Nationa

l Emissio n Standard

s fo rHazardou s Ai rPollutants : Secondar y Lea d Smelting " Propose d Rule . Federal Register76, No. 97

(Ma y 19 , 2011 ) htro.V/ww.epa.gov/ttri/atw/lead^d/irl9mv l l.pd f Accesse d Jul y 24 . 201 4 12. Yanca , C.A. ; Barth , D.C ; Petterson, K.A. ; Nakanishi , M.P. ; Cooper , J.A. ; Johnsen , B.E. ; Lambert, R.H. ; Bivins , D.G. ; J. Airand Waste Manage. Assoc. 2006,56, 1733-1742 . 13 . Rigo , H.G. ; Chandle rA.J. ; J. Airand WasteMange. Assoc. 1999 , 49, 399-411. 14. America n Societ

y o f Mechanica l Engineers , Researc h Committee o n Industria l an d Municipa l Waste . Reference Method Accuracy and

Precision (ReMAP): Phase 1, Precision oj"Manual

Stack Emission'Measurements; Repor tNo . CRTD-60 ; America n Societ y o f Mechanical Engineer s International ; Washington , DC , 2001 . 15 . U.S . Environmenta l Protectio n Agency . Evaluation of Two Methods forthe Measurement of Mercury Emissions in Exhaust Gases from a Municipal Waste Combustor; EP A 450/4 - 92-013 . U.S . Governmen tPrintin g Office : Washington , DC , 1991 16. U.S . Environmenta l Protectio n Agency . OtherTes tMetho d 16 , Specification s fo rX-ra y Fluorescence Base d Multi-Metal s CEM S a tStationar

y Sources . http://w\w.epa.gov/tln/emc/preUm/otml6.pd f Accesse d July_24,2014 . 17 . U.S . Environmenta l Protectio n Agenc y Othe rTes tMetho d 20 . Quality Assurance Requirement

s fo rX-ra y Fluorescence Base d Multi-Metal s CEM S a tStationar

y Sources . htrp://www.epagov/tta/em Accesse d Jul y 24 , 2014 . 18 . Microraatte rCo . 400 4 Westbrook Mall , Vancouver , B.C . V6 T 2A3 , Canada . 19 . U.S . Environmenta l Protection Agency . Compendiu m Metho d 10-3.3 : Detenninatio n o f Metal s i n Ambien tParticulat e Matte rUsin g X-ra y Fluorescence (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 . 20 . U.S . Environmenta l Protection Agency . Metho d 30B . Determinatio n o f Tota l Vapo r Phas e Mercury Emission s Fro m Coal-Fire d Combustio n Sources Usin g Carbo n Sorben t Traps . In Code of

Federal Regulations 40 CFR 60. U.S . Governmen tPrintin g Office . Washington , DC , 21 . Coope rEnvhonmenta l Services LLC . Feasibility o f Monitorin g Heav y Meta l Emission s from a Coa l Fire d Hazardou s Wast e IncineratorUsin g a Multi-Meta l Continuou s 13



### VES01680 8Emission s Monitor . EP A Contrac tI D EP-D-07-026 . Apri l 30 , 2007 . 22 . Th e Avagadro Grou p LLC , Continuous X-Ra y Fluorescence Mercur y Emission s Monitor , Unofficia l Relative Accurac y Tes tAudit , Apri l 28 t h2009 . 

## KEYWORD S Multi-Metal s CEMS , Hazardous Wast e Incinerators , X-ra y Fluorescence

# VES016810-016945.pd f

### U S Arm y Corp s o f Engineers « Enginee rResearc h an d Developmen t Cente r



# X-Ra y Fluorescence-Base d Multi-Meta l Continuou s Emissio n Monito r Technolog y Demonstratio n K

. Jame s Hay , Veer a M

. Boddu , Bruc e E

. Johnsen , an d Joh n A

. Coope r Marc h 200 5

4mt CE S

publi c release ; distributio n i s unlimited

.



### VES01681 0

### ERDC/CER L TR-05- 9 Marc h 200 5



# X-Ra y Fluorescenc e Base d Multi-Meta l Continuou s Emissio n Monitor : Technolog y Demonstratio n

K

. Jame s Ha yan d Veer a M

. Bodd u Construction

Engineering

Research

Laboratory PO Box 9005 Champaign, IL61826-9005


### Bruc e E

. Johnse n an d Joh n A

. Coope r Cooper Environmental

Services 10170 SW Nimbus

Avenue, Suite

H5 Portland, OR

97223-4340



### Fina l Repor t Approve d fo rpubli c release ; distribution i s unlimited .



### Prepare d fo rU.S

. Arm yCorp s o f Engineer s

Washington , D C 20314-100 0 Unde rWor k

Uni t #CNE-B09 1



### VES01681 1ABSTRACT : Arm y demilitarizatio n incinerator s wil l nee d t o compl y wit h th e Hazardou s Wast e Combusto rNa tiona l Emissio n Standard fo rHazardou s Ai rPollutant s tha twil l regulate metal s an d metal compound s liste d unde r th e Clea n Ai rAc tAmendments . A larg e proble m fo rthes e incinerato roperation s i s limite d knowledg e o f the typ e and quantit

y o f emitte d metals , so tha tcomplianc e ma y b e determine d onl y throug h tria l bu m emissio n tests . A con tinuou s emissio n monito r(CEM ) fo rmulti-metal s wil l provid e the emissio n data , a too l t o hel p mee tcomplianc e requirements , an d th e opportunit

y t o adjus tbur n strategie s fo rincrease d production . A user-friendl y multi-meta l C E M tha

tuse s x-ra y fluorescence (XRF ) a s th e analytica l metho d an d a n automate d samplin g syste m thatprovide s extractiv e batc h samplin g ont o a filte rtap e (XCEM ) wa s demonstrate d a tth e 1236 Deactivatio n Furnac e a tTooel e Arm y Depot , Utah . Th e uni twas compare d t o EP A Referenc e Metho d 2 9 durin g two separat e test s (200 1 an d 2002) . Th e secon d tes twas performe d afte rimprovement s wer e mad e t o th e sampl e transportan d syste m calibrations . Th e result s indicat e tha

tth e XCE M ha

s me tth e propose d Performanc e Specificatio n 1 0 fo rmulti-meta l CEM s excep tfo r relativ e accurac y requirement s fo r4 o f

9 metals . It

s failure s ar

e attribute d mostl y 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 i s read y fo rimplementatio n a tothe rArm y demilitarizatio n incinerators .

DISCLAIMER : The content s o f thi s repor tar e no tt o be use d fo radvertising, publication, o rpromotiona

l purposes . Citation o f

trad e name s doe s no tconstitut

e a n officia l endorsemen

to rapprova

l o f th e us e of suc h commercia

l products . Al l produc

tname s an d trademark

s cite d ar e th e propert

y o f thei rrespectiv

e owners. The findings ofthi s repor tar e no tt o b e construe d a s a n official Departmen

to f th e Arm y positio n unles

s s o designate

d by othe

rauthorize

d documents . DESTRO Y THI S REPOR T WHE N I T I S N O LONGE RNEEDED . D O NO T RETUR N I T T O TH E ORIGINATOR .



### VES01681 2ERDC/CER L TR-05- 9 ii i



# Content s

Lis to f Figure s an d Table s v Conversio n Factor s vi i
Prefac e vii i
1 Introductio n 1 Backgroun d 1 Objective 3 Approac h 4 Mod e o f Technolog y Transfe r 4 2 Fiel d Testin g 200 1 5 Brief Descriptio n o

f XCE M 5 Extraction

System

5 Sampling

and Analysis

System

6 Control System

7 Executio n o

f Field-Testin g Activitie s 7 Test Plan 8 EPA Verification

9 TEAD Interface

9 Test Objectives

10 Site Description

11 Experimental

Design

14 Result s 1 5 XCEM Reported

Concentrations

15 Sampling

and Response

Time 19 Zero and Calibration

Drift. 19 Correlation

with Reference

Method

2 0 Response

to Changes

in Metal Concentration

25 Relative Accuracy

2 5 Precision

3 3 Low-Level

Metal Response

• 3 5 Bias 3 6 Summar y 3 7



### VES01681 3i v ERDC/CER L TR-05- 9

3 Transpor tan d Calibratio n Improvements 3 9 Transpor

t Lin e Change s 3 9 Recalibratio n 4 0 Summar y of Transpor

t an d Calibratio n Evaluation s 4 0 4 M2 9 Compariso n Testin g o f XCE M 2002 42 Result s 4 2 Method 29 Concentrations

42 Predicted

Stack Gas Concentrations

43 XCEM Concentrations

47 XCE M Calibratio n Evaluatio n Usin g A Quan X - XR F an d ICP/M S 5 3 Precisio n 5 3 Discussio n 54 Regulated

Elements

Typically

Found in the Feedstream

54 Regulated

Elements

Not Typically

Found in TEAD Emissions

5 8 Nonregulated

Metals

63 Summar y 6 3 5 XCE M Cos tan d Statu s 6 5 Cos t Estimate s 6 5 Capital Costs 6 5 Annual Costs 6 6 Continue d Us e o

f th e XCE M 6 6 6 Summar y an d Conclusion s 68
Reference s 71 Appendi x A : Test/Q A Pla n fo rVerificatio n o f a Continuou s Emissio n Monito rfo r Multi-metal s a

tTooel e Arm y Depo t(2001 ) 73 Appendi x B : Determinatio n o f XCE M Reporte d Concentration s 200 1 101 Appendi x C : Transpor tan d Calibratio n Evaluation s 10 6 Appendi x D : Mercur y Calibratio n an d Los s Discussio n 200 2 117
Abbreviation s an d Acronym s 12 5 Repor tDocumentatio n Pag e 12 7



### VES01681 4ERDC/CER L TR-05-9 v



# Lis t of Figure s an d Table s

Figure s 1 XCE M stillin g chambe r an d samplin g cassett e 6 2 XCE M chassi s 7 3 Ne

wComponen t Contro l Scree n fo r XCE M softwar e interfac e 8 4 XCE M housin g an d transpor t line , M2 9 samplin g setup , stack , an d cerami c baghous e a

t TEA D 1 0 5 TEA D incinerato r setu p an d sampling/spikin g location s 1 3 6 Spikin g a

t bas e of stac k

durin g validatio n testin g 1 5 7 Palladiu m concentration s durin g M2 9 testin g 2 1 8 XCE M an d M2 9 concentration s durin g TEA D verificatio n testin g 2 2 9 Correlatio n betwee n XCE M an d M2 9 fo r element s spike d a t tw o level s 2 4 1 0 XCE M an d M2 9 lea d concentration s durin g run s 8-1 1 2 8 1 1 Rati o o

f XCE M t o M2 9 concentration s durin g validatio n testin g 3 0 1 2 Uncorrecte d XCE M A s concentration s versu s XCE M Pb concentration s 3 2 1 3 Correlatio n betwee n S n an d othe r APE-123 6 metal s wit h munition s burnin g

an d n o spikin g 4 6 1 4 XCE M ti n measurement s durin g M2 9 testin g 4 6 1 5 XCE M versu s M2 9 lea d fo r validatio n test s 5 6 1 6 Percen t differenc e betwee n M2 9 an d th e XCE M versu s percen t o f H g o n M2 9 filte r 6 0 1 7 200 4 CE S metal s monito r 6 7 C 1 Experimenta l desig n fo r atomizatio n test s 107 C 2 XCE M reporte d concentration s fo r nonspike d element s 11 3 C 3 XCE M reporte d concentration s an d MSE-projecte d concentration s fo r

spike d element s 11 4 D 1 Compariso n o f XCE M x-ray spectr a measure d durin g M2 9 testin g an d 71 day s late r 12 1 D 2 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 filte r 12 3



### VES01681 5v i ERDC/CER L TR-05- 9

Table s 1 Arm y hazardou s wast e combustor s 2 2 Propose d PS-1 0 requirement s 3 3 XCE M test date s an d associate d TEA D incineratio n feedstrea m 9 4 Typica l operatin g parameter s fo r th e APE-123 6 deactivatio n furnac e 1 2 5 TEA D meta l emissio n limit s durin g verificatio n testin g 1 2 6 TEA D incinerato r meta l emissio n limit s an d spikin g level s 1 4 7 Fina l reporte d CE M concentration s fo r M2 9 testin g 1 7 8 Upscal e an d zer o concentration s durin g validatio n testin g 2 0 9 Correlatio n betwee n th e XCE M an d M2 9 2 5 1 0 XCE M measured , M2 9 measured , an d MSE-predicte d meta l concentration s durin g TEA D validatio n testin g 2 6 1 1 Relative accurac y an d correlation s 2 7 1 2 Percen t difference s betwee n M2 9 sampl e train s 3 4 1 3 XCE M an d M2 9 precisio n 3 5 1 4 Metho d 30 1 bia s an d correctio n facto r compariso n 3 7 1 5 Summar

y o f XCE M performanc e relativ e t o propose d PS-1 0 requirement s 3 8 1 6 M2 9 concentration s 4 3 1 7 APE-123 6 stac k flo wrate s durin g M2 9 testin g 4 4 1 8 APE-123 6 stac k concentration s wit h munition s incineratio n but n o spikin g 4 5 1 9 Predicte d stac k concentration s base d o n MSE-T A spikin g an d backgroun d estimate s 4 7 2 0 XCE M concentration s 4 8 2 1 Analysi s o

f XCE M filte r tap e b y Columbi a Analytica l 5 3 2 2 Predicte d (spiked) , XCEM , an d M2 9 precisio n durin g validatio n testin g 5 3 2 3 TEA D emissio n limit s fo r regulate d element s 5 4 2 4 Summar

y o f Pb concentratio n dat a an d ratio s durin g M2 9 testin g 5 5 2 5 Summar

y o f C d concentratio n dat a an d ratio s durin g M2 9 testin g 5 7 2 6 Summar

y of C r concentratio n data an d ratio s durin g M2 9 testin g 5 8 2 7 Summar

y o f A s concentratio n dat a an d ratio s durin g M2 9 testin g 5 9 2 8 Summar

y o f H g concentratio n dat a an d ratio s durin g M2 9 testin g 6 0 2 9 Summar

y o f S b concentratio n dat a an d ratio s durin g M2 9 testin g 6 1 30 Summar

y o f N i concentratio n dat a an d ratio s durin g M2 9 testin g 6 2 31 Summar

y o f B a concentratio n data durin g M2 9 testin g 6 2 32 Summar

y o f Z n concentratio n dat a an d ratio s durin g M2 9 testin g 6 3 3 3 Summar

y o f 200 2 M29/XCE M compariso n results 6 4



### VES01681 6ERDC/CER L TR-05- 9 vi i

B 1 Origina l XCE M reporte d concentration s uncorrecte d fo r calibratio n an d drye r

change s 10 3 B 2 Result s o

f drye r test s 10 5 C 1 Flo

wrate s an d concentration s use d to calculat e atomizatio n concentration s 109 C 2 Atomizatio n vs . XCE M concentration s 10 9 C 3 Tota l capture mas s vs . atomizatio n mas s 11 1 C 4 Lea d normalize d atomizatio n mas s vs . tota l capture 11 1 C 5 Metho d 1 7 vs . XCE M a t TEA D 11 6 D 1 Mercur

y reporte d concentration s durin g Yea r 200 2 M2 9 validatio n testin g 120 D 2 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 test s 122



# Conversio n Factor s

Non-S I unit s o f

measuremen tuse d i n thi s reportca n b e converte d t o S I unit s as follows : Multipl y B y To Obtai n degree s Fahrenhei t (5/9)x(°F-32 ) degree s Celsiu s

Systeme

International

d'Unites

("Internationa

l Syste m o f Measurement"), commonl y know n a s th e "metri c system. "



### VES01681 7vii i ERDC/CER L TR-05- 9



# Prefac e

Thi s stud y was conducte d fo rHeadquarters , Departmen tof th e Arm y unde rPro gra m Elemen t063728A , "Environmenta l Technology Demonstration" ; Project 002 , "Environmenta l Comphanc e Technology" ; Wor k Uni tCNE-B091 , "Hazard ous Ai rPollutant s Technology Demonstrations. " Th e technica l reviewe rwa s Thoma s Logan , U.S . Environmenta l Protectio n Agency . Th e wor k was performe d b y th e Environmenta l Proces s Branc h (CN-E ) of th e Installation s Divisio n (CN) , Constructio n Engineerin g Researc h Laborator y (CERL) . Th e CER L Principa l Investigato rwa s Dr . K . Jame s Hay . Par to f thi s work wa s don

e b y Coope rEnvironmenta l Service s unde rDACA42-02-P-007 2 an d DACA42-01-C-0022 ; MS E Technology Applications , Inc . unde rGS-10F-0212K ; an d th e U.S . Arm y Cente rfo rHealt h Promotio n an d Preventiv e Medicine . Th e technica l edito rwa

s Lind aL . Wheatley , Informatio n Technology Laborator y — Champaign . Dr . Kirankuma rV . Topudurti i s Chief , CN-E , an d Dr . Joh n T . Band y i s Chief

, CN . Th e associate d Technica l Directo rwa s Gar y W . Schanche . Th e Directo ro f

CER L i s Dr . Ala n W . Moore . CER L i s a n elemento f th e U.S . Arm y Enginee rResearc h an d Developmen t Cente r(ERDC) , U.S . Arm y Corp s of Engineers . Th e Commande ran d Executiv e Directo rof

ERD C i s CO L Jame s Rowan , an d th e Directo rof ERD C i s Dr . Jame s R . Houston .



### VES01681 8ERDC/CER L TR-05-9 1



# 1 Introductio n
Backgroun d
Th e U.S . Environmenta l Protectio n Agenc y (EPA ) i s developin g regulation s fo r hazardou s wast

e combustors (HWC ) a s par to f

Titl e II I o f th e 199 0 Clea n Ai rAc t Amendment s (CAAA ) i n th e for m o f a Nationa l Emissio n Standar d fo rHazard ou s Ai rPollutant s (NESHAP) . Th e U.S . Arm y possesse s a numbe ro f demilitari zatio n furnace s tha twil l nee d t o compl y wit h thes e regulations . O f mos tconcern i s meetin g th e requirement s fo rmetal s an d meta l compound s liste d unde rth e CAAA . A larg e proble m fo rthes e incinerato roperation s i s limite d knowledg e o f th e type s an d quantitie s of emitte d metals . Comphanc e ma y b e determine d onl y throug h tria l bur n emissio n test s becaus e o f

thi s limitation . Thes e tests are expensiv e an d requir e worst-cas e scenari o burns . Th e ai rpermit s tha tare the n issue d ar

e base d o n thes e worst-cas e burn s an d impos e limitation s o n th e demili tarizatio n facilities . A continuou s emissio n monito r(CEM ) fo rmetal s woul d pro vid e th e emissio n data , a too l t o hel p meetcomplianc e requirements , an d th e op portunit y t

o adjus tbur n strategie s fo rincrease d productio n an d sustainability . I n addition , th e HW C NESHA Psuggests tha ta CE M woul d b e th e preferentia l metho d o

f emissio n accountability . Multi-meta l CEM s bein g develope d ar e base d o n elementa l sensor s usin g laser induce d breakdow n spectroscop y (LIBS ) o rinductivel y couple d plasm a (ICP) . Non e of th e LIB S monitor s ha s successfull y me tth e EPA-propose d Performanc e Specificatio n 10 (PS-10 ; EP A 1996) fo rcontinuou s multi-meta l monitors . Onl y on e o f the IC Punits , develope d b y Therm o Jarrel l As h Corporation , ha s bee n successfu l i n meetin g th e relativ e accuracy (RA ) criteri a of th e PS-1 0 (Seltze r 2000) . Thi s technology appears to hav e limitation s suc h a s it s complexity , hig h initia l costs , an d hig h operatin g costs . Th e U.S . Arm y Enginee rResearc h an d Developmen tCenter , Constructio n Engineerin g Researc h Laborator y (ERDC / CERL ) decided t

o pursu e th e developmen to f th e X-ra y fluorescenc e (XRF)-base d continuou s emissio n monito r(XCEM ) becaus e i tha d th e potentia l t o b e a reh abl e an d accurate CE M withou tthes e hmitations . Th e basi c approac h o f th e XCE M i s t

o draw a continuou s representativ e sampl e o f stac k gas t

o a stillin g chambe rwher e a smalle rmetere d sampl e i s extracte d an d passe d throug h a chemicall y treate d filte rtha tcollects metal s i n th e particu 

### VES01681 92 ERDC/CER L TR-05- 9

late an d vapo rphases . Followin g sampling , th e filte ri s passe d throug h a n XR F analyze rwhere th e masse s o f u p t o 1 9 metal s are measured . Thi s approach was originall y teste d i n 199 7 a ta n EP A tes tincinerator , wher e th e filter s wer e ana lyze d offlin e (Frenc h 1998) . Coope rEnvironmenta l Service s (CES ) furthe rde velope d thi s metho d int o a n on-lin e syste m tha twa s teste d unde rth e ERDC/CER L Waste Minimizatio n an d Pollutio n Preventio n Progra m a tMS E Technolog

y Applications , Inc.' s (MSE-TA's ) researc h incinerato ri n Butte , Mon tan a (Bryso n etal . 2000) . Th e result s were encouragin g becaus e th e XCE M met th e PS-1 0 R A requirement s fo rchromiu m (Cr ) an d lea d (Pb) . Man y of th e othe r requirements wer e unmet , however , an d furthe rdevelopmen twas needed . It wa s a tthi s poin ttha tERDC/CER L bega n fundin g th e developmen tof thi s tech nology unde rthei rHazardou s Ai rPollutant s (HAP ) program . Th e Arm y currentl y ha s 1 9 existing , new, o rplanne d hazardou s wast e combus tors . Tabl e 1 list s thes e site s (Josephso n 2003) . Tabl e 1 . Arm y hazardou s wast

e combustors . Locatio n Typ e Wast e Treate d Status G O orC O Sierr a A D AP E 123 6 C S Existin g G O Tooel e A D AP E 123 6 C S Existin g G O Tooel e A D AP E 123 6 Tes tFurnac e - C S Existin g G O McAlesterAA P AP E 123 6 C S Existin g G O Hawthorne AA P AP E 221 0 C S Ne w C O FortRichardso n AP E 123 6 C S Ne w G O Kansa s AA P AP E 123 6 C S Existin g C O Cran e AA P AP E 123 6 C S Ne w G O Lak e Cit

y AA P AP E 123 6 Off-spe c conventional Existin g G O Picatinny Arsena l AP E 123 6 Wast e R& D propellant s Ne w G O Pin e Bluf

f Arsenal Fluidize d Be d Pyrotechnic s an d Obscurant s Ne w G O Pin e Bluf

f Arsena l AP E 123 6 Off-spe c pyrotechnic s Existin g G O Radfor d AA P Kil n Off-spe c propellant s Existin g G O Desere tC A Chemica l Che m Existin g G O Umatill a A D Chemica l Che m Ne w G O Pin e Bluf

f Arsenal Chemica l Che m Ne w G O Annisto n A D Chemica l Che m Ne w G O Puebl o C A Chemica l Che m Planne d G O Annisto n A D Kil n De-Paintin g waste s Planne d G O G O - Governmen

tOwne d C O - Contracto rOwne d C A - Chemica l Activit y C S - Conventiona

l Stockpil

e Che

m - Chemica

l Stockpil

e AP E - Ammunitio n Peculia rEquipmen

t AD - Arm

y Depo tAA P- Arm y Ammunitio

n Plan t



### VES01682 0ERDC/CER L TR-05- 9 3


### Objectiv e
Th e overal l objective of th e HA Pprogra m i s t o develop cost-effectiv e technologie s t o hel p th e Arm y meetcurren tan d futur e demand s of HA Pregulations . Towar d thi s objective , th e XCE M was developed . I twa s develope d t

o posses s character istic s tha tmak e i tcompatibl e wit h Arm y operation s an d expectations , suc h a s use rfriendlines s an d affordability . Tha twork i s describe d i n a precedent-settin g report(Ha y etal . 2005) . Th e specifi c objective o f thi s wor k wa s t

o demonstrate th e XCE M a ta n Arm y installation . Th e desire d exi tcriterio n unde rth e HA P Progra m wa s fo rth e monito rt o meet , unde rfiel d conditions , th e propose d PS-1 0 requirements , whic h ar e describe d i n Tabl e 2 . Table 2. Propose d PS-1 0 requirements . Criterion Description Samplin g an d respons e time I ti s require d tha tthe samplin g time b e n o longe rtha n one-third o f the aver agin g perio d fo rth e applicabl e standar d fo ra batch CEM . Th e dela y be twee n th e en d o f

th e samplin g perio d an d reportin g of th e sampl e analysi s shal l b e no greate rthan 1 hour . A batch CE M i s require d t o sampl e con tinuousl y excep twhe n changin g th e samplin g media , whic h shoul d b e n o greate rthan 5 percen tof th e averagin g perio d o r5 minutes , whicheve ri s less . Fo rthi s study , th e averagin g perio d i s 1 2 hours , whic h mean s th e samplin g time shoul d b e n o longe rtha n 24 0 minutes , th e respons e tim e n o greate rthan 6 0 minutes , an d th e maximum tim e allowe d fo rchangin g the samplin g medi a i s 5 minutes . Qualit y assuranc e Calibratio n drift : Th e calibratio n may no tdrif to rdeviate fro m th e referenc e valu e of th e calibratio n standar d use d fo reac h meta l by mor

e than 5 per cen tof th e emissio n standar d fo reac h metal . Mus tallo w fo rdeterminin g o n a daily basis . Zer o drift : Th e zer o poin tfo reac h meta

l shal l no

tdrif tby more than 5 per cen tof th e emissio n standar d fo rtha tmetal . Mus tallo w fo rdeterminin g o n a dail y basis . Span : Th e CE M respons e rang e mus tinclud e zer o an d a hig h level valu e equa l t o the span . Th e spa n valu e i s define d a s 2 0 time s the applicabl e emissio n limi

tfo reac h metal . Thi s i s a n equipmen tspecificatio n (no t tested) . R A Th e R A o f th e CE M mustb e no greate rthan 2 0 percen tof th e mea n valu e o f th e R M tes tdat a i

n term s o f

unit s o f emissio n standar d fo reac h metal , o r 1 0 percen tof

th e applicabl e standard , whicheve ri s greater . Durin g verifica tion , the measur e of

R A a ta singl e concentratio n leve l i s require d fo reac h meta l measure d fo rcomplianc e purposes , an d th e R A mustb e determine d a tthre e concentratio n level s fo ron e meta l (zer o ca n b e on e level) . Source : EP A 1996

.



### VES01682 14 ERDC/CER L TR-05- 9


### Approac h
A s a resul to f

encouragin g developmen twork (Ha y etal . 2005 ) a new monito r was installe d a tth e 1236 productio n deactivatio n furnac e a tTooele Arm y Depo t (TEAD) , Utah . Th e monito rwas compare d t o EP A Referenc e Metho d 2 9 (M29 ) i n 2001 . Th e monito rwa s onl y partl y successful ; severa l improvements were war rante d an d implemented . A second M2 9 field-tes twa s conducte d a yea rlater . Thi s reportinclude s the descriptio n an d result s fro m both M2 9 compariso n test s an d th e modification s tha ttook plac e i n between . Th e XCE M was demonstrate d unde rthi s projectthroug h contract s wit h CE S an d MSE-TA . Th e U.S . Arm y Cente rfo rHealt h Promotio n an d Preventiv e Medicin e (CHPPM ) performe d th e M2 9 stac k samplin g activitie s describe d i n thi s report .



### Mod e o f Technolog y Transfe r
Thi s technolog y wa s developed an d demonstrate d throug h th e ERDC/CER L HA P Program , whic h use s 6. 3 advance d developmentan d field-testing funds . Th e HA PProgra m i s par to f th e Arm y Environmenta l Qualit y Technology (EQT ) Pro gram . A s par to f

th e EQ T process , a technology transfe rpla n i s bein g developed b y th e Arm y Environmenta l Cente r(AEC ) fo rthi s technology as wel l as othe r qualifie d technologie s unde rth e HA Pprogram . A User' s Guid e an d Resource Manua l hav e been develope d t o accompan y th e XCE M fo rfield trainin g an d reference (CE S 2001a , 2001b) . Thi s technology i s read y fo rtransfe rt o Arm y facih ties , an d transitio n has alread y begun . Th e Arm y purchase d anothe rXCE M i n 200 3 fo rus e a tth e 123

6 Tes tDeactivatio n Furnac e a tTEAD . Thi s reportwil l b e made accessibl e throug h th e Worl d Wid e Web at : http://www.cecer.army.mil



### VES01682 2ERDC/CER L TR-05- 9 5



# 2 Fiel d Testin g 200 1

Th e XCE M underwen tM2 9 compariso n testin g a tth e TEA D 123 6 deactivatio n furnac e i n Ma y 2001 . Thi s chapte rpresents a brie f descriptio n ofth e XCEM , th e testin g activities , an d th e result s ofth e testing .


### Brie f Descriptio n o f XCE M
A new XCE M wa

s developed an d buil tfo rdemonstratio n a tth e TEA D facilit y a s describe d i n Ha y etal . (2005) . Th e XCE M extracts a sampl e o f stack ga

s an d concentrate s th e metal s of interes to n a chemicall y treate d filte rtape . Followin g collection , th e filte rtap e i s advance d t o a n analysi s are a where a laboratory grad e XR F instrumen ti s use d t o determin e meta l mass . Th e system i s entirel y automate d an d produce s concentratio n data every 1 0 t o 20 minute s fo ru p t o 19 elements o

f interest . Th e thre e majo rXCE M component s are : a n extractio n sys tem , samplin g an d analysi s system , an d contro l system . Extraction

System
Th e XCE M extractio n syste m collect s a representativ e stac k gas sampl e fro m th e smokestac k an d transports th e sampl e t o th e filter . Th e syste m include s a sam pl e prob e an d insulate d sampl e line . Th e stac k gas temperatur e i s monitore d i n th e sampl e lin e jus tbefor e i tenter s th e enclosure tha thouse s th e XCEM . Th e uni tonl y operates when thi s temperatur e i s abov e th e de

w poin tfo rwater . Upo n enterin g into th e enclosure , th e stac k gas passe s throug h a heat-trace d stillin g chambe rwit h a large rdiamete rtha tslow s th e gas velocit

y (Figur e 1) . Approximatel y 1 percento f th e stac k ga

s tha tenter s th e stillin g chambe ri s sam ple d throug h a n extractio n tub e fo rconcentratio n o n a filter . Th e remainin g 9 9 percen to f

th e ga s i s transporte d ou tof th e stillin g chamber , throug h a flo w me ter , an d vente d orreturne d t o th e stack (

2 t o 3 standar d cubi c fee tpe rminute , SCFM) . A n eductor, locate d downstrea m o f th e stillin g chamber , i s use d t o pul l th e stac k gas throug h th e extractio n system .



### VES01682 36 ERDC/CER L TR-G5- 9

Figur e 1 . XCE M stillin g chambe r(vertica l pipe ) an d samplin g cassett e (bottom) . Sampling

and Analysis

System Approximatel y 0. 8 liter s pe r minut e (Lpm ) i s extracte dan dconcentrate do n a filte r tap e fo r

analysis

. Followin g nitration , th e extracte dstac k ga s i s trans

porte dt o th e XCE M chassi s wher e dryin g an dvolum e determinatio n tak e plac e (Figur e 2)

. Th e samplin g cassett e hold s a4-wee k suppl y o f

filte r tap e o n areel-to-ree l sys te mtha t

i s automate dt o accuratel y mov e th e tap e fro mth e samplin g t o a n analysi s position

. Samplin g an danalysi s occu r simultaneously , resultin g i n a continuou s monitorin g syste mtha t report s meta l concentratio n measurement s ever y 1 0 t o 2 0 minutes

.



### VES01682 4ERDCfCER L TR-05- 9 7

Figur e 2 . XCE M chassis . Meta l mas s o n th e filte r i s determine dusin g amodifie dThermoNora n Quan X energ y dispersiv e XR Fanalyzer

. Th e Quan X i s capabl e o f simultaneousl y meas urin g 1 9 element s an dapalladiu m(Pd ) qualit y assuranc e (QA ) standard

. Al

- thoug h th e Quan X ca n readil y quantif y element s wit h atomi c numbe r 1 3 an d above , th e XCEM-modifie dQuan X i s mos t efficien t

a t quantifyin g an dreportin g hazardou s element s wit h a n atomi c numbe r greate r tha n 2 4 (Cr)

. Sinc e XR Fi s nondestructive , th e retentat e o n th e filte r tap e ca n b e reanalyze di f th e end-use r require s additiona l data

. Control System
Th e XCE M i s controlle db y apersona l compute r usin g acusto mWonderWare " (Progressiv e Softwar e Solutions , Inc. , Albany , OR ) softwar e interfac e (Figur e 3)

. A l l day-to-da y function s o f th e XCE M ar e automated , includin g flo w an dtem

peratur e control , concentratio n determination , an dQ A routines

. Flow , tempera

ture , concentration , pressure , an derro r message s ar e automaticall y recorde di n asecur e database

. Th e dat aca n readil y b e importe dint o Exce l o r a n equivalen t progra mfo r

subsequen t

evaluation

. Flow , temperature , concentration , an dpres sur e measurement s ar e logge di n real-tim e o n th e screen .


### Executio n o f Field-Testin g Activitie s
Befor e shipmen t

t o Tooele , th e XCE M wa s teste dan da n initia l calibratio n wa s completed

. Du e t o atigh t timetabl e fo r

thi s project , afina l calibratio n wa s no t conducte dunti l afte r th e tests
. Tes t

dat awer e modifie daccordin g t o th e final calibration , resultin g i n a n 8 percen t increas e i n reporte dmeta l concentrations

. A l l calibratio n adjustment s wer e complete dprio r t o receivin g M2 9 results

.



### VES01682 58 ERDC/CER L TR-05- 9



## XCE M

sctccnLWocfic-c iLogo n ^ Admi n p : Report

s Trend s 3 Sciccn e^Alarms

' 6fcS{0i

. 10:35: » Se t qf t Range s 1 1 se tqf l Parameter

s j | SetanaloqRanijes j | Loo p Tunin g Figur e 3 . Ne w Componen tContro l Scree n fo rXCE M softwar e interface . Followin g installation , preliminar y onsit e trainin g wa s conducte dfo r TEA D per sonnel

. Onsit e trainin g consiste do f a n introductio n t o th e XCE M an dit s capa bilities

. Althoug h th e XCE M ha s bee n designe dfo r eas e o f

use , i t i s recom mende dtha t

additiona l trainin g b e provide dt o ensur e successfu l integratio n o f th e XCE M int o incinerato r dail y operations

. Test Plan
A tes t pla n wa s develope dt o verif y capabilitie s o f th e XCE M t o measur e metal s unde r typica l incinerato r

condition s (Appendi x A)

. Th e tes t pla n outline dmeth

odolog y fo r

compariso n testin g betwee n EP A M2 9 an dth e XCE M a t th e TEA D incinerator

. Specifically , th e tes t pla n calle dfo r

a t leas t 1 2 EP A M2 9 test s wit h eac h tes t

ru n lastin g 2 hours

. Arseni c (As) , bariu m(Ba) , Cr , cadmiu m(Cd) , nicke l (Ni) , mercur y (Hg) , antimon y (Sb) , an dzin c (Zn ) wer e spike ddurin g th e referenc e metho dtestin g t o ensur e quantifiabl e concentration s o f awid e variet y o f metals

. Lea dwa s als o measure dfo r eac h tes t

bu t wa s no t

spike dbecaus e i t

i s foun di n quantifiabl e concentration s i n TEA D incinerato r emission s unde r

nor ma l operatin g conditions

. Th e actua l date s o f th e test , associate dM2 9 ru n num bers , an dTEA D incineratio n feedstrea mar e show n i n Tabl e 3

.



### VES01682 6ERDC/CER L TR-05- 9 9

I n general , the tes tpla n (Appendi x A ) was followe d a s writte n wit h th e followin g exceptions :

• Th e Arm y chose t o bur n bullet s durin g th e firs ttw o M2 9 test

s rathe rtha n fuse s a s specifie d i n th e tes tplan .
• Th e XCE M observe d hig h level s o f P b durin g th e firsttwo tes truns . Th e TEA D operators believ e tha tth e hig h P b wa s relate d t

o a fault y bypas s valve . Consequently , th e TEA D site manage rdecide d t o ru n M2 9 testin g wit h n o am munitio n bein g incinerate d unti l repair s coul d b e completed . Th e repair s wer e complete d afte rru n 11 .
• A 13t

h M2 9 tes tru n wa

s added .
• Delay s i n completin g a tria l bur n tes tatth e Arm y incinerato rforce d a 2-day postponementi n XCE M testing . T o mak e up fo rlos ttime , fou rM2 9 tes trun s were complete d o n bot h 15 an d 1 6 May . Tabl e 3 . XCE M tes tdate

s an d associate d TEA D incineration feedstream . 1 4 Ma y 1

5 Ma y 1 6 Ma y 1

7 Ma y Ru n 1 Ru

n 2 Ru n 3 Ru n 4 Ru

n 5 Run 6 Ru

n 7 Ru n 8 Ru n 9 Ru n 1 0 Ru n 1 1 Ru n 1 2 Ru n 1 3 5 0 Calibe r 5 0 Calibe r N o Amm o N o Amm o N o Amm o No Amm o N o Amm o N o Amm o N o Amm o N o Amm o N o Amm o MK34

4 Fuses MK34

4 Fuses EPA Verification
Tes tactivitie s wer

e coordinate d wit h EPA' s Environmenta l Technology Verifica tio n (ETV ) program . ETV s charte ri s t o provid e objective an d quality assure d performanc e dat a o n environmenta l technologies , s o tha tusers , developers , regu lators , an d consultants hav e a n independen tan d credibl e assessmen to f a n in strument' s performance . Battell e Memoria l Institute , headquartere d i n Colum bus , OH , i s EPA' s partne rfo rth e ET V Advance d Monitorin g System s (AMS ) Center . Th e scope of th e AM S Cente rcover s verificatio n of

monitorin g method s fo rcontaminants an d natura l specie s i n air , water , an d soil . Fo rthes e tests , ET V representative s reviewe d th e tes tpla n an d monitore d testin g procedures . The y als o conducte d a n onsite audi to f th e Arm y laborator y tha tanalyze d th e M2 9 samples . CE S provide d ET V representative s wit h th e XCE M meta l concen tration s fo reach tes trun . Th e M2 9 tes tresult s wer e submitte d independentl y t o th e ET V representatives . Thes e data , combine d wit h a n evaluatio n of th e qual it y of th e test , have bee n documente d i n a final ET V repor t(Myer s etal . 2002) . TEAD Interface
Th e XCE M sample d th e stac k ga s throug h a prob e an d transpor tline . Ideally , th e prob e woul d hav e bee n shrouded , whic h allow s fo rincrease d flexibilit y i n isokineti c samplin g an d reduce s particulat e los s i n th e probe . However , th e shroude d probes are speciall y manufacture d b y Anderson Instruments , Inc .



### VES01682 71 0 ERDC/CER L TR-05- 9

(Smyrna , GA) , an dprocurin g th e specia l prob e require s significan t lea dtime

. Wit hth e shor t

projec t timeline , amor e easil y buil t custo mprob e wit h asimple r desig n wa s supplie db y Millenniu mInstruments , In c (Sprin g Grove , IL)

. Th e prob e wa s locate da t th e sam e elevatio n a s th e referenc e metho dprobe s withi n 8 6 inche s o f

th e to p o f

th e stack

. Th e XCE M an dM2 9 probe s wer e locate d approximatel y 2 7 fee t abov e th e bas e o f

th e exhaus t

stack

. Th e neares t flo w disturbance s wer e 9. 8 duc t diameter s upstrea m(induce ddraf t fan ) an d4. 3 duc t diameter s downstrea m(to p o f th e stack ) fro mth e sampl e ports
. Thes e distance s ar e adequat e t o ensur e tha t thes e flo w disturbance s d o no t affec t th e sampling

. Th e transpor t

lin e consiste do f

approximatel y 3 5 f t o f 1.5-in

. diamete r

stainles s stee l tubin g tha t

extende dfro mth e prob e t o th e XCE M shed , whic h wa s o n th e groun dnea r

th e stac k

(Figur e 4)

. Test Objectives
Th e overal l objectiv e o f th e tes t

wa s t o provid e quantitativ e verificatio n o f th e performanc e o f

th e XCE M unde r

fiel dconditions

. EPA' s draf t performanc e speci

ficatio n documen t

PS-1 0 (EP A 1996 ) i s apropose ddescriptio n o f ho w t o asses s th e acceptabilit y o f

amulti-meta l CE M upo n installatio n an dthereafter

.

Figur e 4 . XCE M housin g an d transpor tline , M2 9 samplin g setup , stack , an d cerami c baghous e a tTEAD .



### VES01682 8ERDC/CER L TR-05- 9 1 1

Th e goal s of

th e verificatio n tes twere t o mee tth e proposed PS-1 0 requirements for : 1

. Response time an d reporting time fo ra batc h CEM . 2. QA b y passin g dail y zer o an d calibratio n drif

tchecks . 3 . Relative accuracy fo rth e element s i n the feedstream of the TEA D incinerato r(Sb , Ba , Cd , Cr , an d Pb) . Thi s includes evaluatin g the response t o change i n concentratio n by testin g atleas ton e elementa

ttw o concentration levels . A secondar

y objective wa s t

o mee tth e R A criteri a fo radditiona l regulate d an d unregulate d metals , whic h ar e no ttypicall y foun d i n th e feedstrea m (As , Hg , Ni , an d Zn) . Additiona l performanc e parameter s examine d durin g th e testin g included :

• correlatio n wit h referenc e metho d

• precisio n

• low-level meta l respons e

• bias . Th e XCE M ha s a n automate d check fo rcalibratio n drif ttha tmeasure s a P d standar d with each XCE M tes trun . Calibratio n drif twa s als o checke d b y th e automate d dail y XCE M zer o an d upscal e Q A measurements . Fo rth e verificatio n test , respons e tim e was determine d a s th e tim e betwee n th e star to f on e sam plin g perio d an d th e beginnin g of a secon d samplin g period . Th e effectivenes s o f th e XCE M t

o measure lo w concentration s wa s determine d b y a compariso n t o C r an d A s referenc e metho d concentrations . Bia s wa s identifie d usin g EP A Metho d 30 1 - Fiel d Validatio n of Pollutan tMeasuremen tMethod s fro m Variou s Wast e Medi a(EP A 1992) . I twa s beyon d th e scop e of thi s verificatio n tes tt o durabilit y fo rroutin e long ter m use . Thi s tes tevaluate d th e performanc e o f a ne w XCE M ove ra relativel y shor ttes tperiod , operate d b y skille d personnel . I tmus tbe note d tha tth e long ter m performanc e ma y b e differen tfro m tha tobserve d i n th e testin g describe d here . Th e XCE M di d notexhibi tan y mechanica l problem s durin g th e test ; i t complete d more tha n 15 0 tes trun s durin g th e week withou tan y downtime . Site Description
Verificatio n testin g took place a tTEA D buildin g 132 0 deactivatio n incinerato r APE-1236 . Th e TEA D incinerator , whic h run s o n diese l fuel , i s designe d t o in cinerat e decommissione d munitions . Typica l operatin g parameter s fo rth e incin erato rare shown i n Tabl e 4 . Th e TEA D incinerato ri s classifie d a s a dry stack



### VES01682 91 2 ERDC/CER L TR-05- 9

with wate rconten trangin g fro m 5 t o 1 0 percent . Typica l stac k P M concentra tion s ar e i n th e rang e o

f 1 0 microgram s pe rdr y standar d cubi c meter . Th e TEA D incinerato ri s currentl y regulate d unde rth e Resourc e Conservatio n an d Recover

y Ac t(RCRA ) fo rSb , As , Ba , berylliu m (Be) , Cd , Cr , Pb , Hg , Ni , sele niu m (Se) , silve r(Ag) , an d thalliu m (Tl) . O f th e 1 2 regulate d elements , 5 are typicall y foun d i n th e feedstream : Sb , Ba , Cd , Cr , an d Pb . Th e XCE M was teste d fo rits measuremen tcapabilitie s o f th e fiv e elements foun d i n th e feed strea m a s wel l a s As , Hg , Ni , an d a nonregulate d metal , Zn . Thes e element s were selecte d i n orde rt o challeng e th e XCE M overa larg e rang e of analysi s con dition s an d elementa l concentrations . Fo rth e verificatio n test , metal s i n th e TEA D incinerato rstac k gas wer e regu late d unde ra Temporar y Authorizatio n permi t(Tabl e 5) . O f th e 1 2 regulate d metals , P b i s th e onl y elemen ttha twas consistentl y foun d i n measurabl e con centration s i n th e stac k gas . Figur e 5 shows th e deactivatio n incinerato rsetu p an d th e location s fo rsamplin g an d spikin g durin g th e test . Tabl e 4. Typica

l operating parameter

s fo rth e APE-123 6 deactivation furnace . Temp . (°F ) 163 0 Baghous e A P(in . H2O ) 4 Baghous e Inle

tTemperatur e (°F ) 86 0 Kiln Fee d En d Draf

tPressur e (in . H2O

) -0. 2 Kil n Fee d En d Temperatur e (°F ) 37 5 Kil n Burne rEn d Temperatur e (°F ) 1000 0 2 -CEM(% ) 1 5 C O (ppm

) 8 Stac k Temperature (°F ) 50 0 Stac k Ga s Velocit

y (ft/sec ) 4 6
Tabl e 5 . TEA D meta

l emissio n limit

s durin g verificatio n testing . Elemen t Limi

t(g/hr ) Element Limi t(g/hr ) Antimony 1 4 Lea d 4. 3 Arseni c 0.1 1 IVlercur y 1 4 Barium 240 0 Nicke l 93 0 Beryllium 0.2 0 Seleniu m 180 Cadmiu m 0.2 6 Silve r 140 Chromiu m 0.0 4 Thalliu m 1 4



### VES01683 0ERDC/CER L TR-05- 9 1 3

Dischaig e

u 

# i

Cyclon e o

Slack . Fa n

Feed



### To p vie w o f TEA D Incinerato rSetu

p Cerami c Baghous e



### Stac k
Fron tvie

w o f TEA D Stack durin g Samplin g

Fa n Ai r

flo w

XCE M

Figur e 5 . TEA D incinerato rsetu p an d sampling/spikin g locations .



### VES01683 11 4 ERDC/CER L TR-05- 9

Experimental

Design
Bot h th e kil n an d afterburne rwere fire d wit h diese l fue l fo ral l 13 runs . Durin g run s 1 an d 2 , 50-calibe rbullet s wer e incinerated . Th e XCE M observe d unex pecte d hig h P b concentration s durin g thes e runs , however, whic h le d t o a deci sio n no tt

o incinerat e additiona l ammunitio n durin g th e tes tunti l repair s t o a bypas s valv e coul d be made . Fo rthi s reason , n o ammunitio n was burne d durin g run s 3 throug h 11 . Followin g th e bypas s repair , two fina l M2 9 run s were con ducte d whil e incineratin g Mar k 344 fuses . Tabl e 6 show s th e 9 elements tha t were measure d b y th e XCE M durin g al l 1 3 o f th e verificatio n tes truns . Eigh tof thes e metal s were spike d directl y int o th e stac k downstream o f th e controls . Thes e metal s wer

e spike d a tth e leve l show n i n Tabl e 6 . Lead , however , was no t spike d since th e incinerate d munition s provid e measurabl e concentration s of P b withou tspiking . Spikin g wa

s conducte d b y MSE-T A usin g thre e atomizer s t o injec tsolution s con tainin g the metal s directl y int o th e stac k (Figur e 6) . Manufacture rspecification s fo rthe atomizer s determin e drople tsiz e distribution s base d o n pressur e an d air flo w rate . Fo rthes e tests , pressur e an d flo w rate wer e maintaine d t

o kee p drop le tsize s les s tha n 2 8 micron s i n diameter . Whe n dried , th e majorit y of th e parti cl e mas s wa

s calculate d t

o b e i n th e 1 t

o 4 micron diamete rrange . A n analysi s o f th e M2 9 concentratio n dat a durin g validatio n testin g indicate d tha t10 t o 1 5 per cen to f th e spike d meta l mas s wa s los to n th e prob e (CHPP M 2001) . Thi s leve l o f prob e los s i s typica l fo rM2 9 ata n incinerato rand , since particulat e los s i n th e prob e depends i n par to n particl e size , indicate s tha tth e spike d meta l particl e siz e wa s on th e sam e orde ras a typica l incinerator . Table 6. TEA D incinerato rmeta l emissio n limit

s an d spikin g levels .

Element s Emissio n Limits 1 Spikin g Level 1 Element s g/h

r - Mg/dsc

m - ug/dsc m Element s g/h

r - Mg/dsc

m Run s 1-

6 Run s 7-1

3 A s 0.1 1 2 5 1 4 1 4 B a 2,40 0 540,00 0 20 0 20 0 C d 0.2 6 5 8 3 4 34 C r 0.04 1 0 5 5 H g 1 4 3,14 5 28 0 8 8 N i 93 0 209,00 0 46 0 18 0 P b 4. 3 96 6 N S N S S b 1 4 314 5 52 0 20 0 Z n N R N R 46 0 180

1 Th e concentratio

n i n pg/dsc m assumes a stac

k flo w rat e o f abou t450 0 dscm/h

r NR : No tregulate d NS : No

tspike d



### VES01683 2ERDC/CER L TR-05- 9 1 5

Figur e 6 . Spikin g a

tbas e o f

stac k durin g validatio n testing . Thre e separat e solution s wer e prepare dfo r spik e injection

. Th e firs t solutio n containe darseni c oxid e (As 2 0 5 ) , C dmetal , an dchromiu moxid e (Cr0 3 ) dissolve d i nadilut e nitri c aci dsolution

. Th e secon dsolutio n containe dmercur y nitrat e (Hg(NO : J ) 2 ) , nicke l nitrat e (Ni(N0 3 ) 2 ) , an dzin c oxid e (ZnO ) dissolve di n adilut e nitri c acid

. Th e fina l solutio n containe dantimon y tartrat e (K,,(C,H 2 0 B Sb)„ ) an d bariu mnitrat e (Ba(N0 3 ) 2 ) dissolve di n wate r (Bryso n 2001)

. A tota l o f

1 3 dua l M2 9 tes t

run s wer e performe dove r a4-da y perio d(14-1 7 May ) b y th e U.S

. Arm y CHPP M Ai r Qualit y Surveillanc e Program

. Th e M2 9 train s sample dfo r

2 h r whil e XCE M dat awer e recorde dever y 2 0 minute s an dwer e average dfo r

compariso n t o eac h M2 9 tes t run . A s aperformanc e audit , tw o blan k train s wer e quantitativel y spike dwit h al l nin e o f th e metals

. CHPPM' s Directorat e o f Laborator y Service s (DLS ) conducte dlaborator y analy

si s o f th e samplin g trains

.


### Result s XCEM Reported

Concentrations Time-weighte d averag e concentration s Averag e XCE M concentration s durin g th e tim e o f on e M2 9 tes t

ru n wer e calcu

late dusin g Equatio n 1

.



### VES01683 31 6 ERDC/CER L TR-05- 9

where : C ; = XCE M time-weighte d concentratio n fo relemen ti durin g M2 9 tes tru n C ^ = XCE M reporte d concentratio n fo relemen ti durin g tim e interva l j n = numbe rof

XCE M measurement s durin g tes tru n t = numbe ro

f minute s XCE M measure d elemen ti' s concentratio n durin g tim e interva l

j coincidin g wit h M2 9 sampling . i = M2 9 samplin g period .

Dat a correction s Followin g M2 9 testing , bu tprio rto receivin g M2 9 results , CE S recalibrate d th e XCE M an d determine d tha ta 4. 4 percen tgloba l chang e was require d fo rXCE M reporte d concentrations . I n additio n t o th e recalibration , CE S conducte d exten siv e testin g o f

th e sampl e lin e drye ran d determine d tha ta 3. 5 percen tcorrectio n i n flo w was require d sinc e th e drye rdi d notremov e al l of th e moistur e i n th e line . Th e ne tresul to f thes e change s wa s t o uniforml y increas e th e reporte d XCE M concentration s b y about8 percent . Appendi x B include s a complet e dis cussio n o f

thes e changes . I n additio n t

o th e global changes , i twas determine d tha ta spectra l interferenc e betwee n P b an d A s wa s affectin g A s concentrations . Fo rthi s reason , A s concen tration s were correcte d fo rth e P b interferenc e as discusse d i n Respons e t o Change s i n Meta l Concentratio n (pag e 25) . Arseni c correction s were com plete d prio rt

o receivin g M2 9 data . Th e fina l reporte d XCE M concentration s are liste d i n Tabl e 7. Approximatel y si x t o seve n XCE M measuremen ttoo k plac e durin g eac h M2 9 run . Th e "Min . o f Run " colum n i n Tabl e 7 refer s t o th e numbe ro f minute s fo rtha tparticula r XCE M (liste d a s X C i n th e table ) measuremen ttha tcoincide d wit h th e M2 9 run .



### VES01683 4ERDC/CER L TR-05- 9 1 7

Tabl e 7 . Final reported CE M concentrations (pg/dscm ) fo rM2 9 testing . R M No. Dat

e Star

t Sto p X C No . Min . o f Ru n X C Tim e As B a C d C r H g Ni P b S b Z n P d Ru n 1 5/14/0

1 10:4

5 11:0 5 65 0 5. 0 19:48.

0 20. 8 16 6 27. 7 3. 1 5 9 34 3 1,10 2 34 0 29 7 24. 1 Run l 5/14/0

1 11:0

5 11:2 6 65 1 21. 2 21:12.

0 24. 3 17 1 26. 0 2. 5 10 9 43 6 1,12 7 37 2 31 6 23.8 Ru n 1 5/14/0

1 11:2

6 11:4 8 65 2 21. 5 21:32.

0 21. 1 19 2 26. 5 1. 9 15 6 46 7 1,14 9 36 1 32 0 25.6 Ru n I 5/14/0

1 11:4

8 12:0 9 65 3 21. 7 21:42.

0 20. 7 16 5 21. 8 2. 2 20 7 44 9 1,19 6 35 3 31 6 25.5 Ru n 1 5/14/0

1 12:1

0 12:3 1 65 4 21. 7 21:41.

0 25. 3 18 7 28. 2 2. 6 24 2 47 0 1,31 9 37 7 34 2 24. 6 Ru n 1 5/14/0

1 12:3

1 12:5 3 65 5 21. 9 21:51.

0 21. 5 21 8 31. 8 2. 2 25 7 51 5 1,60 7 39 9 37 2 25.4 Ru n 1 5/14/0

1 12:5

3 13:1 5 65 6 7. 0 22:07.

0 23. 8 20 2 27. 2 2. 4 28 3 46 3 70 9 38 6 34 8 24. 2 TimeW eighte

d Avg . 120. 0 21:24.

7 22. 6 18 7 26. 9 23 19

4 46 2 1,24 0 37 2 33 3 Ru n 2 5/14/0

1 13:5

8 14:2 3 65 9 18. 3 25:09.

0 7. 3 23 0 26. 8 2. 3 18 6 37 5 3,42 2 36 0 29 9 25.6 Ru n 2 5/14/0

1 14:2

3 14:4 6 66 0 22. 9 22:56.

0 3. 5 22 4 29. 5 2. 0 23 4 42 7 3,24 8 37 9 34 5 24. 7 Ru n 2 5/14/0

1 14:4

6 15:0 9 66 1 22. 9 22:56.

0 13. 0 24 9 26. 0 1. 2 24 4 42 7 3,01 7 39 8 35 2 25. 1 Ru n 2 5/14/0

1 15:0

9 15:3 2 66 2 22. 9 22:54.

0 23. 8 25 0 22. 3 2. 0 22 0 40 5 2,68 3 37 0 33 2 25. 3 Ru n 2 5/14/0

1 15:3

2 15:5 5 66 3 22. 6 22:36.

0 31. 5 19 4 29. 1 1. 2 23 9 41 5 2,34 7 37 9 34 7 25. 2 Ru n 2 5/14/0

1 15:5

5 16:1 7 66 4 10. 3 22:34.

0 17. 8 17 2 27. 1 2. 6 25 7 39 2 18 2 34 8 31 9 24. 4 Time W eighte d Av g 120. 0 23:10.

8 16. 3 22 4 26. 8 1. 8 22 9 41 0 2,69 0 37 5 33 5 Ru n 3 5/14/0

1 17:0

0 17:2 3 66 7 16. 0 22:45,

0 15. 3 12 7 25. 4 3. 4 25 9 39 5 11 8 33 4 32 0 24. 6 Ru n 3 5/14/0

1 17:2

3 17:4 4 66 8 21. 0 21:00.

0 13. 1 14 0 21. 3 2. 2 26 4 38 8 9 1 33 5 31 9 25. 2 Ru n 3 5/14/0 ! 17:4

4 18:0 5 66 9 20. 9 20:52.

0 13. 0 15 8 27. 0 2. 5 26 5 41 7 6 0 35 5 34 1 25.4 Ru n 3 5/14/0

1 18:0

5 18:2 6 67 0 21. 0 20:58.

0 13. 1 17 5 28. 9 2. 9 26 8 40 9 5 5 36 3 33 9 25. 7 Ru n 3 5/14/0

1 18:2

6 18:4 7 67 1 20. 9 20:53.

0 14. 2 16 8 21. 4 2. 4 25 5 41 3 6 0 35 2 33 3 24. 6 Ru n 3 5/14/0

1 18:4

7 19:0 7 67 2 20. 3 20:54.

0 11. 2 14 7 24. 0 2. 3 24 9 41 4 6 5 36 0 34 7 25. 9 Tim e Weighte

d Av g 120. 0 21:13.

7 13. 2 15 4 24. 6 2. 6 26 0 40 6 7 3 35 1 33 4 Ru n 4 5/15/0

1 8:5

9 9:1 8 68 4 3. 3 19:43.

0 13. 2 14 5 21. 5 4. 5 3 3 29 4 6 9 27 1 23 5 25. 0 Ru n 4 5/15/0

1 9:1

8 9:3 9 68 5 20. 6 20:34.

0 15. 0 17 3 28. 5 6. 2 5 4 40 1 6 9 33 3 31 9 23.4 Ru n 4 5/15/0

1 9:3 9 10:0

0 68 6 20. 9 20:55.

0 15. 6 13 3 33. 2 5. 4 6 9 43 2 6 6 36 2 34 9 24.7 Ru n 4 5/15/0

1 10:0

0 10:2 1 68 7 21. 0 21:00.

0 16. 2 15 4 30. 5 5. 3 8 0 43 2 6 4 37 1 34 8 23. 7 Ru n 4 5/15/0

1 10:2

1 10:4 2 68 8 21. 0 20:58.

0 16. 6 19 1 32. 1 5. 0 8 4 43 3 6 4 37 8 34 4 25. 1 Ru n 4 5/15/0

1 10:4

2 11:0 3 68 9 21. 0 20:57.

0 15. 2 14 5 26. 6 5. 2 8 5 41 8 5 5 36 1 33 9 24.2 Ru n 4 5/15/0

1 11:0

3 11:2 4 69 0 12. 3 20:51.

0 17. 4 18 3 28. 5 5. 5 9 8 44 6 4 5 38 0 36 6 25. 0 TimeW eighte

d Avg . 120. 0 20:42.

6 15. 8 16 1 29. 8 5. 4 7 6 42 2 6 2 36 1 34 0 Ru n 5 5/15/0

1 12:0

6 12:2 7 69 3 15. 6 20:55.

0 18. 0 17 7 31. 4 5. 5 9 3 44 0 4 9 38 3 35 5 24. 7 Ru n 5 5/15/0

1 12:2

7 12:4 8 69 4 20. 9 20:52.

0 16. 2 17 2 33. 7 5. 5 9 7 43 0 5 4 37 1 34 8 24. 3 Run 5 5/15/0

1 12:4

8 13:0 9 69 5 20. 9 20:51.

0 16. 0 15 3 34. 4 6. 1 10 2 41 7 5 2 36 2 33 9 23. 3 Ru n 5 5/15/0

1 13:0

9 13:3 0 69 6 20. 8 20:48.

0 17. 3 18 2 33. 4 5. 3 11 4 45 0 4 7 38 6 36 0 24. 6 Ru n 5 5/15/0

1 13:3

0 13:5 1 69 7 21. 0 20:57.

0 14. 3 18 5 35. 8 5. 7 12 2 44 9 4 5 39 3 36 5 25. 7 Ru n 5 5/15/0

1 13:5

1 14:1 2 69 8 21. 0 20:59.

0 17. 0 18 1 32. 2 5. 4 12 9 44 3 3 8 39 0 35 8 25.2 Time W eighte d Avg . 120. 0 20:53.

7 16. 4 17 5 33. 6 5. 6 11 0 43 8 4 7 38 1 35 4 Ru n 6 5/15/0

1 14:5

4 15:1 5 70 1 7. 2 20:57.

0 17. 8 16 6 31. 4 5. 4 13 7 45 5 3 9 39 2 37 6 25. 6 Ru n 6 5/15/0

1 15:1

5 15:3 6 70 2 21. 0 20:59.

0 15. 5 15 2 31. 9 5. 4 14 6 46 5 3 9 38 6 37 9 24. 9 Ru n 6 5/15/0

1 15:3

6 15:5 7 70 3 21. 0 20:58.

0 12. 4 16 7 31. 4 5. 4 14 2 44 3 4 8 38 7 36 2 24. 4 Ru n 6 5/15/0

1 15:5

7 16:1 8 70 4 20. 9 20:56.

0 12. 9 16 5 31. 3 5. 9 14 0 43 0 4 7 37 2 35 0 26. 2 Ru n 6 5/15/0

1 16:1

8 16:3 9 70 5 20. 9 20:54.

0 14. 0 18 7 34. 1 5. 3 16 8 42 7 3 6 38 1 35 3 24.9 Ru n 6 5/15/0

1 16:3

9 17:0 0 70 6 20. 9 20:55.

0 15. 2 18 5 32. 9 5. 5 16 4 44 2 3 5 38 9 36 3 24. 5 Ri m 6 5/15/0

1 17:0

0 17:2 1 70 7 8. 2 20:58.

0 13. 7 16 4 36. 7 6. 2 16 6 46 2 4 6 38 7 36 9 25.0 Time W eighte d Avg 120. 0 20:56.

7 14. 2 17 0 32. 6 5. 6 15 2 44 3 4 1 38 4 36 3 Ru n 7 5/15/0

1 18:0

3 18:2 4 71 0 18. 1 20:55.

0 16. 9 18 3 35. 6 5. 8 15 4 47 7 4 5 39 6 38 6 24.9 Ru n 7 5/15/0

1 18:2

4 18:4 5 71 1 21. 0 20:58.

0 18. 5 16 6 34. 5 6. 4 13 4 47 8 4 4 40 4 39 5 24. 2 Ru n 7 5/15/0

1 18:4

5 19:0 6 71 2 21. 0 20:58.

0 16. 5 19 1 28. 8 6. 0 12 0 49 1 4 5 37 7 37 7 25. 3 Ru n 7 5/15/0

1 19:0

6 19:2 7 71 3 21. 0 20:59.

0 16. 1 16 8 30. 9 5. 6 12 1 45 9 4 0 37 5 35 9 25. 3 Ru n 7 5/15/0

1 19:2

7 19:4 8 71 4 20. 8 20:50.

0 16. 2 17 5 30. 7 5. 7 13 2 41 9 3 4 36 7 33 7 25.9 Ru n 7 5/15/0

1 19:4

8 20:0 9 71 5 18. 1 20:41.

0 15. 1 15 9 33. 3 5. 5 13 7 43 6 3 0 37 9 35 1 24. 3 Tim e Weighte

d Avg . 120. 0 20:53.

5 16. 6 17 4 32. 2 5. 8 13 2 46 1 4 0 38 3 36 7



### VES01683 51 8 ERDC/CER L TR-05- 9

Tabl e 7 (Cont'd) . Fina

l reporte d XCE M concentration s (pg/dscm ) fo rM2 9 testing . R M No. Dat

e Star

t Sto p X C No . Min . o f Ru n X C Tim e As B a C d C r H g Ni P b S b Zn Pd Ru n 8 Ru n 8 Ru n 8 Ru n 8 Ru n 8 Ru n 8 Ru n 8 5/16/0

1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 8:5 8 9:1 8 9:3 9 10:0 0 10:2 0 10:4 1 11:0 1 9:1 8 9:3 9 10:0 0 10:2 0 10:4 1 11:0 1 11:2 2 72 5 72 6 72 7 72 8 72 9 73 0 73 1 15. 3 20. 6 20. 6 20. 6 20. 4 20. 4 2. 3 20:24.

0 20:33. 0 20:33. 0 20.33. 0 20:26. 0 20:24. 0 20:30. 0 17. 6 20. 3 16. 5 18. 0 12. 5 18. 7 17. 1 11 1 13 9 14 5 15 6 17 6 15 2 16 2 32. 5 31. 8 32. 3 29. 4 36. 3 32. 7 32. 4 5. 2 6. 0 5. 4 5. 3 5. 1 5. 7 5. 7 1 7 2 0 2 2 2 8 3 3 3 6 4 4 19 3 22 0 22 2 19 7 20 4 21 6 22 6 29 0 24 2 23 1 19 9 20 2 22 6 21 4 14 1 13 4 12 5 13 6 13 5 13 4 14 1 13 4 15 0 15 1 14 8 14 1 15 0 15 0 23. 8 24. 2 25.6 24.6 24. 4 24. 3 23.9 TimeW eighte

d Avg . 120. 0 20:29.

0 17. 3 14 8 32. 5 5. 4 2 7 21 0 22 9 13 4 14 6 Ru n 9 Ru n 9 Ru n 9 Ru n 9 Ru n 9 Ru n 9 Run 9 5/16/0

1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 11:4

2 12:0 3 12:2 3 12:4 4 13:0 4 13:2 5 13:4 5 12:0 3 12:2 3 12:4 4 13:0 4 13:2 5 13:4 5 14:0 5 73 3 73 4 73 5 73 6 73 7 73 8 73 9 7. 1 20. 4 20. 4 20. 3 20. 4 20. 3 11. 1 20:28.

0 20:26. 0 20:21. 0 20:18. 0 20:24. 0 20:19. 0 20:23. 0 21. 1 14. 8 18. 8 16. 6 17. 0 18. 6 16. 0 18 3 17 0 15 4 20 6 14 3 13 8 15 1 33. 1 32. 7 30. 7 35. 4 31. 1 28. 8 29. 1 4. 5 5. 6 5. 3 6. 5 5. 2 5. 2 5. 2 4 9 5 0 4 9 5 6 5 4 5 9 6 0 21 0 20 1 20 4 22 3 21 5 20 0 22 8 19 0 17 0 16 2 19 1 15 1 15 3 15 5 13 6 13 9 14 2 15 4 14 5 14 5 14 8 14 7 14 2 14 6 15 2 14 5 14 4 14 3 25.0 24.0 24. 1 24.9 24. 7 24. 5 25. 1 TimeW eighte

d Av g 120. 0 20:22.

7 17. 3 16 2 31. 6 5. 5 5 4 21 0 16 6 14 5 14 6 Ru n 1 0 Ru n 1 0 Ru n 1 0 Ru n 1 0 Ru n 1 0 Ru n 1 0 Ru n 1 0 5/16/0

1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 14:4

6 15:0 7 15:2 7 15:4 8 16:0 8 16:2 9 16:4 9 15:0 7 15:2 7 15:4 8 16:0 8 16:2 8 16:4 9 17:0 9 74 2 74 3 74 4 74 5 74 6 74 7 74 8 17. 2 20. 4 20. 4 20. 3 20. 4 20. 3 1. 2 20:24.

0 20:21. 0 20:23. 0 20:16. 0 20:21. 0 20:20. 0 20:20. 0 19. 2 22. 3 17. 0 17. 1 17. 5 18. 3 12. 7 15 6 18 7 14 1 19 2 16 1 16 7 13 9 34. 7 37. 0 32. 5 31. 6 36. 2 30. 9 29. 9 6. 0 5. 4 5. 4 5. 4 5. 5 5. 6 5. 4 9 1 8 9 8 2 9 1 9 5 9 5 10 9 21 0 21 6 19 2 20 8 20 8 20 3 18 6 14 6 26 1 11 5 13 4 10 8 9 5 11 0 14 8 15 4 13 4 14 6 16 3 14 0 15 2 14 6 15 1 13 3 14 9 14 5 13 7 13 7 25.2 25. 6 24.9 25. 6 24. 2 24. 7 24.5 TimeW eighte

d Av g 120. 0 20:20.

7 18. S 16 7 33. 8 5. 5 9 1 20 6 14 3 14 7 14 3 Ru n 1 1 Ru n 1 1 Ru n 1 1 Ru n 1 1 Ru n 1 1 Ru n 1 1 Ru n 1 1 5/16/0

1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 5/16/0 1 17:3

2 17:5 2 18:1 2 18:3 3 18:5 3 19:1 3 19:3 4 17:5 2 18:1 2 18:3 3 18:5 3 19:1 3 19:3 4 19:5 4 75 0 75 1 75 2 75 3 75 4 75 5 75 6 6. 3 20. 3 20. 3 20. 3 20. 2 20. 2 12. 3 20:21.

0 20:18. 0 20:20. 0 20:18. 0 20:12. 0 20:12. 0 20:17. 0 15. 7 15. 8 15. 5 16. 4 17. 3 17. 2 15. 0 17 8 14 7 17 0 17 8 15 2 16 7 15 2 31. 3 30. 2 29. 3 30. 2 26. 4 32. 8 33. 2 6. 0 5. 2 5. 3 5. 4 5. 8 5. 5 4. 6 10 1 9 6 9 5 9 5 9 6 9 2 8 4 211 20 9 20 4 19 2 19 1 20 1 21 2 10 8 10 2 10 4 9 1 8 9 8 9 9 6 15 0 14 7 14 1 14 7 14 7 14 3 14 7 14 3 14 1 14 5 13 8 14 1 14 6 14 5 25. 0 25. 5 24.6 25. 6 24.8 24. 9 24. 0 TimeW eighte

d Av g 120. 0 20:16.

9 16. 2 16 3 30. 2 5. 4 9 4 20 1 9 6 14 5 14 3 Ru n 1 2 Ru n 1 2 Ru n 1 2 Ru n 1 2 Ru n 1 2 Ru n 1 2 Ru n 1 2 5/17/0

1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 11:1

2 11:3 2 11:5 2 12:1 2 12:3 2 12:5 3 13:1 3 11:3 2 11:5 2 12:1 2 12:3 2 12:5 3 13:1 3 13:3 3 77 0 77 1 77 2 77 3 77 4 77 5 77 6 13. 0 20. 1 20. 2 20. 3 20. 2 20. 2 6. 0 20:01.

0 20:08. 0 20:14. 0 20:16. 0 20:12. 0 20:12. 0 20:07. 0 17. 8 17. 2 20. 5 16. 7 18. 4 12. 3 14. 1 17 4 19 5 17 4 22 6 15 3 17 7 15 0 26. 5 23. 2 30. 5 24. 4 31. 7 28. 0 28. 2 4. 1 4. 2 4 3 4. 0 4. 8 4. 5 4. 1 2 4 3 5 5 5 7 3 7 9 8 3 8 6 22 4 23 8 22 2 22 1 20 6 20 4 19 1 17 0 23 2 27 3 20 4 16 1 13 8 14 0 13 7 15 9 16 5 15 8 15 8 15 5 15 5 13 3 14 6 15 7 16 1 15 1 14 3 15 1 24. 6 25. 9 25. 3 25.4 24. 1 24.4 26.0 Tim e W eighte

d Avg . 120. 0 20:10.

0 17. 0 18 2 27. 5 4 3 6

2 21 8 19 5 15 6 15 0 Run B Run B Run B Ru n 1 3 Run B Run B Run B 5/17/0

1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 5/17/0 1 14:1

4 14:3 4 14:5 4 15:1 4 15:3 5 15:5 5 16:1 5 14:3 4 14:5 4 15:1 4 15:3 4 15:5 5 16:1 5 16:3 5 77 9 78 0 78 1 78 2 78 3 78 4 78 5 6. 1 20. 2 20. 2 20. 2 20. 2 20. 0 13. 1 20:15.

0 20:10. 0 20:09. 0 20:10. 0 20:12. 0 20:02. 0 19:57. 0 19. 1 19. 9 17. 4 20. 3 21. 3 19. 2 8. 3 16 2 21 0 15 9 14 0 19 6 16 5 9 4 35. 9 33. 9 36. 1 33. 8 40. 7 39. 1 18. 7 5. 1 5. 3 6. 1 5. 8 5. 9 6. 0 4. 0 8 0 8 0 8 2 8 3 8 4 7 4 4 6 20 1 21 3 23 5 21 2 17 3 17 0 7 0 11 9 12 2 11 7 11 2 12 9 12 1 8 5 17 1 17 0 16 8 17 0 16 9 16 6 7 7 14 6 14 6 14 9 15 0 11 7 8 2 2 2 24.0 25. 3 25.0 25. 1 24. 4 25. 1 25. 2 Tim e Weighte

d Avg. 120. 0 20:07.

9 18. 4 16 5 34. 7 5. 6 7 7 18 6 11 6 15 9 11 8



### VES01683 6ERDC/CER L TR-05-9 1 9

Sampling

and Response

Time
Th e XCE M metPS-1 0 samplin g an d respons e tim e criteria fo ra batc h CEM . Thes e criteri a ar e tha t(1 ) th e samplin g tim e b e n o longe rtha n one-thir d ofth e averagin g perio d fo rth e applicabl e standard , (2 ) th e delay betwee n th e en d of th e samplin g perio d an d reportin g o f th e sampl e analysi s shal l b e n o greate r tha n 1 hour , an d (3

) samplin g i s t

o b e continuou s excep ti n tha tth e paus e i n samplin g whe n sampl e collectio n medi a ar e change d shoul d b e n o greate rtha n 5 percen tfo rth e averagin g perio d o r5 minutes , whicheve ri s les s (EP A 1996) . Exhibitin g no mechanica l problems , th e XCE M ha d a n effectiv e up-tim e of 10 0 percen tdurin g th e 40 hour s of verificatio n testing . Th e XCE M sample d continu ousl y exceptfo ra 4-second perio d betwee n eac h 20-minute sampl e ru n whe n th e filtertap e was move d t o a new analysi s position . XCE M result s ar e reporte d immediatel y afte reach 20-minute analysi s resultin g i n a 20-minute respons e tim e between th e en d of samplin g an d reporting . Zer o and

Calibration

Drift
Th e XCE M ha s automate d dail y zer o an d upscal e check s an d reports a P d con centratio n wit h each sampl e t o tes tfo rcalibratio n drift . T o determin e th e zer

o check , th e XCE M measure s a n unexpose d regio n ofth e filtertape . Followin g th e zero check , a plunge ri s extende d int o th e analysi s region . Th e ti p o f th e plunge r contain s Cr , Cd , Hg , an d P b embedde d i n a resin . Analysi s o f thi s spike d resi n provide s a n upscal e check fo rth e XCEM . Zer o an d upscal e checks were conducte d o n eac h of th e fou rtes tday s wit h th e result s shown i n Tabl e 8 . Sinc e th e zero an d upscal e checks ar e evaluation s o f mas s measurements , the y ar e reporte d a s mas s pe runi tare a o n th e filter (ug/spot) . Equivalen tzer o an d upscal e concentration s i n microgram s pe rdry standar d cubi c mete rar e als o show n i n Tabl e 8 an d reflec tth e typica l samplin g rat e o f 1 6 L pe rspot. Zer o value s determine d durin g th e TEA D tes tindicat e n o measurabl e blan k bia s i n th e mas s measurement . Th e XCE M detectio n limit s fo rCr , Cd , Hg , an d P b ar e 0.75 , 3.0 , 1.0

, an d 1. 0 pg/dscm , respectively . Th e XCE M zer o value s wer e be lo w th e detectio n limit s fo rCd , Hg , an d P b an d onl y slightl y highe rtha n th e C r detectio n limit . Th e upscal e chec

k indicate d goo d precisio n fo rth e hig h concentratio n mas s measurements . Th e precisio n ove rth e 4 day s was les s tha n 1 percen tfo rCd , Hg , an d P b an d about2. 3 percen tfo rth e Cr .



### VES01683 72 0 ERDC/CER L TR-05- 9

Tabl e 8. Upscal e and zero concentrations during validation testing . Dat e Upscal e Values (pg ) Zero Values (ug) 1 Dat e C r C d H g P

b C r C d H g P

b 5/14/0 1 5.2 3 156 27. 6 30. 4 0.01 2 0.04 6 0.00 8 0.00 8 5/15/0 1 5.5 3 15 8 28. 0 30. 9 0.01 6 0.04 2 0.00 8 0.00 8 5/16/0 1 5.4 5 156 27. 9 30. 8 0.01 4 0 02 4 0.01 0 0.00 8 5/17/0 1 5.4 2 15 6 27. 9 30. 6 0.01 1 0.02 4 0.00 5 0.02 3 Avg . 5.4 1 15 7 27. 8 30. 7 0.01 3 0.03 4 0.00 8 0.01 2 S D 0.1 3 0.74 0.1 8 0.23 %RS D 2.3 3 0.4 7 0.6 5 0.7 6

Dat e Equiv. Upscal e Value s (ug/dscm) 2 Equiv . Zero Values (pg/dscm) 1,2 Dat e C r C d H g P

b C r C d H g P

b 5/14/0 1 32 7 9,76 5 1,72 4 1,898 0.7 5 2.8 6 0.5 0 0.47 5/15/0 1 34 6 9,85 0 1,75 0 1,93 1 1.0 1 2.6 5 0.5 0 0.5 0 5/16/0 1 34 1 9,77 2 1,74 2 1,925 0.8 5 1.5 0 0.6 3 0.5 0 5/17/0 1 33 9 9,74 4 1,746 1,91 2 0.6 7 1.50 0.2 9 1.4 2 Avg . 33 8 9,78 3 1,74 1 1,91 7 0.82 2.1 3 0.4 8 0.72 S D 7.8 8 46.1 4 11.2 5 14.6 4 %RS D 2.3 3 0.47 0.6 5 0.7 6 1 ) Gra y value s were nondetects . Nondetec ttreate d a s one-hal f of Detectio n Limit. 2 ) Equivalen tconcentration s determine d usin g 1 6 liters pe rsample . S D = standar d deviation ; RS D = relative standar d deviatio n Palladium , whic h i s measure d wit h every sample , als o displaye d good precisio n overth e 4 day s of

testin g (Figur e 7) . Overall , th e P d concentratio n ha d a preci sio n o f abou t2.5 percentwit h al l 11 3 measure d P d concentration s lyin g withi n 6 percen to

f th e average concentration . Analysi s o f th e P d concentratio n tren d i n Figur e 7 indicate s tha tn o significan tdrif

toccurred . Ove rth e 4-da y tes tperiod , th e average P d concentratio n change d b y les s tha n 1 percen twit h n o observabl e trendin g occurring . Correlation

with Reference

Method
Th e compariso n between th e XCE M an d M2 9 concentratio n measurements ar e shown i n Figur e 8 . I n thi s figur e th e dashe s represen tth e M2 9 concentratio n overth e samplin g period , whil e th e diamond s represen tth e individua l XCE M measurements . Th e degre e o f correlatio n betwee n th e XCE M an d M2 9 i s show n i n Figur e 9 an d Tabl e 9 . Fiv e metal s (Ni , Pb , Sb , Zn , an d Hg ) were presen ti n th e stac k ga

s a tvaryin g concentrations . O f thes e elements , Ni , Sb , an d Z n showed correlation s o f 0.9 5 o rbetter . Lea d shows a hig h correlatio n of 0.99 7 fo r al l 13 runs , bu ta correlatio n of 0.76 fo rth e 1 1 run s i n whic h P b concentration s wer e use d fo rR A comparisons . Mercur y di d no tshow a hig h correlatio n betwee n th e two methods .



### VES01683 8ERDC/CER L TR-05- 9 2 1



### Palladiu m 3 0 |

- - - 1 2 9 | j 2 8 j

~ > 2 7i
2 £ 2 5 - mm m miMwyiii— I I mi l IIII I 'ivTimnim f nihility— M fiiip t r»rT»»»Mmy ^uiiiiL»i M mmm^^^^ ||if " nin m 

## i 2 5 

## ! .-t&6

2 3 j 2 2 • ! 2 1 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1 |
7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0

— —Averag e Palladiu mEffectiv e Concentratio n

— — —On e S D fro mAvg

. P dConcentratio n

— —5 % fro mAvg

. P dConcentratio n Figur e 7 . Palladiu m concentration s durin g M2 9 testing . Unlik e th e othe r

elements , th e XCE M H g concentration s wer e consistentl y lowe r tha n M29 , bu t

b y avariabl e amount
. Durin g th e earl y run s fo r eac h day , th e XCE M reporte dlo w concentration s relativ e t o M29

. A s th e da y progressed , th e XCE M H g concentratio n woul dgraduall y increas e unti l i t approximate dM2 9 reporte dconcentrations

. Thi s sam e increasin g H g concentratio n tren dwa s ob

serve do n eac h o f

th e fou r

tes t day s (Figur e 8)

. I t i s believe dtha t

th e H g wa s los t

durin g transpor t

fro mth e stac k

t o th e XCEM

. Th e M2 9 sample s wer e collecte dnex t t o th e stac k

an dwer e no t

transporte d throug h alon g sampl e lin e a s th e XCE M sample s were . Th e TEA D incinerato r wa s shu t

dow n eac h evenin g an dstarte di n th e mornin g 1 hou r befor e validatio n testing

. Consequently , th e transpor t line , whic h wa s insulate dbu t no t heat

traced , wa s coole r

durin g th e earl y runs . Som e researc h indicate s tha t H g ca n b e los t t o astainles s stee l surfac e a t lo w temperature s (Hal l e t al

. 1990 ; Wan g e t

al

. 1983)

. I n th e laboratory , th e XCE M wa s teste dwit h oxidize dH g an dme t wit h goo dsucces s (Ha y e t

al

. 2005)

. Th e laborator y tests , however , wer e conducte da t elevate dlin e temperatures
. I t i s recommende dtha t ashroude dprob e an dheat

trace dtubin g b e use dt o overcom e potentia l H g transpor t problems

.



### VES01683 92 2 ERDC/CER L TR-05- 9

Cadmiu m 4 5 • - - 41 ) • - - V

s ; „ I • * *** * * « * * . ii s i U10 l --- - - - ^ —- *

5 1 • o I • • A . 7:0 0 [5:0( 1 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1 Chromiu m 8 -- - : - - 

## i f l 

## TV^ r T^j^^

i~Di ^ eseass ; «s » w * * * •

; j 3 • ** > •

' 1 * " ? » 0 , * , , , , 7:0 0 IS:W ) 23:0 0 7:0( 1 15:0 0 23:01 1 7:0( 1 15:0 0 23:0 0 7(1 0 1 vO O 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1 Nicke l 60 0 -
„ 50 0 * , j l 30 0 * *

0 - » • - * — - ----

- 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:01 ) 23:0( 1 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/01 5/17/0 1 Lea d 4,000 ---- - - - 3,50 0 «

_wjm r £3.00 0 • | 2,50 0 * J 2,00 0 H I 50 0 (j 1,00 0 -

- - - ----

- - - -

7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1 Figur e 8 . XCE M an d M29 concentration s durin g TEA D verificatio n testing .



### VES01684 0ERDC/CER L TR-05- 9 2 3

Lea d (Run s 3-13)

—40 0 - 

## I

^ 30 0 j 5 *

. J 20 0 : ' c • ° »
o • • 

# ; •

.15 0 30 0 — I 25 0 - * i f 20 0 - ^ 

# -»•

# ~ 

# 7 * • > § 10 0 Bariu m

80 0 70 0 

### ? 60 0 u

- o 50 0 "of c 40 0 30 0 o U 20 0 100 0 Antimon y

Zin c 60 0 50 0 £ in 40 0 3 . 30 0 £ c 20 0 c 10 D 0 15:1) 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1



## - • • - —— - • --*\ 5 0 - - - - - --- j
* ••i <)••.* • i 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1

• • • t • \ • m • 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 1

• , • - , - m — — ,-+ — 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 23:0 0 7:0 0 15:0 0 5/14/0 1 5/15/0 1 5/16/0 1 5/17/0 ! Figur e 8 (Cont'd) . XCE M an d M29 concentration s durin g TEA D verificatio n testing .



### VES01684 12 4 ERDC/CER L TR-05- 9

)5( l 31) 0 • ? 251 ) ; "S i 20 0 : • a . 15 0 i • u e o io n • U 5 0 i •

0 J • 15:0 0 5/14/0 1 Mercur y

7:0 0 15:0 0 23:0 0 5/15/0 1 7:0 0 15:01 ) 23:0 0 5/16/0 1 

# /

;

7:0 0 15:0 0 5/17/0 1

% 2 0 • a 1 ' 5 i i o o U Palladiu m i i i n

7:01 ) 15:0 0 5/14/0 1 7:0 0 ! 5:0 0 5/15/0 1 7:0 0 15:0 0 5/16/0 1 7:0 0 15:0 0 5/17/0 1 Figur e 8 (Cont'd) . XCE M an d M2 9 concentration s durin g TEA D verificatio n testing .

Antimon y M2 9 vs . XCE M soi l 601 ) 40 0 20 0

100 20 0 30 0 40 0 XCE M

Nicke l M2 9 vs . XCE M

Mercur y M2 9 vs . XCE M Zin c M2 9 vs . XCK M [>0 0 50 0 40 0 30 0

20 0 XCE M

Lea d M2 9 vs . XCE M

50 0 i .DO O 1,50 0 2.0(H) 2.50 0 3.00 0

XCE M

Lea d Minu s Hig h Run s M2 9 vs . XCK M

Figur e 9 . Correlatio n betwee n XCE M an d M2 9 fo relement s spike d a ttw o levels .



### VES01684 2ERDC/CER L TR-05- 9 25

Table 9. Correlation betwee n th e XCE M and M29. Elem . Correlation (R 2 ) (1 3 Runs) Correlation (R 2 ) (11 Runs) 1 Spike Ratio 2 Hig h Runs : Lo

w Run s Elem . Correlation (R 2 ) (1 3 Runs) Correlation (R 2 ) (11 Runs) 1 MS E M2 9 XCE M N i 0.948 2 0.975 3 2.5 7 2.5 2 2.1 2 P b 0.996 6 0.762 3 N S N S N S S b 0.960 9 0.968 2 2.5 2 2.5 6 2.5 1 Z n 0.976 6 0.973 8 2.5 7 2.5 4 2.5 0 H g 0.400 2 0.352 6 3.0 9 3.1 1 2.1 7 NS : No tspike d
1 Run s 3 throug

h 1 3
2Hig h run s ar e run s 3-7 ; lo w run s ar e run s 8-1 3 Response

to Changes

in Metal Concentration MSE-T A spike d Ni , Sb , Zn , an d H g a ttw o distinc tconcentratio n levels . Th e theoretica l ratio , base d o n spiking , between hig h an d lo w concentratio n run s range d fro m 2.5

2 fo rS b t

o 3.09 fo rH g (Tabl e 9) . Sinc e thes e fou relements are typicall y notfoun d i n th e stac k ga s i n significan tquantities , i twa s expecte d tha t th e theoretica l rati o woul d be measure d b y bot h th e M2 9 an d XCEM . Excep tfo r th e XCE M H g concentrations , both th e XCE M an d M2 9 ratio s were i n ver y good agreemen twit h th e theoretical rati o of concentrations . Thi s agreement , alon g wit h th e hig h correlatio n coefficients , indicate s tha tth e XCE M was precisel y an d consistentl y measurin g Ni , Sb , Zn , an d P b an d wa s responsiv e t o changin g con centrations . I n addition , th e XCEM' s respons e t o change s i n th e P b concentra tion , whic h change d b y almos ttwo order s of magnitude , was consisten twit h th e M2 9 result s illustrate d i n Figur e 8 . Relative Accuracy
Tabl e 1 0 show

s XCEM , M2 9 reporte d concentrations , an d MSE-predicte d spik e concentrations . Th e R A o f th e XCE M wit h respec tt o th e M2 9 wa s determine d usin g PS-1 0 criteria . O f th e 1 3 M2 9 runs , 1 1 were use d t o calculat e R A an d av erage concentrations . Durin g run s 1 an d 2 , th e incinerato rexperience d prob lem s wit h a fault y bypas s valve , whic h le d t o extremel y hig h P b concentration s (1,00 0 t o 3,000 pg/dscm) . Althoug h th e XCE M tracke d th e problem , an d was i n fac tuse d t

o identif

y an d rectif

y th e problem , i twas notfel ttha tthes e condition s represente d th e typica l operatin g condition s ofth e plant . Fo rthi s reason , run s 1 an d 2 were no tuse d t o calculate R A an d averag e concentrations . Sinc e 1 1 vali d referenc e metho d tes trun s were completed , th e R A procedure state d i n PS-1 0 allowe d fo romissio n o f u p t o tw o additiona l run s fro m th e R A calculation . Tabl e 1 1 show s th e R A fo ral l 1 1 run s an d th e bes t9 runs . I n gen eral , wit h th e exceptio n of Pb , th e omissio n of

tw o additiona l run s di d notsignifi cantl y affec tR A calculations .



### VES01684 3Tabl e 10 . XCE M measured , M2 9 measured , an

d MSE-predicted meta

l concentrations (pg/dscm ) during TEA D validation testing . Ru n A

s Ba C d C r Hg N i P

b S

b Z n No . X C M2

9 MS E x c M2

9 MS E X C M2

9 MS E X C M2

9 MS E X C M2

9 MS E X C M2

9 MS E X C M2

9 MS E X C M2

9 MS E X C M2

9 MS E 1 2 3 1 1 1 2 18 7 25 6 23 0 2 7 3 0 3 2 2 4 3 19 4 29 2 28 5 46 2 38 5 47 4 1,24 0 1,61 8 N S 37 2 56 5 54 6 33 3 46 7 47 9 2 1 6 1 1 1 2 22 4 29 8 22 3 2 7 3 8 3 1 2 4 3 22 9 27 6 28 1 41 0 40 1 46 6 2,69 0 3,24 2 N S 37 5 62 9 53 0 33 5 47 1 47 2 3 1 3 9 1

1 15 4 20 1 20 6 2 5 3 0 3 0 3 4 3 26 0 28 6 28 1 40 6 37 7 46 9 7 3 8 4 N S 35 1 53 5 51 6 33 4 41 8 46 9 4 1 6 1 2 1 4 16 1 25 5 20 0 3 0 3 4 3 6 5 7 5 7 6 31 8 26 9 42 2 45 2 44 8 6 2 6 4 N S 36 1 64 3 49 9 34 0 49 5 44 8 5 1 6 1 2 1 4 17 5 24 1 19 9 3 4 3 5 3 5 6 6 5 11 0 31 8 26 7 43 8 41 8 44 4 4 7 4 6 N S 38 1 62 7 49 7 35 4 45 4 44 4 6 1 4 1 2 1 4 17 0 27 1 19 8 3 3 3 5 3 5 6 6 5 15 2 31 9 27 0 44 3 47 3 45 0 4 1 4 5 N S 38 4 69 4 49 5 36 3 51 2 450 7 1 7 1 2 1 4 17 4 27 9 19 5 3 2 3 4 3 6 6 6 5 13 2 31 8 27 0 46 1 48 6 45 0 4 0 5 2 N S 38 3 71 2 48 9 36 7 54 0 450 8 1 7 1 2 1 4 14 8 26 2 20 0 3 2 3 5 3 6 5 7 5 2 7 10 4 9 2 21 0 20 6 18 4 22 9 19 8 N S 13 4 27 2 20 0 14 6 21 9 18 4 9 1 7 11.3 7 14.3 3 16 2 22 3 19 8 3 2 3 5 3 6 5 7 5 5 4 10 5 9 0 21 0 17 8 17 9 16 6 7 7 N S 14 5 23 7 19 8 14 6 19 3 17 9 1 0 1 8 11.4 2 14.1 6 16 7 21 4 19 7 3 4 3 4 3 5 6 6 5 9 1 10 1 8 8 20 6 16 1 17 5 14 3 8 4 N S 14 7 22 ! 19

7 14 3 17 5 17 5 1 1 1 6 11.4 3 14.1 6 16 3 23 3 19 7 3 0 3 3 3 5 5 6 5 9 4 10 1 8 7 20 1 18 6 17 5 9 6 5 4 N S 14 5 25 6 19 7 14 3 20 1 17 5 1 2 1 7 9 1

1 18 2 21 4 20 0 2 7 2 8 2 6 4 5 4 6 2 10 8 8 8 21 8 16 1 17 7 19 5 18 7 N S 15 6 23 6 20 0 15 0 18 1 17 7 1 3 1 8 1 2 1 4 16 5 24 8 19 5 3 5 3 6 3 6 6 6 5 7 7 8 4 8 2 18 6 15 6 16 3 11 6 10 9 N S 15 9 28 6 19 5 11 8 17 3 16 3 Avg. (Run s 1 6 1 1 1 4 16 6 24 0 19 9 3 1 3 3 3 4 5 6 5 10 3 19 7 17 1 30 9 29 6 30 1 11 0 9 1 25

0 42 9 33 5 23 7 32 4 30 1 3-13 ) 8 5

XC : XCE M NS : No tspike d



### VES01684 4ERDC/CER L TR-05- 9 2 7

Table 11 . Relativ

e accurac

y and correlations .

Elem . Avg . M2

9 Cone , (ug/dscm) Avg . XC

Cone , (ug/dscm

) Avg . MS E predicted Cone , (ug/dscm

) %R

A (Run s 3-13 ) %R A ( 9 Runs ) Notes
C d 3 3 3 1 3 4 1 0 8 MetR A criterion . C r 6 5.2 5. 0 1 9 1 5 Me tR A criterion . N i 29 6 30 9 30 1 1 1 11 MetR A criterion . P b 91 11 0 N S 4 5 2 2
B a 24 0 16 6 19 9 3 9 3 7 Spike d wit h Sb . XCi s consistentl y low

. S b 42 9 25 0 33 5 5 8 5 5 Spike d wit h Ba . X C i s consistentl y low

. Z n 324 23 7 30 1 3 7 3 5 Potential calibratio n error . X C i s consistentl y low. A s 11.3 16. 4 13. 6 5 5 4 8 X C ha d correctabl e P b interferenc e fo rAs .

H g 197 103 17 1 78 6 8 Consisten tpatter n o f increas e throughoutda y unti l concentratio n approache s M2 9 value . NS : No tspike d XC : XCE M
Cadmium , chromium , an d nicke l
Th e XCE M an d M2 9 reporte d concentration s fo rCd , Cr , an d N i ar e i n good agreement . Th e averag e XCE M concentration s fo rthes e thre e metal s were 31 , 5.2 , an d 30

9 pg/dscm , respectively , whil e th e M2 9 averag e concentration s were 33 , 6.0 , an d 35 4 pg/dscm . Th e hig h correlatio n betwee n th e tw o method s i s re flecte d i n th e lo w relativ e accuracie s o f 1 0 percen tfo rCd , 19 percen tfo rCr , an d 1 1 percen tfo rNi . Al l thre e elements woul d hav e me tth e R A requirement s of th e draf tPS-10 . Th e R A fo rC rwoul d hav e bee n significantl y improve d i f no tfo ra hig h bia s i n th e M2 9 result s du

e t o protocol assumption s an d hig h analytica l uncertaintie s i n M2 9 back-hal f

concentrations . EP A M2 9 protocol require s th e assumptio n tha t th e detectio n limi tb e use d fo rth e concentratio n whe n th e concentratio n i s i n fac tbelow th e detectio n limit . I n mos tcases , th e detectio n limi ti s lo w relativ e t o th e measure d concentrations . I n th e cas e o f Cr , however , i ti s almos t20 percen t o f th e tota l C rfoun d i n th e M2 9 sampl e train .



### VES01684 52 8 ERDC/CER L TR-05- 9

Lea d
Th e averag e reporte dXCE M P b concentratio n wa s 11 0 pg/dsc mfo r run s 3 throug h 13 , whil e th e averag e M2 9 concentratio n wa s 9 1 pg/dscm

. I n general , th e XCE M an dM2 9 concentration s wer e i n goo dagreement
. O n 1 6 May , how

ever , bot h th e XCE M an dM2 9 method s reporte dhighe r P b concentratio n a t

th e star t o f th e da y tha n wa s observe do n 1 5 May

. Th e XCE M reporte daconsisten t gradua l declin e i n concentration s throughou t th e da y whil e M2 9 showe damor e rapi ddecreas e i n concentratio n (Figur e 10)

. Althoug h th e averag e XCE M an d M2 9 concentration s differe db y onl y abou t 2 percen t

fo r run s 3 , 4 , 5 , 6 , 7 , 8 , 12 , an d13 , th e larg e differenc e foun di n run s 9 , 10 , an d1 1 wa s enoug h t o rais e th e R A fro mabou t

1 4 percen t

fo r thes e 8 run s t o almos t 4 5 percen t

fo r al l 1 1 runs . PS-1 0 allow s fo r

2 o f th e 1 1 run s t o b e dropped

. Thi s woul dhav e give n a n R A o f 2 2 percen t

fo r th e XCE M P b concentrations

. I t i s no t know n wh y th e XCE M an dM2 9 differe do n 1 6 May

. Th e XCE M wa s abl e t o rapidl y transitio n fro mmuc h highe r concentration s durin g th e firs t tw o run s t o amuc h lowe r concentratio n durin g th e thir dru n o n 1 4 Ma y an dwa s i n goo dagreemen t

wit h M2 9 fo r

th e thir dru n o n tha t day

. Th e 1 4 Ma y XCEM/M2 9 comparison s indicat e tha t th e XCE M i s responsiv e t o rapi dchange s i n P b con centratio n an di s resistan t t o sampl e lin e contamination , whil e M2 9 dat ashowe d goo dprecisio n an dQA/Q C fo r 1 6 May

. Th e XCE M ha s historicall y measure dP b accuratel y wit h RA s belo w 2 0 percen t durin g th e MSE-T A tes t (Bryso n 2000 ) an d th e laborator y tes t

i n 200 0 (Ha y e t

al

. 2005)

.

50 0

^ 45 0• * XCEM - P b | 40 0 - • M29 -P b 

# I 35 0 • 

## I 25 0 •

e o U * •• • 20 0 - •••»•• • #* 15 0 Run 8 * • io o 5 0 • Ru „ 9 Run , 0•••••• • | ;

7:1 2 9:3 6 12:0 0 14:2 4 16:4 8 19:1 2 21:36 ! Figur e 10 . XCE M an d M29 lea d concentration s durin g run s 8-11 .



### VES01684 6ERDC/CER L TR-05-9 29

Bariu m an d antimon y Bariu m an d antimon y wer e spike d i n th e sam e solutio n an d exhibite d simila r behavio rdurin g M2 9 testing . Fo rboth metals , th e averag e XCE M concentra tion s wer

e significantl y lowertha n th e M2 9 reporte d concentratio n (3 0 percen t lowe rfo rB a an d 4

0 percen tlowe rfo rSb) . Th e XCE M t

o M2 9 ratio s fo rB a an d S b were 0.7 0 ± 0.08 an d 0.5 9 ± .06 , respec tivel y (Figur e 11) . Th e consisten tdifferenc e i n concentration s i s reflecte d i n the XCE M an d M2 9 abilit y t o measur e S b a ttwo concentratio n levels . Antimon y was spike d a ttw

o differen tlevel s tha twere theoreticall y 2.52-fol d differen ti n concentration . M2 9 measure d a 2.5 6 fol d differenc e betwee n hig h an d lo w S b concentration s whil e th e XCE M showed a simila rchang e wit h a 2.5 1 ratio . Th e XCE M an d M2 9 S b correlatio n i s reflecte d i n a hig h R 2valu e of 0.9 6 fo rthei rcorrelatio n plo t(i n Figur e 9) . Th e average M2 9 reporte d concentration s fo rB a an d S b were 24 0 an d 429 pg/m 3 respectively , whic h i s mor e tha n 2 0 percen thighe rtha n th e predicte d maximu m stac k concentratio n base d o n stac k spikin g (Tabl e 11) . Th e XCE M B a an d S b concentration s compare d favorabl y t o th e MSE-predicte d concentrations . Th e XCE M ha s a n R A o f

les s tha n 20 percen tfo rB a whe n compare d directl y wit h th e MSE-predicte d concentrations . Th e difference s betwee n th e XCE M an d predicte d concentration s are believe d t o b e du e t o particulat e los s i n th e unheate d XCE M transpor tlin e an d calibratio n errors .



### VES01684 73 0 ERDC/CER L TR-05- 9

2. 0

iii. o As

• • • • •

7 9 Ru n No . 1. 0 0. 8 B 0. 6 a 1 0.4 1 e 0. 2 0. 0 B a

11 1 3

1. 2 g 1. 0 5 0.8 | 0-6 I 0.4 | 0. 2 0.0 C d

7 9 Ru n No . C r

• • • • •

_* *

7 9 Ru n No . 1 1 1

3

1. 0 g O.g a « 0. 6 

## I 0.4 S 6 0. 2 z 0. 0 H g

7 9 Ru n No . 1 1 1

3 Ni

1 0. 6 1 0. 4

1 1 1

3

1. 0 I °- 8

« 0. 6 I 0. 4 S S 0.2 Z 0. 0 S b

• •
• •

7 9 11 1 3 Ru n No . Z n

• •

Ru n No . P b

• • •

• < 

# • •

11 1 3 Figure 11 . Rati

o o f XCE M t o M2 9 concentration s during validation testing . 11 1 3



### VES01684 8ERDC/CER L TR-05- 9 3 1

Zin c Lik e B a an d Sb , th e XCE M Z n concentration s wer e consistentl y lowe rtha n th e M2 9 concentration s b y about30 percent . XCE M Z n concentration s were highl y correlate d wit h M2 9 (Figur e 9 ) wit h a n R 2valu e o f 0.98 . Zin c wa

s spike d a ta hig h concentratio n leve l fo rrun s 1 throug h 7 an d a 2.5 7 fol d lowe rleve l fo rrun s 8 t o 13 . Th e XCE M wa s responsiv e t

o thi s differenc e showin g a 2.50 concentra tio n multiplie rbetween th e averag e hig h an d lo w concentrations , whic h i s i n good agreemen twit h th e M2 9 rati o of 2.54 . Unlik e B a an d Sb , however, th e othe relements spike d wit h Z n showed no indica tio n of unifor m los s durin g transport . Nicke l me tth e PS-1 0 R A requirement s an d XCE M N i concentration s wer e slightl y highe rtha n M2 9 N i concentrations . Mercury , a

s discusse d earlier , ha d potentia l transpor tproblem s t o th e XCE M unde rcoolercondition s bu twas approximatel y equa l t o M2 9 concentration s fo r4 of th e 1 1 runs . Sinc e th e elements spike d i n th e sam e solutio n wit h Z n di d not sho w systemati c los s durin g transport , i ti s believe d tha tth e low Z n concentra tion s ar e notsimpl y a functio n o f transpor tproblems . CE S calibrate d th e XCE M usin g thi n fil m standard s produce d b y MicroMatte r Inc . (Dee rHarbor , WA ) an d a selec tfe w Nationa l Institut e of Standard s an d Technology (NIST ) traceabl e standards . Durin g calibration , th e NIS T standard s an d MicroMatte rstandard s di d no tagre e fo rZn . A decisio n wa s mad e t

o us e th e NIS T standard , whic h produce d significantl y lowe rreporte d Z n values . Follow in g testing , i twa

s determine d tha tth e NIS T Z n standar d i s noti n agreemen t wit h th e NIS T C u standar d an d ma y b e incorrect . Iti s believe d tha tth e Z n difference s are primaril y a functio n o f thi s calibratio n error . Us e of th e MicroMat te rcalibratio n standar d instea d o f th e NIS T standar d woul d hav e give n XCE M concentration s about1 5 percen thigher .
Arseni c I n general , th e XCE M A s concentration s were consistentl y highe rtha n th e pre dicte d (spiked ) an d measure d M2 9 concentrations . Durin g M2 9 testing , i twas observe d tha tP b concentration s were highl y correlate d wit h A s (Figur e 12) . Sinc e no significan tA s wa s expecte d i n th e backgroun d stac k ga s concentratio n an d th e A s was spike d a ta constan trate , th e observe d correlatio n wa s deter mine d t o b e du e t

o a n XR F spectra l interference . Arseni c concentration s are es tablishe d usin g a K aline , whic h i s overlappe d b y th e L alin e of Pb . Fo rthi s rea son , i n XR F analysis , hig h P b concentration s ca n interfer e wit h A s measure ments , althoug h th e revers e i s nottrue .



### VES01684 93 2 ERDC/CER L TR-05- 9

A s a firs tcut , th e interferenc e impac twa s estimate d usin g th e simpl e linea rre gressio n shown i n Figur e 12 . Tha tis , abou t5. 4 percentofth e P b concentratio n was bein g adde d t

o th e measure d A s concentration . CE S adjuste d th e A s num ber s accordingl y prio rt o receivin g M2 9 data . Eve n wit h thi s firs torde radjust ment , th e XCE M fina l reporte d A s concentration s were stil l highe rtha n the M2 9 an d predicte d concentration s wit h th e greates tdeviation s occurrin g durin g hig h P b runs . Overall , th e average fina l reporte d XCE M concentratio n wa s 16.3 pg/dscm whil e th e averag e M2 9 concentratio n wa s 11. 3 pg/dscm . Sinc e the XCE M save s each XR F spectrum , i twas possibl e t o revie w individua l spectr a an d adjus tfo rth e As/P b interferenc e usin g a second spectra l resolutio n approach . Thi s tas k was complete d afte rreceivin g th e M2 9 dat a fo rrun s 8 throug h 1 1 o n 16 May . Thes e adjuste d XCE M result s base d o n thi s second spec tra l analysi s approac h wer e withi n 4 percen to f th e M2 9 results . I ti s believe d tha ta chang e i n th e spectra l resolutio n approac h wil l resolv e th e Pb/A s overlap problem . Th e XR F ca n b e calibrate d usin g a variet y of method s tha twil l tak e into accountthe Pb/A s interference . Fo rexample , durin g th e fal l 200 0 tests , a calibratio n metho d wa s use d tha tcontaine d both arseni c an d Pb . N o As/P b interferenc e was observe d durin g thes e test s (Ha y etal . 2005) .

20 0

XCE M Lea d Cone . (ug/mJ ) Figur e 12 . Uncorrected XCE M A s concentration s versu s XCE M P b concentrations .



### VES01685 0ERDC/CER L TR-05- 9 33

Mercur y A s discusse d earlier , th e XCE M t o M2 9 H g ratio s varie d fro m ru n t o run . A tth e beginnin g o

f each tes tday, th e XCE M reporte d lo w H g concentration s relativ e t o M29 . A s th e da y progressed , th e XCE M concentratio n woul d graduall y increas e unti l i tapproximate d M2 9 reporte d concentrations . Th e patter n suggest s tha t th e transpor tlin e fro m th e stac k to th e XCE M neede d to b e heate d t o a highe r temperatur e t

o improv e transmissio n efficiency . Th e us e o f a heat-trace d trans portlin e shoul d improv e H g transmissio n efficiency . Interestingly , more tha n 98 percen to f th e H g measure d b y M2 9 passe d throug h th e filte ran d wa s collecte d i n th e bac k hal f o f th e sampl e trai n indicatin g tha t the vas tmajority of

th e H g wa s i n th e vapo rphase . Sinc e th e XCE M ha d good comparison s t

o M2 9 o n a tleas tfou rrun s (3 , 10 , 11 , an d 13) , th e tes tindicate s tha tth e XCE M was abl e t o efficientl y tra p an d measur e H g a s a vapor . Precision
Precisio n wa

s calculate d i n term s o f th e percentrelativ e standar d deviatio n (RSD ) of

a serie s of

XCE M measurement s mad e durin g relativel y stabl e opera tio n of th e TEA D incinerator , wit h metal s injecte d a ta relativel y constan trate . Thi s precisio n reflect s notonl y th e XCE M variabihty , bu tals o th e variabilit y i n th e stack concentrations , spikin g rate , an d flo w variability .
Metho d 2 9 dua l sampl e trai n precisio n Durin g testing , CHPP M ra n dua l M2 9 sampl e trains . Percen tdifference s be twee n th e tw

o train s are shown i n Tabl e 12 . Overall , th e averag e meta l concen tratio n agreemen tbetween th e M2 9 train s wa s about6 percen t(CHPP M 2001) . Thi s resul ti s significantl y bette rtha n th e typica l agreemen tbetween trains , whic h i s o n th e orde ro f 1 5 percen t(EP A 1999) . Thi s better-than-typica l agree men tindicate s tha tM2 9 samplin g an d analysi s were conducte d i n a precis e manner .
Metho d 2 9 vs . XCE M precisio n Th e spik e injectio n rat e wa s altere d o n th e firs tday o f testing , 1 4 May , t

o ensur e spike d emission s were withi n th e sit e permi tlimitations . O n 1 7 May , stac k con dition s wer

e no tstabl e followin g stac k repairs . However , MSE-T A an d TEA D reporte d reasonabl y stabl e condition s o n 15 an d 16 Ma y an d th e spikin g preci sio n wa s estimate d a t2 percent . Fo rthi s reason , th e eigh trun s o n 1 5 an d 1 6 Ma y wer

e use d fo rprecisio n calculations .



### VES01685 13 4 ERDC/CER L TR-05- 9

Th e average M2 9 an d XCE M precision s fo rth e eigh tspike d element s o n 1 5 t

o 1 6 Ma y are liste d i n Tabl e 13 . Th e averag e M2 9 precisio n fo rthes e run s wa s abou t 6 percent , whil e th e XCE M averag e precisio n was abou t1 0 percent . Th e XCE M precision , however, was heavil y influence d b y th e highl y variabl e H g results . Fo rth e non-H g elements , th e precisio n of th e XCE M wa s 3.7 percent , whil e th e averag e M2 9 precisio n fo rth e sam e grou p of elements wa s 6.8 percent . Th e XCE M als o measure s P d wit h ever y sample . Th e averag e XCE M P d concen tratio n wa

s 2 5 ± 0. 6 pg , whic h give s a precisio n o f about2. 5 percent . Palladiu m concentration s reflec tXR F precision , bu tare independen tof flow , spiking , an d samplin g variability . Overal l then , th e XCE M performe d i n a ver y consisten tmanne ran d exhibite d precisio n o n th e sam e orde ras o rslightl y bette rtha n M2 9 fo ral l element s excep t Hg . Tabl e 12 . Percen tdifference s betwee

n M2 9 sampl e trains. 1 

### Ru n A s B a C d C r H g N i P b S b Z n Avg . %

Dif f 1 9 - 6 - 2 7 2 3 -1 9 - 4 - 9 

### 7 2 

### 1 1

5 9 5 -3 0 0 - 1 - 1 4 3 -2 - 5 0 8 3 - 1 1 1 1 5 4 4 -2 - 6 - 8 -2 6 3 - 5 5 - 4 - 2 

### 7 5 - 9 -1 2 - 6 -1 5 1 -1 1 - 3 -1 1 - 9 

### 9 6 0 - 8 1 0 0 - 2 6 - 9 - 5 

### 3 7 3 - 8 - 3 - 2 0 - 6 - 1 - 9 - 7 4 8 1 - 3 - 5 - 4 4 - 9 -1 4 -1 1 -1 0 

### 7 9 6 - 8 -3 1 2 0 9 7 3 7 

### 6 10 0 6 - 5 - 5 - 2 1 1 2 5 5 

### 5 11 - 4 - 3 - 5 - 5 - 1 -1 0 

### - 1 -1 0 -1 3 

### 6 1 2 6 14 8 8 0 1 1 1 1 5 1 2 

### 8 1 3 -2 -1 4 - 1 - 1 1 -1 1 - 2 -1 4 - 9 

### 6 Avg . % Diff . 4 

### 8 4 

### 8 2 7 6 7 7 6
i Averag

e percen tdifferenc

e i s determine

d by averagin g th

e absolut

e value o

f the differenc

e betwee

n sample trains .



### VES01685 2ERDC/CER L TR-05- 9 3 5

Table 13. XCE M an

d M2 9 precision . I T la m M2 9 Avg . M2 9 Cone . M29 % Avg . X C Cone . X C % RS D iLicni . Run s (Ug/dscm) RS D (ug/dscm) (B y Run ) A s 4-1 1 1 2 2.

3 1

6 7.

6 B a 4-1 1 24 7 9.

4 16

5 5.

2 C d 4-1 1 3 4 2.

3 3

2 4.

5 C r 4-1 1 6 5. 7 6 2.6 Hg(high ) 4-

7 21 1 0. 2 9

2 35.

4 H g (low ) 8-1 1 10 3 1.

9 6

7 48.

4 N i (high ) 4-

7 45

7 6.

5 43

8 3.6 N i (low ) 8-1 1 18 3 10.1 20 7 2.

0 Sb (high ) 4-7 66 9 6. 1 37 5 2.9 S b (low ) 8-1 1 24 6 9.

0 14

3 4.2 Z n (high ) 4-

7 50

0 7.

2 35

4 3.

4 Z n (low ) 8-1 1 19 7 9.

2 14

4 1.

2 Avg . (Al l elem.) 5. 8 10. 1 Avg . (N o Hg) 6. 8 3.7
Low-Level

Metal Response
Low-leve l metal respons e wa s determine d b y compariso n of M2 9 an d XCEM reporte d C ran d A s concentrations . Neithe ro f thes e element

s i s foun d i n signifi can tquantitie s i n TEA D stac k emission s an d both ar e regulate d t o low level s unde rth e site-base d RCR A hmitations . Bot h elements wer e spike d a s particu late s b y MSE-T A a tlow concentration s wit h typica l C rstack concentration s i n th e 5 pg/dscm rang e an d A s i n th e 1 4 pg/dsc m range . Th e XCE M accuratel y measure d C rrelativ e t o M2 9 wit h a n R A o f 1 9 percent . Th e averag e XCE M C rconcentratio n was 5. 2 ± 0. 9 pg/m 3 whil e th e M2 9 averag e wa s 6.0 ± 0.8 pg/m 3 . Th e M2 9 concentration s reporte d th e detectio n limi tfo rth e bac k hal f

whe n no C rwa s measured , whic h occurre d fo rmor e tha n hal f

of th e samples . Sinc e th e M2 9 bac k hal f detectio n limi twa s about0.5 pg/m 3 , th e M2 9 concentration s were biase d hig h b y a tleas t10 percent . Correctio n fo rth e M2 9 back-hal f

detectio n limi timprove s th e R A t o bette rtha n 10 percent . Thi s consis ten tagreementbetwee n th e two method s demonstrate s th e capabilit y o f th e XCE M t o measure metal s a tlo w concentration s eve n i n the presence of hig h con centration s o f

interferin g elements suc h as Ba . A s discusse d earlier , th e XCE M A s concentration s were biase d b y P b interfer ence . Fo rthi s reason , th e XCE M A s concentration s were routinel y highe rtha n th e M2 9 concentrations .



### VES01685 336 ERDC/CER L TR-05- 9

Bias
Bia s between th e tw o M2 9 samplin g train s an d th e M29/XCE M dat a was deter mine d usin g a n EP A Metho d 30 1 approach (EP A 1992) . Th e result s ar e teste d fo rstatisticall y significan tbia s b y calculatin g th e t-statisti c an d determinin g i f th e mea n o

f th e difference s between th e tw o samplin g train s i s significan tatth e 80-percentconfidenc e level . Th e t-statisti c i s calculate d b y findin g th e standar d deviatio n ofth e difference s betwee n th e tw o samplin g trains .

d j = th e differenc e between th e tw o sampl e trai n value s d „ = mea n o f

th e d . value s n = numbe rof

paire d sample s Usin g the standar d deviatio n determine d i n Equatio n 4 , th e t-statisti c i s the n calculate d a

s follows :

Base d o n EP A criteria , a statisticall y significan tbia s i n a data setexists i f th e tstatisti c valu e i s greate rtha n a critica l valu e (0.8 8 fo r1 1 runs) . Usin g Equation s 4 an d 5 an d EPA' s critica l valu e fo r1 1 runs , i twa s determine d tha tM2 9 experience d statisticall y significan tbia s betwee n th e paire d sampl e train s fo rBa , Cd , Cr , Hg , Ni , Sb , an d Zn . However , th e M2 9 bia s wa s small , o n th e orde rof

3 t o 6 percent . Furthermore, th e bia s wa s no tconsisten tb y elemen t wit h sampl e Trai n A bein g highe rfo rC ran d H g whil e Trai n B was slightl y highe rfo rAs , Ba , Cd , Ni , Sb , an d Zn . Overall , th e M2 9 sampl e train s ha d a n av erag e absolut

e percen tdifferenc e of about6 percen t(Tabl e 9) . Sinc e th e M2 9 bia s fo rindividua l elements wa s relativel y smal l an d no consisten tdifference s between sampl e train s wa s noted , i twa s determine d tha tth e averag e M2 9 con centratio n woul d b e use d fo rcompariso n purpose s an d n o correctio n woul d b e take n t o compensat

e fo rbias . [Eq4 ]

where :

[Eq5 ]



### VES01685 4ERDC/CER L TR-05-9 3 7

Relativ e t

o M29 , th e XCE M showed significan tbia s fo ral l elements (Tabl e 14) . Thi s bia s i s believe d t o b e a produc to f

XCE M transpor tan d calibratio n prob lems . Metho d 30 1 outline s a procedure fo rdeterminin g correctio n factor s tha t ca n b e applie d whe n bia s i s present . I f th e Metho d 30 1 correctio n facto rha d bee n applie d t

o th e XCE M concentrations , th e XCE M woul d hav e metth e 2 0 percen tR A criterio n fo ral l o f th e elements excep tHg . Althoug h thi s metho d shows th e existenc e o f ahig h leve l o f

correlation , i ti s importan tt o not e tha tth e XCE M correctio n factor s ar e outsid e o f th e acceptabl e rang e fo rvalidatio n of Pb , Ba , Sb , Zn , As , an d Hg .
Tabl e 14 . Metho d 30 1 bia s an

d correctio n facto rcomparison . Elemen t T-Sta

t Significant

Bia s Correctio n

Facto r RAwit

h Corr . Facto r (Runs 3-13

) Correcte d R

A Meet s PS-1 0 C d 5.3 3 Ye s 1.0 8 3. 9 Ye s C r 6.4 1 Ye s 1.1 7 6. 3 Ye s Ni 1.2

7 Ye s 0.9 6 8. 0 Ye s P b 1.87 Ye s 0.8 3 20. 2 Yes 1 B a 9.5 9 Ye s 1.4 6 8. 7 Ye s S b 6.1 7 Ye s 1.7 3 6. 5 Ye s Z n 5.6 4 Ye s 1.38 6. 1 Ye s A s 11.7 5 Ye s 0.6 9 7. 8 Ye s H g 3.4 4 Ye s 1.9 1 35. 9 N o Usin g onl y nin e run s a s suggeste

d i n PS-10 , P

b R A woul d hav e bee n 1 4 percent

.


### Summar y
Th e XCE M wa

s constructed , installe d a tth e TEA D incinerator , an d teste d agains tM29 . Th e primar y objective was t o meetth e propose d requirement s o f PS-10 . Followin g i s a lis to f th e individua l requirement s an d discussio n of th e performanc e ofth e XCEM : 1 . Response time and reporting time: Th e XCE M ha d a respons e tim e of 20 minutes , meetin g the PS-1 0 criterio n fo rbatc h CEMs . I texperience d no me chanica l problem s an d ha d a n effectiv e up-tim e of 10 0 percent . 2 . QA: Th e XCE M showed a calibratio n drif to f les s tha n 0.5 percen tan d Q A precisio n of

abou t2 percen tfo rdail y zer o an d upscal e checks . 3 . Relative accuracy: a . Th e XCE M metPS-1 0 accurac y criteria fo rCd , Cr , an d N i b y havin g rela tiv e accuracie s tha twere les s tha n 20 percent .



### VES01685 53 8 ERDC/CER L TR-05- 9

b . Th e XCE M di d no tmeetth e P b accuracy criterio n wit h a n R A of 2 2 per cent . c . Th e reporte d XCE M concentration s were uniforml y hig h fo rA s du e t o a spectra l resolutio n problem . d . Th e XCE M wa s consistentl y lo w fo rZn . Th e Z n difference s are believe d t o b e du e t

o a n incorrec tXCE M calibratio n standar d tha tlowere d th e XCE M concentration s b y abou t15 percent . e . Th e XCE M was als o consistentl y low fo rB a an d Sb . Thes e difference s are believe d t

o b e a functio n o f

transpor to rcalibratio n problems . f . Th e XCE M di d no tsuccessfull y measure Hg , whic h exhibite d a concentra tio n patter n tha tsuggest s los s t o th e unheate d sampl e transpor tline . g . Th e XCE M ha d a correlatio n (r 2 ) o f bette rtha n 0.95 fo rthre e (Ni , Sb , Zn ) of th e fou relements tha twere spike d a tvaryin g concentrations . I n addition , durin g th e test s th e XCE M functione d i n a completel y automate d manne ran d automaticall y recorde d concentrations , temperatures , flo w rates , an d Q A data . I tals o showed a precisio n of bette rtha n 4 percen tfo rperiod s whe n spikin g an d stac k condition s were hel d relativel y constant . A n analysi s o f

reporte d concentration s usin g EP A Metho d 30 1 correctio n factor s indicate s tha tth e XCE M woul d mee tth e 2 0 percen tR A criterio n fo ral l elements excep tHg , onc

e th e bia s i s take n int o account . However , th e correctio n factor s are outsid e th e acceptabl e rang e fo rvalidation . Tabl e 15 summarize s th e result s relativ e t

o PS-10 . Tabl e 15 . Summar

y of XCE M performance relativ e t o propose d PS-1 0 requirements . Tes tGoal Me

tCriterion ? Discussio n Samplin g an d Respons e Tim e Ye s Exhibite d a 100 % up-time fo rtest . Sample d fo rgreate rtha n 99.5 % of

the time . Reporte d tim e average d concentration s ever y 2 0 minute s wit

h a 20-minut

e la g betwee n samplin g an d reporting . Q A Ye s Th e XCE M exhibite d a precisio n of 1 t o 2 % fo rzer o drift

. Th e XR F calibratio n drif

twa s les s than 0.5 % fo rth e 4 day s of testing .

R A Ye s fo r3

N o fo r6 element s Met20 % R A criteri a fo rCd , Cr , an d Ni . Ha d a 22 % RAfo rPb .

Wa s systematicall y biase d fo rBa , Sb , Zn , an d As . Did not successfull y measur e Hg . Fo rrespons e t o chang e i

n concentration , ha d correlatio n (r 2 ) of 0.9 5 o rbetterfo rNi , Sb , an d Zn . Underline d element s ar e regulate d element s typically foun d i n th e Tooel e feedstream .



### VES01685 6ERDC/CER L TR-05- 9 3 9



# 3 Transport an d Calibratio n Improvement s

Durin g th e M2 9 compariso n tests o f Ma y 2001 , th e XCE M me tth e PS-1 0 criteri a fo rQ A an d samplin g an d respons e time , bu tonl y me tth e R A criterio n fo rthre e elements (Cr , Cd , an d Ni) . A n evaluatio n o f th e tes tparameter s indicate d tha t change s t

o th e transpor tline , improvements i n calibration , an d testin g of th e XCE M vs . stac k spikin g woul d improv e th e XCE M RA . Durin g th e sprin g o

f 2002 , improvements were mad e t o th e XCE M transpor tlin e an d a secon d serie s o f preliminar y tests were conducte d t o bette runderstan d calibratio n an d stac k spikin g efficiency . Thi s chapte rdiscusse s the change s t o th e transpor tline , calibration , an d tes tresults . 

### Transport Lin e Change s
Th e initia l transpor tlin e use d b y th e XCE M a tTEA D wa s insulated , bu tnot hea ttraced . Th e line , whic h extende d horizontall y 20 ft , showed problem s wit h H g transport . Durin g Ma y 200 1 testing , XCE M H g concentration s were lowe r tha n M2 9 value s atth e beginnin g o f th e da y whe n temperature s wer e lower , bu t as th e lin e temperatur e increased , th e XCE M H g concentration s approache d M2 9 results . Fo rthi s reason , i twas determine d tha tth e XCE M require d a heate d transpor tline . I n Marc h 2002 th e XCE M shelte rwa s move d t

o a locatio n tha trequire d onl y 13 f to f horizonta l transport . Followin g th e move , th e lin e wa s hea ttraced , insu lated , an d maintaine d at22 0 2 F . I n addition , a shroude d prob e wa s installed . Th e shroude d probe , manufacture d b y Anderso n Instruments , ha s been show n t o minimiz e th e impac tof variation s i n stac k velocity o n deviation s fro m isokineti c samplin g (McFarlan d an d Rodger s 1993) . Th e combine d effecto f thes e changes wa s t o minimiz e H g an d particulat e los s i n th e sampl e line .



### VES01685 74 0 ERDC/CER L TR-05- 9



### Recalibratio n
Durin g th e wee

k o f 8 Apri l 2002 , CE S recalibrate d th e instrumen tusin g thin fil m MicroMatte rstandards . Th e thin-fil m standard s ar e developed b y flashin g th e meta l of

interes tont

o a nuclepor e filter , resultin g i n a know n concentratio n o f meta l i n microgram s pe rsquar e centimete r(pg/cm 2 ) . Th e XR F uni tuse d b y th e XCE M ha d no

tbee n calibrate d sinc e Augus t2001 . Befor e recalibrating , CE S analyzed th e MicroMatte rstandard s (previousl y purchase d b y th e Arm y a s un knowns ) t

o evaluate th e XRF' s stability . Th e XR F reporte d value s withi n 1 0 per cento f th e calibratio n standards , whic h indicate d tha ti tha d maintaine d good stabilit y fo r9 month s an d woul d nothav e neede d recalibratio n unde rnorma l operatin g conditions . Followin g th e initia l check , severa l changes were mad e t o th e calibratio n proce dur e t o improv e spectral deconvolution . Thes e change s included :

• Developmen to

f a representativ e filte rtap e backgroun d reference spectr a

• Subtractio n ofth e filte rtap e backgroun d spectr a

• Developmen to

f bette rpur e elemen treferenc e spectr a

• Inclusio n o f

additiona l element s as backgroun d spectr a t o correctfo rpoten tia l interferences . Followin g recalibration , th e Arm y MicroMatte rstandard s wer e agai n evaluate d as unknowns . Th e standard s wer e withi n 1. 5 percen tofth e liste d value s fo ral l elements excep tS b ( 6 percent) an d B a (1 5 percent) . Th e accuracy o f th e Arm y MicroMatte rstandard s was i n question , s o the y wer e compare d t o CE S Micro Matte rstandard s atth e CE S laboratory . Some inconsistencie s fo rC d an d P b were note d between th e Arm y an d th e CE S MicroMatte rstandards . The y wer e als o compare d with standard s fro m NIST . Th e result s fro m th e analysi s o f th e NIS T an d CE S MicroMatte rstandard s wer e compare d wit h th e Arm y MicroMat te rstandards , an d i twas determine d tha tth e Arm y standard s fo rC d an d P b were hig h b y 1

2 percentan d lo w b y 4 percent , respectively . Th e XR F calibratio n wa s adjuste d accordingly .


### Summar y o f Transport an d Calibratio n Evaluation s Change s t

o th e transpor tlin e wer e teste d b y comparin g XCE M concentration s t o concentration s based upo n stac k spikin g estimate s an d a n in-stac k EP A Refer ence Metho d 1

7 (M17) filter . Overall , no measurabl e los s of particulate s i n th e improve d XCE M transpor tlin e wa s observed . Th e calibratio n was teste d usin g a



### VES01685 8ERDC/CER L TR-05- 9 4 1

Quantitativ e Spik e Injectio n Syste m (QSIS) . I twa s determine d tha tth e elemen ta l concentration s were bein g reporte d withi n thei rexpecte d uncertaintie s fo ral l elements exceptC d an d Ag . Appendi x C give s description s an d detaile d result s o f thes e tests .4 2 ERDC/CER L TR-05- 9



# 4 M29 Compariso n Testin g o f XCE M 200 2

I n Ma y 200

2 a new serie s o f

M2 9 test s were conducte d t o evaluate th e measure men tcapabilitie s ofth e improve d XCEM . Th e tes tobjectiv e was t o compare M2 9 an d th e XCE M an d determin e th e XCE M RAs . Th e testin g wa s conducte d a t TEA D wit h a tes tpla n simila rt o th e pla n use d i n th e 200 1 M2 9 compariso n tests . Te n metal s were measure d b y M2 9 an d th e XCEM . Thi s chapte rpresents th e result s o f

th e M2 9 sampling , predicte d concentration s base d o n th e spiking , an d th e XCE M sampling . Als o presented : a calibratio n evaluatio n base d o n th e reevaluatio n of

th e XCE M filters, a discussio n o f th e precisio n of

th e thre e con centratio n determinations , an d a detaile d discussio n of th e M2 9 comparison .


### Result s Method 29 Concentrations
Metho d 2

9 tests were conducte d usin g duplicat e sampl e train s locate d a tth e sam e stac k heigh ta

s th e XCE M probe . I n general , th e tw o train s were i n goo

d agreemen t(CHPP M 2002) . A s show n i n Tabl e 16 , mor e tha n 90 percen tof th e paire d M2 9 concentration s wer e withi n 1 0 percen to f eac h other . O f

th e 1 1 re porte d concentration s tha twer e no twithi n 10 percent , 9 were measurements o f Sn . Metho d 2

9 ha s notbee n approve d fo rS n (EP A 1992) . Ti n i s no ta regulate d metal , bu tmeasurin g i ti s usefu l t o TEA D fo ridentifyin g deactivate d munitions . Overall , trai n A wa s highe rtha n trai n B b y abou t3 percen twit h about78 per cen to f th e concentration s i n trai n A bein g highe rtha n thei rtrai n B counterpart . A n average o f

train s A an d B wa s use d fo rcompariso n t o th e XCE M reporte d concentrations . Metho d 2

9 dat a use d fo rcompariso n t o th e XCE M i s th e sam e a s reporte d i n th e M2 9 report(CHPP M 2002) wit h th e exceptio n o f a1- 3 percen tcorrectio n compen satin g fo rth e laboratory' s inadverten tsubtractio n of a n estimate d blan k concen tratio n whe n th e blan k concentration s were below th e method-reportin g limit. *

Persona l communication : Rober tWeidenfeld, Severe

n Tren tLab , wit h Joh n Cooper

, CES , 9 Jul

y 2002 .



### VES01686 0ERDC/CER L TR-05- 9 43

Table 16. M2

9 concentrations (ug/dscm) . RU N Pb C d C r A s • S b RU N A B A V G A B A V G A B A V G A B A V G A B A V G A B A V G 1 7 4 7 1 7 3 31 2

8 2 9 3. 5 3. 6 3. 6 8. 1 7. 4 7. 8 34 4 32 0 33 2 15 4 14 8 15 1 2 7 5 7 8 7 7 3 2 3 2 3 2 4. 0 4. 1 4. 0 8.

4 8.0 8.

2 33 7 33 1 33

4 18 8 17 6 18 2 3 9 9 9

6 9 8 3 6 34 3

5 6. 7 6. 2 6.4 11.7 11.

2 11. 4 306 28

3 29 4 18 7 18 0 18 3 4 3 7 3 9 3 8 31 31 31 4.8 5. 2 5.0 11.

5 12. 1 11.

8 34 7 30 7 32 7 16 8 16 4 16 6 5 29 2

6 2 8 3 2 30 3

1 5. 3 5. 2 5. 2 12. 3 11. 1 11.

7 31 9 31 7 31 8 17 2 16 3 16 8 6 14 8 14 6 14 7 3 2 31 3

1 5. 0 4.7 4.8 11. 6 10. 9 11. 2 29 1 26 9 280 16 0 16 3 16 2 7 13 8 13 2 13 5 3 2 3 1 3

2 5. 0 4.8 4. 9 11.

8 11. 4 11. 6 279 29 1 28

5 16 9 15 9 16 4 8 131 12

6 12 8 3 3 3 2 3 2 5. 2 4. 9 5. 1 12.6 11. 8 12. 2 30 9 30 3 30 6 16 5 15 8 16 2 9 12 1 12 2 12 2 3 2 3 2 3 2 4. 9 5.

4 5. 2 12.0 12.

2 12. 1 31 2 30

5 30 9 15 3 16 1 15 7 10 14 0 12 9 13 5 31 2

9 30 5.

0 4.8 4. 9 11.

3 10. 8 11. 0 29 4 289 29

2 16 4 15 1 15 7 1 1 119 11

8 11 9 3 2 3 1 31 4. 9 4.7 4. 8 11. 7 11. 5 11.6 29

7 29 3 29 5 16 2 16 4 16 3 1 2 11 4 11 1 11 3 3 1 31 31 4. 8 4.8 4.8 11.9 11. 7 11. 8 308 27

8 29 3 15 4 15 4 15 4

RC N N i B a Z n S n RC N A B A V G A B A V G A B A V G A B A V G 1 209 19

1 20 0 22 2 206 214 20

3 18 6 19 5 13 2 14 4 13 8 2 23 5 23 5 23 5 24 9 248 24

8 21 6 20

8 21 2 131 16

8 14 9 3 240 22

8 23 4 25 2 24 3 24 7 22 2 208 21 5 20

7 19 9 20 3 4 20 7 22 0 21 3 19 5 21 1 20

3 19 2 20 1 19

6 66 9

0 7 8 5 22 7 23 5 231 21 5 19

8 20 7 20 2 19 1 19 6 5 7 6 9 6 3 6 23 6 214 22

5 21 7 21 5 21 6 21 8 200 20 9 13 1 10 8 12 0 7 23 0 20

5 218 22

0 20 4 212 20

6 19 8 20 2 6 0 7 4 6 7 8 22 4 213 21 9 21 4 206 21 0 21 1 19 6 20 4 4 7 4 8 4 7 9 22 2 22 1 22 1 20 4 209 20

6 20 4 200 20

2 4 1 3

5 3 8 1 0 21 9 19

2 20 5 21 8 19

9 20 8 20 5 19 2 19 9 8 8 6 4 7 6 11 21 8 21 4 21 6 21 0 21 0 21 0 20 5 20 1 20

3 44 36 40 1 2 20 2 19 5 19 9 20 8 20 1 20

4 19 9 19 2 19 6 31 2

5 2 8 Predicted

Stack Gas Concentrations
Predicte d stac k gas concentration s were determine d b y addin g th e MSE-T A cal culate d spike d concentration s wit h backgroun d concentration s base d o n XCE M measurements whe n munition s wer e bein g burne d bu tno spikin g was occurring . Th e backgroun d was essentiall y zero fo rfiv e elements : Cr , As , Hg , Sb , an d Ni . Fo rCd , Ba , an d Zn , th e backgroun d correctio n wa s smal l relativ e t o th e MSE-T A spike d concentrations , whic h were 17 , 15 , an d 8 percent , respectively . Fo rPb , however , the backgroun d accounte d fo r10 0 percen to f

th e P b i n run s 1- 5 an d 3 5 percen to

f th e P b i n run s 6-12 . MSE-T A spik e injectio n Durin g M2 9 testing , MSE-T A spike d know n masse s of Pb , Cd , Cr , As , Hg , Sb , Ni , Ba , an d Z n into th e stac k (Bryso n 2002) . Thes e spike d masse s were divide d b y th e stac k flo w t

o obtai n concentration s i n pg/dscm . MSE-T A mas s concentra tion s i n solutio n were cross-checke d b y submittin g aliquot s fro m M2 9 run s 5 an d 6 t o a n independen tlaboratory fo ranalysi s (HK M Labs , Butte , MT) . HKM' s re sult s were withi n 7 percen to f MSE-TA' s estimate s fo ral l elements excep tAs ,



### VES01686 14 4 ERDC/CER L TR-05- 9

whic h was 2 3 percentlowe raccordin g t o HK M tha n reporte d b y MSE-TA . N o adjustments were mad e t o MSE-T A reporte d data . Th e potentia l impac to f th e A s differenc e i s discusse d i n a repor tb y Coope retal . (2002) . Measurement s of

stack flo w b y CHPP M were cross-checke d wit h th e stac k con tinuou s velocit

y monito rfo raccurac y an d wer e foun d t o b e withi n 6 percen to f each othe r(Tabl e 17) . Th e CHPP M flow s were determine d usin g a velocit y trav ers e a tth e sam e stac k heigh ta s th e XCE M prob e an d ar e believe d t o b e more representativ e o f

tru e flows tha n th e continuou s velocity monitor . Fo rthi s rea son , th e CHPP M flow s wer e use d t o calculat e th e predicte d concentrations . Tabl e 17 . APE-1236 stac

k flo w rate s durin g M2

9 testing . Run TEA D stac k monitor (dscm/hr ) M29

A (dscm/hr

) M29

B (dscm/hr ) Avg . CHPPM

M2 9 (dscm/hr

) TEA D stack

/ Avg . M2 9 (% > 1 5,173 4,71 8 4,65 9 4,68 9 11 0 2 5,03 7 4,63 8 4,65 2 4,64 5 108 3 4,99 8 4,52 7 4,53 2 4,53 0 11 0 4 4,88 9 4,68 0 4,68 8 4,68 4 104 5 4,83 8 4,67 2 4,68 8 4,68 0 10 3 6 4,97 0 4,57 8 4,58 0 4,57 9 10 9 7 4,82 6 4,60 7 4,61 3 4,61 0 10 5 8 4,78 5 4,64 1 4,64 7 4,64 4 10 3 9 4,67 6 4,66 2 4,672 4,66 7 100 1 0 4,06 0 4,58 9 4,60 0 4,59 4 11 0 1 1 4,96 0 4,59 3 4,66 2 4,62 8 107 1 2 4,87 9 4,66 0 4,67 0 4,66 5 10 5 AV G 4,92 4 4,63 0 4,63 9 4,63 5 10 6 Backgroun d metal concentratio n TEA D incinerate d 2 0 m m TPM55A 2 bullet s durin g al l 1 2 M2 9 runs . Thi s am munition , whic h i s use d fo rtarge ttraining , doe s no tcontai n significan tquanti tie s o f hazardou s elements . However , measurabl e residua l concentration s o f Pb , Cd , Ba , Zn , an d S n wer e foun d i n th e stac k ga s fro m earhe rincineratio n o f othe r munitions . Tabl e 18 show s XCE M result s fo relement s measure d o n 13 an d 15 Ma y whil e th e 20 m m bullet s were bein g burne d an d MSE-T A wa s no tspikin g into th e stack . Th e 13 Ma y meta l concentration s wer e significantl y highe rtha n

* Persona

l communication : Mik

e Pattison

, U.S . Arm

y CHPPM , wit

h Bruc e Johnsen , CES , June 2002 .



### VES01686 2ERDC/CERL TR-05- 9 4 5

th e 15 Ma y concentrations , whic h i s consisten twit h incineratio n o f relativel y clea n munition s scourin g th e stack . Backgroun d concentration s fo rCr , As , Hg , Ni , an d S b wer

e belo w XCE M detectio n limit s ( 1 ug/dscm ) an d wer e reporte d as 0 pg/dscm . Tabl e 18. APE-123 6 stac

k concentration s (ug/dscm ) wit h munitions incineration bu tn o spiking . Dat e XCE M

Ru n P b C d B a Z n S n 5/13/0 2 899 94. 5 11. 5 68. 7 38. 3 48 7 5/13/0 2 90

0 85. 9 5. 9 64. 8 42. 7 604 5/13/0 2 90 1 78. 2 8. 4 43. 6 39. 3 46 6 5/13/0 2 90

2 60. 0 9. 9 20. 1 22. 9 22 7 5/13/0 2 90

3 68. 2 10.0 74. 5 26. 5 272 5/13/0 2 90

4 53. 3 12.2 41. 1 39. 3 282 5/13/0 2 90

5 53. 8 6. 4 10.6 40. 3 23 1 5/13/0 2 906 44. 7 8. 0 18. 1 21.2 20 5 5/13/0 2 90

7 54. 7 6.0 22. 3 23. 9 275 5/13/0 2 908 44. 5 5. 7 49. 3 22. 6 25 9 Averag e 63. 8 8. 4 41. 3 31. 7 33 1 5/15/0 2 990 22. 3 0.6 12. 6 8.4 12 0 5/15/0 2 99 1 25. 0 4. 9 29. 4 8. 8 13 5 5/15/0 2 99

2 21. 4 1. 3 5. 6 6.7 114 5/15/0 2 99

3 8.9 0. 1 29. 4 2. 9 3 8 Averag e 19. 4 1. 7 19. 3 6. 7 10 2

Us e o f S n a s a surrogat e fo rbackgroun d metal s Figur e 1 3 shows th e relationshi p betwee n Pb , Ba , Zn , an d S n whe n spikin g wa s notoccurring . Th e correlation s indicat e tha tPb , Ba , Zn , an d S n backgroun d con centration s stem fro m th e sam e source . Sinc e S n was no tspike d b y MSE-TA , it s concentratio n was use d a s a n indicato rofth e backgroun d durin g spikin g periods . Th e backgroun d contributio n of th e othe relement

s wa s estimate d b y thei rrela tionshi p to S n accordin g t o th e equation s i n Figur e 13 . Figur e 14 show s th e XCE M measurements o f S n durin g M2 9 testing . A surg e i n S n concentration s i s observe d each mornin g afte rth e bypas s dampe ri s opened . Th e surg e i s followe d b y a gradua l decreas e i n S n concentration s throughou tth e day . Althoug h C d was no tfoun d i n hig h enough concentration s t o certif y it s relationshi p wit h Sn , i twa s assume d t

o behave i n th e sam e manne ra s th e othe rmetals . Combinin g th e MSE-T A spik e injectio n estimate s wit h th e estimate d backgroun d concentra tion s resulte d i n predicte d concentration s a s shown i n Tabl e 19 .



### VES01686 34 6 ERDC/CER L TR-05- 9

XCK M Lea d vs . XCK M Ti n Durin u Non Spikin g Period s XCE M Zin c vs . XCE M Ti n Durin g Non Spikin g Period s

20 0 400 600 Ti n (ug/DSCM ) 20 0 40

0 60

0 Ti n (ug/DSCM ) 80 0

XCK M Bariu m vs . XCK M It u Durin g Non Spikin g Period s

! 0 20

0 40

0 60 0 80 0 | Ti n Oig/DSCM ) Figur e 13 . Correlatio n betwee n S n an d othe rAPE-123 6 metal s with munition s burnin g an d n o spiking .

Ti n Durin g M2 9 Testin g Ma y 1 5 Ma y 1 3 Ma y 1 4 M a y 1 6

Figur e 14 . XCE M ti n measurement s durin g M2 9 testing .



### VES01 rERDC/CER L TR-05-9 4 7

XCEM Concentrations
XCE M concentration s wer e determine d ever y 2 0 minute s fo rPb , Cd , Cr , As , Ni , Hg , Ba , Sb , Zn , an d S n (Tabl e 20) . A P d ro d i s permanentl y mounte d i n th e XR F detectio n are a an d i s measure d wit h ever y sample . Th e consistency of th e P d concentration s provide s Q A of th e instrument s stability durin g M2 9 testing , th e XCE M successfull y carrie d ou t12 0 run s wit h onl y 2 run s fallin g outsid e o f th e P d Q A criterio n due t o air-conditionin g problems . Thi s represent s a n uptim e of 98 percent . Table 19. Predicted stack concentration s (ug/dscm) base d o n MSE-T A spikin g an d background estimates . CHROMIU M CADMIU M LEA D ARSENI C NICKE L RU N MS E B K G PR D MS E BK G PR D MS E B K G PR D MS E B K G PR D MS E BK G PR D 1 2. 9 0. 0 2. 9 32. 0 9. 4 41. 5 0.

0 6 7 6 7 10. 6 0. 0 10. 6 26 7 0. 0 26 7 2 2.9 0.

0 2.9 31.

5 8. 4 39. 8 0.0 6

1 6 1 10. 7 0. 0 10. 7 26 8 0. 0 26 8 3 5.

2 0. 0 5. 2 37. 5 11.1 48. 6 0.

0 7 7 7 7 16. 7 0. 0 16. 7 27 5 0. 0 27 5 4 5. 0 0. 0 5. 0 36. 5 5. 0 41. 6 0.0 4 1 41 16. 1 0.0 16.1 26

5 0. 0 26 5 5 5. 0 0. 0 5. 0 37. 2 4. 1 41. 4 0.0 3 6 3 6 16. 1 0. 0 16. 1 26

6 0. 0 26 6 6 5. 0 0. 0 5. 0 36.9 8.

5 45. 4 10

5 6 1 16 7 16. 0 0. 0 16. 0 271 0.0 271 7 5. 1 0. 0 5.1 37.

7 6. 0 43. 7 10

4 46 15

0 16. 4 0.0 16.

4 26 9 0. 0 26 9 8 5. 1 0. 0 5.1 37. 1 4.4 41. 5 10 3 3 7 14 0 16. 2 0. 0 16. 2 26 7 0. 0 26 7 9 5. 1 0. 0 5.1 37. 1 3.

4 40. 5 10

3 3 1 13 4 16. 2 0. 0 16. 2 26 6 0. 0 26 6 1 0 4.

8 0. 0 4.8 35.

3 5. 9 41. 1 10

5 46 15

1 15. 2 0. 0 15. 2 27 0 0. 0 27 0 1 1 5.

0 0. 0 5. 0 36.5 3.

5 39. 9 10

4 3 2 13 6 16. 0 0. 0 16. 0 26 8 0. 0 26 8 1 2 5.

1 0. 0 5. 1 36.6 2.

4 39. 0 10

3 2 6 12 8 16. 2 0. 0 16. 2 266 0.

0 26 6 AVG . 4.

7 0. 0 4. 7 36.0 6.

0 42. 0 6

1 4 7 10 7 15. 2 0. 0 15. 2 268 0.0 26

8 S D 0.

8 0. 0 0. 8 2. 1 2.

7 2. 7 5

3 16 4

7 2. 2 0.0 2.

2 2.8 0.

0 2. 8

RU N MERCUR Y BARIU M ANTIMON Y ZIN C RU N MS E B K G PR D MS E BK G PR D MS E B K G PR D MS E BK G PR D 1 32 4 0. 0 32 4 19 2 45. 3 237 19

2 0.0 19

2 26 7 32. 5 30 0 2 32

5 0. 0 32 5 19 6 41. 2 238 19

6 0. 0 19 6 26 8 29. 3 29 7 3 33

3 0. 0 33 3 201 51.6 25

3 201 0.

0 201 27

5 37. 3 312 4 32

2 0. 0 32 2 19 4 28. 3 22 3 19 4 0.0 19

4 26 5 19. 5 28 5 5 32

3 0. 0 32 3 19 3 25.0 21 8 19

3 0.0 19

3 26 6 16. 9 28 3 6 32

9 0. 0 32 9 19 9 41.6 24

0 19 9 0.0 19

9 27 1 29.6 301 7 32

7 0. 0 32 7 19 7 31.9 229 19

7 0.0 19

7 26 9 22. 2 291 8 32

5 0. 0 32 5 19 2 25.9 21 8 19

2 0.0 19

2 26 7 17. 6 28 5 9 32

4 0. 0 32 4 18 9 22. 1 21 2 18

9 0.0 18

9 26 6 14. 7 28 0 1 0 32

8 0. 0 32 8 19 4 31.6 22

6 19 4 0. 0 19 4 27 0 22.0 29

2 1 1 32

6 0. 0 32 6 19 3 22. 5 21 5 19

3 0.0 19

3 26 8 15. 0 28 3 12 32

2 0. 0 32 2 19 0 18. 4 209 19

0 0. 0 19 0 26 6 11. 9 27 8 AVG . 32

6 0. 0 32 6 19 4 32. 1 22

6 19 4 0. 0 19 4 26 8 22. 4 29 0 S D 3.

3 0. 0 3. 3 3.4 1

1 1 3 3.4 0 3 2. 8 8 10



### VES01686 5Tabl e 20 . XCE M concentrations . Dat e STAR T STO P X C M2 9 XCE M CONC . (fig/DSCM ) CE S CONC . (ug/DSCM ) Dat e STAR T STO P RU N RU N A S B A C D C R H G N I PB S B S N Z N A S B A C D C R H G N I P B S B S N Z N 5/1 3 7:5 7 A M 8:1

7 A M 89

9 O.

O 6 9 11. 5 1. 2 2 1 9

5 0 48

7 3 8 5/1 3 8:1 7 A M 8:3

7 A M 90

0 0.

4 6 5 5.9 0.

6 1 0 8

6 0 60

4 4 3 5/1 3 8:3 7 A M 8:5

7 A M 90

1 0.

2 4 4 8. 4 0. 3 2 1 7

8 1 46

6 3 9 5/13 8:5

7 A M 9:1 7 A M 90 2 2.

1 2 0 9.9 0.

8 1 0 6

0 3 22

7 2 3 5/1 3 9:1 8 A M 9:3

7 A M 90

3 O.

O 7 5 10. 0 1. 3 0 0 6

8 5 27

2 2 7 5/13 9:3

7 A M 9:5

7 A M 90

4 2.

2 4 1 12. 2 0. 9 1 2 5

3 1 28

2 3 9 5/1 3 9:5 7 A M 10:1

7 A M 90

5 O.

O 1 1 6. 4 0. 7 1 0 5

4 5 23

1 4 0 5/13 10:1

7 A M 10:3

7 A M 90

6 1.

3 1 8 8. 0 0. 3 1 0 4

5 3 20

5 2 1 5/1 3 10:3 7 A M 10:5

7 A M 90

7 O.

O 2 2 6. 0 0. 6 1 1 5

5 5 27

5 2 4 5/13 10:5

7 A M 11:1

7 A M 90

8 1.

4 4 9 5. 7 0. 4 1 1 4

5 3 25

9 2 3 5/1 3 11:1 7 A M 11:3

6 A M 90

9 8.

5 12 9 26. 4 3. 4 21 8 20 0 4 4 10 6 25 0 21 0 5/1 3 11:3

7 A M 11:5

7 A M •)1

0 1 8.

0 24 2 30. X 2.9 34

7 25 4 4 8 18 7 24 9 26 9 8. 6 21 0 27.

5 3.2 261 27

0 5 1 17 2 22 6 29 6 5/1 3 11:5

7 A M 12:1

7 P M 91 1 1 10. 1 20 2 33.2 3.

2 36 0 25 7 4 6 17 0 23 8 27 3 10. 8 18 8 28. 0 2. 6 26

4 26 8 4 6 17 6 22 4 29 5 5,1 3 12:1

8 P M 12:3

8 P M 91

2 1 9.1 22

2 35. 0 3.7 36

5 27 3 4 7 18 4 26 8 28 3 9. 5 22 2 31. 9 3. 6 26

9 27 7 5 7 17 2 271 30

6 5/1 3 12:3

8 P M 12:5

0 P M 913 ] 8.1 21 5 32. 0 4. 1 35 6 26 4 5 9 19 2 331 27

9 9. 0 21 0 29.5 3. 8 24 4 24 7 6 3 16 1 31 8 27

6 5/1 3 12:5' ) P M 1:1 9 I' M 914 1 11. 5 22 3 40.4 3.7 3X

5 27 8 8 7 18 2 484 301 8.

5 20 6 29. 9 3. 1 26

3 26 2 8 4 15 9 39 9 29 7 5/1 3 1:1'

) P M 1 Mi I' M 91 5 1 10. 9 26 5 37. 4 3. 8 371 27

9 9 4 19 0 55 K 30 3 8. 6 19 3 27. 5 3. 0 24

4 24 8 8 8 16 1 46 0 28 6 5/1 3 1:4

0 P M 2:0

1 P M 91 6 1 12. 6 256 34. 1 3. 7 371 28 0 8 3 18 1 471 30

2 11. 3 20 8 29.5 2.8 26

0 27 6 8 3 17 0 41 1 31

2 2:0 1 I'M 2:2

2 I'M <i

; " 36. 9 3. 5 38 7 28 5 7 9 19 1 43 7 31 3 9. 4 22 9 29. 3 3. 0 26 4 28 4 7 9 17 4 37 4 32 1 2:2 2 I'M 2:4

7 I' M u | s • I 2 2^ 0 35. 0 • i n 36 6 27 5 7 7 19 2 39 4 29 7 10. 4 23 1 30. 0 3. 3 27 8 29 3 8 0 18 3 35 3 32 5 5/13 2:4

7 P M 3:0

8 P M 91 9 2 9. 6 27 2 34. 3 3. 7 38 1 27

8 7 6 20f t 38 9 29 5 10. 3 24 7 28.8 3. 1 26

8 27 3 7 5 17 3 34 1 301 5/13 3:0

8 P M 3:2

9 P M 92

0 2 7.1 24 1 37. 5 4.8 394 28 1 77 19

1 379 J0 0 10.

4 20 9 28. 4 3.2 25

8 27 5 6 9 18 2 31 6 30

3 * M 3:2

9 P M 3:5

0 P M 92

1 2 11.

0 23 3 39.0 3.7 380 29 0 7 2 20 6 33 5 30 2 10. 4 231 33.0 3.4 26 4 28 8 7 1 18 3 306 314 571 3 3:5 0 P M 4:1 0 P M 92 2 2 8.

7 255 32. 0 3. 8 390 29 4 67 20

6 33 8 308 9.

4 20 9 26.5 3. 0 23

0 25 7 6 1 17 1 27 5 281 5'13 4:1 1 P M 4:31 P M 92 3 2 10.

5 23 1 38. 0 3.9 37

4 27 8 59 19

6 30 9 29 1 10. 2 20 7 29. 3 3. 1 24

0 27 5 5 8 17 2 26 1 30 1 5/1 3 4:31 P M 4:5 2 P M 92

4 2 9.

1 23 0 33.3 4.

4 36 0 27 3 4 7 19 1 22 1 28 0 11. 0 22 8 30. 9 3.5 24

5 29 2 4 9 18 7 19 8 31 8 5/1 4 7:0

4 A M 92 6 6.

8 13 6 20.6 3.

4 14 8 14 2 5 0 10 2 25 3 15 8 8. 3 11 7 18. 0 3. 0 9 3 15 0 5 2 8 7 22 7 ! ; 5/14 7:2

5 A M 7:4

5 A M 92

7 13.

8 20 1 42.8 5.

6 30 9 24 3 7 9 17 8 35 9 28 3 14. 6 21 1 35.8 4.

7 22 2 26 0 7f i 16 0 31 4 ;. i • 5'I 4 7:4 5 A M X:(l(

, \ M 92

8 3 13.

6 21 0 38. 6 6. 1 35 0 25 9 84 18

5 417 29

0 12. 8 17 3 31.7 4.7 25

3 267 8

1 14 5 36 9 31 1 5/1 4 8:0

6 A M 8:2

6 A M 92

9 3 14.

8 21 6 39.7 6.

2 35 3 26 5 95 18

9 50 8 29 4 13. 2 18 2 33. 1 5.

2 24 7 25 6 9 6 15 6 44 3 30 0 5/1 4 8:2

7 A M 8:4

7 A M 93

0 3 14.

5 229 34. 7 5. 1 35 4 25 0 8 0 18

7 431 27

7 13. 6 20 7 30. 0 4.

3 25 4 25 0 7 8 15 3 37 8 28 3 5/1 4 8:4

7 A M 9:11

8 A M 931 3 10. 5 21 8 36.

7 5. 5 34 7 24 5 7 8 17 5 43 5 26 9 14. 2 212 32.0 4. 9 28 3 28 0 8 7 15 6 40 7 31 S 5/14 9:0

8 A M 9:2

9 A M 93

2 3 12.

2 27 5 37. 0 6.

2 380 26

6 8 1 19 3 43 1 29

2 13. 3 19 9 31.5 4. 9 271 25 9 7 8 16 8 37 3 29 3 o



### VES01686 6Tabl e 2 0 (Cont'd) . XCE M concentrations . Dat e STAR T STO P X C M2 9 XCE M CONC . (ug/DSCM ) CE S CONC . (ug/DSCM ) Dat e STAR T STO P RU N RU N A S B A C D C R H G N I P B S B S N Z N A S B A C D C R H G NI P B S B S N Z N 5/1 4 9:4' ) A M 10 :1 0 A M 93 4 15.

7 9 9 35. 6 6.4 391 27 8 6 0 6 3 34 0 29 4 5/14 10 :1 0 A M 10 :3 1 A M 93 5 13.

2 58 36.2 5.

8 35 6 26 1 6

1 4 5 31 7 27

8 5/1 4 10 :3 1 A M 10 :5 1 A M 936 15. 5 17 0 40. 0 5.

4 35 4 25 8 5 1 16 1 30 4 27 5 5/1 4 10 :5 1 A M 11:1 2 A M 93

7 15.0 2

1 38.2 6.

2 37 3 27 5 47 1

2 28 2 28 7 5/1 4 11:1 2 A M 1 1:3

2 A M 93

8 14.6 18 2 36. 0 5.6 37

3 27 7 46 18

1 26 8 28 7 5/1 4 11:3

2 A M 11:5

3 A M •)3<

i 4 14.8 21 3 37.4 5. 3 36 0 26 5 4 0 18

1 22 0 27 3 14. 3 17 9 30. 5 4. 8 30 1 27 4 4 3 17 2 203 29 4 5/1 4 11:5

3 A M 12:13 P M 940 4 12. 7 20 8 38. 7 6. 1 36

2 26 2 4 3 19

8 21 6 268 14.

3 19 0 32. 2 5. 1 31 9 29 9 4 3 17 5 20 3 32 0 5/1 4 12:1 3 P M 12:3 4 I' M 94 1 4 14. 2 19 7 34. 1 4. 9 35

3 256 3 6 18

8 20 3 266 14.

5 213 31. 6 5. 1 30 4 28 4 4 2 17 0 19 3 30 2 5/1 4 12:3

4 P M 12:5

4 P M 94

2 4 12.4 22 4 37. 1 5. 9 380 280 3 6 18 7 19 4 28 5 13.

7 205 32. 7 5.2 305 28 5 3 9 17

9 179 30 5 5/1 4 12:5

4 P M 1:1

5 P M 943 4 16. 1 20 7 39. 7 6. 0 376 27 8 3 3 18

9 16 7 280 14. 8 21 5 33.3 5.4 28 6 27 5 3 3 17

7 16 4 29 1 5/1 4 1:1

5 P M 1:3

5 P M 94

4 4 15. 6 209 38. 9 6. 6 376 27 6 2 9 19

3 18 2 28 2 15.5 20

4 34. 7 5. 0 29

2 291 34 18

2 16 5 3U< . 5'1 4 1:3

5 P M 1:5

6 P M 94

5 13.

5 18 3 5.0 36

8 2

9 1 7 0 19 1 27 5 14. 4 19 8 33. 3 5. 4 31 2 28 1 3 0 16. 3 16 5 •i>i i 5/14 1:5

6 I ' M 2:16 P M 94 6 14.

8 3 3 36. 3 6.6 36

3 '6 8 1

3 16 5 ">"7 3 14. 0 40 30.

3 5. 2 29 1 > - 3

0 1 0 15 7 5/1 4 2:1 6 P M 2:37 P M 947 5 M. I 225 41. 3 5. 1 36 9 26 9 2 9 19 6 18 1 27 4 1 1. 4 19 8 30. 0 5.2 33 1 28 3 3 0 17

8 15 4 2W 5/1 4 2:37 P M 2:5 7 P M 948 5 17. 1 207 35. 5 6.2 387 28 2 26 19

U 17 3 28 6 14. " 19

0 2S. 0 5. 1 311

9 266 2

7 16 9 14 9 28 3 5/1 4 2:5

7 P M 3:1 8 I' M 949 5 14. 7 23 5 41. 7 6. 9 390 28 1 29 19 0 16 7 28 1 13.

7 19 7 3U. 4 4. 7 300 25

5 2 6 16 4 13 7 27 1 5/1 4 3:1 8 P M 3:3 8 P M 95 0 5 16. 1 22 0 30. 6 5. 8 37

8 27 5 25 19

5 15 7 273 14.1 20

0 28.2 5. 1 31 1 26 9 26 16

6 14 3 28 6 5'I4 3:3 8 P M 3:5 9 P M 95 1 5 15. 9 22 2 36. 8 5. 9 37

4 268 22 19

6 15 7 271 12. 8 18

6 31. 7 4. 1 28 8 24 2 2 4 16 6 129 25 7 5'1 4 3:5 9 I' M 4:1 9 P M 95 2 5 13. 9 25 8 35.3 6.3 37

4 271 2 6 20

2 15 5 276 14.

2 19 0 29. 7 5.7 30 9 28 1 2 5 18 4 13 3 29 5 5/1 4 4:21

) I' M 4:40 P M 95 3 5 14. 1 22 8 40. 7 6.

2 39 5 28 6 2 6 209 14

7 28 7 16. 0 21 7 35. 3 5.7 346 31) 0 2 7 19 6 14 2 31 9 5/15 6:5

7 A M 7:1

8 A M 95

6 5. 6 7

0 20.5 3. 1 14

8 13> i 7

0 1 2 13 8 5/15 7:18 A M 7:3 8 A M 95

7 11.0 19 1 41.3 5.8 341 ?7 ~ 13 9 19 1 21 6 27

5 14. 0 17 6 27.5 5.

2 28 6 27 6 13 8 15 4 18 5 29 8 5/1 5 7:38 A M 7:5 8 A M 95 8 6 15. 6 22 5 38. 9 h. h 38 6 291 16 3 19 5 41 5 30 6 15. 1 22 8 30. 6 4. 8 29

3 26 5 15 4 15 6 33 9 29 6 5/1 5 7:58 A M 8:1 9 A M 95 9 6 13.5 22 1 40. 1 5. 8 387 28 6 15 0 19 4 26 2 29 7 14. 8 20 1 32. 8 5. 9 296 27 0 13 8 16 9 224 29 2 5/1 5 8:1 9 A M 8:3 9 A M 96

0 6 15.

3 22 0 34. 9 5. 9 37

2 27 2 15 2 19 4 37 8 28 1 15.

0 17 0 lil.i l 5. 0 27

8 25 3 14 3 15 5 324 27 9 5/1 5 8:3 9 A M 9:0 0 A M 96 1 6 1S. 0 22 0 39. 2 18. 0 36 1 279 14 9 19 2 32 5 284 13.

2 16 8 28. 3 7. 7 27

2 24 1 13

4 15 3 257 26 2 5'I5 9:00 A M 9:2 1 A M 96 2 6 13. 9 23 6 41. 3 5.

7 375 28

3 16 2 19 5 348 293 15. 1 18 9 29. H 4. 8 299 26

0 14 2 16 6 28 1 28 3 5/1 5 9:2 1 A M 9:4 1 A M 96 3 6 12.5 209 V V 5. 9 388 27 8 15 0 19 4 305 29

2 12. 5 17 5 24.3 4. 4 29

2 26 9 14 1 15 5 250 28 9 5/1 5 «):4 I A M 10:0 2 A M 96

4 6 4. 1 22 ^ I2.f i 1.1 38

4 28 3 14 7 20 2 30 0 288 1.

9 17 2 1(1. 1 1. 7 285 26

5 14 1 14 9 23 9 28 3 5/1 5 10:0

2 A M 10:2

2 A M 96

5 14. 1 l'< - 37. 9 5.8 38 4 27 7 14 1 19 8 270 284 16.

3 21 1 31.2 5.

5 33 0 28 5 14 6 16 6 24 3 30 7



### VES01686 71 8 Tabl e 2 0 (Cont'd) . XCE M concentrations . Dat e STAR T STO P X C M2 9 XCE M CONC . (ug/DSCM ) C E S CONC . (fig/DSCM ) Dat e STAR T STO P RU N RU N A S B A C D C R H G M P B S B S N Z N A S B A C D C R H G N I P B S B S N Z N 5/1 5 111:2 2 A M 10:4

3 A. M 96

6 7 I3.f

i 23 3 36.9 5.

9 38 4 28 0 13 7 20 5 25 1 28 3 11. 9 18 7 26. 8 4. 0 24 1 22 6 11 6 14 3 18 9 24 1 5/1 5 10:4 3 A M 11:11

3 A M 96

7 7 14.

2 21 2 34. 1 6.

1 40 2 29 4 14 1 20 3 25 4 29 4 13. 3 21 3 30. 7 5. 1 30 1 28 7 14 5 16 9 21 6 3(1 6 5/1 5 11:0 3 A M 11:2

4 A M 96

8 7 15.

4 22 3 35. 5 5. 9 39 6 29 2 13 9 20 8 24 5 29 7 14. 8 201 ) 31. 3 5. 3 31 0 28 7 14 5 17 9 22 4 30 4 5/1 5 11:2 4 A M 11:4

5 A M 96

4 7 17.

9 25 3 34. 9 4. 9 39 4 29 1 13 8 19 7 23 7 29 6 14. 5 19 3 32. 7 5. 2 31 7 30 3 15 1 18 4 21 4 31 8 5/1 5 11:4 5 A M 12:0

5 P M 97

0 7 15.

5 18 0 44. 6 5. 0 38 4 28 4 13 6 19 6 22 7 28 9 13. 2 19 4 30.9 5.

4 30 9 28 8 14 2 17 5 2(1 1 30 4 5/1 5 12:0 5 P M 12:2 6 I' M 97

1 7 17.

2 19 2 31.8 6.

1 38 2 28 6 12 9 19 1 20 8 29 0 14. 5 20 2 32. 7 5. 5 31 4 29 8 14 3 18 2 19 2 31 2 5/1 5 12:2 6 I' M 12:4

6 I' M 97

2 7 13.

0 23 0 40. 7 5. 7 39 9 29 2 13 3 18 8 21 5 29 2 12. 1 17 8 26. 0 4. 5 26 8 25 3 12 2 15 6 17 3 26 5 5/1 5 1 2:4

6 I'M 1:0

7 P M 97

3 15.

6 1 8 5 34. 7 5. 8 39 6 285 13 5 18 6 19 6 292 1 "

> • • 18 1 29. K . - 27

7 253 12

0 1 5 7 16 1 267 5/1 5 1:0 7 PM 1:2

7 PM 97

4 8 14.

4 18 8 41. 4 6. 1 40 6 29 6 13 3 18 9 18 3 28 8 13. 9 19 3 31. 7 4. 9 29 4 27 2 12 9 16 6 15 5 28 4 5/1 5 1:2 7 I' M 1:4

8 PM 97

5 8 15.

1 23 2 33. 6 6. 8 40 2 29 2 12 8 18 2 17 1 28 7 13. 8 18 5 30. 7 4. 5 29 4 27 4 12 8 16 7 14 6 28 7 5/1 5 1:4 8 I' M 2:0

9 I' M 97f

t X 15.

3 20 2 35. 8 4. 9 39 5 28 6 13 2 18 7 19 2 28 5 13. 6 19 1 29.9 4.

8 30 2 29 4 14 1 17 0 16 6 31 1 5/1 5 2:0 V I' M 2:2

9 P M 97

7 8 12.

9 215 35. 1 5.

6 41 2 29 9 13 2 18 8 P 9 30

1 14. 6 18 3 31.5 5.

2 31 0 28 8 13 3 17 9 15 1 30 1 5/1 5 2:2 9 PM 2:5

0 P M 97

8 8 12.

3 24 0 41. 2 5. 8 41 0 30 2 13 7 19 0 17 3 29 6 14. 3 21 7 33.9 S.1 30

3 29 8 13 7 17 8 15 3 31 1 5/1 5 2:5 0 P M 3:10 PM 97

9 8 16.

4 20 5 39. 8 5. 8 41 3 30 3 13 0 17 9 14 9 311 0 12. 5 17 1 28. 7 4. 2 26 5 25 6 12 1 15 8 12 8 26 6 5'I S 3:11 1 I' M 3:3

1 PM 9X1

1 8 15.

4 20 0 40. 8 4. 9 39 3 28 9 12 7 19 0 15 7 28 5 13. 8 17 2 31. 3 5. 3 28 9 28 0 13 0 16 9 13 4 29 1 \i ] *\ 3:3 1 I'M 3:5 1 I'M 13.0 21 5 4 1 7 39

8 29 0 11 9 1 8

5 284 14. 0 18 7 34. 8 5.

3 32 3 31 9 14

5 19 2 33 0 5/1 5 3:5 1 PM 4:1

2 P M 98

2 9 16.

1 20 2 38.8 6.

0 40 6 29 3 12 X 19 8 14 3 29 7 13. 2 20 8 31. 3 4.6 27

5 26 2 11 9 16 3 11 5 27 2 5/1 5 4:1 2 I' M 4:3

2 PM 9X

3 9 14.

0 21 6 34. 7 6. 3 41 0 29 8 13 2 19 3 14 6 30 1 13. 6 201 1 31. 5 5. 4 29 9 28 8 12 9 16 9 12 8 29 9 5/1 5 4:3 3 I' M 4:5

3 P M •>X

4 9 12.

7 21 7 34. 3 6. 0 40 5 29 5 13 2 19 9 13 6 29 5 13. 1 18 0 30. 4 4. 9 26 3 26 4 11 8 17 2 11 3 27 2 5/1 5 4:5 3 PM 5:1

4 P M 98

5 9 14.

7 219 38.

4 6. 1 39 5 28 4 12 3 19 0 13 0 28 4 13. 2 18 9 30. 7 4.9 27

4 27 8 12 2 17 2 11 0 28 8 5'1 5 5:1 4 I' M 5:3

4 P M 98

6 9 13.

3 18 6 39. 3 5. 5 40 3 29 1 12 7 19 4 12 0 28 6 14. 6 20 0 34. 2 6. 9 31 0 30 5 13 3 18 3 11 3 316 5/1 5 5:3 4 I' M 5:5

5 P M 98

7 9 13.

0 17 0 39. 4 5. 5 415 30

1 12 9 19 7 12 4 29 7 14. 1 18 4 31.0 5.

2 30 3 29 6 13 1 16 9 10 1 30 5 5/1 5 5:5

5 I'M 6:1 5 P

M 988 15.0 18 3 29. 1 5.0 41 8 304 12 3 19 5 110 29 9 12.

7 19 3 20. 3 5.4 308 13 3 17 4 10 0 320 5/1 5 6:1 5 P

M 6:3 6 P

M 98 9 4. 5 9 7 16.5 2.3 14 7 7 6 4 8 68 10

7 79 5.

3 8 1 12.7 2. 8 10

0 7 2 4 6 5

2 8 7 79 5/1 5 6:3 6 P

M 6:5 9 I'M 99 0 0. 0 13 0. 6 0.2 20 1 2 2 5 12

0 8 0. 0 2 0 1. 2 1. 5 1 9 2 2

3 2 10

4 9 5/1 5 6:5

9 P M 7:1 9 P

M 991 0,0 2 9 4. 9 0. 6 1 3 2 2

5 2 13

5 9 0. 0 2 9 0. 0 0. 1 1 5 1 26 5 11 5 1 0 5/1 5 7:1 9 P

M 7:38 P

M 992 0. 4 6 1.

3 0. 0 10 0 2 1 4 1 1

4 7 5/1 5 7:3

8 P M 7:58 P

M 99

3 0. 0 2 9 0. 1 0.4 9 0 9 0 3 8 3 5/1 6 7:0

5 A M 7:2

5 A M 995 11. 9 18 3 37. 8 8. 6 28 6 24 7 14 0 15 5 26 9 25 9 14.

3 15 9 30. 3 10. 0 20

3 25 4 14

0 15 3 23 2 27 6 5/1' . 7:2

5 A M 7:4

5 A M 99 6 13. 2 21 6 39. 3 7.

1 374 26 8 15

1 17 2 29 0 28 0 13. 0 21 6 33. 8 12.5 28 7 26 9 15

1 15 8 24 9 ^K

9 51 6 7:4

5 4 M 8:0

6 A M 99

7 1 0 13. 7 18 8 38. 5 6. 1 40 4 28 4 15 4 18 2 26 2 29 8 14. 2 19 7 32. 9 6. 9 28 3 27 2 14 6 16 7 23 1 29 4 5/1 6 8:0 6 A M 8:2

6 A M 99

8 1 0 16. 7 20 8 38. 2 6. 1 39 7 28 4 15 0 18 2 24 4 30 1 13. 7 18 6 28. 8 4. 7 26 9 27 3 14 3 16 0 20 3 29 2 5:1 6 8:2 6 A M 8:4

7 A M 99

9 1 0 12. 0 210 25.

4 3. 7 40 3 29 0 14 4 19 8 26 2 29 6 9. 5 19 5 21. 5 6. 1 28

6 28 2 14 2 16 0 21 4 29 6 5; 1 6 8:4 7 A M 9:0

8 A M 1 1

0 14. 1 19 ) 35. 7 5. 3 39 6 28 4 13 7 19 7 23 6 29 4 14. 4 17 8 28. 8 5. 0 28 7 28 5 14 0 16 6 20 8 30 4 5/1 6 9:0 8 A M 9:2

8 A M 2 1

0 13. 9 20 8 37. 3 6. 0 38 5 28 1 13 4 19 5 21 6 28 6 14. 2 17 9 28.0 5.

1 29 0 29 0 14 0 16 2 19 2 30 5 t n 73 D O O m 73



### VES01686 8Tabl e 20 (Cont'd) . XCE M concentrations . Dat e STAR T STO P X C Y12 9 XCE M CONC . (ug/DSCM ) CE S CONC . (ug/DSCM ) Dat e STAR T STO P RU N RU N A S B A C D C R H G N I P B S B s \ / \ A S B A C D C R H G N T P B S B S N Z N 5/I d 10:3(

1 A M 10:5

0 A M 6 1

1 16. 2 18 3 34. 6 5.

3 39 3 286 12

6 20 2 16 3 28 1 14. 7 21 8 32. 0 4.8 28 4 28 1 12

9 17 4 14 4 29 2 10:51 1 A. M 11:1 1 A M 7 1 1 15. 9 20

4 34. 1 5.

2 394 28 6 11 9 19 3 15 2 285 14.

7 209 32. 1 5.4 30 2 30 5 13

6 18 5 14 1 31 5 5/1 6 11:1 1 A M 11:3 1 A M 8 1 1 14.4 19 3 35. 9 5.8 38

2 280 11 8 18

3 14 3 27 8 15.

3 19 6 28. 8 7. 0 27

5 279 12

2 17 2 12 5 28 6 5/1 6 11:3 1 A M 11:5 2 A M 9 11 10. 6 204 34. 3 4. 9 405 29 8 13 0 19 2 13 3 29 5 14.

5 20 6 29. 4 5.2 28 8 298 12 8 18 2 119 MW 5/1 6 11:5

2 A M 12:13 P. M 1 0 1 1 23. 1 19

4 37. 5 5.

4 405 289 112 19 1 12 8 290 14. 7 21 6 33. 5 5. 3 29 2 29 9 131 18

6 11 6 31 1 5/1 6 12:1

3 I' M 12:3

3 P M 11 1

1 12.7 20

2 33. 5 5. 6 401 290 12 5 19 8 12 9 28 6 14.

4 22 6 30.2 5.0 27

4 29 1 12

8 17 9 111 30 1 5/1 6 12:3

3 P M 12:5

4 P M 1

2 1 1 15. 6 201 311. 3 4. 9 37

4 27 3 11 5 18

9 110 269 12.9 206 29.2 7.0 26 3 280 12

1 18 3 9( i 28 8 5/1 6 12:5

4 PM 1:1

4 P M 1

3 12.

5 20 8 32.3 5 7 38

6 281 1 1

9 19 8 9 5 28 3 : 4 ' i 19

8 33.1 5.

0 291 30

2 13 0 18 1 9 2 : i . . 5/1 6 1 I' M 1:3 5 I' M 1

4 14.

8 18 3 3 3 9 s 1 40

2 29 8 12 4 21 1 10

0 701 ) i(

i 20 3 33.6 * ? 26

0 29 1
. _'f , 18

0 8 6 -IH 5/1 6 1:3

5 P M 1:5

6 P M 1

5 1 2 15. 3 23 4 35. 4 5.

2 395 288 11

8 19 4 10 6 29 1 13.9 20

3 31. 0 5. 1 286 30 1 13 0 19 1 9 7 .'•O K 5/1 6 1:5

6 P M 2:1 6 P M 1 6 1 2 14. 3 234 33. 4 4. 9 38 9 28 9 11 8 19 6 10 5 279 14.1

1 208 31. 8 6.0 25 2 28 6 12 3 18 1 8

7 29 5 5/1 6 2:1 6 P.

M 2:37 P M 1

7 1 2 12. 9 18

4 .13. 0 5. 1 38 1 28 1 117 18 9 90 27

2 14.

- " 191 30.2 4. 9 26 4 29 1 12

4 17 8 8 0 30 1 5/1 6 2:3

7 P M 2:5

7 P M 18 1

2 14. 6 17

9 35. 9 5.

2 37 6 28 4 113 19

5 82 27

3 14. 4 21 1 32. 5 5.4 268 296 12 7 18 1 8 9 30 4 5/1 6 2:5

7 P M 3:1 8 P M 1 9 1 2 16.9 19

6 18. 8 5. 9 406 29 1 12 0 19 1 9 4 28 6 14.

5 21 3 32.3 12.

4 27 4 29 7 12 7 18 9 8 5 30 3 1 10.1 23

2 34. 7 3. 6 36

5 26 9 6 6 18 4 37 1 28 7 2 9. 3 24 4 35. 7 4.1 38

0 28 2 6 6 19 9 32 8 296 3 13.

7 22 8 37. 3 5. 8 36 4 26 2 8 1 18 9 436 28

7 13, 4 19 4 31. 7 4.8 26

2 26 2 8 4 15 6 39 4 30 1 4 14.

3 21 0 37. 6 5.

8 36 8 26 9 3 6 18 9 19 7 27 6 14. 5 201 32.

5 5. 1 301 28

5 3 9 17 6 18 4 30 3 5 15.1 22

8 37.4 6.

0 38 1 27 6 2 6 19 7 16 2 27 8 14. 3 19 7 30. 5 5. 1 313 271 2

7 17 5 14 1 28 7 6 12.

9 22 3 34.4 5.

4 37 9 28 2 15 3 19 5 33 3 29 1 12. 5 18 6 26. 6 4. 9 28

8 26 0 14 2 15 8 27 3 28 3 UN W EIGHTE D AVERAG E 7 15. 3 21 8 36. 9 5.

7 39 2 28 8 13 6 19 8 23 4 29 2 13. 5 19 5 30. 2 5. 0 29 4 27 7 13 8 17 0 20 1 29 3 8 14. 5 21 2 38.3 5.

7 40 4 29 5 13 1 18 6 17 2 29 2 13. 8 18 8 31. 1 4. 9 29

4 28 0 13 1 17 0 14 8 29 3 9 13.

9 20 2 37.5 5.

9 40 6 29 4 12 8 19 5 13 3 29 3 13. 7 19 4 31. 5 5. 3 28 7 28 2 12 5 17 1 11 3 29 2 1 0 14.6 19

9 35. 1 5.

5 39 5 28 6 13 9 19 2 23 0 29 3 13. 5 18 9 28.5 5.

4 28 2 28 2 14 0 16 4 19 9 29 8 1 1 15. 5 19 7 34.3 5.

3 39 3 28 6 12 0 19 3 13 7 28 4 14. 5 21 1 30.

7 5. 8 28 3 29 0 12 8 18 0 12 2 30 0 1 2 14.8 20

5 35.5 5.

3 38 9 28 6 11 7 19 3 9 6 280 14.

3 20 5 31. 6 6.

8 26 9 29 4 12 6 18 4 8 7 303 A L L 13.7 21 6 36.2 5. 3 38 5 28 1 10

0 19 3 23 6 28 7 13.8 19

6 30.5 5.

3 28 7 27 8 10 8 17 0 18 6 29 5 St. Dev . 5. 1 69 10.7 2. 2 12 9 9 4 4 4 6 8 116 8

9 3. 0 36 5.

7 1. 7 5 2 49 4

3 3 4 9 3 5 1



### VES01686 95 2 ERDC/CER L TR-05- 9

Th e XCE M dat a wer e the n average d fo reach M2 9 ru n usin g equatio n 7 :

n [Eq7 ]

where : C ; = XCE M time-weighte d concentratio n fo relemen ti durin g M2 9 tes t

ru n C ^ = XCE M reporte d concentratio n fo relementi durin g tim e interva l j n = Numbe rof

XCE M measurement s durin g tes tru n t j = Numbe ro

f minute s XCE M measure d elemen ti' s concentratio n dur in g tim e interva l

j coincidin g wit h M2 9 samplin g M2 9 samplin g period .
Al l XCE M dat a use d fo rcomparison s t o M2 9 were th e sam e a s reporte d durin g M2 9 testin g wit h th e followin g fou rexceptions : 1

. Durin g M2 9 ru n 1, a n evaluatio n of th e calibratio n factor

s wa s undertaken . I t wa s observe

d thatSb , Ba , an d H g calibratio n factor s wer e to o hig h relativ e t

o the cahbratio n standard s b y 15,15 , an d 7 percent , respectively . Th e calibratio n fac tor s wer e changed prio rto ru n 2 (Appendi x D) . 2 . H g cahbratio n factor s wer e determine d t

o b e hig h relativ e t

o th e cahbratio n curv e b y 4 percen

tan d wer

e change d followin g the M2 9 tes t(se e Appendi x D fo r a complet

e discussio n o f

H g cahbration) . 3. Durin g ru n 961 , a n unusuall y hig h C rnumbe r(1 8 ug/dscm - mor e tha n 6 S D fro m th e averag

e durin g norma l spikin g conditions) was observed . Th e spectra showe d Fe , Cr , and N i i n the sam e rati o a s stainles s steel an d a spec k wa s noted o n th e filte rtape . Th e spec k wa s believed t

o be from contaminatio n tha twa s no t representative ofth e stac k gas . Fo rthi s reason , ru n 96 1 fo rC rwa s notuse d dur in g th e averagin g t

o compar

e t o M29 . 4 . Th e XCE M shed' s ai rconditionin g faile d o n 1 6 May , whic h meanttha tthe P d Q A concentratio n di d notmee tth e 90—11

0 percen tcriterio n fo rXCE M run s 102 1 an d 1022 . Thes e run s represented 23 minute s ofM2 9 ru n 12. Consequently , XCE M concentrations fo rru n 1 2 wer e base d o n a time-weighted average ofth e 9 7 min utes tha tthe XCE M produced validate d data . Th e modifie d XCE M dat a were submitte d before receivin g th e M2 9 results . N o modificatio n t

o th e XCE M dat a wa s mad e afte rreceivin g M2 9 results .



### VES01687 0ERDC/CER L TR-05- 9 5 3



### XCE M Calibratio n Evaluatio n Usin g A Quan X - XR F an d ICP/M S
Sinc e XR F analysi s i s nondestructive , th e concentrate d particulat e matte ro n th e filte rca n b

e reanalyze d ata late rdate . T o evaluate th e XCE M calibration , CE S reanalyze d eac h spo tusin g a Quan X XR F analyze rlocate d a tCES . Th e CE S Quan X analyze ri s one o f fou ri n th e natio n tha tha s bee n approve d fo rmeasur in g PM 2 S metal s concentration s fo rEPA' s speciatio n program . Consequently , th e analyze rhas undergon e a serie s o f roun d robi n tests wit h othe rlaboratorie s a s wel l a s rigorou s qualit y contro l checks . Th e Quan X analysi s was conducte d ap proximatel y 6 weeks afte rM2 9 testing . Wit h th e exceptio n o f Hg , whic h ap peare d t

o b e los tfro m th e XCE M filter , th e materia l collecte d o n th e filte r seeme d t

o b e intac tan d representativ e o f th e sampl e collecte d atTEAD . Th e Quan X calibratio n evaluatio n dat a ar e shown i n Tabl e 20 a s CE S Concentratio n (CE S CONC) . Followin g th e reanalysis , filte rspot s tha tcorrelate d wit h M2 9 run s 5 an d 6 wer e combine d an d submitte d to Columbi a Analytica l (Vancouver , WA ) fo ranalysi s usin g ICP/mas s spectrometry (MS) . Tabl e 2 1 shows result s o f thi s analysis . Tabl e 21 . Analysi s o

f XCE M filte rtape b

y Columbi a Analytica

l (ug/dscm) . Ru n A s C d C r B a H g N i P b S b S n Z n 5 14.0 36. 4 5. 0 17 6 27 4 226 2

2 17 4 7 4 25 2 6 13. 3 34. 2 4. 7 15

9 25 4 22 0 12 9 15 2 12 7 24 5



### Precisio n Fiv e element

s wer e spike d b y MSE-T A ata constan trat e throughou tth e testing : Ba , Hg , Ni , Sb , an d Zn . Althoug h B a an d Z n ha d backgroun d concentration s o f abou t10 percent , thei rlimite d variabilit y durin g testin g affecte d th e predicte d concentration s precisio n b y onl y a fe w percent . Overall , thes e elements wer e spike d wit h a precisio n o f bette rtha n 5 percent . Bot h th e XCE M an d M2 9 show good precisio n fo rthes e elements wit h th e XCE M precisio n abou t3

0 percen tlowe rtha n M2 9 (Tabl e 22) . Tabl e 22. Predicted (spiked) , XCEM , and M2 9 precisio n (%

) during validation testing. 1 Approach Hg S b N i B a Z

n Predicte d 1.

0 1. 7 1. 1 5. 9 3.

5 XCE M 3. 8 2. 5 3.7 6. 9 2.4 M2 9 6. 1 6. 1 5. 7 7. 2 3.

3

1 Determine

d b y percen tRS D o f 1 2 concentration

s reporte d fo rM2 9 runs.



### VES01687 15 4 ERDC/CER L TR-05- 9



### Discussio n Regulated

Elements

Typically

Found in the Feedstream Althoug h th e APE-123 6 i s regulate d fo rnin e elements , onl y thre e element s — Pb , Cd , an d C r—ar e foun d i n hig h enoug h quantitie s i n stac k emission s t o po tentiall y limi tincineratio n fee d rate s (Tabl e 23 ; B e i s no tliste d i n thi s tabl e be caus e i tcanno tb e measure d b y th e XCEM) . Th e XCE M successfull y measure d al l thre e of

th e ke y elements an d me tth e 2 0 percen tR A requirement s i n pro pose d PS-1 0 wit h RA s of 4 , 17, an d 1

5 percent , respectively . Table 23 . TEA D emissio n limit s fo rregulated elements . Elemen t Stat

e B/hr Limi

t Mg/dscm 1 Interi

m MAC T Limi

t pg/dsc m Fina

l MAC T Limi t Mg/dsc m Potentia

l to Limi t Fee d Rat

e

P b 4. 3 93 2 24 0 5 9 Ye s C d 0.2 6 5 6 24 0 5 9 Ye s C r 0.0 4 1 0 9 7 8 4 Ye s A s 0.1 1 2 4 9 7 8 4 N o H g 1 4 3,03 6 130 13 0 N o S b 1 4 3,03 6 N R N R N o N i 93 0 201,74 0 N R N R N o B a 2,40 0 521,24 3 N R N R N o

' Assume

s 4,63 5 dscm/h

rbased o

n averag e rat e fro m Tabl e 16 . NR : No tregulated ; MACT : Maximu m achievabl

e contro l technolog

y (rule )

Lea d
Lea d i s th e elemen ttha tmos tofte n limit s incineratio n rate s a tAPE-1236 . Th e TEA D incinerato rha s a state-mandate d P b stac k emissio n limitatio n of 4.3 g/hr. A ttypica l stac k flo w rates , thi s equate s t o about900 pg/dscm . EPA' s HW C in teri m maximu m achievabl e contro l technology (MACT ) rul e (EP A 1999 ) currentl y limit s P b an d C d emission s t o 24 0 pg/dscm . Th e fina l MAC T rule , whic h wa s publishe d 20 Apri l 200 4 (FR21210 ) an d wil l be i n effect3 year s afte ri tpromul gates , wil l furthe rlimi tth e combine d P b an d C d emissio n rat e t o 59 pg/dscm . Currently , P b concentration s withi n th e munition s are determine d fo reach typ e o f ordnanc e before incineration . Munitio n fee d rate s int o th e incinerato rare re stricte d usin g a mode l tha tassume s tha ta fractio n o f th e P b i n th e munition s wil l b e transporte d throug h th e ai rpollutio n contro l device s an d emitte d fro m th e stack . Th e effectivenes s of th e mode l depend s upo n severa l assumption s in cludin g transpor tunde rvariou s meteorological regimes , incinerato rtemperatur e effects , an d chemica l interactions . Direc tmeasuremen tof P b concentration s i n



### VES01687 2ERDC/CER L TR-05- 9 55

th e stac k gas allow s fo rimprove d understandin g of th e relationshi p between munition s incineratio n an d stack emissio n rate s a s wel l a s a n enhance d mecha nis m fo rregulatin g fee d rates . Tabl e 2 4 show s th e P b result s fo rth e MSE/backgroun d predicte d concentration s (PRD) , M29 , XCE M (XC) , th e post-tes tanalysi s of th e XCE M spot

s usin g th e CE S Quan X (QN) , an d th e ICP/M S analysi s of th e XCE M filte rtap e b y Columbi a Analytica l (CA) . I n general , th e result s are i n ver y goo d agreemen twit h th e PRD , M29 , XCEM , an d Q N concentrations , agreein g t o withi n 7 percent . Th e XCE M an d M2 9 P b concentration s ar e als o highl y correlate d wit h a n r 2of 0.98 (Figur e 15) . Lea d i n the firs tfiv e M2 9 run s wa s exclusivel y fro m residua l concentration s i n th e incinerator . Followin g ru n 5 , MSE-T A began spikin g a n additiona l 10 5 pg/dscm o

f Pb . Durin g testing , both M2 9 an d th e XCE M reporte d concentration s rangin g fro m 25 t

o 15 0 pg/dscm . Th e R A fo rth e XCE M wa s 4.4 percent . Thi s agreementbetwee n th e XCE M an d M2 9 demonstrate s th e capability o f th e XCE M t

o accuratel y measur e P b a tth e incinerato runde ra wid e rang e of con centrations . Table 24 . Summar

y o f P b concentration (pg/dscm ) dat a an d ratios durin g M2

9 testing . RU N PR D M2 9 X C O N C A XC/Q N XC/PR D M29/PR D XC/M2 9 ON/M2 9 1 6 7 7 2 6 7 6 8 0.99 1.0 1 1.0

8 0.9

3 0.9

4 2 6

1 7 7 6 7 6 4 1.0

4 1.1 1 1.2 7 0.8

7 0.8

4 3 7

7 9 8 8 1 8 4 0.97 1.0 6 1.2

7 0.8

3 0.8

6 4 41 3

8 36 39 0.93 0.8 8 0.9

3 0.95 1.0 3 5 3

6 2 7 26 2

6 2 2 0.9 9 0.7

3 0.7

7 0.9

4 0.9

5 6 16

7 14 7 15 4 14 1 12 9 1.0 9 0.9

2 0.8

8 1.0

5 0.9

6 7 15

0 13 5 13 7 14 1 0.97 0.9 1 0.9 0 1.0

1 1.0

5 8 14

0 12 8 13 2 13 2 1.0

0 0.9

4 0.9

2 1.0

3 1.0

3 9 13

4 12 2 12 8 12 5 1.0

2 0.9

5 0.91 1.0 5 1.0

3 1 0 15

1 13 5 14 0 14 0 1.0

0 0.9

3 0.8

9 1.0

4 1.0

4 1 1 13

6 11 8 12 1 12 9 0.9

4 0.8

9 0.8

7 1.0

2 1.0

9 1 2 12

8 11 3 11 7 12 6 0.9

3 0.9 1 0.8 8 1.0

4 1.1

2 AVG . 10

7 101 101 10

1 7 5 0.99 0.9

4 0.9

6 0.98 0.9 9 S D 4

7 3 9 4

3 4 3 7 6 0.05 0.0

9 0.1 6 0.07 0.0 9



### VES01687 35 6 ERDC/CER L TR-05- 9



### E 20 0

0 5 0 10 0 15 0 20 0



### M29 Lea d (ug/dscm

)
Figur e 15 . XCE M versu s M2 9 lea d fo rvalidation tests .
Cadmiu m Th e APE-123 6 state-mandate d emissio n limi tfo rC d i s about60 ug/dscm unde r typica l stac k flo w rates . Cadmiu m stac k concentrations , whic h are derive d fro m incineratio n of

shel l casings , ca n occasionall y approac h thi s limit . Fo rthi s test , approximatel y 8

0 percento f

th e stack' s C d wa

s fro m MSE-TA , whil e 2 0 percen t wa s estimate d t

o b e background . Tabl e 2 5 show s th e M2 9 an d XCE M result s fo r C d durin g th e validatio n tests . Overall , th e XCE M an d M2 9 wer e i n goo d agreementfo rCd . O n average , th e XCE M was about1

4 percenthighe rtha n M2 9 wit h a n R A o f 1 7 percent . Th e re analysi s o f

th e XCE M filte rtap e yielde d mixe d result s wit h th e Quan X XR F withi n 3 percen to f

M2 9 an d th e Columbi a Analytica l concentration s withi n 4 percen to f

th e XCEM . Th e inconsistenc y betwee n th e XCE M an d CES-Quan X result s suggest

s tha ta n XCE M calibratio n erro rma y hav e been responsibl e fo r th e differenc e between M2 9 an d th e XCEM .



### VES01687 4ERDC/CER L TR-05- 9 5 7

Table 25 . Summar

y of C d concentration (pg/dscm ) dat a an d ratios during M2

9 testing . RU N PR D M2 9 X C 9 N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 41.5 29.

4 35. 2 29. 3 1.2

0 0.8

5 0.7 1 1.2 0 0.9

9 2 39.8 32.0 35. 8 29.4 1.2

2 0.9

0 0.8

0 1.1

2 0.9

2 3 48. 6 34. 6 37. 2 31. 6 1.1

8 0.7

7 0.7 1 1.0 8 0.91 4 41. 6 31.0 37. 7 32. 6 1.1

6 0.9 1 0.7 4 1.2

2 1.0

5 5 41.4 30.8 36. 4 30.0 36.

4 1.2 2 0.8

8 0.7

4 1.1

8 0.9

7 6 45.4 31.

2 37. 2 28. 6 34.

2 1.3 0 0.8

2 0.6

9 1.1

9 0.9

2 1 43.7 31.8 36.6 30.9 1.1 9 0.8

4 0.7

3 1.1

5 0.9

7 8 41.5 32.4 37. 7 31. 1 1.2

1 0.9 1 0.7 8 1.1

6 0.9

6 9 40.5 32.0 37. 4 31.5 1.1

9 0.9

2 0.7

9 1.1

7 0.9

8 1 0 41. 1 29.8 34.6 27. 9 1.2 4 0.8

4 0.7

3 1.1

6 0.9

4 1 1 39. 9 31.

3 34.9 30.9 1.1 3 0.8

7 0.7

8 1.1

2 0.9

9 1 2 39.0 31.

2 35. 5 31. 6 1.1

2 0.9 1 0.8 0 1.1

4 1.0

1 AVG . 42.0 31. 5 36. 4 30.4 35.

3 1.2 0 0.8

7 0.7

5 1.16 0.9 7 S D 2.7 1.

3 1.1 1.

4 1. 5 0.0

5 0.0

5 0.0

4 0.0

4 0.0

4

Chromiu m Th e APE-123 6 ha s a n effectiv e C remissio n limi to f les s tha n 1 0 ug/dscm unde r typica l stack operatin g conditions . Sinc e th e backgroun d C rconcentration s were uncertai n a tth e star to f th e validatio n test , MSE-T A spike d a nomina l 3 pg/dsc m durin g M2 9 run s 1 an d 2 . Followin g thes e runs , i twa s determine d tha tth e backgroun d C rconcentration s wer e insignifican tan d MSE-T A raise d thei rspik in g rat e t

o 5 pg/dscm fo rth e remainde ro f th e tests . Overall , th e XCE M wa s con sistentl y 1 0 percenthighe rtha n M2 9 a tbot h concentratio n level s (Tabl e 26) . Thi s represent s a differenc e of abou t0. 5 pg/dscm . Th e agreementbetwee n th e XCE M an d M2 9 atbot h th e 3 an d 5 pg/dsc m level s validate s th e abilit y of th e XCE M t o accuratel y measur e C ra tver y lo w concentrations . Th e C rR A wa

s 1 5 percent , meetin g th e PS-1 0 criterion . Subsequen tmeasure ments ofth e XCE M filte rtap e b y th e CES-Quan X an d IC Pwere withi n 3 percen t o f th e M2 9 concentrations . Th e consistency of M2 9 wit h th e predicte d value s an d subsequen tmeasurement s o f th e XCE M filte rtap e suggest s tha tth e differ ence betwee n th e tw

o method s i s du e t

o XCE M error .



### VES01687 55 8 ERDC/CER L TR-05- 9

Tabl e 26. Summar

y o f C rconcentration (ug/dscm ) dat a and ratio s durin g M2 9 testing . RU N PR D M2 9 X C Q N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 2.9 3. 6 3.

7 3. 2 1.1

6 1.2

8 1.2

4 1.0

3 0.8

9 2 2.9 4.0 4. 0 3. 2 1.2

7 1.3

9 1.3

8 1.0

1 0.7

9 3 5.

2 6. 4 5. 8 4. 8 1.2

0 1.11 1.2 4 0.9

0 0.7

5 4 5.

0 5. 0 5. 8 5. 1 1.1

4 1.1

5 0.9

9 1.1

6 1.0

2 5 5.

0 5. 2 6.1 5.

0 5. 0 1.2 2 1.2

1 1.0

4 1.1

6 0.9

6 6 5. 0 4.8 5.

8 5. 3 4.7 1.0

9 1.1

6 0.9

7 1.2

0 1.1

0 7 5.1 4. 9 5.6 5. 2 1.0

9 1.1

0 0.9

6 1.1

5 1.0

5 8 5. 1 5. 1 5. 8 4. 8 1.2

0 1.1

3 1.0

0 1.1

4 0.9

5 9 5. 1 5.

2 5. 9 5. 3 U O 1.1 7 1.0

2 1.1

4 1.0

3 1 0 4.8 4. 9 5.

4 5. 4 1.0

1 1.1

4 1.0

3 1.1 1 1.1 0 1 1 5.

0 4.8 5.

4 5. 5 0.9

7 1.0

7 0.9

6 1.1 1 1.1 5 1 2 5. 1 4.8 5.

3 6. 9 0.7

6 1.0

4 0.9

5 1.1

0 1.4

4 AVG . 4.7 4.9 5. 4 5. 0 4.8 1.10 1.16 1.0 7 1.10 1.0 2 S D 0.

8 0.7 0.

8 1. 0 0. 2 0.14 0.0

9 0.1 4 0.0 8 0.1 8 Regulated

Elements

Not Typically

Found in TEAD Emissions
APE-123 6 i s regulate d fo rsi x additiona l element s tha tar e no ttypicall y foun d i n th e feedstrea m i n quantitie s tha tapproac h th e regulator y limits : As , Hg , Sb , Ni , Ba , an d Be . Th e XCE M doe s notmeasur e Be . Th e XCE M me tPS-1 0 measure men tcriteri a fo rS b (2 0 percent

) an d B a (

4 percent) , bu twa

s highe rtha n M2 9 fo r As , Hg , an d N i wit h relativ e accuracie s of 27 , 33 , an d 33 percent , respectively .
Arseni c Arseni c result s ar e shown i n Tabl e 27 . Th e XCEM-reporte d concentratio n was i n good agreementwit h th e post-tes tanalysi s o f th e filte rtap e b y both Quan X an d Columbi a Analytical . Thei ragreemen tindicate s tha tth e XCE M calibratio n wa s correctt

o withi n a fe w percent . Th e XCE M concentratio n i s als o i n good agree men twit h th e predicte d concentration . Although , a s discusse d earlier , th e HK M analysi s showed a 2

3 percentlowe rvalu e fo rth e calibration . Th e XCEM' s R A o f

2 7 percen tdi d no tmeetPS-1 0 criterion . Overall , th e XCE M concentration s wer

e 25 percen thighe rtha n M2 9 concentration s fo rAs . Othe r potentia l sources error s fo rth e XCE M besides calibratio n suc h as los s durin g transport , low filte rtrappin g efficiency , an d deposi tpositionin g error s ca n b e rule d outbecaus e the y woul d resul ti n XCE M concentration s lowe rtha n M29 . I t i s highl y possibl e tha tthe difference s i n concentratio n ar e due t o M2 9 errors . Th e XCE M was als o highl y correlate d wit h M2 9 A s (r 2 =0.85 ) showin g goo

d re sponsivenes s t

o changes i n A s concentration .



### VES01687 6ERDC/CER L TR-05- 9 5 9

Table 27 . Summar

y o f A s concentration (pg/dscm ) dat a and ratio s during M2 9 testing . RU N PR D M2 9 X C O N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 10.

6 7. 8 10. 1 9.

4 1.0

7 0.9

5 0.7

4 1.2

9 1.2

0 2 10.

7 8. 3 9. 3 10. 2 0.9 1 0.8 8 0.7

7 1.1

3 1.2

4 3 16.

7 11. 5 13. 7 13. 4 1.0

2 0.8

2 0.6

9 1.19 1.1 7 4 16.1 11.

9 14. 3 14. 5 0.9

8 0.89 0.7 4 1.2

0 1.2

2 5 16.1 11.

8 15. 3 14. 1 14.

0 1.0 9 0.9

5 0.7

3 1.3

0 1.2

0 6 16.

0 11. 3 13.9 13.

8 13. 3 1.0 1 0.8

7 0.7 1 1.2 3 1.2

2 7 16.

4 11. 7 15.6 13.

7 1.1

4 0.96 0.71 1.3 4 1.1

8 8 16.

2 12. 3 14. 4 13. 8 1.0

5 0.89 0.7 6 1.1

8 1.1

2 9 16.

2 12. 2 13.9 13.

7 1.0

2 0.86 0.7 5 1.1

4 1.1

2 1 0 15.

2 11. 1 14.

3 13. 3 1.0

7 0.9

4 0.7

3 1.2

8 1.2

0 1 1 16.

0 11. 7 15. 5 14. 7 1.0

5 0.97 0.7 3 1.3

2 1.2

5 12 16.

2 11. 9 14. 8 14. 3 1.0

3 0.9 1 0.7 3 1.2

4 1.2

1 AVG . 15.

2 11. 1 13. 8 133 13.7 1.0 4 0.9 1 0.7 3 1.2

4 1.19 S D 2.

2 1. 5 2. 0 1.

7 0. 5 0.06 0.05 0.0 2 0.0

7 0.0

4
Mercur y Unlik e the othe relements , H g i s primaril y i n th e vapo rphas e i n typica l stack emissions . Fo rexample , durin g th e 2001M2 9 tests a tTEAD , th e particulat e H g capture d o n th e M2 9 filte ran d prob e represente d 1 percen tof th e tota l Hg . Th e XCE M relie s upo n a speciall y treate d filte rmembran e t o captur e th e vapo r phas e H g whil e M2 9 use s a n impinge rtrain . Th e APE-123 6 H g limi ti s abou t3000 pg/dscm . Mercury , however , i s typicall y notpresen ti n TEA D stac k emissions . A n earlie rmulti-metal s monito rwa s certi fie d fo rus e atTEA D withou tmeasurin g H g (Seltze r2000) . Fo rth e curren tvali datio n test , H g was spike d b y MSE-T A wit h result s show n i n Tabl e 28 . Th e XCE M an d M2 9 concentration s ha d acceptabl e agreemen tdurin g run s 1- 5 wit h th e XCE M 1 6 percen thighe rtha n M29 . Followin g ru n 5 , however, th e XCE M wa

s consistentl y 34 percenthighe rtha n M29 . I ti s believe d tha tthes e difference s ar e due t

o vaporizatio n of

particulat e H g fro m th e M2 9 filter . Durin g run s 1-5 , th e H g solutio n containe d Z n an d Ni . Followin g ru n 5 , P b wa s adde d t o thi s solution . Althoug h H g was spike d a ta constan trate , M2 9 H g concentration s decrease d b y 8 percen tfollowin g P b injection . Th e source o f thi s decreas e may b e relate d t o the unusuall y hig h leve l o f particulat e phas e H g presen tdurin g thi s validatio n test . Particulat e H g i s capture d o n the M2 9 quart z fibe rfilte ran d ca n be readil y volatilize d i f th e filte ri s no tcooled . Eve n thoug h tota l M2 9 H g decreased followin g ru n 5 , th e fraction o f H g o n th e M2 9 filte rincrease d fro m 1 8 percenti n run s 1- 5 t o 3 0 percen ti n run s 6-1 2 (CHPP M 2002) . Th e H g capture d o n th e filte rrepresent s particulat e phas e Hg , whic h i s typicall y onl y a coupl e of percentof

th e tota l Hg . A s such , M2 9 does notrequir e



### VES01687 76 0 ERDC/CER L TR-05- 9

refrigeratio n of

th e M2 9 filter, so i twas no tcooled whil e bein g shippe d t o Californi afo ranalysis . Durin g thi s time , a significan tquantit y o f th e H g o n th e filte rcoul d hav e vaporized . Figur e 1 6 show s th e relationshi p between the leve l o f H g o n th e M2 9 filteran d th e percen tdifferenc e betwee n M2 9 an d th e XCEM . Th e XCE M filte rals o showed a los s o f about30 percen to f it s H g a s demon strate d b y a n analysi s o f th e spectr a availabl e durin g validatio n testin g an d a few weeks late rwhe n th e tap e wa s reanalyze d b y th e CE S QuanX . Interestingly , th e CE S tap e ha d previousl y show n good retentio n o f vapo rphas e H g o n earlie r tests (Coope retal . 2000 ; Chapte r3) so th e H g los s seems t o depen d upo n th e quantity i n th e particulat e phase . Se e Appendi x D fo ra more detaile d discus sion . Tabl e 28. Summar

y o f Hg concentration (ug/dscm) dat a and ratios durin g M2 9 testing . RU N PR D M2 9 X C QN 1 C A 1 XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 32

4 33 2 36 7 25 7 1.4

2 1.1

3 1.0

2 1.1

0 0.7

7 2 32

5 33 4 38 1 25 1 1.5

2 1.1

7 1.0

3 1.1

4 0.7

5 3 33

3 29 4 36 5 26 2 1.3

9 1.0

9 0.8

8 1.2

4 0.8

9 4 32

2 32 7 36 8 30 1 1.2

2 1.1

4 1.0

2 1.1

3 0.9

2 5 32

3 318 37

9 30 8 27 4 1.2 3 1.1

8 0.9

9 1.1

9 0.9

7 6 32

9 28 0 37 8 28 8 25 4 1.3 1 1.1

5 0.8

5 1.3

5 1.0

3 7 32

7 28 5 39 2 30 2 1.3

0 1.2

0 0.8

7 1.3

7 1.0

6 8 32

5 30 6 40 6 29 4 1.3

8 1.2

5 0.9

4 1.3

3 0.9

6 9 32

4 30 9 40 5 28 7 1.4

1 1.2

5 0.9

5 1.3

1 0.9

3 1 0 32 8 29 2 39 5 28 2 1.4

0 1.2

0 0.8

9 1.3

5 0.9

7 1 1 32

6 29 5 39 7 28 6 1.3

9 1.2

2 0.9

0 1.3

5 0.9

7 1 2 32 2 29 3 38 9 26 7 1.4

6 1.2

1 0.91 1.3 3 0.91 AVG . 32

6 30 5 38 5 28 2 26 4 1.3 7 1.18 0.9 4 1.2

7 0.9

3 S D 3.

3 19 1

4 1 9 13.8 0.0

9 0.0

5 0.0

6 0.1 0 0.0 9 1 ) Mercur y los

tfro m filter .

0 1

0 2

0 3 0 

### •

4 0 Percento f

H g on M2 9 Filte r Figur e 16. Percen

tdifference betwee

n M2 9 an d th e XCE M versu s percen tof H g on M2 9 filter.ERDC/CERL TR-05- 9 6 1

Antimon y Antimon y result s are shown i n Tabl e 29 . Overall , th e XCE M was highe rtha n M2 9 b y abou t1 8 percent , bu tmetR A criteri a wit h a n R A o f 19. 9 percent . Sub sequen tanalysi s of

th e filte rtap e b y th e CE S Quan X wa s i n bette ragreemen t wit h M29 . Fo rthi s reason , i ti s believe d tha tth e XCEM/M2 9 difference s were du e to XCE M calibratio n error s of abou t15 percent . Tabl e 29 . Summar

y o f S b concentration (pg/dscm) dat a an d ratio s durin g M2 9 testing . RU N PR D M2 9 X C Q N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 19

2 15 1 18 4 16 6 1.1

0 0.9

6 0.7

9 1.2

1 1.1

0 2 19

6 18 2 20 0 17 7 1.1

2 1.0

2 0.9

3 1.1

0 0.9

7 3 20

1 18 3 19 0 15 6 1.2

1 0.9

4 0.9 1 1.0 3 0.8

5 4 19

4 16 6 18 9 17 6 1.0

8 0.9

8 0.8

5 1.1

4 1.0

6 5 19

3 16 8 19 5 17 2 17 4 1.1 4 1.0

1 0.8

7 1.1

6 1.0

3 6 19

9 16 2 19 4 15 9 15 2 1.2 2 0.9

8 0.8 1 1.2 0 0.9

8 7 19

7 16 4 19 8 17 4 1.1

4 1.0

1 0.8

3 1.2

1 1.0

6 8 19

2 16 2 18 6 17 0 1.0

9 0.9

7 0.8

4 1.1

5 1.0

5 9 18

9 15 7 19 5 17 1 1.1

4 1.0

3 0.8

3 1.2

5 1.0

9 10 19

4 15 7 19 3 16 2 1.1

9 0.9

9 0.8 1 1.2 3 1.0

3 1 1 19

3 16 3 19 3 18 0 1.0

7 1.0

0 0.8

4 1.1

8 1.1

0 1 2 19 0 15 4 19 3 18 3 1.0

5 1.0

1 0.8 1 1.2 5 1.1

9 AVG . 19

4 16 4 19 2 17 1 16 3 1.1 3 0.9

9 0.8

4 1.1

8 1.0

4 S D 3 1

0 5 8 1

5 0.0

6 0.0

3 0.0

4 0.0

6 0.0

8

Nicke l Validatio n tes tresult s fo rN i are reporte d i n Tabl e 30 . Th e XCE M was about30 percen thighe rtha n M2 9 an d ha d a n R A of 3 4 percent , whic h di d notmeetth e PS-1 0 criterion . Althoug h th e XCE M N i concentration s were supporte d b y th e CE S Quan X filte revaluatio n an d predicte d concentrations , th e M2 9 result s were simila rt

o result s fro m Columbi a Analytical . A tthi s time , th e XCE M appear s t o hav e bee n calibrate d correctly . A s discusse d earlie ri n th e sectio n o n Arsenic , sinc e th e XCE M wa

s highe rtha n M29 , th e differenc e appear s t o b e du e t

o M2 9 analytica l problems . Nicke l i s nottypicall y foun d i n TEA D stac k emission s an d th e site ha s a 140,000 pg/dsc m stac k emissio n limit . A s such , th e conservativ e number s produce d b y th e XCE M shoul d serve t o adequatel y ensur e tha tN i i s belo w th e emissio n limit .



### VES01687 96 2 ERDC/CER L TR-05- 9

Tabl e 30. Summar

y of N i concentration (ug/dscm ) dat a an d ratio s durin g M2

9 testing . RU N PR D M2 9 X C O N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 26

7 20 0 27 0 26 2 1.0

3 1.0

1 0.7

5 1.3

5 1.3

1 2 26

8 23 5 28 3 27 6 1.0

2 1.0

6 0.8

8 1.2

0 1.1

8 3 27

5 23 4 26 2 26 2 1.0

0 0.9

5 0.8

5 1.1

2 1.1

2 4 26

5 21 3 26 9 28 5 0.9

5 1.0

2 0.8

0 1.2

6 1.3

4 5 26

6 23 1 27

4 26 7 22 6 1.0 3 1.0

3 0.8

7 1.1

9 1.1

5 6 271 22

5 28 1 25

9 22 0 1.0 8 1.0

3 0.8

3 1.2

5 1.1

5 7 26

9 21 8 28

9 28 5 1.0

1 1.0

7 0.8 1 1.3 3 1.3

1 8 26

7 21 9 29

6 28 1 1.0

5 1.1 1 0.8 2 1.3

5 1.2

8 9 26

6 221 29

4 28 3 1.0

4 1.1 1 0.8 3 1.3

3 1.2

8 10 27

0 20 5 28 5 281 1.0

2 1.0

6 0.7

6 1.3

9 1.3

7 1 1 26

8 21 6 28

8 29 2 0.9

9 1.0

7 0.8 1 1.3 3 1.3

5 1 2 26 6 19 9 28 6 29 4 0.9

8 1.0

8 0.7

5 1.4

4 1.4

8 AVG . 26

8 21 8 28 1 27

7 22 3 1.0 2 1.0

5 0.8 1 1.3 0 1.2

8 S D 2. 8 1

2 1 0 1 2 4. 9 0.0

4 0.0

4 0.0

4 0.0

9 0.1 1
Bariu m Bariu m result s fo rth e validatio n tests ar e show n i n Tabl e 31 . Fo rBa , th e pre dicte d concentrations , M2 9 results , XCE M results , an d Quan X reanalysi s al l agree t o withi n 10 percen twit h a n XCE M R A o f 4 percent . Althoug h th e stac k limi ti s 500,000 pg/dscm , typica l B a concentration s foun d i n th e stac k are i n th e 0 t o 20 0 pg/dsc m range . Durin g thes e validatio n tests , th e XCE M demonstrate d good accurac y relativ e t o M2 9 fo rB a unde rrealisti c stac k conditions . Tabl e 31 . Summar

y of B aconcentration (ug/dscm ) dat a an d ratio s during M2

9 testing . RU N PR D M2 9 X C Q N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 23 7 21 4 22 9 20 4 1.1

2 0.9

6 0.9

0 1.0

7 0.9

5 2 23

8 24 8 24 4 22 2 1.1

0 1.0

3 1.0

5 0.9

8 0.8

9 3 25

3 24 7 22 8 19 5 1.1

7 0.9

0 0.9

8 0.9

2 0.7

9 4 22

3 20 3 210 20

1 1.0

4 0.9

4 0.9 1 1.0 3 0.9

9 5 21 8 20

7 23 0 19 4 17 6 1.1 8 1.0

5 0.9

5 1.11 0.9 4 6 24

0 21 6 22

2 18 6 15 9 1.1 9 0.9

2 0.9

0 1.0

3 0.8

6 7 22

9 212 21

5 19 7 1.0

9 0.9

4 0.9

2 1.0

2 0.9

3 8 21 8 210 215 18 9 1.1

4 0.9

9 0.9

7 1.0

2 0.9

0 9 212 20

6 20 2 19 3 1.0

4 0.9

5 0.9

8 0.9

8 0.9

4 1 0 22 6 20 8 19 8 18 7 1.0

6 0.8

8 0.9

2 0.9

5 0.9

0 11 215 210 19 7 21 1 0.9

3 0.9

2 0.9

8 0.9

4 1.0

0 1 2 20 9 20 4 20 3 20 6 0.9

8 0.9

7 0.9

8 0.9

9 1.0

1 AVG . 22

6 21 6 21 6 19

9 16 7 1.0 9 0.9

6 0.9

5 1.0

0 0.9

3 S D 1

3 1 6 1 5 1 1 1

3 0.0

8 0.0

5 0.0

4 0.0

5 0.0

6



### VES01688 0ERDC/CER L TR-05- 9 63

Nonregulated

Metals
Tw o nonregulate d metals , S n an d Zn , were measure d b y th e XCE M durin g vali datio n testing . A s discusse d earlier , M2 9 i s no tapprove d fo rSn , an d th e M2 9 S n result s were notconsidere d valid . Zin c was spike d b y MSE-T A wit h XCE M re porte d concentration s shown i n Tabl e 32 . Overall , th e XCE M Z n concentration s were consistentl y abou t40 percen thighe r tha n M29 . Th e XCE M Z n concentration s were i n goo d agreementwit h both th e CE S Quan X an d Columbi a Analytica l tap e evaluations , indicatin g tha tcalibra tio n was notth e primar y source o f thi s difference . I ti s believe d tha tth e differ ence i s primaril y du e t o M2 9 errors . Tabl e 32 . Summar

y o f Zn concentration (ug/dscm ) dat a and ratio s during M2 9 testing . RU N PR D M2 9 X C Q N C A XC/Q N XC/PR D M29/PR D XC/M2 9 QN/M2 9 1 30

0 19 5 28 8 29 4 0.9

8 0.9

6 0.6

5 1.4

8 1.5

1 2 29

7 21 2 29 7 30 3 0.9

8 1.0

0 0.71 1.4 0 1.4

3 3 31

2 21 5 28 7 30 1 0.9

6 0.9

2 0.6

9 1.3

4 1.4

0 4 28

5 19 6 27 6 30 3 0.9

1 0.9

7 0.6

9 1.4

0 1.5

4 5 28

3 19 6 27 7 28 2 25 2 0.9 8 0.9

8 0.6

9 1.4

1 1.4

4 6 30

1 20 9 291 28

3 24 5 1.0 3 0.9

7 0.6

9 1.3

9 1.3

5 7 29

1 20 2 29 2 30 1 0.9

7 1.0

0 0.6

9 1.4

5 1.4

9 8 28

5 20 4 29 3 29 4 1.0

0 1.0

3 0.7

2 1.4

4 1.4

4 9 28

0 20 2 29 3 29 3 1.0

0 1.0

5 0.7

2 1.4

5 1.4

5 1 0 29 2 19 9 29 3 29 8 0.9

8 1.0

0 0.6

8 1.4

7 1.5

0 11 28

3 20 3 28 6 30 3 0.9

4 1.0

1 0.7

2 1.4

1 1.4

9 1 2 27 8 19 6 27 9 30 2 0.9

2 1.0

1 0.71 1.4 3 1.5

4 AVG . 29

0 20 2 28 8 29 6 24 8 0.9 7 0.9

9 0.7

0 1.4

2 1.4

7 SD 1

0 7 7 7 5 0.0 3 0.0

3 0.0

2 0.0

4 0.0

6



### Summary
Th e XCE M me tth e propose d PS-1 0 R A requirement s fo rth e thre e potentia l emission-limitin g element s foun d i n APE-123 6 tha tcoul d potentiall y approach emissio n limits : Pb , Cd , an d Cr . Th e XCE M als o me tth e R A requirement s fo r two othe rregulate d metal s B a an d S b bu twas hig h fo rAs , Hg , Ni , an d th e unregulate d Zn . A n analysi s o f potentia l source s o f erro rsuggest

s tha tth e XCE M number s fo rAs , Hg , Ni , an d Z n bes treflec tactua l stac k ga s concen trations . However , calibratio n error s were note d fo rCd , Cr , an d S b eve n thoug h the y me tth e R A requirements . Th e XCE M wa s responsiv e t o change s i n concentratio n an d showed good correlatio n wit h th e referenc e metho d fo r elements tha twere spike d a tmor e tha n one level . I n addition , th e XCE M successfull y measure d lo w meta l concentration s as demonstrate d b y th e XCEM' s trackin g of

M2 9 Cr' s low concentration s whe n change s o f onl y 2 pg/m 3 occurre d



### VES01688 16 4 ERDC/CER L TR-05- 9

betwee n run s 2 an d 3 . Tabl e 3 3 summarize s th e compariso n betwee n M2 9 an d th e XCEM . Table 33 . Summar

y o f 200 2 M29/XCE

M compariso n results . Elemen t Averag

e M2 9 Cone , (pg/dscm

) Average XCE M Cone , (pg/dscm) Average Predicted

Cone , (pg/dscm) R

A (% ) Me

tPS-1 0 R

A Criterion P b 10

1 10

1 10

7 4 Ye s C d 42. 0 31. 5 36. 4 1 7 Ye s C r 4. 9 5.4 4. 7 1 5 Ye s As 11. 1 13.8 15.2 2 7 No H g 30

5 38

5 32

6 3

3 N o S b 16

4 19

2 19

4 2

0 Ye

s N i 21 8 28 1 268 3 3 No B a 21 6 21 6 226 4 Ye s Z n 20

2 29

0 28

8 4

3 N

o



### VES01688 2ERDC/CER L TR-05-9 6 5



# 5 XCE M Cos t an d Statu s

Cos testimate s fo rth e Arm y t o purchas e an d operate a new XCE M ar e discusse d i n thi s chapter . Th e value s ar e presente d i n $1,00 0 unit s ($K) an d were curren t i n Jul y 2004 . Als o presente d i s a summar y o f th e continue d operatio n o f th e XCE M atTEA D an d statu s ofth e technology .


### Cos t Estimate s Capital Costs Capita l cost

s include : 1 . XCEM : Include s x-ra y fluorescenc e (XRF ) spectrometer , operation s manuals , extractio n system , compute ran d contro l module , software , samplin g system , enclosure , an d calibratio n equipment , a s wel l as in-hous e acceptanc e testin g ($195K) . 2 . Prob e an d Transpor tLine : Include s shroude d probe , corrosio n resistan t transpor tline , hea ttracing , an d insulatio n ($10K) . 3 . Shippin g an d Installation : Typicall y include s shippin g o f equipment , on site installation , onsite instrumentshakedown , an d fina l onsite calibratio n check . Sit e wil l b e responsibl e fo rliftin g an d connectin g transpor tlin e ($25K) . 4 . Training : Onsit e trainin g fo ru p t o si x people , includin g trainin g manuals , hands-o n training , powerpoin tpresentations , an d custome rsuppor tfollow in g installatio n ($8K) . 5 . Housing : Include s temperature-controlle d housin g as eithe ra n instrumen t grad e traile ro ra shelte rdependin g upo n end-use rrequirement s ($ 5 t o $15K) . Th e tota l estimate d capita l cost s ar e betwee n $243 Kan d $253K .



### VES01688 36 6 ERDC/CER L TR-05- 9

Annual Costs
Annua l cost

s include : 1 . Consumables : Include s 1 yea rof filte rpape ran d al l othe rconsumables . Thi s costwil l depen d o n usage . Th e lo w estimate i s fo ra typica l 4 0 hr/week schedul e an d th e hig h estimate i s fo ra 24/ 7 schedul e ($5 Kt

o $20K) . 2 . Labor : Include s changin g filte rtap e ( 1 h ronc e ever y 3 week

s fo r24/ 7 usage ; onc e ever y 2 month s fo r40 hr/wee k usage) , an d regula rmaintenanc e (clean in g uni tan d replacin g filters , 6 h rever y 3 months ) 30-4 1 hr/yea rx $80/h r ($2.4Kto$3.3K) . 3 . Warranty : Include s 1-yea rfull-servic e warrant y coverin g al l part s an d maintenance . Warrant y include s onsite assistanc e a s neede d ($25K) . Th e tota l estimate d annua l cost s ar e betwee n $32.4 Kan d $48.3K .


### Continue d Us e o f th e XCE M
Followin g th e conclusio n o f th e M2 9 tests , th e XCE M was use d i n a serie s o f di agnosti c tests t

o evaluate ai rpollutio n contro l technology installe d atAPE-1236 . Usin g th e XCEM , TEA D personne l develope d baselin e dat a fo rP b an d Z n durin g incineratio n of

variou s munitions . TEA D stac k operators als o conducte d tests usin g the XCE M i n whic h the y determine d tha tth e metal s emission s coul d be significantl y reduce d b y completel y cuttin g of f th e bypas s syste m durin g opera tion . Blockin g th e bypas s ductwit h a meta l plate resulte d i n a greate rtha n 9 0 percen tdrop i n meta l concentrations . Usin g thi s data , TEA D wa s bette rabl e t

o understan d sources o f P b i n the emissions . Th e XCE M ha s als o been use d b y th e Ammunitio n Equipmen tDirectorat e (AED ) o n thei rtes tfurnac e atTEAD . Th e continue d us e of th e XCE M t

o diagnos e an d assis twith proces s contro l indicate s th e valu e of havin g a n installe d CE M fo r multi-metal s atTEAD . Mor e recentl y (2003) , AE D purchase d a second XCE M uni tfo rthei rtes tfurnace . Itwa s installe d durin g 2004 . El i Lill y Corporatio n ha s recentl y (Ma y 2004) purchase d an d installe d a n XCE M uni tfo ron

e of thei rhazardou s waste incinerators . The y hav e submitte d a n Alternativ e Monitorin g Pla n (AMP ) wit h th e EP A with th e intentio n o f usin g th e monito rfo rcompliance purposes . Th e AM Pshoul d b e finalize d i n th e nea r



### VES01688 4ERDC/CER L TR-05- 9 6 7

future

. Th e monito r ha s bee n successfull y integrate dint o th e dat aacquisitio n syste mfo r

th e sit e an dgenerate s a12-h r rollin g averag e a s required

. Improvement s hav e bee n mad e t o th e technolog y sinc e th e origina l XCE M wa s tested

. I n ane w XCE M (2004) , th e Quan X XR Finstrumen t ha s bee n replace d wit h acusto mXR Fdetectio n approac h improvin g th e detectio n limi t t o 0.1—0. 2 ug/dsc mfro m1- 3 ug/dsc m(15-minut e sampl e time)

. Th e monito r ca n no w monito r u p t o 2 5 metal s simultaneously

. Th e softwar e ha s bee n upgrade dt o accommodat e th e physica l change s an dt o improv e th e eas e o f integratio n t o externa l dat aacquisitio n systems
. Th e physica l siz e o f th e monito r

ha s als o decreased

. Figur e 1 7 show s th e 200 4 XCE M mode l fro mCE S (Xact i s th e marketin g nam e tha t CE S ha s give n th e XCEM)

. CE S ha s developed , i n th e las t year , aquantitativ e aeroso l generato r (QAG ) tha t

i s capabl e o f

deliverin g a know n aerosolize dmeta l concentration

. CE S believe s tha t usin g th e QA Gi s a reliable , consistent , an daccurat e metho dfo r ensurin g tha t

th e calibratio n ha s bee n entere dcorrectly

. Th e QA Gi s currentl y bein g evaluate db y th e EP A fo r us e i ncomplianc e applications

.

CE S Meuli Monito

r

Figur e 17 . 200 4 CE S metal s monitor .



### VES01688 56 8 ERDC/CER L TR-05- 9



# 6 Summary an d Conclusion s

A ne w prototyp e XCE M wa s constructe d an d installe d a tth e TEA D APE-123 6 incinerator . Itunderwen ta n M2 9 compariso n tes tdurin g a 4-da y perio d i n Ma y 2001 . Durin g thi s test , th e monito rfunctione d i n a completel y automate d man ne ran d automaticall y recorde d th e tes tdata . Th e objective of th e tes twas to mee tth e requirements ofth e propose d PS-10 . Th e monito rme tth e PS-1 0 samplin g an d respons e tim e criterio n b y havin g a n effectiv e up-tim e of

10 0 percen tan d reportin g tim e average d concentration s ever y 20 minute s (20-minut e la g betwee n samplin g an d reporting) . I tals o me t th e Q A criterio n wit h a precisio n n o more tha n 2 percen tfo rzer o an d upscal e checks , an d a calibratio n drif to f 0. 5 percent . Th e XCE M metth e PS-1 0 R A cri terio n (les s tha n orequa l t o 20 percent) fo rthre e o f th e nin e metal s tested : Cd , Cr , an d Ni . Th e R A fo rP b wa s 2 2 percent . Th e result s fo rBa , Sb , Zn , an d A s showe d systemati c biases . I ti s believe d tha tth e monito rdi d no tsuccessfull y measur e H g becaus e o f los s t o th e unheate d sampl e line . Wit h regar d t o re spons e t

o chang e i n concentration , th e XCE M result s ha d a correlatio n (r 2) o f 0.95 o rbette rfo rNi , Sb , an d Zn . I n Marc h 2002 , th e XCE M was move d t o a close rlocation , hea ttraced , insulated, an d equippe d wit h a shroude d probe . Th e combine d effec tof thes e change s wa s t o minimiz e H g an d P M los s i n th e sampl e line . I n Apri l 2002 , severa l improve ment s were mad e t

o th e calibratio n procedure , an d th e XCE M wa s recalibrated . Th e transpor tsystem was evaluate d b y performin g a compariso n tes tbetwee n th e XCEM , predicte d concentration s base d o n spiking , an d M1 7 filte rsampling . N o measurabl e los s i n particulate s was observed . Th e recalibratio n was evalu ate d usin g a QSIS . Th e resultin g elementa l concentration s were withi n thei r expecte d uncertaintie s fo ral l elements excep tC d an d Ag . I n Ma y 2002 , a serie s of 1 2 compariso n tests wit h EPA' s M2 9 were conducted . Durin g thi s testing , th e XCE M ha d a n "uptime " of bette rtha n 98 percent , me t al l Q A parameters , an d ha d a precisio n tha twa s bette rtha n M29 . Th e XCE M als o showed good correlatio n wit h Metho d 29 fo relements tha tha d significan t variabilit y i n concentratio n durin g testing .



### VES01688 6ERDC/CER L TR-05-9 69

APE-123 6 emission s hav e th e potentia l t o approach state-mandate d emissio n limit s fo rthre e elements : Pb , Cd , an d Cr . Th e XCE M me tth e PS-1 0 2 0 percen t R A criterio n fo ral l thre e o f thes e elements . XCE M data were als o compare d t o M2 9 dat a fo rfiv e elements tha tar e typicall y foun d i n concentration s wel l below th e site emissio n limits : As , Hg , Sb , Ni , an d Ba . A fina l nonregulate d element , Zn , was als o spike d an d examine d durin g validatio n testing . Th e XCE M me tth e R A criterio n fo rB a an d Sb , bu twa s uniforml y hig h relativ e t o M2 9 fo rAs , Ni , Zn , an d Hg . A n erro ranalysi s wa s conducte d t o determin e th e source o f th e differenc e be twee n M2 9 an d th e XCEM . Calibratio n error s an d spectra l interference s wer e checke d b y reevaluatin g th e XCE M filte rwit h CES' s Quan X an d submittin g fil te rsample s t

o a n independen tlaborator y fo ranalysis . Th e result s indicat e that , fo rCd , Cr , an d Sb , calibratio n appeare d t o caus e som

e error , eve n thoug h thes e elements stil l me tth e R A criterion . However , fo rAs , Ni , an d Zn , th e XCE M cali bratio n wa

s no tth e primar y sourc e of error . Othe rpotentia l XCE M sources of erro rsuch as los s durin g transport , lo w filte rtrappin g efficiency , an d deposi tpo sitionin g error s ar e highl y unlikel y becaus e the y woul d resul tonl y i n XCE M con centration s lowe rtha n M29 . Th e difference s i n concentratio n fo rAs , Ni , an d Z n appea rt o be du e t

o M2 9 analytica l errors . A n analysi s o f

H g o n the XCE M filte rdetermine d tha tparticulat e phas e H g was bein g vaporize d overtime . A compariso n o f XCE M spectr a generate d durin g th e tes twit h reanalysi s 6 weeks late rshowe d a los s of 30 percen tof

th e H g fro m th e XCE M filter . M2 9 particulat e concentration s o n th e M2 9 niter s were 15 t o 30 time s highe rtha n typica l an d wer e highl y correlate d wit h difference s between th e XCE M an d M29 . Th e filters , whic h wer e notcooled whil e bein g shippe d t o th e M2 9 laboratory , coul d hav e los tth e H g prio rt o analysis . I ti s eviden ttha t th e mos tsignifican tobstacl e i n meetin g th e PS-1 0 R A criterio n fo rth e XCE M i s th e accurac

y problem s ofth e comparativ e referenc e metho d (M29) . Itwa s observed fo rbot h M2 9 compariso n tests tha tth e bes tmetho d fo rcalibrat in g th e XCE M ha d no tbee n determined . Bot h test s reveale d some error s i n cali bratio n with som

e correction s mad e afte rth e M2 9 tests bu tprio rt o th e XCE M resul tsubmissions . Thi s ma y caus e some speculatio n ove rth e performanc e o f th e monito rbecaus e th e calibratio n rule s seemed t o chang e afte rth e test s started . Becaus e thi s monito rsample s i n a nondestructiv e manner , th e result s can b e reanalyze d an d verifie d a ta late rdate . I ti s thes e analyse s tha tallo w th e determinatio n of

th e sources o f

error , includin g cahbration . Thi s ha s clearl y benefite d th e developmento f th e XCE M calibratio n procedure s wit h eac h subse quen ttest . However , t o ensur e confidenc e i n th e monitor' s eventua l us e i n th e



### VES01688 77 0 ERDC/CER L TR-05- 9

field , a reliable , consistent , an d accurate calibratio n protoco l need s t o b e estab lished . Wit h th e assistanc e of th e XCEM , TEA D was abl e t o identif

y tha tblockin g th e bypas s ducto n th e 1236 furnac e wit h a meta l plate resulte d i n a greate rtha n 9 0 percentdro

p i n meta l concentrations . Th e continue d us e of th e XCE M t

o diag nos e an d assis twith proces s contro l a tTEA D indicate s th e valu e o f havin g a n installe d CE M fo rmulti-metals . Th e curren tcos testimate s fo rth e Arm y t o purchas e an d operate a ne w XCE M ar e betwee

n $243,000 an d $253,000 i n capita l costs , an d betwee n $32,400 an d $48,300 fo rannua l costs . Thes e figure s were curren ti n Jul y 2004 . Recently , AE D an d El i Lill y purchase d XCEM s fo rthei rfurnaces . Improvements i n the XCE M hav e resulte d i n a monito rtha tca n measure 25 metal s simultaneousl y an d wit h detectio n limit s between 0. 1 an d 0.2 pg/dscm . I n addition , CE S ha s re centl y developed th e QA G spikin g metho d tha twil l provid e a reliable , consistent , an d accurat

e mean s fo rensurin g tha tth e calibratio n ha s bee n entere d correctly .



### VES01688 8ERDC/CER L TR-05-9 7 1



# Reference s

Bryson , S . (2001) . Fina l Repor t- Stac k Spikin g Repor tfo ra Multi-Meta l CEM S Tes ta tth e Tooel e

Arm y Depo tDeactivatio n Furnace . Prepare d fo rU.S . Arm y Corp s o f Engineer s b y MSE TA , Inc. , Butte , MT .

. (2002) . U S Arm y Constructio n Engineerin g Researc h Laborator y (CERL) , Wast e Minimizatio n an d Pollutio n Preventio n Program : Stac k Spikin g Repor tfor a Multi-Meta l CEM S Tes ta tth e Tooel e Arm y Depo tDeactivatio n Furnac e - 2002 . Prepare d fo rU.S . Arm y Corp s of

Engineer s b y MSE-TA , Inc. , Butte , MT . Bryson , S. , C . Whitworth , an d S . Kujawa . (2000) . Fina l Repor t- Tes tan d Evaluatio n o f a n X-Ra y Fluorescenc e Base d Multi-Elemen tMetal s Continuou s Emissio n Monitor . Prepare d fo r U.S . Arm y Cor p o

f Engineer s b y MSE-TA , Inc. , Butte , MT . Cente rfo rHealt h Promotio n an d Preventiv e Medicin e (CHPPM) . (2001) . Ai rPollutio n

Managemen tStud y No . 43-EL-6498-0 1 Verificatio n o f Multi-Metal s Continuou s Emissio n Monito ra tTooel e Arm y Depot . Tooele , Utah , Ma y 14-17 , 2001 .

. (2002) . Ai rPollutio n Managemen tStud y No . 43-EL-4755-0 2 Verificatio n of Multi Metal s Continuou s Emissio n Monito ra tTooel e Arm y Depot . Tooele , Utah , Ma y 13-16 , 2002 . Coope rEnvironmenta l Service s (CES) . (2001a) . "XCE M User' s Guide, " Beaverton , OR .

. (2001b) . "XCE M Resourc e Manual, " Beaverton , OR . Cooper , J. , B . E . Johnsen , K . J . Hay , an d W . Watso n (2000) . Continuou s Hazardou s Elemen t

Analysi s Syste m fo rAmbien tan d Emission s Monitoring . Presente d a tregiona l AWM A Conference : Recen tAdvance s i n th e Scienc e an d Managemen to f Ai rToxics . Apri l 10 , 2000 . Cooper , J.A. , B.E . Johnsen , S.C . Fry , an d M.P . Nakanishi . (2002) . "Limitation s i n th e Us e o f EP A Referenc e Metho d 2 9 fo rEvaluatin g th e Relativ e Accurac y o f Candidat e Multi-Meta l Continuou s Emissio n Monitors. " CE S Report , Septembe r2002 . Environmenta l Protectio n Agenc y (EPA) . (1992) . Metho d 30 1 - Fiel d Validatio n of Pollutan t Measuremen tMethod s fro m Variou s Wast e Media . Foun d o n th e EP A websit e at : http://www.epa.gov/ttn/emc/promgate/m-301.pdf .

. (1996) . PS-10 , Propose d Performanc e Specificatio n 1 0 forMeta l CEM S (Propose d 04/19/96 ) Foun d o n th e EP A websit e at : http://www.epa.eov/ttn/emc/propperf.html .

. (1999) . Fina l Standard s fo rHazardou s Ai rPollutant s fo rHazardou s Wast e Combustors ; Fina l Rule . FR52827-FR53077 , Vo l 64 , No . 189 .



### VES01688 97 2 ERDC/CER L TR-05- 9

. (2004) . Nationa l Emissio n Standard s fo rHazardou s Ai rPollutant s fo rHazardou s Wast e Combustor s (Phas e I fina l Replacemen tStandard s an d Phas e H) ; Propose d Rule . FR2U97-21385 , Vo l 69 , No . 76 . French , N . (1998) . 1997 Performanc e Testin g of Multi-Meta l Continuou s Emission s Monitors . Summar y Repor tPrepare d fo rth e U.S . EP A an d U.S . DO E b y Sky+ , Napa , CA . Hall , B. , O . Lindqvist , an d E . Ljunstrom . (1990) . Mercur y Chemistr y i n Simulate d Flu e Gase s

relate d to Wast e Incineratio n Conditions . Environ. Sci. Technol., Vo l 24 , No . 1 . Hay , K . J. , B . E . Johnsen , an d J . Coope r(2005) . X-Ra y Fluorescence-Base d Multi-Meta l

Continuou s Emissio n Monitor : Development . U.S . Arm y Enginee rResearc h an d Developmen tCente r(ERDC)/CER L Technica l Repor t(TR)-05-3 , Januar y 2005 . Josephson , Pau l (2003) . Hazardou s Wast e Combusto rManagemen tPla n - AE C (fo rTabl e 1) . Lemieux , P. , J . Ryan , N . French , W . Haa s (1998) . Result s ofth e Septembe r1997 DOE/EP A

Demonstratio n o f

Multi-Meta l Continuou s Emissio n Monitorin g Technologies . Presente d a tInternationa l Conferenc e o n Incineratio n an d Therma l Treatmen tTechnologies .
McFarland , A.R. , an d J.C . Rodgers . (1993) . Single-Poin tRepresentativ e Samplin g wit h Shroude d

Probes . Lo s Alamo s Nationa l Laboratory , LA-12612-MS , Augus t1993 . Myers , J. , T . Kelly , C . Lawrie , an d K . Riggs . (2002) . Environmenta l Technolog y Verificatio n

Report : Coope rEnvironmenta l Services , XCE M Multi-Metal s Continuou s Emissio n Monitor , Ma y 2002 . Fro m EP A website : http://www.epa.gov/etv/pdfs/vrvs/02_vr_cooper_xmcem.pdf . Seltzer , M.D . (2000) . "Performanc e Testin g o f a Multimetal s Continuou s Emission s Monitor, " J. AirWaste Mgt. Assoc., Vo l 62 , No . 6 . Wang , R.G. , M.A . Dillon , an d D . Spence . (1983) . Journal of Chem. Phys., 7

9 (2) , 1100 .



### VES01689 0ERDC/CER L TR-05- 9 7 3



# Appendi x A : Test/Q A Pla n fo r Verificatio n

o f a Continuou s Emissio n Monito r fo r Multi-metal s a t Tooel e Arm y Depot (2001) *

1. 0 INTRODUCTIO N
1.1 Test Description
Thi s test/quality assuranc e (QA ) pla n provide s detaile d procedure s fo ra verifica tio n tes tfo ra n X-Ra y Fluorescence-base d Continuou s Emission s Monito r (XCEM ) use d t

o measur e metal s i n source emissions . Th e U.S . Arm y Construc tio n Engineerin g Researc h Laborator y (CERL ) wil l perfor m th e verificatio n test . Th e U.S . Arm y i s intereste d i n identifyin g a n effectiv e mean s o f continuousl y measurin g metal s i n stac k emission s generate d b y thei rdemilitarizatio n incin erators . Th e U.S . Environmenta l Protectio n Agency' s (EPA's ) Environmenta l Technology Verificatio n (ETV ) Progra m wil l verif y th e tes tprocedure s an d re sults . Th e purpos e o f th e ET V i s t

o provid e objective an d qualit y assure d per formanc e dat a o n environmenta l technologies , s o tha tusers , developers , regula tors , an d consultants hav e a n independen tan d credibl e assessmen to f wha tthe y ar e buyin g an d permitting . Battell e Memoria l Institute , headquartere d i n Columbus , Ohio , i s EPA' s partne r fo rth e ET V Advance d Monitorin g System s (AMS ) Center . Th e scope ofth e AM S Cente rcovers verificatio n of monitorin g method s fo rcontaminants an d natura l species i n air , water , an d soil . Verificatio n testin g wil l follo w procedure s speci fie d i n thi s test/Q A pla n an d th e qualit y requirement s i n th e "Quality Manage men tPla n fo rth e ET V Advance d Monitorin g System s Pilot " (EP A 2000) .

* Prepare

d fo rCER L b

y Coope rEnvironmenta

l Services , Beaverton

, OR , 8 Ma

y 2001 .



### VES01689 17 4 ERDC/CER L TR-05- 9

Testin g wil l tak e plac e atth e Tooele Arm y Depo t(TEAD ) deactivatio n furnac e locate d i n Tooele , UT . 1.2 Test Objective
Th e objectiv

e of th e verificatio n tes ti s t o quantif

y th e performanc e of th e XCE M b y compariso n t

o referenc e meta l measurements unde rfull-scal e condition s ata combustio n facility . 1.3 Organization

and Responsibilities
Th e CERL , TEAD , an d Battell e wil l perfor m an d evaluate th e verificatio n tes ti n cooperatio n wit h Coope rEnvironmenta l Service s (CES) , whic h wil l provid e th e XCE M fo rverification . MS E Technology Applications , Butte , M T (MSE-TA ) wil l b e responsibl e fo rspikin g th e stack , an d th e U.S . Arm y Cente rfo rHealt h Pro motio n an d Preventiv e Maintenanc e (CHPPM ) wil l conductth e referenc e metho d testing . Th e organizatio n char ti n Figur e 1- 1 show s th e individual s who wil l hav e responsibilitie s i n th e verificatio n test . Th e specifi c responsibilitie s o f thes e individual s ar e detaile d i n th e followin g paragraphs .

To m Kell y Battell e De e Russel l TEA D Facilit y Manage r

Joh n Coope r CE S XCE M Vendo r Stev e Bryso n MSE-T A Stac k Spikin g Mik e

Pattiso n CHPP M Ref . Measure . Figur e 1-1 . Organizationa l Char tfo rVerificatio n Tests
1.3. 1 Constructio n Engineerin g Researc h Laborator y Dr . KJame s Ha y i s th e CER L verificatio n testin g leader . Dr . Ha y wil l hav e overal l responsibility fo rensurin g tha tth e technical , schedule , an d costgoal s establishe d fo rth e verificatio n tes tare met . I f question s aris e concernin g Q A



### VES01689 2ERDC/CER L TR-05- 9 7 5

problems , Dr . Ha y ha s th e authority t o sto p o rdelay th e test . A s th e tes tleader , Dr . Ha y will :

• Coordinate TEAD , Battelle , CHPPM , MSE-T A an d CE S staf f t o conductth e verificatio n test .
• Hav e overal l responsibility fo rdevelopmen to f atest/Q A plan .
• Revis e th e draf

ttest/Q A pla n i n respons e t o reviewer' s comments .
• Hav e overal l responsibility fo rensurin g tha tthi s test/Q A pla n i s followed .
• Serve as th e primar y poin tof contactfo rCE S representatives . 1.3. 2 Battell e Dr . Thoma s J . Kell y i s th e ET V AM S Center' s Verificatio n Testin g Leader . I n thi s role , Dr . Kell y wil l b e responsibl e fo rreviewin g th e test/Q A plan , evaluatin g field-testin g t

o ensur e tha tth e test/Q A pla n i s bein g followed , an d developin g a n E T V verificatio n repor tan d statement . Mr . Charle s Lawri e i s th e AM S Center' s Qualit y Manager . A s such , h e wil l b e responsibl e fo rassessin g tha tqualit y re quirements of

thi s test/Q A pla n are met . Mor e specifically , thes e Battell e staf f will :

• Review th e draf

ttest/Q A plan .
• Coordinate Battell e an d EPA/ET V staf f durin g verificatio n testing .
• Observ e th e CHPPM/MSE-TA/CE S tea m i n thei rperformanc e o f th e verifica tio n test .
• Repor

ttes tqualit y problem s t o CERL . I f

significan tqualit y problem s ar e observe d an d no trectified , Battell e ca n discontinu e th e tes tas a n ET V verifica tion .
• Prepar e a draf

tET V verificatio n repor tan d statemen tusin g tes tdat a an d summar y tes trepor tprovide d b y CES .
• Overse e revisio n of th e draf

tET V verificatio n reportan d statemen ti n re spons e t o reviewer' s comments .
• Coordinate technica l pee rreview s o f th e test/Q A pla n an d ET V verificatio n reportan d statement .
• Conducta technica l syste m audi tan d repor tresult s o f tha taudit . 1.3. 3 Tooel e Arm y Depo t
Th e verificatio n tes twil l b e conducte d i n collaboratio n wit h De e Russel l of TEAD . Mr . Russell' s responsibilitie s are :

• Coordinate th e operatio n ofth e facilit y durin g verificatio n testing .
• Coordinate th e installatio n o f th e XCE M atth e TEA D incinerator .
• Communicate need s fo rsafet y an d othe rtrainin g of staf f workin g a tth e facil ity .
• Contribut e t

o th e developmentofth e draf ttest/Q A plan .



### VES01689 37 6 ERDC/CER L TR-05- 9

• Provid e inpu to n facilit y operatin g condition s an d procedure s fo rth e sum mar y an d ET V verificatio n report .
• Revie w th e draf

ttest/Q A plan .
• Provid e inpu tfo rth e summar y tes trepor tan d ET V verificatio n report .
• Revie w draf

treports .
• Assembl e traine d staf f t o operat

e th e TEA D incinerator .
• Ensur e tha tth e facilit y i s full y functiona l prio rt o th e times/date s neede d i n th e verificatio n test .
• Overse e technica l staf f i n facilit y operatio n durin g th e verificatio n test .
• Ensur e tha toperatin g condition s an d procedure s fo rth e TEA D incinerato r are recorde d durin g th e verificatio n test .
• Revie w an d approv e al l dat a an d record s relate d t o facilit y operation .
• Provid e suppor ti n respondin g t o an y issue s raise d i n assessmen treports an d audit s relate d t

o facilit y operation . 1 .3 . 4 Coope r Environmenta l Service s Coope rEnvironmenta l Service s o f Beaverton , O Rmanufacture s th e XCEM . CE S staf

f will :

• Develo p th e draf

ttest/Q A pla n an d submi tpla n t o CERL , Battelle , TEAD , CHPPM , an d MSE-T A staff . Revis e th e test/Q A pla n i n accordance wit h review ers ' comments .
• Approv e th e fina l test/Q A plan .
• Participat e i n require d safet y trainin g a tth e tes tfacilit y befor e installatio n ofth e XCEM .
• Atten d a pre-stud y site visi tt o revie w facilit y requirement s fo rtesting .
• Provid e a n XCE M fo rth e duratio n o f th e verificatio n test .
• Commi ta traine d technica l membe rof staf f t o operate , maintain , an d repai r th e XCE M throughou tth e verificatio n test .
• Participat e i n verificatio n testing , includin g providin g dat a acquisitio n fo r th e XCEM .
• Provid e dat a fro m th e XCE M a tth e conclusio n of eac h tes tday .
• Prepar e a summar y tes treportfo rCERL . Th e summar y tes trepor twil l be use d a s th e basi s fo rth e ET V verificatio n report .
• Revie w th e draf

tverificatio n repor tan d verificatio n statement . 1 .3. 5 Cente r fo r Healt h Promotio n an d Preventiv e Medicin e Referenc e metho d testin g wil l b e conducte d b y CHPP M unde rth e directio n of Mik e Pattison . Mr . Pattiso n will :

• Revie w th e draf

ttest/Q A plan .
• Adher e t

o th e quality requirements i n thi s test/Q A plan .



### VES01689 4ERDC/CER L TR-05- 9 7 7

• Assembl e traine d technica l staf f t o conductreferenc e metho d samplin g fo r th e verificatio n test .
• Contrac tfo ran d oversee laborator y analysi s o f th e referenc e metho d sam ples .
• Provid e referenc e metho d analytica l an d qualit y assuranc e result s an d dat a i n a n agreed-upo n forma tt o Battelle , CES , and/o rCER L a s needed .
• Provid e suppor ti n respondin g t o an y issue s raise d i n assessmen treports an d audit s relate d t

o facilit y operation . 1 .3. 6 MS E Technolog y Applications , Inc . MSE-T A wil l be responsibl e fo rinjectio n of th e metal s o f

interes tinto th e TEA D incinerator . MSE-T A will :

• Quantitativel y spik e metal s of interes tint o th e TEA D incinerato rdown strea m ofth e controls .
• Provid e measurabl e concentration s of th e metal s o f

interes ta tthe XCE M an d reference metho d samplin g points .
• Ensur e tha tparticl e siz e fo rth e metal s o f interes tar e representativ e o f typi cal stac k gas conditions .
• Ensur e tha tal l applicabl e regulator y emissio n limit s ar e maintained . 1 .3. 7 U.S . Environmenta l Protectio n Agenc y EP A manage s th e ET V progra m an d partner s wit h Battell e fo rth e ET V AM S Center . A s such , EP A ha s th e optio n t o conduc

ta technica l system s audi tof th e verificatio n test . I n addition , EP A wil l participat e i n th e pee rrevie w of th e test/Q A pla n t

o b e prepare d b y CE S an d th e ET V verificatio n reportt o b e pre pare d b y Battelle .



### 2. 0 APPLICABILIT Y
2.1 Subject
Thi s test/Q A pla n i s applicabl e t o th e verificatio n testin g of a commerciall y availabl e continuou s emissio n monito r(CEM ) syste m fo rdeterminin g multi meta l concentration s i n combustio n source emissions . Th e syste m bein g teste d i s a n X-ra y Fluorescence-base d CE M (XCEM ) manufacture d b y CES . Th e XCE M extracts a representativ e stac k ga s sampl e an d concentrate s th e particulat e mat te ran d gas phas e hazardou s metal s o n a filter , whic h i s the n analyze d wit h x ra y fluorescenc e (XRF ) usin g a n adapte d Quan X analyzer . A prototyp e of th e



### VES01689 57 8 ERDC/CER L TR-05- 9

XCE M wa s assesse d atth e MSE-T A tes tfacilit y i n Butte , M T (Bryso n 2000) an d ha s bee n redesigne d fo rincrease d ease-of-us e an d automate d Q A routines . Verificatio n testin g wil l b e conducte d atTEAD . Th e TEA D facilit y ha s a well characterize d feedstrea m an d wa s th e sit e fo rmulti-meta l CE M tests conducte d i n 1999 . Th e TEA D sit e ha s a deactivatio n furnace , APE-1236 , fo rincineratio n o f muni tions . Th e incinerato ri s currentl y regulate d unde rth e Resourc e Conservatio n an d Recovery Ac t(RCRA ) fo rantimony , arsenic , barium , beryllium , cadminum , chromium , lead , mercury , nickel , selenium , silver , an d thalliu m (Sb , As , Ba , Be , Cd , Cr , Pb , Hg , Ni , Se , Ag , an d Tl) . O f th e twelve regulate d elements , fiv e ar e typicall y foun d i n th e feedstream : Sb , Ba , Cd , Cr , an d Pb . Th e XCE M wil l b e verifie d fo rit s measurementcapabilitie s of th e fiv e element s foun d i n th e feed strea m a s wel l a

s As , Hg , N i an d a nonregulate d metal , zin c (Zn) . Thes e ele ments wer e selecte d i n orde rt o challeng e th e XCE M ove ra larg e rang e of analy si s condition s an d elemental concentrations . EP A Metho d 29 (M29 ) i s currentl y recognize d a s th e mos tsuitabl e procedur e t o determin e multi-meta l concentration s i n source emission s (EP A 1990) . Metho d 2 9 draw s stac k gas throug h a filte ran d a serie s of impinger s providin g a 1 - t o 3-hou raverag e concentration . Fo rth e verificatio n testing , a batter y o f twelv e 2 - hou rM2 9 tests wil l b e conducte d b y CHPPM . Analysi s o f th e M2 9 sampl e trai n wil l b e unde rth e directio n o f CHPP M an d wil l include , a s a minimum , determi natio n o f

th e nin e element

s measure d b y th e XCEM . 2.2 Scope
Th e overal l objective o f th e verificatio n tes tdescribe d i n thi s pla n i s t o provid e quantitativ e verificatio n o f th e performanc e of

th e XCE M unde rreal-worl d con ditions . EP A ha s publishe d a draf tperformanc e specificatio n documentdesig nate d as PS-1 0 (EP A 1996 ) a s a propose d descriptio n o f ho w t o asses s th e accept abilit y o f

a multi-meta l CE M upo n installatio n an d thereafter . Th e goal s o f th e verificatio n tes twil l be me ti f th e XCE M meet

s th e propose d PS-10 : 1. Relative accuracy criteria fo rth e element s i n th e feedstream of

the Tooel

e incin erato r(Sb , Ba , Cd , Cr , an d Pb) . 2 . Quality assurance criteria b y passin g dail y zero , span , an d drif tchecks . 3 . Response time and reporting time criteria fo ra batc h CEM . 4. Measurement

criteria b y testin g several element s attwo concentration level s (Hg , Ni,Zn,andSb) .



### VES01689 6ERDC/CER L TR-05- 9 7 9

A secondary objective i s t o meetth e relativ e accurac y criteri a fo radditiona l regu late d an d unregulate d metals , whic h ar e nottypicall y foun d i n th e feedstream (As , Hg , Ni , an d Zn) . Th e performanc e parameter s tha tare addresse d b y thi s test/Q A pla n include :

• Relativ e accuracy

• Correlatio n wit h referenc e metho d

• Precisio n

• Instrumen tdrif

t

• Spa n an d zer

o

• Respons e tim e

• Bia s

• Lo w leve l meta l response . Relativ e accuracy , correlatio n wit h th e referenc e method , an d precisio n (i.e. , re peatabilit y a tstabl e tes tconditions ) wil l b e assesse d fo rth e element s bein g measure d b y th e XCEM . Instrumen tdrif twil l b e base d upo n th e precisio n o f th e dail y XCE M spa n an d zero Q A measurements . Th e XCE M ha s a built-i n addi tiona l check fo rinstrumen tdrif twhic h measure s a palladiu m standar d wit h eac h XCE M tes trun . Fo rth e verificatio n test , respons e tim e wil l b e determine d as th e tim e between th e star tof one samplin g perio d an d th e beginnin g of a sec on d samplin g period . Bia s wil l b e identifie d usin g EP A metho d 30 1 protocol s as discusse d i n sectio n 5.6 . Low-leve l meta l respons e wil l b e determine d b y a com pariso n t

o chromiu m an d arseni c referenc e metho d concentrations , whic h wil l b e les s tha n 6 an d 1 8 pg/dscm respectively . I ti s beyon d th e scope of thi s verificatio n tes tt o simulat e th e agin g an d expo sure s tha tma y affec ta n XCE M durin g routin e long-ter m use . Thi s verificatio n tes tevaluate s th e performanc e o f a new XCE M overa relativel y shorttes tpe riod , i n th e hand s of

staf f skille d i n it s operation . Itmus tb e note d tha tth e long ter m performanc e ma y b e differen tfro m tha tobserve d i n th e testin g describe d here . Th e effortspenti n installin g an d maintainin g th e XCE M wil l b e docu mented , however, an d th e amoun to f tim e th e XCE M i s operationa l overth e veri fication tes tperio d wil l b e recorded , t o asses s dat a completeness .


### 3.0 SIT E DESCRIPTIO N
Verificatio n testin g wil l tak e plac e a tth e TEA D buildin g 132 0 deactivatio n in cinerato rAPE-123 6 (Figur e 3-1) . Thi s sectio n o f th e test/Q A pla n describe s th e TEA D incinerato ran d th e procedure s fo roperatin g i tfo rthi s test .



### VES01689 78 0 ERDC/CER L TR-05- 9

3.1 Test

Facility
Th e TEA D incinerator , whic h run s o n diese l fuel , i s designe dt o incinerat e de

commissione dmunitions

. Typica l operatin g parameter s fo r th e incinerato r

ar e show n i n Tabl e 3-1

. Th e TEA D incinerato r i s classifie da s adr y stac k wit h wate r conten t rangin g fro m5 t o 1 0 percent
. Typica l stac k P M concentration s ar e i n th e 1 0 mg/dsc mrange . A numbe r o f sensor s (temperature , ga s flow , pressur e differ

ential , combustio n gases , etc. ) ar e use dt o monito r operatin g condition s a t vari

ou s point s i n tb e system
. Signal s fro mthes e sensor s ar e monitore dan dcom pare dt o prese t

operatin g standards

. Th e incinerato r consist s o f

amai n contro l panel , CEMS , Wast e Fee dRat e Monitorin g Syste m(WFRMS) , dua l conveyo r fee dsystem , rotar y furnace , furnac e shroud , cyclone , afterburner , discharg e con veyor , hig h temperatur e cas t cerami c filter s baghouse , hig h temperatur e draf t fan , an dexhaus t

stack

. 1 ) Mai n Contro l Panel . Th e mai n contro l pane l contain s variou s piece s o f contro l equipmen t

t o monito r

an dcontro l th e furnac e operation

. Proces s control

ler s ar e use dt o contro l th e rotar y furnac e fee den dtemperature , negativ e pres sur e i n th e furnace , an dafterburne r temperature
. A multi-poin t digita l recorde r i s use dt o recor dproces s parameters
. Logi c contro l fo r th e furnac e i s performe d b y aPLC

. Th e PL C control s th e moto r starters , th e WFRMS , safet y interlocks , an dalarms

. Th e compute r syste mi s a n industrial-base dmachin e runnin g dat a acquisitio n software , whic h provide s centralize dan dintegrate ddat amanage ment , proces s graphics , operato r interface , an drepor t generation

.

Figur e 3-1

. TEA D Deactivatio n Incinerato r Buildin g 1320

.



### VES01689 8ERDC/CER L TR-05- 9 81

Tabl e 3-1

. Typica l operatin g parameter s fo r th e APE-123 6 deactivatio n furnace

. Typica l Operatin g Parameter s fo r th e APE-123 6 Deactivatio n Furnac e Afterburne r

Temp

. (°F ) 160 0 Baghous e A P (in

. H 2 0 ) 9 Baghous e Tem p (°F ) 68 0 Kil nFee dEn dDraf t

Pressur e (in

. H2O ) 0. 3 Kil nFee dEn dTem p (°F ) 60 0 Kil nBurne r

En dTem p (°F ) 120 0 O a- CE M (% ) 1 4 C O (ppm ) 1 1 Stac k Temp

. (°F ) 55 0 Stac k Ga s Velocit y (ft/sec ) 4 6 Stac k Pressur e (in

. H2O ) 0. 3

Figur e 3-2

. TEA D Incinerato r Stack

.



### VES01689 9