# VE S 000620.pdf

### 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 Developmen t 

### K . Jame s Hay , Bruc e E . Johnsen , an d Januar y200 5 Joh n A . Coope r

Pressur e Qamnl p Lea k

Chec k Transduce r sampl e Valv

e " SAMPL E RETUR N LIN E

Extractio n Syste m

Samplin g a n d Analysi s Syste m

Approve d fo r publi c release ; distributio n i s unlimited . 

### VE S 0006 2

### VE S 0006 2

### ERDC/CER L TR-05- 3 Januar y200 5 

# X-Ra y Fluorescence-Base d Multi-Meta l Continuou s Emissio n Monitor : Developmen t K . Jame s Ha y 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 Report Approve d fo rpubli c release ; distributio n i s unlimited .



### Prepare d fo rU.S . Arm yCorp s of Engineer s

Washington , D C 20314-100 0 Unde rWor k

Uni t #CNE-B09 1ABSTRACT : Arm y demilitarizatio

n incinerator

s wil l nee dt o compl y wit h th e Hazardou

s Wast e Combusto

r Nationa l Emissio n Standard s fo r Hazardou s Ai r Pollutant s tha t wil l regulat

e metal s an dmeta l compound

s liste dunde r th e Clea n Ai r Act Amendments . A larg

e proble mfo r thes e incinerato

r operation s i s limite dknowledg

e of th e type s an dquantitie s of emitte dmetals . Complianc

e ma y b e determine

donl y throug h tria l bu memissio n test s becaus e o f thi s limitation . A continuou s emissio n monito r (CEM ) fo r multi-metal

s wil l provid

e th e emissio n data , atoo l t o hel p mee t complianc

e requirements , an

dth e opportunit

y t o adjus t bur n strategie s fo r increase dproduction . Th

e XCE M multi-meta l CE M wa s develope dusin g x-ra y fluorescenc

e (XRF) a s th e analytica l metho dan da n automate dsamplin g syste mtha t provide s extractiv e batc h samplin g ont o afilter tape . Th e syste mi s operate

dwit h user-friendl

y WonderWare

® softwar e tha t provide s automation

, calibratio n routines , an

drepor t generation. A prototyp

e XCE M wa s teste di n th e laborator

y wit h aspike dga s strea magains t U.S . Environmenta

l Protectio n Agenc y Referenc e Metho d2 9 fo r fou r sampl e runs . Th

e XCE M me

t th e relativ e accurac y criteriafo

r fou r of seve n metals . A fieldread y XCE M wa

s buil t fo r demonstratio

n a t th e 1236 Deactivatio

n Furnac e a t Tooel e Arm y Depot , Utah .

DISCLAIMER : Th e content s o f thi s repor t ar e no t t o b e use d fo radvertising , publication , o rpromotiona l purposes . Citatio n o f trad e name s doe s no t constitut e a n officia l endorsemen t o rapprova l ofth e us e o f suc h commercia l products . A H produc t name s an d trademark s cite d ar e th e propert yo f thei rrespectiv e owners . Th e findings o f thi s repor t ar e no t t o b e construe d as a n officia l Departmen t o f th e Arm ypositio n unles s s o designate d b y othe rauthorize d documents . DESTRO Y THI S REPOR T WHE N I T I S N O LONGE R NEEDED . D O NO T RETUR N I T T O TH E ORIGINATOR .ERDC/CER L TR-05- 3 ii i



# Content s

Lis t o f Figure s an d Table s v Conversio n Factor s v " Prefac e vii i 1 Introductio n 1 Backgroun d 1 Objectiv e 3 Approac h 3 Mod e o f Technolog yTransfe r3 2 XCE M Developmen t 4 XCE M Descriptio n 5 Extraction

System

5 Sampling

and Analysis

System 7 Control System 9 Integratio n o f Sensor s 1 0 Operator Accessible

Control

Screens

10 Administrator

Accessible

Control

Screens

17 Samplin g Platfor m Modification s 1 9 Quality Assurance

Modifications

19 Ease-of-use

Modifications

2 3 Safety Modifications

2 4 3 Laborator y Testin g 2 5 Mercur ySamplin g 2 5 Experimental

2 5 Mercury RIF Results 2 5 Mercury Oxidation

Automation

2 6 Mercur y XCEM Results 2 7 Metho d 2 9 Compariso n Test s 2 7 Spike Injection

System

2 7 Test Design 3 0 XCEM Results

During Method

29 Testing 31 XCEMvsM29 3 7 Method 29 and XCEM Precision

and Accuracy

3 9 

### VE S 00062 .i v ERDC/CER L TR-05- 3

4 Field-read y XCE M 4 3 5 Summar y an d Conclusion s 4 6 Reference s 4 8 Abbreviation s an d Acronym s 4 9 Repor t Documentatio n Pag e 5 1ERDC/CER L TR-05- 3 v



# Lis t o f Figure s an d Table s Figure s 1 Schemati c o f XCE M component s minu s th e contro l compute r5 2 XCE M analysi s system , compute rcontrol , an d samplin g cassett e 6 3 XCE M samplin g cassett e 7 4 Ga s samplin g proces s i n th e sampl e cassett e 8 5 X-ra ydetectio n proces s 8 6 Componen t Contro l scree n 1 1 7 Diagnostic s scree n 1 2 8 Meta l Concentratio n scree n durin g M2 9 testin g 1 2 9 Qualit yAssuranc e scree n 1 3 1 0 Temperatur e Tren d scree n 1 4 1 1 Pressur e Tren d scree n 1 4 1 2 Flo w Tren d scree n 1 5 1 3 Concentratio n Tren d scree n 1 5 1 4 Dat a outpu t scree n 1 6 1 5 Alar m scree n 1 7 1 6 Se t Q A Range s scree n 1 8 1 7 Se t Analo g Range s scree n i 9 1 8 XCE M Q A progra m 2 0 1 9 PL C contro l fo rth e XCE M 2 1 2 0 Zer o an d spa n tes t plunge r2 2 2 1 P d wire-mounte d fo rQ A 2 2 2 2 XCE M samplin g cassett e an d XR F contro l pane l 2 4 2 3 Schemati c o f H g captur e fo rfirs t phas e experiment s 2 6 2 4 RI F H g captur e efficienc yversu s ai rflo w rat e throug h filte r2 6 2 5 XCE M elementa l concentration s durin g M2 9 testin g 3 2 2 6 XCE M cadmiu m versu s othe rspike d metal s durin g M2 9 testin g 3 5 2 7 Comparison s o f XCE M an d M2 9 concentratio n b yru n 4 0 2 8 XCE M an d M2 9 normalize d concentration s b yelemen t 4 1 2 9 Ne w Componen t Contro l Scree n fo rXCE M softwar e interfac e 4 3



### VE S 0006 2v i ERDC/CER L TR-05- 3

3 0 XCE M cassette s 4 4 3 1 XCE M extraction syste m an d cassett e an d chassi s 4 4 3 2 XCE M wit h cabine t doo rope n 4 5 3 3 XCE M wit h compute rsyste m installe d a t TEA D 4 5 Table s 1 Arm yhazardou s wast e combustor s 2 2 Evaluatio n o f spik e injectio n option s 2 9 3 Tes t condition s durin g M2 9 samplin g 3 1 4 Elementa l concentration s a t XCE M an d M2 9 Port s durin g pre - an d post-test s 3 6 5 Relativ e accuracie s o f M2 9 Por t versu s XCE M Por t durin g pre - an d post-test s 3 6 6 Reporte d XCE M an d M2 9 concentration s 3 8 7 Averag e meta l concentration s fo reac h samplin g ru n 3 8 8 XCE M an d M2 9 relativ e accuracie s 3 9



### VE SERDC/CER L TR-05- 3 vi i



# Conversio n Factor s Non-S I unit s o f

measuremen t

use di n thi s repor t

ca n b e converte dt o S I unit s a s follows : Multiply B y T o Obtain degree s Fahrenhei t (5/9 ) x(° F - 32 ) degree s Celsiu s fee t 0.304 8 meter s inche s 0.025 4 meter s

* Systeme

International

d'Unites

(Internationa l Syste m o f Measurement) , commonl y know n a s th e metri c system .vii i ERDC/CER L TR-05- 3



# Prefac e

Thi s stud y wa s conducte dfo r Headquarters , Departmen t o f th e Arm y unde r

Pro gra mElemen t

063728A . "Environmenta l Technolog y Demonstration" ; Projec t 002 , "Environmenta l Complianc e Technology" ; Wor k Uni t CNE-B091 , "Hazard

ou s Ai r Pollutant s Technolog y Demonstrations. " Th e pee r reviewe r

wa s Thoma s Logan , U.S . Environmenta l Protectio n Agency , Offic e o f Ai r Qualit y an dPlan

nin g an dStandards , Ai r Measurement s an dQualit y Group . Th e wor k

wa s performe db y th e Environmenta l Proces s Branc h (CN-E ) o f th e Installation s Divisio n (CN) , Constructio n Engineerin g Researc h Laborator y (CERL) . Th e CER L Principa l Investigato r wa s Dr . K . Jame s Hay . Par t o f thi s wor k wa s contracte dt o Coope r Environmenta l Service s unde r DACA42-02-P 0072 , DACA42-01-R-008 , an dDACA42-00-P-0245 . Th e technica l edito r wa s Lind aL . Wheatley , Informatio n Technolog y Laboratory . Dr . Kirankuma r V . Topudurt i i s Chief , CN-E , an dDr . Joh n T . Band y i s Chief , CN . Th e associate d Technica l Directo r

wa s Gar y W . Schanche . Th e Directo r o f CER L i s Dr . Ala n W . Moore . CER L i s a n elemen t

of th e U.S . Arm y Enginee r Researc h an dDevelopmen t Cente r (ERDC) , U.S . Arm y Corp s o f Engineers . Th e Commande r an dExecutiv e Directo r o f ERD C i s CO L Jame s R . Rowan , EN , an dth e Directo r o f ERD C i s Dr . Jame s R . Houston .ERDC/CER L TR-05- 3 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 Combustor s (HWC ) a s par t o f Titl e II I o f

th e 199 0 Clea n Ai r Ac t Amendment s (CAAA ) i n th e for mo f aNationa l Emissio n Standard s fo r Haz ardou s Ai r

Pollutant s (NESHAP) . Th e U.S . Arm y possesse s man y demilitariza

tio n furnace s tha t

wil l nee dto compl y wit h thes e regulations . O f mos t concer n i s bein g abl e t o mee t

th e requirement s fo r

metal s an dmeta l compound s liste dun de r th e CAAA . Thes e incinerato r operation s hav e alarg e proble mbecaus e o f limite dknowledg e o f

the type s an dquantitie s o f metal s emitted . Complianc e ma y b e determine donl y throug h tria l bu memissio n test s becaus e o f thi s limita

tion . Thes e test s ar e expensiv e an drequir e worst-cas e scenari o burns . Th e ai r permit s tha t

ar e the n issue dar e base do n thes e worst-case burn s an dimpos e limitation s o n th e demilitarizatio n facilities . A continuou s emissio n monito r (CEM ) fo r

metal s woul dprovid e th e emissio n data , atoo l t o hel p mee t compli

anc e requirements , an dth e opportunit y t o adjus t bur n strategie s fo r

increase d productio n an dsustainability . I n addition , th e HW C NESHA P suggest s tha t a C E M woul db e th e preferentia l metho do f emissio n accountability . Multi-meta l CEM s bein g develope dar e base do n elementa l sensor s usin g laser

induce dbreakdow n spectroscop y (LIBS ) o r inductivel y couple dplasm a(ICP) . Non e o f th e LIB S monitor s ha s successfull y me t th e EPA-propose dPerformanc e Specificatio n 1 0 (PS-1 0 1996 ) fo r continuou s multi-meta l monitors . Onl y on e o f th e IC P units , develope db y Therm o Jarrel l As h Corporation , ha s bee n successfu l i n meetin g th e relativ e accurac y (RA ) criteri ao f th e PS-1 0 (Seltze r

2000) . Th e multi-meta l CEM S technolog y appear s t o hav e practica l limitation s suc h a s it s complexity , hig h initia l cost , an dhig h operatin g costs . Th e U.S . Arm y Enginee r Researc h an dDevelopmen t Center , Constructio n Engineerin g Researc h Labora

tor y (ERDC/CERL ) decide dt o pursu e th e developmen t o f th e X-ra y fluorescenc e (XRF)-base dcontinuou s emissio n monito r (XCEM ) becaus e i t

ha dthe potentia l t o b e areliabl e an daccurat e CE M withou t thes e limitations . Th e basi c approac h o f the XCE M i s t o dra w acontinuou s representativ e sampl e o f stac k ga s t o astillin g chambe r wher e asmalle r

metere dsampl e i s extracte d an dpasse dthroug h achemicall y treate dfilte r tha t collect s metal s i n th e particu

-2 ERDC/CER L TR-05- 3 lat e an dvapo r

phases . Followin g sampling , th e filte r i s passe dthroug h a n XR F analyze r wher e th e masse s o f

u p t o 1 9 metal s ar e measured . Thi s approac h wa s originall y teste di n 199 7 at a n EP A tes t

incinerator , wher e th e filter s wer e ana lyze dofflin e (Frenc h 1998) . Coope r Environmenta l Service s (CES ) furthe r de

velope dthi s metho dint o a n onlin e syste mteste dunde r th e ERDC/CER L Wast e Minimizatio n an dPollutio n Preventio n Progra ma t MS E Technolog y Applica

tions , Inc.' s (MSE-TA's ) researc h incinerato r i n Butte , M T (Bryso n e t al . 2000) . Th e result s wer e encouragin g becaus e th e XCE M me t th e PS-1 0 R A require

ment s fo r

chromiu m(Cr ) an dlea d(Pb) . Man y o f the othe r

requirement s wer e unmet , however , an dfurthe r developmen t

wa s needed . I t

wa s a t thi s poin t

tha t ERDC/CER L bega n fundin g the developmen t o f XCE M technolog y unde r thei r Hazardou s Ai r

Pollutant s (HAP ) program . Tabl e 1 list s th e Army' s 1 9 existing , new , o r planne dhazardou s wast e combustor s (Josephso n 2003) . Tabl e 1 . Arm y hazardou s wast e combustors . Locatio n Typ e Wast e Treated Statu s G O o rC O Sierr a A D A P E 123 6 C S Existin g G O Tooel e A D A P E 123 6 C S Existin g G O Tooel e A D A P E 123 6 Tes t Furnac e - C S Existin g G O McAleste rAA P A P E 123 6 C S Existin g G O Hawthorn e AA P A P E 221 0 C S Ne w C O For t Richardso n A P E 123 6 C S Ne w G O Kansa s AA P A P E 123 6 C S Existin g C O Cran e AA P A P E 123 6 C S Ne w G O Lak e Cit yAA P A P E 123 6 Off-spe c conventiona l Existin g G O Picatinn yArsena l A P E 123 6 Wast e R& D propellant s Ne w G O Pin e Bluf f Arsena l Fluidize d Be d Pyrotechnic s an d Obscurant s Ne w G O Pin e Bluf f Arsena l A P 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 t C 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 Arsena l 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 t Owne d C O - Contracto r Owned C A - Chemica l Activit y C S - Conventiona l Stockpil e Che m - Chemica l Stockpil e AP E - Arm y Peculia r Equipment A D - Arm

y Depo t AA P - Army Ammunitio n Plan t R& D - Researc h an d Developmen tERDC/CER L TR-05- 3 3

Objectiv e Th e overal l objectiv e o f th e HA P progra mi s t o develo p cost-effectiv e technologie s t o hel p th e Arm y mee t curren t an dfutur e demand s o f HA P regulations . Th e specifi c objectiv e o f

th e wor k

reporte dhere wa s t o develo p amulti-meta l CE M fo r us e at a n Arm y installation . I t i s importan t

tha t thi s monito r

b e easy t o transitio n t o th e Arm y b y incorporatin g characteristic s tha t mak e i t compatibl e wit h Arm y operation s an dexpectations , suc h a s use r friendlines s an d affordability . Ultimately , th e desire dexi t criterio n unde r

th e HA P Progra mi s fo r th e monito r

t o mee t th e complet e requirement s o f th e propose dPS-1 0 unde r fiel dconditions . Thi s objectiv e wil l b e pursue di n afollow-o n report . Approac h Th e XCE M wa s develope dunde r thi s projec t

throug h contract s wit h CE S (DACA42-00-P-024 5 an dDACA42-01-R-008) . A prototyp e wa s constructe din

corporatin g necessar y improvement s determine dfro mth e Butt e testing , suc h a s use r friendliness , automation , an dth e capabilit y t o monito r mercur y (Hg) . Thi s prototyp e wa s the n teste di n th e laborator y b y comparin g i t agains t th e EP A Referenc e Metho d2 9 (M29) . A ne w monito r wa s constructe dan dreadie dfo r demonstratio n a t

the 123 6 productio n deactivatio n furnac e a t Tooel e Arm y De po t (TEAD) , UT .

Mod e o f Technolog y Transfe r Thi s technolog y wa s develope dthroug h th e ERDC/CER LHA P Program , whic h use s 6. 3 advance ddevelopmen t an dfield-testin g funds . Th e HA P Progra mi s par t o f th e Arm y Environmenta l Qualit y Technolog y (EQT ) Program . A s par t o f th e EQ T process , atechnolog y transfe r pla n i s bein g develope db y the Arm y En vironmenta l Cente r

(AEC ) fo r

thi s technolog y an dothe r qualifie dtechnologie s unde r th e HA P program . A User' s Guid e an daResourc e Manua l hav e bee n de

velope dt o accompan y th e XCE M fo r fiel dtrainin g an dreferenc e (CE S 2001a,b) . Thi s repor t

wil l b e accessibl e throug h the Worl dWid e We b (WWW ) at URL : http://www.cecer.army.mi l4 ERDC/CER L TR-05- 3



# 2 XCE M Developmen t Regulators , governmen t agencies , an dindustr y hav e expresse dsuppor t fo r de

velopmen t

o f instrumentatio n capabl e o f continuou s measuremen t o f metal s fro mstationar y sources . Th e EP A recentl y reemphasize dit s positio n i n th e fina l Maximu mAchievabl e Contro l Technolog y (MACT ) standar dfo r hazardou s wast e incinerators . I n thi s standard , continuou s monitorin g i s place da t the to p o f

th e Complianc e Monitorin g Hierarch y an dunderscore da s th e "stron g preference " (Federa l Registe r

[FR ] 52925) . Th e incentive s provide di n th e MAC T standar d fo r usin g multi-meta l CEM s includ e bypassin g feedstoc k measuremen t

an dde

crease drequirement s fo r performanc e testing . I n addition , en duser s o f multi

meta l CEM s hav e real-tim e acces s t o proces s contro l informatio n an dthe poten tia l fo r enhance dpubli c acceptance . Ove r th e pas t

fe w years , CE S ha s develope dinstrumentatio n capabl e o f continu

ou s multi-meta l measurement . Th e CE S approac h use s XR Ft o measur e stac k ga s particulat e matte r (PM ) tha t

ha s bee n concentrate do n afilter . I n 199 7 CE S demonstrate dth e feasibilit y o f thi s approac h usin g a n offlin e continuou s sam plin g syste ma t

a n EP A tes t

incinerato r

i n Nort h Carolin a(Frenc h 1998) . Fur the r adaptatio n o f

th e approac h le dto a n onlin e XCE M capabl e o f determinin g meta l concentration s ever y 1 0 t o 1 5 minutes . Th e prototyp e XCE M wa s success full y teste di n 199 9 a t th e MSE-T A tes t

facilit y (Bryso n e t

al . 2000) . Durin g thes e tests , th e XCE M demonstrate da n R A fo r tw o MAC T metals , C r an dPb , o f les s tha n 2 0 percent . Furthe r refinemen t

wa s needed , however , to mee t EPA' s PS-10 . Specifically , th e MSE-T A repor t recommende dtha t

th e followin g task s b e performed : 1 . Senso r

Integration : Integrat e temperatur e an dpressur e sensor s int o auser friendl y computer

interface . 2 . Samplin g Platfor mModifications : Modif y th e samplin g platfor mfo r improve d ease-of-use , an dintegrat e a n automate dqualit y assuranc e (QA ) progra mint o th e samplin g platfor mdesign . 3 . Mercur y Sampling : Conduc t additiona l laborator y testin g fo r H g captur e effi

cienc y an dautomatio n o f XCE M H g oxidatio n system . Conduc t furthe r H g R A testing . 4 . Spik e Injectio n System : Develo p a n injectio n metho dcapabl e o f supplyin g ade

quat e concentration s o f metal s fo r

routin e testing . Conduc t furthe r XCE M R A testin g usin g th e ne w spik e injectio n system .ERDC/CER L TR-05- 3 5

Thi s chapte r

present s agenera l descriptio n ofth e XCE M an dth e improvement s t o th e XCE M tha t

addres s th e firs t

tw o recommendation s mad e i n th e MSE-T A report : senso r integratio n an dsamplin g platfor mmodifications . XCE M Descriptio n Figur e 1 show s majo r XCE M component s an drelativ e flows . Th e XCE M com prise s thre e majo r

subsystems : a n extractio n system , samplin g an danalysi s system , an dcontro l system . Extraction

System Th e extractio n syste mi s designe dt o transpor t arepresentativ e sampl e o f stac k ga s fro mth e stac k

t o th e filte r

tape . I t include s aprobe , 1-inch-diamete r tubing , stillin g chamber , an dflo w measuremen t an dcontro l components . Temperatur e i s measure da t

fiv e locations , an dal l tubin g prio r t o th e filte r

i s hea t traced . Pressur e Lea k Chec k Transduce r Valv e SAMPL E RETUR N LIN E

Extractio n Syste m

Samplin g a n d Analysi s Syste m Figur e 1. Schemati c o f XCE M components minu s the contro l computer .6 ERDC/CER L TR-05- 3

Th e extractio n syste mdraw s a n isokineti c sampl e fro mth e stac k usin g alarge

diamete r probe . Th e ga s i s transporte dt o a3-inch-diamete r stillin g chamber , whic h slow s th e ga s velocity , decreasin g th e Stoke s numbe r s o tha t smal l quanti

tativ e subsample s ca n b e extracted . Th e subsample , les s tha n 1 percen t o f th e ga s sampl e i n th e stillin g chamber , i s remove dfro mth e stillin g chambe r throug h aone-quarter-inch-diamete r extractio n tube . Insid e th e extractio n tube , adilu

tio n an dmixin g chambe r allow s the additio n o f chlorin e an dothe r

gase s to dr y an doxidiz e th e sample . Th e oxidize dsampl e i s the n draw n throug h aresin

impregnate dfilte r

(RIF ) wher e particulat e an dvapo r phas e metalli c specie s ar e concentrate dfo r

subsequen t

XR Fanalysis . Afte r

passin g throug h th e filter , th e ga s i s drie dwit h aUniversa l Analyze r dryer , measure dwit h amas s flo w control

ler , an dreturne dt o th e stac k throug h adiaphrag msamplin g pump . A post filte r pressur e transduce r

provide s assuranc e tha t n o leak s ar e presen t

i n th e system . Th e volum e o f th e remainin g 9 9 percen t o f th e stillin g chambe r

stac k ga s i s measure dan dreturne dt o th e stac k usin g aregenerativ e blower . Th e en tir e extractio n syste mi s show n i n Figur e 1 . Th e XCE M softwar e interfac e control s ke y extractio n syste mcomponent s includ

ing : thermocouples , apressur e transducer , blower , pump , an dsevera l flow

meters . Temperature , flow , an dpressur e dat aar e automaticall y recorde di n a n electroni c database . Figur e 2 show s th e sampl e cassett e ato p th e XR Fanalyze r nex t t o th e compute r

contro l enclosure .

Figur e 2. XCE M analysi s system , compute r control , and samplin g cassette .ERDC/CER L TR-05- 3 7 Sampling

and Analysis

System Onc e th e stac k

ga s subsampl e leave s th e stillin g chamber , i t i s draw n int o a sampl e cassett e (Figur e 3) . Thi s cassett e contain s asteppe r motor , infrare dtap e brea k sensor , an dfilte r

tap e mounte do n reels . Stac k ga s enterin g th e cassett e i s transporte dthroug h th e extractio n tub e acros s a0. 3 cm 2spo t o n th e filte r tape . Ever y 1 2 minute s th e filte r tap e i n th e cassett e i s advance dfro mth e sam plin g locatio n t o th e analysi s positio n locate d1 inc h away . A Kevex-Spectrac e Quan X XR Finstrumen t (Therm o Kevex , Therm o Electro n Corp. , Waltham , MA ) the n analyze s th e metal s mas s concentrate do n th e filter . Followin g analysis , th e sampl e i s advance dagai n an dcollecte do n atake-u p reel . Figur e 4 show s a schemati c o f

thi s process . Durin g th e XR Fanalysis , x-ray s ar e emitte dfro mth e x-ra y tub e ont o th e filte r tap e sample . Resultan t x-ray s ar e produce dtha t ar e characteristi c o f

the metal s o n the sampl e (Figur e 5) . Thes e x-ray s ar e detecte d b y th e XR Fdetecto r

an dasigna l tha t

i s proportiona l t o th e mas s fo r eac h meta l i s sen t t o th e computer . Th e compute r acquire s thes e signal s an dcompare s i t t o know n mas s pe r

signa l ratio s develope ddurin g calibration . XR Fresult s ar e the n reporte da s microgram s pe r sample .

1

Figur e 3 . XCE M samplin g cassette .8 ERDC/CER L TR-05- 3

Gas Sampl e i n

Extractio n Cassett e Wheel

Filtere d Gas out Figur e 4 . Ga s samplin g proces s i n the sampl e cassette . Filte r Tap e Sampl e CZ. 1. 'L. 1

Figur e 5 , X-ra y detectio n process .



### VE SERDC/CER L TR-05- 3 9 Sinc e XR Fi s nondestructive , meta l mas s o n th e take-u p ree l i s availabl e i f neede dfo r

subsequen t

chemica l analysis . Eac h cassett e hold s a2- 4 wee k suppl y o f tap e an di s engineere dt o b e portabl e an deasil y removed . I t i s anticipate d tha t eac h XCE M wil l come wit h tw o cassettes , whic h wil l enabl e th e operato r to exchange tape s i n aclea n environmen t an dtranspor t

th e entir e cassett e int o th e field . A n additiona l benefi t o f havin g tw o cassette s i s aduplicatio n o f compo nents . I n th e even t

o f equipmen t

failure , th e duplicat e cassett e ca n b e i n plac e withi n afe w minutes , decreasin g instrumen t downtime . Th e cassett e i s de

signe dt o fi t

directl y onto th e XR Finstrumen t an dinclude s interlock s t o preven t th e XR Ffro moperatin g whe n th e cassett e i s no t i n place . Th e Quan X energ y dispersiv e XR Fha s a n electronicall y coole dlithiu mdrifte d silico n detector . Locate dimmediatel y abov e th e detecto r i s apermanentl y mounte dpalladiu mrod , whic h i s analyze dwit h eac h sampl e t o determin e i f in

strumen t drift i s occurring . A s a n additiona l Q A source , aro di s mounte do n a pneumati c plunge r

nea r th e detector . Thi s ro dha s a n epox y coatin g wit h signifi

can t quantitie s o f

Cadmiu m(Cd) , Cr , Hg , an dPb . Eac h da y th e XCE M activate s th e plunge r

an dextend s th e ro dint o th e analysi s are afo r spa n an dzer o tests . Detectio n limit s fo r

th e XR Far e determine db y filte r blan k concentration s an d analysi s time . I f

asampl e i s take n ever y 1 0 minutes , detectio n limit s fo r al l o f th e MAC T metal s ar e les s tha n 3. 5 ug/m 3 (microgram s pe r cubi c meter) . Detec tio n limit s ca n b e improve db y increasin g samplin g time . Th e XR Fautomati

call y determine s metal s concentratio n an duncertainties . Th e dat aar e the n transmitte dt o asecon dcomputer , whic h run s th e WonderWare ® softwar e con tro l interface . Control System XCE M flow s an dtemperature s ar e controlle dusin g WonderWare ® softwar e interfac e o n apersona l computer . Thi s interfac e record s pressure , temperature , metal s concentrations , Q A data , an dsamplin g times , an dprint s ahar dcop y repor t wit h eac h sampl e analysis . A n electroni c cop y o f th e dat ai s kep t

i n a WonderWare ® database , whic h canno t b e altere dwithou t

bein g flagged . Thes e dat aca n b e mad e availabl e ove r aloca l intrane t

o r asecur e Interne t

website . A secon dpersona l compute r run s th e XR Fsoftware . Automatin g th e XCE M t o mak e i t auser-friendl y too l wa s aprimar y objectiv e o f thi s work . Th e automatio n an dcontro l feature s tha t wer e develope dar e discusse di n th e nex t

section .1 0 ERDC/CER L TR-05- 3

Integratio n o f Sensor s Th e MSE-T A repor t

recommende dcompute r contro l o f

XCE M components , dat a storage , an dQA . I n respons e to thi s recommendation , th e XCE M ha s bee n full y automate dusin g aWonderWare ® softwar e interface . Thi s interfac e include s a variet y o f

screen s tha t

allo w the use r

t o contro l components , diagnos e problems , vie w concentratio n trends , an doutpu t data . Eac h scree n contain s a n alar msig

na l i n the lowe r

right-han dcorne r

tha t flashe s i f

some componen t

o f th e syste m i s no t workin g o r

i f th e metals ' concentration s excee duser-define dlimits . Th e XCE M interfac e i s passwor dprotecte dan dca n b e accesse db y eithe r a n operato r wit h limite dXCE M contro l o r a n administrato r

wit h ful l use r

rights . Operator

Accessible

Control

Screens Th e compute r

interfac e allow s th e use r t o vie w anumbe r

o f screen s tha t

presen t operationa l dat afo r

contro l o f

th e XCEM . Thos e screen s ar e presente dbelow . Componen t Contro l Scree n Th e Component

Control scree n (Figur e 6 ) contain s aschemati c o f the XCE M sys tem . Thi s schemati c include s icon s representin g ke y XCE M component s an d real-tim e dat afo r

temperatures , pressures , an dflows . Adjacen t t o th e sche

matic , aSystem Start/Stop butto n begin s an dcomplete s samplin g wit h asingl e click . Thi s scree n als o provide s user s wit h th e optio n o f manuall y adjustin g in

dividua l component s o f th e samplin g system . User s logge do n a s operator s ca n contro l heater s o r

tur n th e pum p an dblowe r o n b y doubl e clickin g o n th e appro priat e ico n an drespondin g t o th e pop-u p dialogu e box . User s logge do n a s ad

ministrator s hav e the furthe r capabilit y o f

controllin g flow rate s an dvalves . Thi s pag e i s considere dthe "hom e page " fo r th e interfac e an dca n b e accesse d fro man y scree n b y clickin g o n th e hous e ico n i n th e lowe r left-han dcorne r

o f th e page .ERDC/CER L TR-05- 3 1 1

| jt~j & |Us « Warn

s None Scree n LDcke aLogo n ] ' ^ Admi n ; ff t Report s j Q Trend s ; 3 Screen s ) AtHfffi s •- 9/e/o o j 4:57:2 5 Componen t Contr d 1 Metal s Conccnb-attan s J ) Qualif y tesurance j j Figur e 6 . Componen tContro l screen . Diagnostic s scree n Th e Diagnostics scree n (Figur e 7) i s aread-onl y interfac e designe dt o giv e th e operato r a n easy-to-rea dsyste mstatu s check . Th e Diagnostics scree n display s curren t temperature , flow , Q A an dmeta l concentration s an dlight s indicatin g i f th e syste mi s functionin g properly . Buffe r range s define db y the syste madmin

istrato r fo r eac h componen t

ar e displaye do n thi s screen . Measurement s tha t fal l withi n thes e buffe r range s ar e give n agree n light . Measurement s slightl y beyon dth e range ar e signifie dwit h ayello w light , an ddat asignificantl y beyon d th e buffe r

rang e warran t

are dlight . Yello w an dre dlight s ar e liste da s alarm s b y th e XCE M interface . Metal s Concentratio n scree n U p t o 2 0 real-tim e metals ' concentration s ar e displaye do n th e Metals Concentration scree n (Figur e 8) . Operator s ca n grap h u p t o eigh t o f thes e concentration s simultaneousl y an dacces s a12-hou r rollin g averag e char t tha t display s Hig h Volatil e Metal s (HVM) , Semi-Volatil e Metal s (SVM) , an dLo w Volatil e Metal s (LVM) . Th e char t

wa s develope di n accordanc e wit h th e MAC T rul e fo r hazard

ou s wast e incinerator s an dca n b e se t t o includ e buffe r

range s t o aler t

th e opera to r o f hig h meta l concentration s i n th e stack . A s wit h al l graph s withi n th e1 2 ERDC/CER L TR-05- 3

XCE M interface , th e Metal s Concentratio n graph' s tim e axi s ca n b e se t t o dis

pla y dat afo r

period s betwee n afe w hour s u p t o 6 weeks . CE S Sanpt e Lin e Pie s sur e CE S XCE M i Diagnostic s : awn q Chambe r Tetnperstur

e 3rtln

_Chambe r Inte l Twrp f fslm e ' S A Parwrde t

Zao Cadmiu mCurren t Valu e 12-HOU R ROLLIN

G AVERAG E BUT O RANG E

COMPONENT

S j HVMtHg ) B 0, 0 0. 9 9. 1 (svM (cd6Pb ) , 0. 0 0. 9 9. 1 [T V M (A s aCr ) • . 0. 0 0. 9 9, 1

. . . ___. _ STATU S CURREN T BAJFFE RRANG E ! Matnlln e Flo w (ocfin ) 0. 0 1. 0 9. 0 j CBddan'tFb w (ml . mb ) • ' 0. 0 3. 0 4OQ. 0 ] Sampl e Flo w (dslpm ) 0, 1 1. 0 9.0 j Stad<Terr^.rtjj. . .pC ) B : 21. 8 16. 0 340. 0 j Uppe r ChAtrterTetnpsraturB t?C} B ' 4CO. 0 16. 0 340, 0 \Lowe r Oambe r

TemperatLr e (°C ) B 4CO. 0 16. 0 340. 0 I Mai n Fla w Terrperatur e (. Q • B 21. 5 16. 0 340. 0 | File r Temperatur e {°c > 22. 5 36. 0 340. 0 ] sanpl ath e Pressur e <psfi ) ' B 14. 1 0, 2 5. 0 QUALIT Y ASSURANCE

| Spa n Metal s (cr , Cd , Pb ) j 2er o Metal s (Cr , Cd , Pb ) STATU S

____ _ [ Q A Flo w Differenc e

rpsladU m STATU S

___ _ 1

' 1 S~eenLWod<et| Logo n | j & Admi n j P i Reports ) Q Trend s ) •Screen s J 00:2 0 • | | CarnfM-VfltGanlr d | J " Dlagia-tlr s "H f [ Metal s Caxentratfai s f | Qua-lty&swaic B Figur e 7 . Diagnostic s screen . Inloij . hWmrluwVtrMi' i

12-HOU R ROLLIN G AVERAG E

, 12-HOU R RCtUN G ' GRAP H j W M (Hg ) ! SV M (C d8 . Pb ) STATU S CUWtEN T SUFTOPAMG E § § | 113,6 6 ug/dsc m0. 0 250, 0 ! § 185.6 3 yg/dicin D. O 250. 0 I LV M (A s a Cr

) 

## • 198.9 6 pg/dsc m 0, 0 250. 0 CURRENT META L CONCENTRATIO N UstSamptePeriod : 12:32:2 6 T o 12:44:0 5 Etermn t Concentratio n Elemen t Cc*ncentra_or i 232. 5 203. S 1M. 4 - 145, 3 116. 3 % - u p L_

I i )^r - -4_P = —'3- . -w-^^t-i^p - &jg/dscrr) ) f A S • 0, 0 C O 0. 3 { O r • a o i ' N i 0. 4 { C d• 0, 0 • r C u 1, 7 ! H g D . 0. 0 i S T H 0, 0 j "p b B B 0. 0 B r 2, 3 0. 0 T l 0, 0 j A g i D. D r V 1, 9 j S b O. D r M n 0. 0 I B a Q. O • r N.U .

1. 9 • r 2143. 2 " Vie wTren d Ful l Scree n

I S 3 _ ^ iUse

r Nam-' , adrrfnlstr-lor ! Screenuntocio

- f j 3 ' Logo n j & Admi n j ff» , Report s : Q Trend s . E 3 Screen s j Alarm s j li/ia /Q Q j iOrfOi- 7 ' . CcmporientC_*- d Oi'arjit-tic s Metal . OGncentratit- - Quallb / Assuranc e Figur e 8 . Meta l Concentratio n scree n durin g M2 9 testing .ERDC/CER L TR-05- 3 1 3

Qualit y Assuranc e scree n Th e Quality Assurance scree n (Figur e 9 ) i s aread-onl y displa y tha t show s his

torica l Q A results . Palladiu m(Pd ) i s measure dwit h eac h sampl e whil e dail y spa n an dzer o test s fo r ke y metal s ar e conducte da t user-define dtimes . Th e tim e a t whic h th e lates t

Q A chec k

wa s undertake n i s als o liste di n atex t bo x o n th e right-han dside . Trend s screen s Trend s fo r

temperature , pressure , flow , an dmetal s concentration s ar e al l dis

playe da s individua l screen s b y th e XCE M compute r interfac e (Figure s 10-13) . Eac h scree n ca n displa y u p t o eigh t trend s simultaneousl y an dca n b e custom ize dt o includ e combination s o f dat afro mth e othe r

trend s screens . Fo r

example , stac k temperatur e an dmetal s concentration s ca n b e graphe dsimultaneously . A l l figure s ca n b e printe db y usin g the Print Trend butto n i n th e lowe r

right

han dcomeY

o f th e screen . 

### XCE M Diagnostic s [Sampl e Lin ePress StiBi g Clmmfiy

r Tempera!Of

c i Stiiir g Chambe

r hte t Ternp y |Q A Paiamete

r I ato cadrfMu

mCurrer . vau _ 12-HOU R ROLLIN G AVERAG E STATUS . CURREN T BUFFE RRANG E j HVM01g

> 0. 0 0. 9 9, 1 \swfcdapb ) D. 0 0, 9 9. 1 UvMiAsacr ) 

## • 0. 0 a. e 9. 1 COMPONENT

S STATU S CURREN T BUFFE RRANG E

Marin aFte w (scfm ) • . 0 1. 0 s. o

, Oxidan t

Fto w (ml/min ) 

## • D. O 3. 0 400, 0 i Sampl e Flo w (dsfpm ) 0. 1 1. 0 9. 0

' Stad < Temperatur e fC ) m

. 21. B 16. 0 340, 0 * Uppe r Chambe r

Temperatur e (=C ) B 400. 0 16. D 340. 0 | Lowe r Chambe r

Terrperatur e 0_

) 1 1 400. 0 16. 0 340, 0

• Mai n Fb w Temperatur e TO m 21. 5 16, 0 340. 0 ; Filt_ pTemperatur e (°C ) 22. 6 16. D 340. 0

• Sampl e Lin e Pressur e (psla ) n ^ 14. 1 0. 2 5, 0 QUALIT Y ASSURANC E STATU S STATU S

I SpanMetals(Cr,Cd,Pb ) m i | Q A Flo w Differenc e n . fzer aMetal s (Cr , Cd , Pb ) ^ PabiU m 

## •

a- Name : «dmlrtslr_o r (Scree n Unlocke df| ) ' Logo n ] Admi n } fjl ) Report s \ jf j Trend s ! 3 Screens ! £ j Alarm s j sye /O O j . 5;00;2 O Canpcnen t Contro l Diagnostic s Metal s Cancentration s ~ j Qualit y Pwssurant e Figur e 9 . Qualit

y Assuranc e screen .1 4 ERDC/CER L TR-05- 3

lnloui. h WindonViewe f

Ik.. "3 5 >03 ' 5 > l b 0 5

-: )Jo-'0 5 157. 0

137. 3

117. 7

98. 1

78. 5

58. 9

39: 2

19. 6

0 0 '_ ' i; - 3 i 5 7 © Ha * • StillJn g Chante r

Q Rtter H staling chante r

Inlet @ swin g Chante r Outle t 1 3 Not

Use d • Not Use d H Mo t Use d Prin t Tren d

' u? l l%3

• #fuserNam " adrrfttetrator . i r SwenLoaed~'fl i : & logo n } %.Admi n i f % Report s j ^Trend s I •Screen s | j £Alarms j Ii/I3f0 0 j I3i32. , 0 ? ; Concentratio n Tren d j Pressur e Tren d Temperatur e Tren d Figur e 10. Temperatur e Trend screen .

i i t Touc h - WinilowVittwu i

• No t Use d

• Not Use d • fktUsad

• Ho t Use d • Mo t Use d H No t Use d f^j l Prin t Tren d

: tj 2 O & j Use r

Name : admJmstrata

r ! scree n Locke d\\=) Logo n j ^ Admi n ! Ifs j Reports, ' QTrends J £ 3 Screen s J & Alarm s 5 U/13/0 0 > I3i3iil 0 ; Concentratio n Tren d fl Temperatur e Tren d Figur e 11 . Pressur e Trend screen .

VE S 000 &ERDC/CER L TR-05- 3 1 5

- WmdowVicwp i Deuelopmert J 

# !

4 , 0

3 . 5

3 . 0

2 . 5 -

2 . 0 •

1 . 5 -

1 . 0 -

0 . 5 •

0 . 0

M Sampl e Lin e S I Otfoan t Vi 2 c

13:28:5 8 '. M

I Ma n Lin

e O wo tUse d M Nause d i No t Use d i Not use d f ^ h Prin t Tren d

'.il l ii i fc* fuserltoee : edmlrjslrelc r j ) coitenlratior i Tren d j Tsweenucte d | 3 ; ^

Logo n j Admi n i p i Repbr s j £ 3 Trend

s r• Screen s ] ff Alarm t j n/13/o o i 13:29.0

8 : J Tempefattir e Tren d j i Figur e 12

. Flo w Trend screen .

i. I n Touc h - WindowViewe i FO e Logi c Specia l

No v 0 5 03:34 : K 2 3 2 5

203. 5

174. 4

145. 3 116, 3

87. 2

58. 1

29. 1

0 . 0 : ' J

H MjaA-Pd-C

V

• NJIC.S e a Nov 0 5 06-04:1 6 No v 0 5 Oij-34'1 6 No v 0 5 11:04-1 6 Nov 0 5 !3:34:1l

5 I i I I i I I ' j L 

# 'W\ j ! • i

j i M_ECjCf_C

V 3 MJXJCCLC V 1 H_£C_fto_C V Prin t Tren d

tf l fi3 fl 1 Wamfl : , " , T * I ^eeflTocKed

" fig ) Logo n j . lif

e Admi n j - P i Report s j Q Trend s 1 a Screens j % fidarms j n/iajo o j 13:34:3

1 [ j ' Tenipeta^ e Tren d | ]•

• Concentratio n Tren d Pressur e Trerid ^ J | Figure 13 . Concentratio n Trend screen .1 6 ERDC/CER L TR-05- 3

Dat a outpu t Th e contro l progra mautomaticall y save s Q A an dmetal s concentratio n data . XCE M operator s hav e th e optio n t o convert th e dat ato acomma-delimite dfor

ma t tha t i s readil y opene dusin g Microsoft ® Exce l o r othe r spreadshee t

pro grams . Usin g th e Data Output scree n (Figur e 14) , th e operato r ca n selec t

u p t o 6 week s o f

historica l data . Th e outpu t i s automaticall y average dove r auser define dsampl e period . Dat aoutpu t includes : 1 . Sampl e date 2 . Samplin g tim e 3 . Concentration s of

analyze delement s 4 . Uncertaint y i n concentration s o f analyze delement s 5 . Pressur e i n samplin g loo p 6 . Temperature s 7 . Mai n line , oxidan t

an dsampl e flow s 8 . Dat afla g an dcod

e i f re dalar mi s triggered . Dat aar e automaticall y flagge di f apotentia l proble moccurre d(i.e. , aparamete r i s outsid e th e user-define dQ A limits/ranges) . Th e XCE M administrato r define s acceptabl e boundarie s fo r al l temperature , flow , an dpressur e reading s a s wel l a s Q A parameters , individua l meta l concentrations , an d12-hou r average concen trations .

STAR T DATE AN D TIM E

; Star t Tlm B Hou r i Star t Tim e Mtrut e

DURATIO N O F SAMPL E

Ma x lengt h of tin e fo r duratio n i

» si x wseks . " 3 Fractiona l value s ere edowed . (.25D-6hoirs , 1

W - 1 Week

) W =Non e

W "Wee k 0 =Ds y H»Hou r M -Hrnlt e SAMPL E INTERVA L Max lengt

h o f tim e fo r duratio n i s si x weeks . Tine Tim e Perio d

tT-acSwia

l V<AJ Wor e allowed , (2M-2Mnut»i , .5H-30Minutes ) W = Wee k D " = Da y H = Hou r M =Minut

& S - Second CONTRO L AN D STATU S \CS V 5av e Filenam e &.\zfs mp\XRFTEST11050 0 ] Initiat e CS V Fil e Writ e t Sav e t o j Operattori R N O ERROR S i Las t Erro r Messag e

I [£ g ^ j Use-Name ; wtrtrtrrtratt w . [screenUttocto d- ^ logo n ' ^.Adm'ml p ) Report s } Q Trend s j E 3 Screen s Alarm s jTlf(3fo o j &.33-.2a i Write/SayB/Vie wCS V File ] Figur e 14

. Dat a outputscreen .ERDC/CER L TR-05- 3 1 7

Fo r chain-of-custod y purposes , neithe r th e operato r

no r th e administrato r

ca n chang e th e recorde ddat ai n th e XCE M databas e withou t flaggin g the data . Alarm s Whe n a n alar mconditio n exists , aflashin g re dalar msigna l i s show n a t th e bot

to mrigh t

o f eac h scree n an dadiscussio n o f th e alar mconditio n i s show n i n th e uppe r righ t o f eac h compute r

screen . Detaile dinformatio n abou t th e alar mca n b e foun do n th e Alarm scree n (Figur e 15) . Alar mcondition s includ e filte r tap e breakage , diagnosti c o r Q A parameter s ou t

o f th e buffe r

range , samplin g cassett e lid s incorrectl y mounted , an d12-hou r rollin g average s ou t

o f the buffe r

range . Whe n a n alar mconditio n i s remedied , i t remain s liste di n th e Alarm scree n wit h green , blue , o r

blac k fon t colors . Th e XCE M wil l continu e t o sampl e despit e a n alar mcondition ; however , dat awil l b e flagged . Administrator

Accessible

Control

Screens Onl y a n individua l logge di n a s a n administrato r ca n se t componen t

an dQ A buffe r ranges , scal e analo g reading s fro mth e instrumen t an dbypas s the norma l instrumentatio n routines . Administrato r acces s i s passwor dprotected . Th e fol

lowin g screen s ar e onl y accessibl e b y a n administrator .



### XCE M .Sampl e Lin e Pressur

e Alarm s .Sillin g Chambe r TerrperBtur

e i StOTin g Chambe

r Inle t Temperatur

e iQ A Paramete

r Zer o Cadmiu

mCurren t Valu e >113TO?vlC:.. U ALAT5M 3

Dal e Tim a Stal e Typ e Ope r P n Cm t Nam e Va l O B Se p 20O 0 17000 6 A C K HIHI VW/XCEM/a r 1 Sampl e Lin e Pressur e W M PI10 5 14.G79 8 0 8 Se p 200 0 17:00:0 6 A C K HIHI WWXCEM/a c 1 Stillin q Chambe r Temperatur e W WTC00 3 40 0 0 8 Se p 20D 0 17:00:0 6 A C K HIHI WWXCEM/a c 1 Stillin q Chambe r Inle t Temperatur e W WTC00 2 40 0 0 8 Se p 200 0 17:00:0 6 A C K LOL O WWXCEM/a e 1 Q A Paramete r Zer o Cadmiu mCmren t Valu e M Q A Zer o C dC V 0 0 8 S«p200 0 17:00:0 6 A C K LOL O WWXCEM/a c 1 O A Paramete r Zer o Chromiu mCurren t Valu e M O A Zer o C r C V 0 0 8 Se p 200 0 17:000 6 A C K LOL O WWXCEM/a c 1 Q A Paramete r Zer o Lea dCurren t

Valu e M O A Zer o P b C V 0 0 8 Se p 200 0 17:00:0 6 A C K LOL O WWXCEM/a c 1 Q A Paramete i Palladiu mCurren t Valu e M Q A P dC V D 0 8 Se p 200 0 17:00.0 6 A C K LOL O WWXCEM/a c 1 L V M (As/Cr ) 1 2 Hou r Rollin q Averaq e Cunen l Valu e M LV M 12 H C V 0 0 8 Se p 200 0 17:00:0 6 A C K LOL O WWXCEM/a e 1 S V M (Cd/Pb ) 1 2 Hou r Rollin q Averaq e Curren t Valu e M SV M 12 H C V 0 0 8 Se p 200 0 17:00:0 6 A C K LOL O WWXCEM/a c 1 H V M (Hq ) 1 2 Hou r Rollin aAvBraq e Curren t Valu e M HV M 12 H C V 0 0 8 Sa p 200 0 17:000 6 A C K L O WWXCEM/a c 2 Mai n Lin e Flo w W WFI10 4 0 0 8 Sa p 200 0 17:00:0 6 A C K L O WWXCEM/a c 2 Sampl e Lin e Mas s Flo w W WFI10 1 0 0 8 Se p 200 0 17,00:0 5 A C K L O WWXCEM/a c 2 Oxidan t Mas s Flo w W WFI10 2 0 0 8 Se p 200 0 17:00:0 6 A C K DS C WWXCEM/a c 1 X R FPlat e No t I n Positio n Faul t W WZJ30 6 FAUL T 0 8 Se p 2GO 0 17:00.0 6 IJWAC K RT N OP R VWAICEM/a c 99 9 HewAlar m Site/Alar m O F F 0 8 Se p 2CO 0 17:00:0 4 IJWAC K RT M SYST E administrato r 99 9 Ae-ceesLave l SAccessLeve l 999 9 0 8 Se p 2CO 0 17:00:0 4 UMAC K RT N SYST E Wan e 9S 9 Operato r ^Operato r adirnnrs l 0 8 Se p 203 0 16:51:4 3 A C K RT N OS C Non e Fille r Tap e Erea k W WZI30 I IICRI-1A I 0 8 Se p 2CO 0 1 6 51:4 3 UHAC K HIH I Non e Sampl e Lin e Pressur e W WPHO S 1 4 079 3 0 8 Se p 2O3 0 15:5 1 4 3 A C K PI N LOL O Non o Filte r Tempoulur o WI TCOO E 22. 9 0 8 Se p 200 0 16:5 1 4 3 m RTI M LOL O Non e Stillin q Chambe r Outle t Temperatur e WV' / TC00 4 2 1 3 0 8 Se p 2CO 0 16.5 ! 4 3 UHAC K HIH I Non e Stilhn u Chambe r Temperatur e VA/ V TC00 3 40 0 O S Se p 2CO 0 16.5 1 4 3 UKAC K H H Hon e Stillin q Chambe r Inle t Temperatur e W WTC00 2 40 0 0 3 Se p 203 0 16.51.4 3 A C K RT N LOL O Non e Slac k Temperatur e WV' / TCOO t 22 '

- 1 1 " • Updat e Successful Jjj

j History^

] | £ 3 Current

J A C K Selected ] [ j| t AC K Ai l

' fjy j I

User Name : administrato

r i saee n Urtocke aj ^ Logo n , Admin ; ^ Report s j Trend s j a Screen s j Alarm s j sfefo o j 5:zoizt j ^cenfratfEg i Tren d ] 3 Pressur e Tren d Temperatur e Tren d Figure 15. Alar

m screen .1 8 ERDC/CER L TR-05- 3

Se t Q A Range s Administrator s ca n se t buffe r range s usin g th e Set

QA Ranges scree n (Figur e 16) . Lo w an dhig h targe t range s ar e entere do n thi s page . Measurement s tha t fal l withi n th e targe t

rang e wil l giv e agree n ligh t o n the Diagnostics screen . Re dligh t

range s ar e als o defined . Whe n measure ddat alie s betwee n th e targe t rang e an dre dligh t

range , ayello w ligh t

i s displaye do n th e diagnostic s scree n an da n alar mi s signaled . Administrator s usin g th e Set QA Ranges scree n ca n als o se t th e hou r

o f th e da y tha t aQ A analysi s wil l occur , conduc t a n immediat e zero/spa n tes t o r apea k shap e test , an dvie w milli-amper e (mAmp ) reading s fo r instrumentation . Se t Analo g Range s Administrator s als o hav e acces s t o th e Set Analog Ranges scree n fo r XCE M (Fig

ur e 17) . Thi s scree n relate s th e 4 t o 2 0 mAm p signa l receive db y component s t o ascal e use db y the program . Fo r example , aflo w mete r ma y hav e a4 mAm p signa l designate da s 0 scf m(standar dcubi c fee t pe r minute ) an da2 0 mAm p signa l designate da s 1 2 scf musin g thi s screen . CE S E 'i ; n srwental Se

t 

### XCE M Se t Q A Range s iStiBin g Chambe

r Temperatur

e iSMn g cnamDe

r his t Temperatur

e i O A Paramete

r Zer o Cadmiu m Curren

t Value SE TCOMPONENT AN D Q A RANGES Targe t Rang e Lo w Hig h Re dLigh t La w H^f i Buffe r Rang e Lo w Hig h Re dLigh t Lo w Hig h . ! Sample Lh e Mas s Flow FU0 1 (dslpm ) 1, 0 9, 0 0, 0 10, 0 J 'HVMfHg ) 0. 9 9. 1 0, 5 9. 5 ] Oxidan t Mas s Flo w FI10 2 (rrJ/mln ) 3, 0 400. 0 • 0. 0 459. 0 j ' SVM(Cd&Pb ) 0. 9 9. 1 D. S 9. 5 HalniSneFkm FIH W (scfm ) 1. 0 9, 0 . 0. 0 10. 0 j tVM(AsftCf ) 0, 9 9. 1 0, 5 9. 5 J SampteUi e Pressur

e PI10 5 (psla ) D 2 5. 0 • 0. D e, o i Pe&aAum XW) 0, 9 9, 1 0. 5 9. 5 I Stsc k Temperatur

e TC00 1 C O 16. 0 340. 0 • 15. G . 350, 0 I Spa n Chrorrau

m 0. 9 9. 1 0, 5 9, 5 j Chambe

r Inlet Temperatur

e TC00 2 (" 0 16. 0 340. 0 : i5. o 350. 0 j 5r^C«feniiirr j 0. 9 9. 1 D. 5 9. 5 i Charrfoe

r Temperatur

e TCG0 3 i"C) . 16. 0 340. 0 ' 15. 0 350. 0 ! Spa n Lead 0. 9 9. 1 0, 5 9. 5 ! Chambe

r Outle t Temperatur

e TCOT M <»C } 16. 0 310, 0 15. 0 350. 0 j Zero Chromiu m 0. 9 9. 1 0, 5 9. 5 | Filte r Temperatur

e TCQQ

5 pc ) 16, 0 34:0,0 15. 0 350. 0 j Zero Cadmiu m 0. 9 9. 1 0, 5 9. 5 j QA Fkw * Differenc e 99. 0 100. 0 j 2w o Lea d 0. 9 9. 1 0. 5 9. 5 Q A STATU S AN D PARAMETERS ; Ltf ^ pfSan^AnalvskTirr * ^^-rtnute s J Se t QA AndysSs Vmo 0 hou r 0 minut

e j EnaW o Q A Aral^f s i .„n .^.^-^^" 3 ^^^^S '< Imrr^l * Pea t 5hap e Reques t j Vie w Componen

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r Name ; whtiirtstrslo r : Scree n Unlocked' Logo n ! & Admin • p i Report s \ jfj j Trend s j £ 3 Screen s j Atann s j G;21J1 3 j | Se tCanponent/Q

A RangB S { 1 Se

tAnalo g Range s ~ | ) loo

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tQ A Range s screen .ERDC/CER L TR-05- 3 1 9 

### ^5^. TM XCE M Se t Analog Range

s 

# f Tipl e Une Press'j

f a lin g Chambe r remperalm- e _ lin g Chambe

r hte t Temperatur

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rZer o Cadmiu m Curren tVatu ? i n ANALO G SCALIN G VALUE S Scalin g Rang e Maximu m Valu e f Sampl e Lin e Mas s Fb wMete r moi (0-999, 9 dspm) 0, 0 5. 0 ••• • \ oxidan t Mas s Fle wMete r FI10 2 (0-999. 9 ml/mm ) 0. 0 5oo. o 

### wmmm •Q A Mas s Flo wMete r R10 3 (0-999, 9 ds^m ) 0. 0 5. o ••• • l ~Mal n Lh e Fto

wMete r •

' R U H <&-999.9.scfm ) o . o \ Sampl e Lin e Pressur e Mete r P11D 5 (0-999. 5 psla ) 0, 0 " r ~B. o mm m - j Sampl e Lin e FlowSetpoln t F1C20 1 (0-999. 9 ds^am ) o. o s-o " ' ~ ••• •I XR F PARAMETERS \ Setcs v Fil e Nam e j Sa t CS V Fi b Offse t Pias tFi b Exist s Btalu s Chec

k : Se t Archiva l Fil e Pati l D:\XRFArchiva l ; las t Archiva l Initiat

e Statu s 0 i Se t CS V Conversio n Fil e Nani e Di^tempNPars e Jtesults.ex e Las t Fi b Rea d Statu s Las t Archiva l Statu s (se t XR F Result s Tex t Fif e Nam e G:y?esul! s

I Si ' ^ luserMeire : athrinWrato r Ta *emUrtocWj| | j £ Logo n ) % ifldmrn) g^ , Report s \

Q Trend s j •Screen s ; ^'Alanri s I 9/s/oo j 5:;2..o ; | Se t GoTirolenVQ A Ranges | \ Se t Analo g Range s j | Loo p Tunin g j j PL C Statu s f | CSt/Too i Figur e 17. SetAnalo g Range s screen . Samplin g Platfor m Modification s Th e XCE M samplin g platfor mwa s modifie dt o provid e automate dQ A feature s an dimprov e operato r

ease-of-use . Quality Assurance

Modifications Th e XCE M wa s reengineere dt o includ e a n automated , user-friendl y Q A pro gra m(Figur e 18) . A WonderWare ® softwar e packag e ha s bee n develope dwit h a custo mprogrammabl e logi c controlle r (PLC ) t o contro l ke y component s an din

dependentl y ru n Q A feature s (Figur e 19) . Q A feature s fo r

th e XCE M focu s upo n th e tw o number s require dto determin e stac k ga s concentration : mas s o f th e meta l o n th e filte r an dsampl e volume . Meta l mas s o n th e filte r i s determine di n microgram s pe r spo t usin g th e XR F whil e sampl e volum e i s i n dr y standar dcubi c meter s pe r spo t a s determine db y mas s flo w meters . A spo t i s equa l t o th e are ao n th e filte r tap e scanne db y the X R Fanalyzer . Th e XCE M progra mbuild s i n automate dredundanc y an ddail y Q A check s fo r

measurin g bot h mas s an dvolume . Acceptabl e Q A boundarie s ar e user-defined . I f

th e measure dvalue s fal l outsid e o f thes e boundaries , suc h a s2 0 ERDC/CER L TR-05- 3 whe n instrumen t

drif t occurs , th e softwar e packag e wil l signa l a n alar man dflag th e data . Al l Q A measurement s ar e logge di n th e XCE M databas e an dar e availabl e fo r

us e b y Microsoft ® Exce l an dAcces s o r compatibl e dat amanagemen t programs .

H H Mas s b y XR F ~y Volum e b y MF M

Multi-Meta l Samvlin g Trai n

M2 9 

### gHir =>Pum p

Automate d Q A Mas s b y XR F • Ever y Sample : P

dInterna l Standar d+ 5% • Periodic : C u pea

k shap e evaluation . • Dail y Zer

o (blank ) an d Spa n (standard

) Checks . Volum e b y Mas s Flo w Mete r • Dail y MF M Calibration Evaluation . • Periodic NIST-Traceable Calibration . M Elementa l Mas s Mult i Meta l Standar d (Hg , Cd , Cr , Pb ) PdWir e C u Wir e 

### 9 . Tap e Analyzed B y

Independen

tLa b Tub e Detecto

r M F M 1 [J

^ MFM- 2 Pum p

Additiona l Q A Option s • Independen

t Tap e Analysi s • Quantitativ

e Spiking Sampl e Volum e Figur e 18. XCE M Q A program .ERDC/CER L TR-05- 3 2 1

Figur e 19. PL C contro l fo rth e XCEM . Mas s measuremen t Q A XCE M mas s measurement s ar e determine dusin g aKevexSpectrac e Quan X XRF . Fo r

thi s project , th e XR Fanalyze r wa s calibrate dusin g thi n fil mstan dard s mad e b y pipettin g aNationa l Institut e o f Standard s an dTechnolog y (NIST)-traceabl e standar dsolutio n containin g equa l masse s o f silve r (Ag) , arseni c (As) , Cd , Cr , Hg , Pb , an dseleniu m(Se ) ont o aMyla r film . A serie s o f

1 0 standard s wit h varyin g concentration s wer e analyze db y th e XRF , an dalinea r relationshi p betwee n x-ra y intensit y an dmas s wa s determined . Th e XR Fi s stabl e ove r

aperio do f

month s an dtypicall y require s calibratio n onl y abou t onc e ever y 6 months . X R Fzer o an dspa n test s ar e conducte dexaminin g blan k filte r tap e an dameta l ro dattache dt o apneumati c plunge r mounte dbelo w th e samplin g cassett e (Fig

ur e 20) . A t

auser-define dtim e o f day , th e XCE M begin s th e Q A proces s b y ad

vancin g clean , unexpose dfilte r tap e int o th e x-ra y bea mare aan danalyzin g th e blan k tap e a s azer o test . Immediatel y followin g thi s test , th e plunge r extend s th e multi-meta l standar dro dint o th e bea marea . Th e rod , whic h contain s rela

tivel y hig h concentration s o f Cr , Hg , Cd , an dPb , act s a s aspa n test . Th e zero / spa n tes t

typicall y take s 20 t o 3 0 minutes .2 2 ERDC/CER L TR-05- 3

T o chec k fo r instrumen t

drift an dprovid e acontinuou s assuranc e tha t th e XR F i s givin g precise , repeatabl e mas s measurements , aP dwir e ha s bee n perma nentl y mounte di n the XR Fx-ra y bea manalysi s regio n (Figur e 21) . Th e P di s measure dwit h ever y sample , allowin g fo r continuou s compariso n t o precedin g value s determine dwhe n the instrumen t wa s las t

calibrated .

Figur e 20 . Zer o an d spa n tes tplunger .

, tut

Figur e 21 . P d wire-mounted fo rQA .ERDC/CER L TR-05- 3 2 3

Flo wmeasuremen t Q A I n additio n t o mas s measurements , th e XCE M assure s qualit y flo w measure ment s usin g aredundan t mas s flo w mete r

in-lin e wit h th e existin g flo w control

ler . Whe n Q A mas s measurement s ar e engaged , th e softwar e interfac e divert s flo w ou t o f th e flo w controlle r

an dthroug h th e secon dmas s flowmeter . Th e tw o flo w rate s ar e the n compared . I f asignifican t

differenc e i s determined , a n alar m wil l b e poste dan dth e dat awil l b e flagged . Havin g aredundan t flo w mete r

pro vide s tw o additiona l benefits . I t ca n ac t a s aback-u p metho dfo r measurin g con centration s i f

th e flo w controlle r

break s down , an dth e Q A mas s flo w mete r ca n b e periodicall y remove dan dsen t ou t fo r recalibratio n withou t affectin g th e XCE M norma l operations . Extractio n syste m Q A Th e accurac y o f

th e extractio n syste mca n b e evaluate dperiodicall y (e.g. , ever y 6 to 1 2 months ) b y spikin g metal s directl y int o the XCEM . A spikin g syste mwa s develope dtha t

use s aNIS T traceabl e standar dsolutio n an danebulizer . Thi s spikin g system , whic h i s inexpensiv e t o operate , demonstrate dgoo dprecisio n an dwa s abl e t o spik e avariet y o f metal s ove r

awid e concentratio n range . Usin g thi s approach , XCEM-reporte dmeta l concentration s ca n b e compare dwit h re sult s fro meithe r

a n M2 9 sampl e trai n o r afilte r gra b sample . Th e XCE M spik

in g syste man dresult s o f M2 9 compariso n test s ar e discusse dlater . Ease-of-use

Modifications I n earlie r

XCE M versions , the samplin g platfor mwa s permanentl y mounte dt o th e to p o f

th e Quan X XRF . Th e update dXCEM , however , ha s bee n reengineere d t o includ e asamplin g cassett e tha t i s attache dwit h onl y fou r thumbscrew s t o th e XR Fanalysi s platform . Th e samplin g cassett e i s lightweigh t (abou t 2 5 pounds ) an dca n b e remove dfro mth e analyze r i n unde r

5 minute s (Figur e 3) . N o tool s ar e require dt o disconnec t th e electronics ' plug , screws , an dtw o pneu mati c line s o n th e cassette . Onc e removed , th e cassett e i s self-supporting , bu t a specia l transpor t

plat e i s available . I t

i s anticipate dtha t

th e nex t

versio n o f

th e XCE M wil l come wit h at leas t tw o samplin g cassettes . Ever y 2 t o 4 weeks , whe n th e XCE M filte r

tap e ha s bee n full y exposed , operator s wil l b e abl e t o rapidl y chang e samplin g cassette s an dtranspor t th e cassett e containin g th e expose d tap e to aseparat e wor k area . I n th e wor k

area , technician s wil l b e abl e t o chang e filte r

tape s i n aclea n environmen t an dconduc t

routin e preventativ e maintenanc e o n th e cassette . I t i s anticipate dtha t

atechnicia n woul db e abl e t o carr y ou t

thes e task s i n unde r

a n hour .2 4 ERDC/CER L TR-05- 3 Safety Modifications Th e portabl e samplin g cassett e contain s amounte dfilter tape , asteppe r

motor , pneumati c plungers , lea dshielding , an datap e breakag e senso r (Figure s 3 , 20 , an d22) . Th e cassett e cove r i s positione dto trigge r interlock s s o tha t

samplin g canno t tak e plac e unles s th e cover s an dshieldin g ar e properl y positioned . I n additio n t o increase defficienc y i n exchangin g filte r tapes , the portabl e cas sett e ensure s tha t

the tap e i s no t

contaminate dprio r

to installatio n int o the unit . Anothe r benefi t i s the syste mredundanc y provide db y th e cassette . I f the step pe r motor , plungers , o r

tap e ar e damaged , th e XCE M operato r ca n rapidl y ex chang e cassette s an densur e monito r uptime .

Figur e 22. XCE M samplin g cassette an d XR F contro l panel .ERDC/CER L TR-05- 3 2 5



# 3 Laborator y Testin g Thi s chapte r

addresse s the las t

tw o recommendation s tha t wer e presente di n th e MSE-T A repor t

(Bryso n et

al . 2000) : H g samplin g an dth e spik e injectio n sys tem . A s discusse di n the previou s chapter , additiona l laborator y testin g wa s neede dt o evaluat e an doptimiz e th e H g captur e efficienc y o f th e automate doxi

datio n system , an dt o compar e XCE M mercur y measurement s wit h M29 . A spik e injectio n syste mwa s develope ds o tha t M2 9 compariso n test s wit h si x metal s i n additio n t o H g coul db e performe di n the laboratory . Thi s chapte r als o present s th e result s o f thes e M2 9 compariso n tests . Mercur y Samplin g Experimental Optimizatio n o f

the XCE M H g samplin g efficienc y wa s accomplishe di n tw o phases . I n the firs t

phas e (Figur e 23) , elementa l H g wa s generate dusin g aH g permeatio n tub e i n acontrolle dtemperatur e environment . Th e elementa l H g vapo r wa s the n converte dt o mercuri c chlorid e usin g chlorin e gas . Th e resultin g mercuri c chlorid e wa s the n capture do n a47-m mdiamete r RI Ftha t

wa s backe d u p b y asecon d47-m mdiamete r RIF . An y H g vapo r

tha t wa s no t trappe db y th e RIF s wa s capture dwit h acarbon-impregnate dfilte r (CIF) . Analysi s o f

the rela

tiv e concentration s o n th e tw o RIF s an dCI Fwer e conducte dt o determin e i f breakthroug h wa s occurring . I n th e secon dphase , H g wa s generate dusin g th e XCE M nebulizatio n syste man dastoc k multi-elemen t

standar dfro mVH GLabs , Inc . (Manchester , NH) . Th e H g wa s injecte ddirectl y int o th e XCE M samplin g syste man danalyze di n rea l time . Th e XCE M real-tim e dat awer e compare dt o result s fro mamodifie dEP A M2 9 samplin g train . Mercury RIF Results Th e primar y purpos e o f first-phas e H g testin g wa s to determin e RI Fvapo r phas e H g captur e efficiencie s unde r varyin g flow , temperature , an doxidan t conditions . Figur e 24 show s atypica l captur e efficienc y curv e whe n flo w rate s varied . I n thi s serie s o f

tests , conducte dwit h afilte r temperatur e o f

14 0 ° F(6 0 °C) , th e pri

mar y RI Fcollecte dgreate r tha n 9 0 percen t

o f th e H g whe n flo w rate s throug h2 6 ERDC/CER L TR-05- 3

th e filte r

wer e les s tha n 0. 8 dr y standar dLpm/cm 2(liter s pe r minut e pe r

squar e centimeter) . Thes e result s indicat e tha t th e RI Fcoul dcaptur e greate r tha n 9 0 percen t o f vapo r phas e (elemental ) H g unde r typica l operatin g conditions . Reactio n Chambe r

Figur e 23 . Schemati c o f H g capture fo rfirs tphas e experiments . 10 0 1 2 £ 7 5 C O o O ) X 

### £ 3 a c o o 5 0 £ 2 5 0 -•"RIF 1 RIF 2 -I • CI F -•"RIF 1 RIF 2 -I • CI F

0.0 0 0.5 0 1.0 0 1.5 0 Flo wThroug h Filte r (Lpm/cm 2 ) Figur e 24 . RI

F H g capture efficienc y versu s ai rflo w rat e through filter . Mercury Oxidation

Automation Th e XCE M continuousl y extract s asmal l subsample , o n th e orde r o f 0. 5 Lpm , o f stac k ga s fro mth e stillin g chamber . Prio r t o collectio n o n th e RIF , thi s subsam

pl e enter s adilution/oxidatio n chambe r wher e a n oxidizin g agent , suc h a s chlo

rin e gas , i s use dt o conver t th e elementa l H g t o ioni c phas e Hg , whic h ca n the n b e capture do n th e RIF . Th e calculation s tha t determin e th e setting s fo r th e oxi

dan t valve , flowmeter , an ddilutio n hav e al l bee n automate dan dar e full y inte

grate dint o th e XCE M compute r contro l system .ERDC/CER L TR-05- 3 2 7 Mercury XCEM

Results Durin g th e secon dphas e o f H g testing , the XCE M tota l H g measuremen t capa bilit y wa s determine dusin g a n M2 9 samplin g train . Mercuri c nitrat e an dothe r metalli c compound s o f interes t wer e spike dint o th e XCE M extractio n syste m an dwer e simultaneousl y collecte db y th e RI Fan da n M2 9 samplin g train . Fou r M2 9 test s wer e conducted , wit h eac h tes t lastin g 3 hours . Sinc e th e XCE M de

termine dH g concentration s ever y 1 2 minutes , atime-weighte daverag e wa s use dto compar e XCE M an dM2 9 results . Overal l th e XCE M an dM2 9 H g concentration s wer e i n goo dagreement . Th e av erag e XCE M H g concentratio n wa s 13 5 ± 8 ug/m 3 (microgram s pe r cubi c meter ) whil e th e averag e M2 9 resul t wa s 12 2 ± 6 ug/m 3 . O n average , a n 1 1 percen t dif

ferenc e existe dbetwee n reporte dsamplin g ru n concentrations , whic h i s withi n M2 9 uncertainty . N o indicatio n o f filte r trappin g inefficiencie s wa s eviden t be

caus e th e XCE M reporte dslightl y highe r H g concentration s tha n M29 . Durin g testing , abou t

7 percen t

o f th e H g wa s i n th e vapo r phas e a s define db y th e M2 9 fron t half/bac k

hal f measurement . Th e XCEM/M2 9 H g R A fo r th e fou r

tes t run s wa s 20. 4 percent , whic h whe n rounde dto tw o significan t digit s marginall y meet s th e PS-1 0 R A criterion . Thi s numbe r wa s calculate dusin g th e metho ddescribe di n PS-10 . Th e R A wil l de

creas e wit h increase dnumber s o f runs , s o tha t

i t i s estimate dtha t

th e R A woul d decreas e t o abou t

1 8 percen t

i f mor e run s wit h simila r result s ha dbee n con ducted . Overal l the M2 9 result s demonstrat e tha t the XCE M ca n adequatel y tra p an d measur e H g concentration s unde r realisti c tes t

conditions . Metho d 2 9 Compariso n Test s Spike Injection

System Approac h Th e qualit y o f

th e XCE M mas s measurement s i s routinel y evaluate dwit h th e P d qualit y contro l standard , zero , an dspa n checks . However , aspikin g syste mi s require dt o confir mXCE M transpor t an dcollectio n efficiencies . A n idea l spik e injectio n syste mshoul dhav e th e followin g capabilities : • Ca n injec t

al l MAC T metal s a t

level s wel l abov e detectio n limit s • Repeatabl e precisio n2 8 ERDC/CER L TR-05- 3

• Eas y an dsaf

e t o implemen t • Relativel y inexpensiv e t o operat e • Abl e t o produc e a n aeroso l wit h hig h transmissio n efficienc y • Quantifiable . Severa l option s wer e reviewe dwhic h coul dpotentiall y mee t th e abov e criteri a (Tabl e 2) . Thes e option s included : • Nebulization . A solutio n containin g element s o f interes t i s aspirate dint o a ga s stream . Th e resultin g droplet s dr y an dcreat e a n aeroso l o f sal t particles . • Aerosolization . A spike dpowde r i s suspende di n acarrie r ga s tha t i s in

jecte dint o th e stac k

ga s stream . Method s o f aerosolizin g aspike dpowde r in

clud e movin g adeposi t unde r aga s jet , fluidize dbe dplu s elutriator , o r micro

scre w injection . • Evaporation . A compoun do f aspikin g elemen t

wit h awell-define dboilin g poin t i s raise dto atemperatur e abov e it s boilin g point . Thi s take s plac e i n a n iner t carrie r ga s tha t

i s introduce dint o the stac k gas . • Combustion/aspiration . A soli do r liqui dcontainin g spikin g element s i s burne di n acarrie r

gas . Th e combustio n product s containin g th e spikin g element s ar e carrie dint o th e stac k ga s wit h th e carrie r

gas . Oil s containin g avariet y o f

element s ar e availabl e an dcoul db e readil y burned . Solid s woul d nee dt o b e speciall y prepare dan dther e woul db e agreate r tendenc y fo r

th e element s t o remai n i n th e ash . • Electri c spark . A hig h voltag e spar k o r ar c i s create dbetwee n tw o carbo n electrode s containin g spikin g elements . Th e sparkin g proces s generate s fin e particle s wit h th e spike delements . • Hydrid e generation . A n iner t ga s i s bubble dthroug h asolutio n containin g th e spikin g elements . Sodiu mtetraborohydrat e i s adde dt o th e solution . Th e hydride-formin g element s ar e exchange dwit h th e carrie r ga s an dcarrie dt o th e stack . • Specialt y gas . A commerciall y prepare dan dcertifie dgaseou s mixtur e con tainin g th e require dspikin g elements . Afte r reviewin g th e options , nebulizatio n wa s selecte da s th e preferre dalterna

tiv e du e t o it s simplicity , potentia l fo r extende doperation , an dquantificatio n ad

vantages . Nebulizer s hav e bee n use dto successfull y generat e aerosol s fo r a numbe r o f year s (Ylatal o e t

al . 2000 ; Flaga n an dSeinfel d1988 ; Fuch s an dStu tugi n 1966) . The y ar e relativel y inexpensiv e an deas y t o use . I n addition , NIS T traceabl e laborator y standard s ar e availabl e fo r al l metal s o f

interest . Thes e standard s ar e availabl e i n awid e variet y o f concentration s (Fro m1 t o 200 0 ug/mL ) an dhav e aguarantee dshel f lif e o f 1 year .ERDC/CER L TR-05- 3 2 9

Tabl e 2. Evaluatio n of spik e injectio n options . Optio n Advantage s Disadvantage s 1 ) Nebulizatio n Eas e o f us e Lo w cos t Readil yavailabl e standard s Humidit yaffect s nebulizatio n rat e Potentia l wate rsuper-saturatio n i n stac k sampl e 2 ) Aeroso l izatio n Eas e o f us e Lo w cos t Uniformit yo f powde rissue s Potentia l agglomeratio n issue s Quantificatio n i s difficul t 3 ) Evaporatio n Eas e o f us e Lo w cos t Los s o f larg e particle s t o wall s Differen t temperature s require d fo r differen t element s 4 ) Combustion /

Aspiratio n Eas e o f us e

Lo w cos t Readil yavailabl e standard s Carrie rparticle s produce d b yth e combustio n proces s Potentia l safet yissue s

5 ) Electri c Spar k Precisio n Eas e o f us e Potentia l safet yissue s Engineerin g expens e Quantificatio n difficultie s 6 ) Hydrid e Generatio n Eas e o f us e Lo w cos t Cos t o f component s Instabilit yo f hydride s No t al l metal s ar e availabl e 7 ) Specialt yGa s Independen t certificatio n Cos t o f ga s Availabilit yo f ga s Desig n Durin g nebulization , compresse dai r i s pushe dint o th e botto mo f anebulize r

cup containin g aliqui dsolution . Th e compresse dai r exit s th e cu p a t

th e to p an d create s apartia l vacuum , whic h draw s liquid s ou t wit h th e air . A DeVilbis s nebulize r

(Illinoi s Too l Works , Glendal e Heights , IL ) wa s use dfo r thes e tests . Th e nebulize r

include da n impactio n plat e designe dt o preven t larg e droplet s fro mescaping . Fo r th e M2 9 testing , the nebulizatio n syste mproduce d10 0 liter s pe r minut e (Lpm ) o f spike dga s wit h concentration s betwee n 11 5 an d18 0 ug/m 3 fo r seve n metals : Ag , As , Cd , Cr , Hg , Pb , an dSe . A commerciall y availabl e solutio n stan dar d(VH G Labs , Manchester , NH ) wa s use dt o spik e the ga s stream . Th e stan dar dsolutio n containe d10 0 ug/m L o f eac h meta l i n 5 percen t nitri c acid . Fo r eac h tes t run , standar dsolutio n wa s adde dt o th e nebulize r cup , whic h wa s the n weighed . Followin g nebulization , th e cu p wa s reweighe dan dth e amoun t o f nebulize dsolutio n wa s determined . Abou t 5 Lp mo f

spike daeroso l fro mth e nebulize r cu p wa s injecte dint o avertica l four-inc h diamete r

pipe . Anothe r

9 5 Lp mo f

dr y ai r wa s draw n int o th e pip e wit h th e spike daerosol . Th e pipe , whic h wa s 3-f t long , wa s hea t

trace dan dkep t a t abou t 22 0 ° F(10 3 °C) . Th e additio n o f hea t an ddr y ai r

serve dt o rapidl y dr y3 0 ERDC/CER L TR-05- 3 th e nebulize dparticles . I t i s estimate dtha t

th e typica l drie dparticl e siz e wa s o n th e orde r

o f 0. 2 micron s i n diamete r onc e i t exite dth e 4-inc h tubing . Th e com bine d10 0 Lp mo f

spike dga s wa s the n draw n int o the stillin g chambe r fo r ex tractio n b y th e XCE M an dM2 9 probes . Spikin g evaluatio n Th e DeVilbis s nebulize r showe dgoo dprecisio n ove r th e 4 day s o f

M2 9 testing . Th e overal l nebulizatio n rate , a s determine db y mas s measurements , wa s 0.2 3 ± 0.0 1 mL/min . Thi s represent s a4 percen t relativ e standar ddeviatio n (RSD) . Followin g M2 9 testing , furthe r nebulizatio n test s unde r mor e controlle dcondi

tion s hav e demonstrate dimprove dprecisio n an da n RS D o f les s tha n 1 percent . Althoug h th e nebulize r precisio n wa s goo ddurin g M2 9 testing , th e mas s o f nebu

lize dsolutio n coul dno t b e use dt o accuratel y predic t stac k concentrations . Despit e th e overal l quantificatio n issue , nebulizatio n remain s apromisin g ap proach . Th e curren t

nebulizatio n syste mi s abl e t o precisel y provid e al l element s o f interes t ove r awid e rang e o f

concentration s allowin g fo r a n effectiv e XCE M tes t rang e o f

1-200 0 ug/m 3 . I t

i s relativel y inexpensive , safe , an deasy t o oper ate , an dawid e variet y o f metal s ar e availabl e a s NIS T traceabl e standar dsolu

tions . Test Design T o tes t XCE M accuracy , fou r modifie dM2 9 tes t

run s wer e conducte dfro m4- 7 Novembe r

2000 . Durin g thes e tests , simultaneou s sample s wer e collecte db y th e XCE M an da n M2 9 samplin g train . Simulate d"stac k gas " wa s provide db y nebulizatio n o f

ametal s solutio n containin g equa l concentration s o f As , Cd , Cr , Hg , Pb , Se , an dAg . Th e M2 9 sampl e prob e extracte dth e stac k ga s fro ma2 - inch-diamete r

pip e locate dapproximatel y 3 fee t downstrea mo f

the XCE M ex tractio n tube . Bot h samplin g site s wer e a t leas t eigh t diameter s downstrea m an dtw o diameter s upstrea mo f an y flo w disturbanc e a s require db y EP A sam plin g protocols . Durin g testing , XCE M an dM2 9 temperatures , flows , an dpres sure s wer e hel dconstant . N o XCE M drye r wa s use dfo r

th e M2 9 test s sinc e wa te r conten t wa s determine dt o b e les s tha n 1 percen t o f th e volume . Tes t parameter s ar e liste di n Tabl e 3 . Th e M2 9 sampl e wa s collecte disokineticall y whil e th e XCE M extracte dsub

isokineticall y fro mth e stillin g chamber . Th e stillin g chambe r desig n slow s stac k ga s an dallow s fo r

non-isokineti c samplin g du e t o it s lo w Stoke' s numbe r (Coope r e t al . 2000) .ERDC/CER L TR-05- 3 3 1

Table 3 . Testcondition s durin g M2 9 sampling . Tes tParameter Tes tParameter Mai n Lin e Flo w (scfm ) 3.5 2 ±0.0 2 Stillin g Chambe rTemperatur e - 23 0 ° F XCE M Sampl e Flo w (sLpm ) 0.5 8 + 0.00 3 Temperatur e a t M2 9 Impinge rInle t - 23 0 ° F M2 9 Flo w (sLpm ) 4.1+0. 2 Temperatur e a t M2 9 Impinge rOutle t <5 2 ° F Nebulizatio n Rat e (mL/min ) 0.2 3 ±0.0 1 M2 9 Sampl e Tim e (min ) 18 0 Nebulize rMeta l Concentratio n (pg/mL ) 10 0 Ambien t Relativ e Humidit y 4 0 - 60 % Nebulize d Metal s A s , Cd , Cr , Hg , Pb , Se , A g Ambien t Temperatur e 5 5 - 6 5 ° F Metal s wer e nebulize dusin g the XCE M spik e injectio n system . Th e nebulize d standar dsolution , provide db y VH G labs , i s NIS T traceabl e an d contain s 10 0 ug/m L o f

eac h meta l i n 5 percen t nitri c acid . Particl e siz e fo r th e tes t wa s estimate dt o b e o n th e orde r o f 1 micro n o r

less . Durin g th e M2 9 tests , th e nebu

lizatio n rat e wa s ver y stabl e an dvarie db y n o mor e tha n 5 percent . Th e XCE M exhibite dn o mechanica l o r functiona l problem s durin g th e 4-day tes t period , whic h include dove r 15 0 tes t runs . XCEM Results

During

Method

29 Testing XCE M result s b y elemen t Th e XCE M reporte dmeta l concentration s i n ug/m 3 ever y 11. 7 minute s fo r eac h o f th e nebulize dmetal s (Figur e 25) . Ever y 2 t o 3 hours , spikin g wa s stoppe dt o re fil l th e nebulize r

cup . Sinc e the refillin g proces s too k abou t 5 minutes , i t

reduce d concentration s fo r

on e XCE M sampl e run . Thes e concentratio n change s ar e show n a s deflection s i n Figur e 2 5 an dillustrat e th e sensitivit y o f the instrumen t t o change s i n meta l concentration . Th e horizonta l magent aline s indicat e the respectiv e meta l M2 9 concentratio n fo r th e duratio n o f

eac h M2 9 sample . T o evaluat e th e XCE M instrumen t stability , aP dro di s situate ddirectl y abov e th e x-ra y tub e an d provide s P d concentration s wit h ever y sample . Fo r thes e tests , th e P dQ A ro dha da n effectiv e concentratio n o f 14 0 ± 1. 0 u g durin g th e 4 - da y tes t perio dwit h aprecisio n o f bette r tha n 1 percen t

(Figur e 25) . Th e consis

ten t P dconcentration s durin g M2 9 testin g indicat e tha t n o XR Finstrumen t

drift occurred .3 2 ERDC/CER L TR-05- 3

ARSENI C 20 0

0 M29- 1 M29- 2 M29- 3 M29- 4

Nov . 4 Nov . 5 Nov . 6 

# 1 Nov . 7 34 8 36

3 37

8 Nebulize r

Refille d 39 3 408 42

3 43

7 Sampl e I D No . 45 2 467 48

2 CADMIU M 20 0 175

_15 0 -

j | 12 5 e c * 10 0 

# I 7 5 i 5 0 25 0 M29 - 1 

# rtfff

Nov . 4 348 36

3 37

8 • Nebulize r

Refille d M29- 3 M29- 4

Nov . 6 Nov . 7 40 8 42

3 437 Sampl e I D No . 452 46 7 482 CHROMIU M M29- 2

Nov . 5 M29- 3

Nov . 6 M29- 4

Nov . 7 348 36

3 378 Nebulize r

Refille d 393 408 42 3 43 7 Sampl e I D No . 45 2 46 7 482 Figur e 25 . XCE M elementa l concentration s durin g M2 9 testing .ERDC/CER L TR-05- 3

34 8 36

3 37

8 • Nebulize r

Refille d • Nebulize rKeuucu

_—— - Fig^C^nt^ ^ dUrin 9 teStm9 -3 4 ERDC/CER L TR-05- 3

SILVE R 20 0

a . u B © M29- 2 M29- 3 M29- 4

Nov . 6 Nov . 7 348 36

3 37

8 Nebulize r

Refille d 39 3 40

8 42

3 43 7 Sampl e I D No . 45 2 46 7 48 2 PALLADIU M 20 0 175 15 0 S 12 5 e n .S * 1 nr v c o O 7 5 5 0 2 5 0 M29- 1 M29- 2 M29- 3 M29- 4

Nov . 4 Nov . 5 Nov . 6 Nov . 7

348 36

3 37

8 39

3 408 42

3 437 45

2 46 7 48

2 Sampl e I D No . PALLADIU M Be a o U QJ >

Averag e Palladium effectiv e concentration Sampl e I D No . On e S D fro m Avg . P d Concentratio n 5 % fro m Avg . Pd Concentratio n Figur e 2 3 (Cont'd) . XCE M elementa l concentration s durin g M2 9 testing .ERDC/CER L TR-05- 3 3 5

XCE M meta l concentration s durin g th e 4 day s o f testin g wer e highl y correlated . Fo r example , i n compariso n t o Cd , al l o f th e metal s exhibite dacorrelatio n o f 0.9 5 o r bette r an dha daslop e betwee n 0.9 5 an d1.1 7 (Figur e 26) . Th e choic e o f C dwa s purel y arbitrary , an d simila r relationship s woul db e see n i f anothe r meta l wa s chosen . Th e slop e i s expecte dt o b e clos e t o 1 becaus e al l the metal s wer e spike dwit h th e sam e concentration . Difference s i n correlatio n ar e expecte d t o b e du e primaril y t o XR Fcalibratio n an dspectra l measuremen t uncertainties . Th e hig h degre e o f

correlatio n an d relativel y unifor mslop e indicat e goo duni

formit y i n th e relativ e concentratio n ofth e spike dstac k gas .

f 15 0

5 0

0 5 0 10 0 15 0

Cadmiu m Con e (ug/m3 ) 2 0 0

y = 1.04x+ 0.4

9 R z= 0.9 8 y = 1.04x+ 0.4

9 R z= 0.9 8

5 0 10 0 15 0 Cadmiu m Con e (ug/m3 ) 2 0 0

0 5 0 10 0 15 0 20 0

Cadmiu m Con e (ug/m3 ) „ 25 0

5 0 10 0 15 0 Cadmiu m Con e (ug/m3 )

5 0 10 0 15 0 Cadmiu m Con e (ug/m 3 ) ] y = 0.9S x + 0.8 3 R J= 0.9 7

5 0 10 0 15 0 Cadmiu m Con e (ug/m3 ) 2 0 0 Figure 26 . XCE M cadmium versu s other spike d metal s durin g M2 9 testing .3 6 ERDC/CER L TR-05- 3

Pre - an d post-test s at XCE M Por t versu s Metho d 2 9 por t Q A testin g wa s conducte dbefor e an dafte r eac h o f th e fou r M2 9 tes t

runs . Dur in g Q A testing , a n open-face dfilte r holde r containin g a n RI Fan dCI Fwa s use d t o collec t agrab sampl e fro mth e M2 9 port . Thi s filte r combination , develope db y CES , i s calle daHazardou s Elementa l Samplin g Trai n (HEST) , an dha s bee n teste di n avariet y o f

stac k environment s a s awa y o f quickl y evaluatin g stac k ga s meta l concentration s (Johnso n e t al . 1998) . Th e HES T sample s wer e ana lyze dusin g alaborator y XR Fan dcompare dt o th e XCE M reporte dconcentra tion s fo r the concurren t

run . Result s fo r

th e pre - an dpost-test s ar e show n i n Tabl e 4 . Overall , th e XCE M reporte daverag e meta l concentratio n wa s 13 8 ± 1 3 ug/m 3 whil e th e M2 9 por t tes t averag e concentratio n wa s 12 6 ± 1 2 ug/m 3 (includ

in g Ag) . Comparin g th e averag e meta l concentratio n i s importan t becaus e al l metal s wer e spike dat identica l concentrations . Especiall y usefu l i s comparin g th e averag e concentration s fo r al l metal s durin g on e samplin g even t (e.g. . ru n 2 pre-tes t o r ru n 3 post-test) . I t

appear s tha t

th e average s ar e withi n th e standar d deviatio n betwee n th e tw o port s an dtha t th e deviation s ar e similar . Usin g th e M2 9 por t

result s a s th e "true " value , th e XCE M reporte dconcentration s fel l withi n th e 2 0 percen t

R A criterio n i n PS-1 0 fo r al l metal s excep t

A g (Tabl e 5) . Thes e calculation s wer e performe dusin g th e eigh t set s o f sampl e value s fo r

eac h metal . Th e M2 9 por t concentratio n fo r

A g wa s lo w b y 1 7 percen t relativ e t o al l othe r reporte dmeta l concentrations , whil e th e XCE M A g concentratio n wa s i n goo dagreemen t

wit h reporte dconcentration s fo r othe r spike dmetals . Table 4 . Elementa

l concentration s a

tXCE M an d M2

9 Port s durin g pre - an d post-tests . A s C d C r H g P b S

e A g XCE M (N o Ag ) M2 9 (N o Ag ) TES T x c M2

9 Por t X C M2

9 Por t x c M2

9 Por t x c M2

9 Por t x c M29 Por t x c M2

9 Por t x c M2

9 Por t Avg SD %

RS D Av g SD %

RS D PR E 11

5 n o 12

2 11 0 13 2 11 4 12 6 12 3 12 3 11 5 12 3 11 0 11 7 9 6 12 4 6 5 11

4 5 5 1 POS T 13

8 14 6 13 7 14 7 16 5 15 2 14 8 16 6 15 3 15 0 14 7 14 7 13 3 12 6 14 8 1 0 7 15

1 8 5 PR E 14

1 13 8 14 7 14 0 16 7 14 3 15 6 15 4 15 0 14 2 14 9 13 8 13 9 11 5 15 2 9 6 14

3 6 4 2 POS T 13

3 14 1 13 6 14 8 14 8 14 6 14 7 16 3 13 9 14 5 13 6 14 3 13 1 11 7 14 0 6 4 14

8 8 5 PR E 12

8 10 9 12 4 11 5 14 4 11 8 13 4 12 5 12 0 11 7 13 0 11 3 1 1 7 8 7 13 0 8 6 11

6 5 5 3 POS T 12

2 11 8 12 0 11 9 13 5 12 3 12 9 13 3 12 1 12 2 12 5 11 9 11 8 9 5 12 5 6 4 12

3 5 4 PR E 12

0 12 0 13 6 12 2 13 3 12 4 12 8 13 5 11 6 12 2 12 5 12 1 11 8 9 5 12 6 7 6 12

4 6 5 POS T 12

8 11 6 13 7 11 6 14 2 12 2 13 3 13 3 12 0 12 2 12 8 11 8 12 1 9 0 13 1 8 6 12

1 6 5 AV ( RAG E 12

8 12 5 13 2 12 7 14 6 13 0 13 7 14 2 13 0 12 9 13 3 12 6 12 4 10 3 13 4 6 5 13

0 6 5 Table 5 . Relativ

e accuracie s of

M2 9 Por tversu s XCE M Portdurin g pre - an d post-tests . Element R

A Meet

s EPA-Propose d Criterion 1 Arseni c 8. 8 Ye s Cadmiu m 11. 3 Ye s Chromiu m 17. 0 Ye s Mercur y 8. 3 Ye s Lea d 4. 4 Ye s Seleniu m 10. 5 Ye s Silve r 27. 6 N o 1 EPA-propose d PS -1 0 fo r Multi-Meta l CEM s requires a n R A Criterio n o f 20% .ERDC/CER L TR-05- 3 3 7

XCEM vs M29 XCE M an d M2 9 analytica l dat a Durin g M2 9 testing , th e XCE M reporte dstac k ga s concentration s fo r As , Cd , Cr , Hg , Pb , an dS e i n ug/m 3 . I n additio n t o a n electroni c copy , th e XCE M printe da har dcop y o f

the result s afte r

eac h tes t

run . Metal s concentration s use di n thi s repor t ar e th e sam e a s th e XCE M hardcop y outpu t wit h th e exceptio n o f correc tion s t o A s an dH g concentrations . Afte r testin g an dbefor e receivin g th e M2 9 results , the XR Fwa s recalibrate dusin g aduplicate/ne w se t o f calibratio n stan dards . A t

tha t time , i t wa s determine dtha t

th e origina l standards ' H g concen tration s wer e to o lo w b y 1 7 percent , givin g areporte dconcentratio n tha t wa s to o high . A s such , th e XCEM-reporte dH g concentration s wer e reduce db y 1 7 per cent . Excep t fo r Hg , al l o f

the element s wer e i n goo dagreemen t followin g calibration . Durin g recalibration , however , i t wa s discovere dtha t

a1 0 percen t

A s correctio n factor , whic h ha dbee n use di n th e shakedow n period , ha daccidentall y bee n left i n th e XR Fcalibratio n equation . Al l XCE M concentration s use di n thi s repor t wer e determine dwithou t th e us e o f

correctio n factors . Accordingly , th e XCEM - reporte dA s concentration s wer e reduce db y 1 0 percent . Afte r makin g thes e corrections , CE S receive dth e M2 9 dat afro ma n independen t laboratory , Cheste r

LabNet . Include dwit h th e M2 9 dat awer e result s fro m blan k an dspik e tests . N o change s wer e mad e t o M2 9 laborator y result s wit h th e exceptio n o f

ablan k subtractio n t o accoun t fo r S e i n th e M2 9 blank . XCE M v s M2 9 tes t result s XCE M an dM2 9 concentration s fo r th e fou r M2 9 tes t

run s ar e show n i n Tabl e 6 . Reporte dconcentration s fo r th e tw o method s ar e i n goo dagreemen t fo r al l ele

ment s excep t

Ag . N o apparen t

overal l bia s i s eviden t betwee n the tw o methods . Indeed , th e over al l averag e non-A g meta l concentration s reporte db y th e tw o method s ar e withi n afe w percen t

o f eac h other . Thi s tren dhold s tru e fo r eac h sampl e ru n (Tabl e 7 ) an dindicate s tha t

i t i s probabl e tha t

n o particulat e los s occurre di n the samplin g system .3 8 ERDC/CER L TR-05- 3

Tabl e 6. Reporte d XCE M an d M2 9 concentrations . Element Metho d Concentratio n Avg . % Element Metho d Run 1 Ru n 2 Ru n 3 Ru n 4 Averag e Diff . A s XCE M

M2 9 12 8

14 0 13 1

14 9 12 0

12 9 11 7

13 0 12 4

13 7 1 0 C d XCE M

M2 9 13 1

15 8 13 8

16 6 12 1

15 6 12 4

15 1 12 9

15 8 1 9 C r XCE M

M2 9 14 9

15 2 15 6

15 9 13 9

15 3 13 1

14 6 14 4

15 2 6 H g XCE M

M2 9 13 9

11 7 14 5

13 1 13 1

11 8 12 6

12 1 13 5

12 2 -1 1 P b XCE M

M2 9 13 9

12 0 14 0

13 1 12 7

11 1 11 7

9 6 13 1

11 4 -1 5 S e XCE M

M2 9 13 4

12 2 14 1

14 6 12 7

13 2 12 3

13 0 13 1

13 2 1 A g XCE M

M2 9 12 8

1 0 13 3

9 12 0

1 0 11 7

5 3 12 5

2 1 -95 1 XCE M (NoAg ) Av g

S D % RS D 13 7

8 6 14 2

8 6 12 7

7 5 12 3

5 4 13 2

7 5 4 M2 9 (NoAg ) Av g

S D % RS D 13 5

1 8 1 3 14 7

1 4 1 0 13 3

1 8 1 4 12 9

2 0 1 5 13 6

1 7 1 3 4

Tabl e 7. Averag e meta l concentration s fo reac h samplin g run . M2 9 Run No . XCE M Avg . Meta l Cone , (pg/m 3 ) M2

9 Avg . Meta

l Cone . (ug/m

3) Percent

Differenc e Ru n 1 13 7 13 5 1. 5 Ru n 2 14 2 14 7 3. 4 Ru n 3 12 7 13 3 4. 5 Ru n 4 12 3 12 9 4. 6 Averag e 13 2 13 6 3. 5 1 Meta l concentration s ar e a n averag e o

f As , Cd , Cr , Hg , Pb , an d S e fo r eac h run . Th e stron g averag e concentratio n correlatio n i s reflecte di n th e positiv e R A re sult s (Tabl e 8) . Eve n wit h onl y fou r samplin g runs , th e R A fo r As , Cr , Hg , an d S e meet s the PS-1 0 R A criterio n o f 2 0 percent . Durin g forma l M2 9 certification , aminimu mo f

nin e run s i s recommende db y EPA' s propose dPS-10 . Ha dthe XCE M bee n teste dfo r nin e runs , i t

i s estimate d(b y usin g avalu e o f nin e fo r th e numbe r of sampl e run s i n th e PS-1 0 R A calculation ) tha t P b woul dhav e als o me t th e R A criterion . Th e onl y MAC T meta l tha t woul dno t

mee t th e R A criterio n wa s C dwit h a n R A o f 2 3 percent . Sinc e M2 9 C dconcentration s were , o n aver age , 1 5 percen t

highe r tha n othe r

M2 9 reporte dconcentrations , i t i s believe d tha t difference s i n th e C dconcentratio n ar e afunctio n o f ahig h M2 9 bia s a s dis

cusse di n th e nex t

section .ERDC/CER L TR-05- 3 3 9

Table 8 . XCE M an d M2 9 relativ e accuracies . RAwit h Est . R A Element Fou rM2 9 wit h Nine Run s M2

9 Run s Arseni c 14. 3 13. 0 Cadmiu m 22. 7 21. 6 Chromiu m 13. 1 11. 0 Mercur y 20. 4 17. 8 Lea d 21. 3 19. 3 Seleniu m 16. 2 13. 2 Silve r 721. 7 662. 6 I n contras t

t o th e othe r

spike dmetals , A g XCE M an dM2 9 concentration s do no t sho w goo dagreement . Th e averag e A g concentratio n durin g M2 9 testin g wa s reporte da s 2 1 ± 2 1 ug/m 3 , whil e th e XCE M A g concentration s durin g the fou r run s wa s 13 1 ± 8 ug/m 3 . Thi s M2 9 averag e A g concentratio n i s mor e tha n fiv e standar ddeviation s fro mth e averag e M2 9 non-A g concentratio n o f 13 6 ± 18 . Althoug h th e pre - an dpost-tes t result s di dindicat e som e potentia l differenc e i n th e A g concentrations , th e averag e reporte dM2 9 por t concentratio n o f

10 3 ± 1 5 ug/m 3 wa s stil l five-fol dhighe r tha n th e M2 9 tes t

ru n results . Th e laborator y tha t performe dth e M2 9 analysi s believe s som e analytica l problem s wer e possi

bl e fo r A g an dcite s th e fac t

tha t A g an dS b ar e the onl y element s exempte dfro m spik e recover y criteri ab y the standar dmethod . Fo r thes e reason s (an dsinc e th e A g spik e di dno t

mee t th e 8 0 t o 12 0 percen t

recover y criterion) , i t i s believe dtha t th e M2 9 A g number s wer e inaccurate . Th e consistenc y betwee n th e overal l averag e XCE M an dM2 9 concentration s i s importan t

becaus e i t

indicate s tha t

particl e los s di dno t

occu r durin g testing . Th e consistenc y i n the elementa l concentration s als o indicate s tha t elementa l fractionatio n wa s no t

occurring . Excep t

fo r Ag , al l 24 reporte dmeta l concentra tion s durin g eac h o f

th e tes t run s wer e withi n the combine d5 percen t XCE M an d 1 3 percen t

M2 9 uncertaintie s (Figur e 27) . Method 29 and XCEM Precision

and Accuracy A s discusse di n th e las t section , n o indicatio n o f particl e los s o r

chemica l frac

tionatio n wa s observe db y eithe r metho ddurin g M2 9 testing . A s such , al l ele

ment s shoul dhav e bee n presen t i n equa l concentration s a t bot h th e XCE M an d M2 9 ports . I n thi s situation , ahypothetica l unbiase dmethod's reportin g o f ele

menta l concentration s fo r agive n sampl e ru n woul db e randoml y distribute d abov e an dbelo w th e "true " elementa l concentration . Th e averag e elementa l con centratio n woul dthe n b e amethod' s bes t estimat e o f

the "true " concentratio n i n th e stack , an dth e rang e o f distribution s aroun dan dabou t th e averag e4 0 ERDC/CER L TR-05- 3 concentratio n woul dreflec t th e method's precision . Elementa l concentration s consistentl y an dsignificantl y abov e o r belo w th e averag e concentratio n woul d indicat e measuremen t problems . Figur e 2 8 show s elementa l concentration s fo r eac h sampl e ru n tha t hav e bee n normalize dt o th e averag e elementa l con centration . Normalize dconcentration s i n Figur e 28 wer e calculate dusin g Equation s 1 an d2 .

_20 0 - | j | nxcEM l S T T 

# _1 "M2 9 j

A s C d C rH g P b Se A g * 20 0 "S i 16 0 12 0 * 8 0 4 0 - i 1 1 OXCE M T T 1 RIJN2 I WM29

A s C d C r H g P b S e A g 200

M16 0 g 12 0 •4 3 * 8 0 S 40 - | 1 1 DXCE M T T[ R U N3 1 [•M2 9 

# m i l

A s C d C r H g P b S e A g

„ 200 R U N 4 • XCE M • M2 9 

# Hi t

A s C d C r H g P b S e A g * Expected concentratio n o f al l element

s shoul d b

e th e same . Figur e 27 . Comparison s of XCE M and M2

9 concentratio n b

y run .ERDC/CER L TR-05- 3 4 1

Cadmium DXCE M

Figur e 28 . XCE M an d M2 9 normalize d concentration s b y element.4 2 ERDC/CER L TR-05- 3

[Eq1 l where , Xn = Normalize dXCE M concentratio n fo r a n elemen t

durin g asamplin g ru n Xc = Reporte dXCE M concentratio n fo r a n elemen t

durin g asamplin g ru n X - Averag e o f

reporte dXCE M As , Cd , Cr , Hg , Pb , an dS e concentration s durin g asamplin g ru n

M n - Normalize dM2 9 concentratio n fo r a n elemen t

durin g asamplin g ru n Me = Reporte dM2 9 concentratio n fo r a n elemen t

durin g asamplin g ru n M = Averag e o f

reporte dM2 9 As , Cd , Cr , Hg , Pb , an dS e concentration s dur

in g asamplin g run . I n Figur e 28 , al l XCE M normalize dconcentration s ar e withi n 1 0 percen t o f th e averag e elementa l concentration , an dtwo-third s o f th e value s ar e withi n 5 per cen t o f th e averag e elementa l concentration . Thi s i s consisten t wit h a n XCE M estimate done-sigm auncertaint y o f 5 percent . Fo r

th e M2 9 samples , however , onl y A s an dS e hav e al l reporte dconcentration s withi n 1 0 percen t o f th e averag e M2 9 elementa l concentration . Two-third s o f th e M2 9 value s ar e withi n 1 3 per cen t o f th e M2 9 average , whic h i s consisten t wit h aM2 9 one-sigm aprecisio n o f 1 3 percent . Interestingly , M2 9 C dan dM2 9 P b concentration s hav e th e greates t deviatio n fro mth e M2 9 average , 1 6 percen t hig h an d1 6 percen t low , respec tively , an dar e th e tw o element s wit h the highes t RA s relativ e t o th e XCEM . Th e M2 9 C dis , o n average , 1 9 percen t highe r tha n th e XCEM , an dth e M2 9 H g is , o n average , 1 1 percen t lower . Thi s indicate s tha t muc h o f

the R A differenc e betwee n the XCE M an dM2 9 fo r C dan dP b ma y b e aproduc t o f M2 9 bias . Overall , th e normalize dconcentration s indicate done-sigm auncertaintie s o f abou t 5 percen t

fo r th e XCE M an d1 3 percen t fo r the M29 . Thi s M2 9 uncer taint y i s i n goo dagreemen t wit h th e EP A uncertaint y estimat e o f 1 0 to 1 5 percen t (MAC T 1999b) . Th e M2 9 normalize dconcentration s showe dsignifican t inter-elementa l difference s indicatin g apossibl e metho dbias , whic h coul db e responsibl e fo r

R A differences . [Eq2 ] where ,ERDC/CER L TR-05- 3 4 3



# 4 Field-read y XCE M CE S constructe dane w XCE M fo r testin g a t

th e TEA D facility . Thi s prototyp e incorporate s al l th e change s describe di n th e previou s chapters . I t als o include s amodifie dThermoNora n Quan X energ y dispersiv e XR Fanalyze r (Therm o Kevex ) fo r

meta l detection . Th e Quan X i s capabl e o f simultaneousl y measurin g 1 9 element s an daP dQ A standard . I n addition , a n educto r downstrea mo f

th e stillin g chambe r

i s use dt o pul l th e stac k ga s throug h the extractio n system . Thi s chang e i s indicate di n th e slightl y modifie dmai n componen t scree n o f

th e custo mWonderWare * (Progressiv e Software , Albany , OR ) softwar e interfac e (Figur e 29) .

t2 l fti 3 S •lUserNsm e earHrtsfrstof j Scree n UntocKe d ^ Logo n 1 i^J j Admi n \ f

(ft Reports i fcl Trend s j 3 Sneun s i Alarms ' I 'stzsjoi | "io;35:2 e J j j SetQflRange e \ | Se tQ A Paramo her s ) | j Se tAnalogRange i | ] Loo p li^n g j ] PL C Statu s ( j CS V To d 1

1 I/ f

Faw ; | | Figur e 29 . Ne

w Componen tContro l Scree n fo rXCE M software interface . A s describe di n th e previou s chapters , al l day-to-da y function s o f th e XCE M hav e bee n automate dincludin g flo w an dtemperatur e control , concentratio n determi

nation , an dQ A routines . Flow , temperature , 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

analysis . Flows ,4 4 ERDC/CER L TR-05- 3 temperatures , concentrations , an dpressur e ar e logge di n real-tim e o n th e screen . Image s o f

th e ne w XCE M an dit s component s ar e show n i n Figure s 30 - 33 . Installatio n o f

thi s uni t

at TEA D i s describe di n mor e detai l i n afollow-o n technica l report .

Figur e 30 . XCE M cassettes .

Figur e 31 . XCE M extractio n syste m an d cassette (left ) and chassi s (right) .4 5 ERDC/CER L TR-05- 3

Figure 32

. XCE M wit

h cabine tdoo r open .



### VE S 0006 74 6 ERDC/CER L TR-05- 3



# 5 Summar y an d Conclusion s Th e XCE M ha s bee n develope dt o provid e fo r automate doperations . I t no w in

clude s feature s tha t

improv e ease-of-us e an dQA . Th e XCE M extraction , meas urement , an ddat arecordin g system s hav e bee n full y automate dusin g aflexibl e WonderWare ® softwar e interface . Th e revise dXCE M ha s bee n equippe dwit h a n automate ddail y zer o an dspa n check , a s wel l a s amechanis mfo r checkin g instrumen t

drift , wit h ever y sample . Th e XCE M RI Fdisplaye dgoo dcaptur e efficiencie s fo r vapo r phas e H g unde r reasonabl e temperatur e an dflo w conditions . Th e XCE M measure dthe mercuri c nitrat e injecte ddurin g M2 9 compariso n test s wit h a20. 4 R A usin g fou r tes t runs . Thi s numbe r

meet s th e EPA' s propose dPS-1 0 R A criterio n whe n rounde d t o tw o significan t

digits . I t

i s estimate dtha t

alarge r numbe r o f tes t run s woul d brin g tha t

valu e belo w 20 , s o tha t the XCE M wil l likel y als o mee t th e R A crite

rio n fo r H g i n futur e testing . A nebulizatio n spikin g approac h wa s use dt o provid e ver y precis e concentration s o f al l MAC T metal s ove r awid e rang e o f

concentration s ( 1 t o 200 0 mg/cm3) . Th e XCE M agree dwel l wit h th e M2 9 tes t run s fo r

al l element s excep t

Ag . Th e XCE M displaye dbette r precisio n tha n M2 9 an dwa s abl e t o repor t dat aever y 1 2 mi n durin g the 4-day tes t period . M2 9 A g concentration s differe ddramaticall y fro man y othe r

M2 9 o r XCE M reporte dconcentration . Fo r thi s reason , an dbe

caus e o f laborator y Q A issues , i t i s believe dtha t

th e lo w M2 9 A g concentration s ar e aresul t

o f M2 9 samplin g o r

analysi s error . Th e XCE M me t

th e propose dPS-1 0 R A criteri afo r As , Cr , Hg , an dS e wit h onl y fou r sampl e runs . I t

i s estimate dtha t

th e XCE M woul dals o hav e me t th e P b R A criterio n i f

nin e test s ha dbee n conducted . Cadmium , wit h a n R A o f 2 3 percent , di dno t mee t th e R A criterion . Althoug h th e simulate dstac k ga s containe dth e metal s o f interes t an drelativel y hig h concentration s o f nitri c aci d(~10 0 ppm) , th e simulate dstac k ga s di dno t contai n sulfu r

dioxide , fl y ash , or

nitroge n dioxid e a s migh t b e see n i n a n actua l incinerato r

stack . Fo r

thi s reason , additiona l testin g unde r actua l stac k

condi

tion s i s neede dt o ensur e tha t the XCE M ca n perfor ma s wel l i n the fiel da s i t di d fo r thes e tests .ERDC/CER L TR-05- 3 4 7

A ne w XCE M incorporatin g th e change s mad e i n thi s repor t wa s constructe dan d installe dat

TEA D wher e i t

underwen t

M2 9 compariso n test s unde r rea l incin

erato r conditions . Th e installatio n an dfieldtestin g o f th e XCE M a t

TEA D ar e presente di n afollow-o n technica l report .4 8 ERDC/CER L TR-05- 3



# Reference s Bryson , S. , C . Whitworth , an d S . Kujawa . (2000) . Fina l Repor t- Tes tand Evaluatio n o f an X-Ray Fluorescenc

e Based Multi-Elemen tMetal s Continuous Emissio n Monitor . Prepare d for U.S . Arm y Cor

p o f Engineers by MSE-TA , Inc. , Butte , MT . Coope rEnvironmental Service s (CES) . (2001a) . "XCE M User' s Guide, " Beaverton , OR , 2001 .

. (2001b) . "XCE M Resourc e Manual, " Beaverton , OR , 2001 . Cooper , J. , B.E . Johnsen , K.J . Hay , an d W . Watson (2000) . Continuou s Hazardous Elemen t Analysi s Syste

m fo rAmbien tand Emission s Monitoring . Presente d a tregiona

l AWM A Conference : Recen

tAdvances i n th e Scienc e an d Managemento

f Ai rToxics . Apri l 10, 2000 . Flagan , R.C. , an d J.H . Seinfel d (1988) . Fundamental s o f Ai rPollutio n Engineering , Prentice-Hall , Englewood Cliffs , NJ , p p 59-62 , 146-159

, 359-384. French , N . (1998) . 199 7 Performanc

e Testin g o

f Multi-Meta l Continuou s Emission s Monitors . Summar y Repor tPrepare d for th e U.S . EP A an d U.S . DO E b y Sky+ , Napa , CA . Fuchs , N.A. , and A.G . Stutugin . (1966) . Aerosol Science, edited b y C N Davies , Academic Press , London , p

p 1-30 . Johnsen , B. , J . Cooper , an d B . Richard s (1998) . Evaluatio n o f a Hazardou s Elementa l Samplin g Trai n Durin g EPA' s Continuous Emissio n Momtorin g Test . Presented a tPacifi c Northwest AWM A Conferenc

e and Internationa

l Conferenc

e o n Incineratio n an d Therma l Treatment Technologies . Octobe

r 1 , 1998 . Josephson , Paul . (2003) . Hazardou s Wast e Combustor ManagementPla n - AEC . Maximu m Achievabl e Contro l Technology . (1999) . Fina l Standard s for Hazardous Ai rPollutants forHazardous Wast

e Combustors . Federal Registe r 52828-FR53077 , Vol . 64, No . 189 .

. (1999b) . Fina l Technical Suppor tDocumen

tfo r HW C MAC T Standards . Vo l III . Selection o

f MAC T Standard s an d Technology . Chapte r 13. USEP A Contract68-D2-0164 . PS-1 0 (1996) , Propose d Performance Specificatio n 1 0 for Meta l CEM S (Propose d 04/19/96

) Foun d o n th e EP A websit

e at : http://www.epa.gov/ttn/emc/propperf.html . Seltzer , M.D . (2000) . "Performanc e Testin g o

f aMultimetal s Continuou s Emission s Monitor" , J . Ai r Wast e Mgt . Assoc. , Vol . 60

, No . 6 . Ytalatalo , S. , H . Toivonen , an d J . Lehtinen . (2000) . Authenticatio n o f Ai rSamples b

y Aerosol . Aerosol Scienc

e and Technolog

y 33:419-426

.ERDC/CER L TR-05- 3 4 9



# Abbreviation s an d Acronym s A E C U.S . Arm y Environmenta l Cente r CAA A Clea n Ai r

Ac t Amendment s (of

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

Environmenta l Service s CI F carbon-impregnate dfilte r EP A U.S . Environmenta l Protectio n Agenc y ERD C U.S . Arm y Enginee r Researc h an dDevelopmen t Cente r EQ T Environmenta l Qualit y Technolog y H A P Hazardou s Ai r Pollutant s HES T Hazardou s Elementa l Samplin g Trai n H V M hig h volatil e metal s HW C hazardou s wast e combustor s IC P inductivel y couple dplasm a LIB S laser-induce dbreakdow n spectroscop y L V M lo w volatil e metal s M2 9 EP A Referenc e Metho d2 9 mAm p milli-amper e MAC T Maximu mAchievabl e Contro l Technolog y MSE-T A M S E Technolog y Applications , Inc . NESHA P Nationa l Emissio n Standard s fo r Hazardou s Ai r

Pollutant s NIS T Nationa l Institut e o f Standard s an dTechnolog y P L C programmabl e logi c controlle r P M particulat e matte r PS-1 0 EP A Performanc e Specificatio n 1 0 Q A qualit y assuranc e R A relativ e accurac y RI F resin-impregnate dfilte r RS D relativ e standar ddeviatio n5 0 ERDC/CER L TR-05- 3

SCF M standar dcubi c fee t pe r minut e S V M semi-volatil e metal s TEA D Tooel e Arm y Depo t (Utah ) XCE M XRF-base dcontinuou s emissio n monito r X R Fx-ra y fluorescenc e 

### Chemical element

s A g silve r A s arseni c C d cadmiu m C r chromiu m H g mercur y P b lea d P d palladiu m S e seleniu m



### VE S 00067 5

### REPOR T DOCUMENTATIO N PAG E Form Approved OMB No. 0704-0188 Publi c reporting burde n fo rthi s collectio n o f informatio n i s estimate d t o averag e 1 hou rpe rresponse , includin g th e tim e fo rreviewin g instructions , searchin g existin g dat a sources , gatherin g an d maintainin g th e dat a needed , an d completin g an d reviewin g thi s collectio n o f information . Sen d comment s regardin g ihis burde n estimat e o ran yothe raspec t o f thi s collectio n o f information , includin g suggestion s fo rreducin g thi s burde n t o Departmen t o f Defense , Washingto n Headquarter s Services , Directorat e fo rInformatio n Operation s an d Report s (0704-0188) , 121 5 Jefferso n Davi s Highway , Suit e 1204 , Arlington , V A 22202 - 4302 . Respondent s shoul d b e awar e tha t notwithstandin g an yothe rprovisio n o f law , n o perso n shal l b e subjec t t o an ypenalt yfo rfailin g t o compl ywit h a coUectio n o f informatio n i f i t doe s no t displa ya currentl y vali d OM B contro l number . PLEAS E D O NO T RETUR N YOU R FOR M T O TH E ABOV E ADDRESS . 1 . REPOR T DAT E (DD-MM-YYYY) 2 . REPOR T TYP E

01-200 5 Fina l 3 . DATE S COVERE D (Fro m - To ) 4 . TITL E AN D SUBTITL E X-Ra y Fluorescence-Base dMulti-Meta l Continuou s Emissio n Monitor : Developmen t 5a . CONTRAC T NUMBE R Sb . GRAN T NUMBE R 5c . PROGRA M ELEMEN T NUMBE R 6 . AUTHOR(S ) K . Jame s Hay , Bruc e E . Johnsen , an dJoh n A . Coope r 5d . PROJEC T NUMBE R 622784AT4 1 5e . TAS KNUMBE R 00 2 5f . WOR KUNIT NUMBE R CNE-B09 1 7 . PERFORMIN G ORGANIZATIO N NAME(S ) AN D ADDRESS(ES ) U.S . Arm y Enginee r

Researc h an dDevelopmen t Cente r (ERDC ) Constructio n Engineerin g Researc h Laborator y (CERL ) P O Bo x 900 5 Champaign , I L 61826-900 5 8 . PERFORMIN G ORGANIZATIO N REPOR T NUMBE R ERDC/CER LTR-05- 3

9 . SPONSORIN G /

MONITORIN G AGENC Y NAME(S ) AN D ADDRESS(ES ) U.S . Arm y Corp s o f

Engineer s 44 1 "G " Stree t

N W Washington , D C 20314-100 0 10 . SPONSOR/MONITOR' S ACRONYM(S ) 11 . SPONSOR/MONITOR' S REPOR T NUMBER(S ) 12 . DISTRIBUTIO N /

AVAILABILITY STATEMEN T Approve dfo r

publi c release ; distributio n i s unlimited .

13 . SUPPLEMENTAR Y NOTE S Copie s are availabl e fro mth e Nationa l Technica l Infonnatio n Service , 528 5 Por t Roya l Road , Springfield , V A 22161 . 14 . ABSTRAC T Arm y demilitarizatio n incinerator s wil l nee dto compl y wit h th e Hazardou s Wast e Combusto r Nationa l Emissio n Standard s fo r Haz ardou s Ai r

Pollutant s tha

t wil l regulat e metal s an dmeta l compound s liste dunde r th e Clea n Ai r

Ac t Amendments . A larg e proble mfo r thes e incinerato r

operation s i s limite dknowledg e ofth e type s an dquantitie s o f emitte dmetals . Complianc e ma y b e determine donl y throug h tria l bur n emissio n test s becaus e o f thi s limitation . A continuou s emissio n monito r (CEM ) fo r

multi-metal s wil l provid e th e emissio n data , atoo l to hel p mee t complianc e requirements , an dth e opportunit y t o adjus t bur n strategie s fo r

increase dproduction . Th e XCE M multi-meta l CE M wa s develope dusin g x-ra y fluorescenc e (XRF ) a s th e analytica l metho dan dan automate dsamplin g syste m tha t provide s extractiv e batc h samplin g ont o afilte r tape . Th e syste mi s operate dwit h user-friendl y WonderWare ® softwar e tha t pro vide s automation , calibratio n routines , an dreport generation . A prototyp e XCE M wa s teste di n the laborator y wit h aspike dga s stream agains t U.S . Environmenta l Protectio n Agenc y Referenc e Metho d2 9 fo r fou r sampl e runs . Th e XCE M me t th e relativ e accurac y crite

riafo r fou r o f seve n metals . A field-ready XCE M wa s buil t fo r demonstratio n a

t th e 123 6 Deactivatio n Furnac e a t Tooel e Arm y De pot , Utah . 15 . SUBJEC T TERM S emission s continuou s emissio n monito r (CEM ) hazardou s waste s

demilitarizatio n incinerator s 16 . SECURIT Y CLASSIFICATIO N OF : 17 . LIMITATIO N O F ABSTRAC T 18 . NUMBE R O F PAGE S 19a . NAM E O F RESPONSIBL E PERSO N K . Jame s Ha y a . REPOR T Unclassifie d b . ABSTRAC T

Unclassifie d c . THI S PAG E

Unclassifie d SA R 6 0 19b . TELEPHON E NUMBE R (in clud e are a code ) (217 ) 373-348 5 NS N 7540-01-280-550 0 Standar d For m 29 8 (Rev . 8-98 ) Prescribe d b yANS I Std . 239.1 8



### VE S 0006 8

# VE S 00068 1 .pd f

# Performanc e Specification YY : Specification

s an d Tes tProcedure

s fo r X-Ray Fluorescenc

e Base d Multi-Metal s Continuou s Emission Monitorin g System s a tStationar

y Source s



# DRAF T Jun e 8 , 200 5

Submitte dto : Th e Environmenta

l Protectio

n Agenc y Researc h Triangl e Park , N C

Prepare dby : Coope r Environmenta

l Services

, LL C 1018 0 S W Nimbu s Blv dSuit e J 6 Portland , Orego n 9722 3

# Performanc e Specification YY : Specification

s an d Tes tProcedure

s fo r X-Ra y Fluorescenc

e Base d Multi-Metal s Continuou s Emission Monitorin g System s a tStationar

y Source s



# DRAF T Jun e 8 , 200 5

Prepare dby : 

### J.A . Cooper

, K . Petterson

, B.E . Johnsen

, C . A . Yanca, M . Nakanishi , D . Bart h Coope rEnvironmenta

l Services

, LL C 1018 0 S W Nimbu s Blv dSuit e J 6 Portland , Orego n 9722 3

# Performanc e Specification YY : Specification

s an d Tes tProcedure

s fo r X-Ra y Fluorescenc

e Base d Multi-Metal s Continuou s Emission Monitorin g System s a tStationar

y Source s

Prepare d by : Date:_ Kra g A . Petterson

, Environmenta

l Scientis t Reviewe d by : Date : Ca y A . Yanca

, Environmenta

l Scientis t Reviewe d by : Date : Bruc e E . Johnson

, Q A Manage

r Approve d by : Date : Joh n A . Cooper

, Directo r

### Executiv e Summar

y Performanc e Specificatio n Y Y detail s the perfonnanc e requirement s fo r amulti-metal s continuou s emission s monito r tha t utilize s x-ra y fluorescenc e (XRF ) as a n analytica l technique . Eac h XR Fbase dmulti-metal s CEM S mus t mee t the criteri afo r

accuracy , stability , an dinstrumental respons e lai dout i n thi s document . I n addition , ever y XR Fmulti

metal s CEM S mus t

mee t th e installatio n requirement s i n PS-Y Y an dthe on-goin g quality contro l an dqualit y assuranc e procedure s se t fort h i n procedure Z i f

i t i s use dfo r

emission s complianc e purposes .

Specification s fo rXRF-Base d Multi-Metal s CEM S (PS-YY ) Pag e i o f i vb 0 CA, Cf QCEMS QCEU CF" = CF, RB= C, £= 

### Lis to f Symbol s Th e y intercep t

o f the bes t fi t lin e Th e slop e ofth e bes t

fi t lin e X-ra y fluorescence calibratio n accurac y Correcte dCEM S concentratio n fo r the i t helement Th e concentratio n ofth e i t helemen t a s reporte db y the CEM S Th e averag e reporte dconcentratio n ofth e CEM S fo r th e i t helement Correctio n facto r

fo r percen t transpor t fo r th e i t helement Th e relativ e bia s correctio n facto r fo r th e i t helement Th e emissio n limi t

ofth e i t helemen

t

X R Fmulti

d, = 

### 1 FS

jcemo jcemu Lf

n PT< PTi PRBi Concentratio n o f the i t helement

a t th e stac k Concentratio n o f

th e i t helement

a t th e samplin g modul e o r

a s reporte db y th e •metal s CEMS . Differenc e betwee n tw o paire dmeasurement s Arithmeti c mea

n o f difference s Ful l scal e valu e o f

you r CEM S volum e (o r

flow) measuremen

t devic e Th e valu e o f

the i t helement

o n the zer o standarddetermine dimmediatel y afte r calibratio n Th e valu e ofth e calibratio n chec k standardreporte db y you r CEM S Th e measure dCEM S respons e t o th e zer o standardfo r

th e i t helement Th e measure dCEM S respons e to th e i" 1 element

i n th e upscal e standard Th e know n valu e o f

th e calibratio n chec k

standard Th e calibrate dvalu e ofth e i t helement o f th e upscal e standard Numbe r o f datapoint s Th e percent

transpor t o f th e i t helement Averag e percent

transpor t fo r the i t helement Relativ e Bia s o f

th e i t helement

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e i i o f i vTh e averag e ofth e referenc e metho dmeasurement s fo r the i t hmetal PRSD t = Th e relativ e percent standarddeviatio n fo r

the i t hmetal r = Th e correlatio n coefficien t SD, = Th e standar ddeviatio n o f

difference s fo r

the i * element Vcemr Sampl e ga s volum e (o r

flow ) as measure db y the CEM S volume chec k devic e VD = Volum e drif t 

### v m

### = Volum e (or flow ) reporte db y you r multi-metal s CEM S UD, = Th e upscal e drif t ofth e i , helement

o n you r CEM S i n percent . x = Arithmeti c mea n X / Valu e o f eac h dat apoin t CEM S reporte dconcentratio n fo r the i t helement ZD , = Th e zer o drif t o f the i t helement

o n you r CEM S i n percent

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e ii i o f i v 

### VE S 00068 !

### Tabl e o f Content s 1. 0 Usin g PS-Y Y 1 1. 1 What

i s th e purpos e an dapplicabilit y o f Perfonnanc e Specificatio n YY ? 1 1.2 What

wil l b e discusse di n PS-YY ? 1 1.3 What

ar e the installatio n an dpre-performanc e specificatio n tes t requirements ? 2 1. 4 What

specia l definition s appl y t o PS-YY ? 3 2. 0 Interferences , Safety , an dEquipmen t Requirement s 5 2. 1 Ar e ther

e any potentia l interference s fo r m y XR Fmulti-meta l CEMS ? 5 2. 2 What

d o I nee dt o kno w t

o ensur e th e safety o f

person s usin g PS-YY ? 5 2. 3 What

equipment

an dsupplie s d o I need ? 5 2. 4 What

regent s an dstandard s d o I need ? 6 3. 0 Performanc e Evaluatio n Procedure s an dReportin g 6 3. 1 What

i s the purpos e o f

the initia l performanc e specificatio n test s an dwha t i s require dto perfor mthe tests ? 6 3. 2 Ho w d o I repor

t the result s o f

the initia l performanc e specificatio n test ? 1 2 4. 0 Performanc e Criteri aan dCalculation s 1 3 4. 1 What

ar e the performanc e criteri afo r my XR Fmulti-metal s CEMS ? 1 3 4. 2 What

calculations , equations , an ddataanalyse s ar e needed ? 1 4 5. 0 Other

Requirement s an dInformatio n 2 0 5. 1 What

qualit y contro l measure s ar e required ? 2 0 5. 2 What

calibratio n an dstandardizatio n procedure s mus t I perform ? 2 0 5. 3 What

pollutio n preventio n procedure s mus t I follow ? [reserved ] 2 0 5. 4 What

wast e managemen

t procedure s mus t

I use ? 2 0 5. 5 What

referenc e table s an dfigure s ar e relevan t

t o PS-YY ? 2 0 5. 6 What

reference s appl y to PS-YY ? 3 0

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e i v o f i v

### 1. 0 Using PS-Y Y /. 1 What

is the purpose and

applicability of

Performance Specification YY? 1.1.1 Purpose Th e purpos e o f

Perfonnanc e Specificatio n Y Y i s to establis h the performanc e requirement s tha

t mus t b e me t b y amulti-metal s continuou s emissio n monitorin g syste m(CEMS ) tha

t utilize s x-ra y fluorescenc e (XRF ) to determin e meta l concentration s i n stationar y sources . Assuranc e o f the continuin g qualit y o f the CEM S dat ama y b e achieve db y followin g the procedure s define di n Procedure Z-XRF Based Multi-Metal

CEMS Quality Assurance Procedures. 1.1.2 Application PS-Y Y applie s t o yo u i f yo u inten dto us e a

n XR Fmulti-metal s CEM S fo r purpose s o f establishin g complianc e wit h federa l regulation s fo r metal emission s fro mstationar y sources . 1.1.3 Measurement

Capabilities A multi-metal s CEM S mus t b e capabl e o f

measurin g tota l concentration s o f a t leas t tw o metal s i n th e unit s o f the applicabl e standar

do r i n unit s tha

t can b e converte dto unit s o f th e applicabl e standard . 1.1.4 Other

Monitoring I f you r XR Fbase dmulti-metal s CEM S i s capabl e o f reportin g ameta l concentratio n i n th e unit s o f

th e existin g regulatio n n o additiona l monitorin g i s necessary . I f you r CEM S doe s no t

repor t concentration s i n th

e unit s o f

the existin g standardthe n othe r monitorm g (e.g. , oxygen , temperature , an dpressure ) ar e necessar

y to conver

t the unit s reporte db y you r

CEM S to th e unit s o f

th e standard . 1.2 What

will be discussed

in PS-YY? PS-Y Y cover s tw o basi c topics : (1 ) the instrumen t requirement s fo r

aXR Fbase dmulti

metal s CEM S an d(2 ) the requirement s tha t eac h XR Fmulti-metal s CEM S mus t mee t durin g the initia l performanc e specificatio n test . 1.2.1 Instrument

Requ irements A multi-metal s CEM S mus t b e abl e t o accuratel y repor t the concentration s o f

a t leas t tw o metals . It

may d o s o b y extractin g arepresentativ e sampl e (pat h o r poin t samplm g may b e use di f

the sampl e i s representative ) o f stac k effluen t an dcapturin g th

e metal analyte s o f

interes t o n amedium . Th e CEM S mus t hav e acycl e tim e tha

t i s les s than on e thir dthe perio do f

the applicabl e standard . Th e rang e o f the instrumen t

mus t b e fro m1 0 percent

t o a t leas t 400 % o f the applicabl e regulatio n a s determine db y fiel do r

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY) ) Pag e 1 o f 1laboratory tests . Finally , the instrumen t o r operato r mus t b e abl e t o perfor mdail y upscale , blank , an dflo w quality assuranc e check s t o ensur e th e accuracy , precision , an dstabilit y ofth e instrument an dit s data . 1.2.2 Initial

Performance Specification Tests Th e purpos e ofth e initia l perfonnanc e specificatio n tes t i s to establis h th

e stability , accuracy , an dprecisio n o f you r XR Fmulti-metal s CEMS . Th e performanc e specificatio n tes t

ca n b e divide dint o tw o phases : (1 ) th e stabilit y test , an d(2 ) th e accurac y test . Th e stabilit y tes t

consist s o f

aseve n da

y chec k o f th e zer o an dupscal e calibratio n drif t an di s don e prio r

t o the accurac y testing . Fo r th e accurac y tests , thre e method s o f metal s generatio n (quantitativ e spiking , non-quantitativ e spiking , an dstac k operation ) an dtw o method s o f

dataanalysi s (percent

relativ e bias , an dlinearity ) ar e available . Th e samplin g an dXR Fmodule s o f you r CEM S may als o b e teste dseparatel y fro m you r stac k samplin g interface . Some option s ma y b e better

tha n other s dependin g o n you r multi-metal s CEMS , o r the condition s existin g a t you r stack . 1.3 What

are the installation and pre-performance specification test requirements? 1.3.1 Installation Requirements Th e samplin g locatio n o f an XR Fmulti-metal s CEM S shoul dbe downstreamo f al l pollutio n contro l equipment a t apositio n where the metal s concentration s ar e directl y representativ e o r

ca n b e correcte ds o a

s t o b e representativ e o f tota l emission s fro mth e stationar y source . It

i s recommende dtha

t the samplin g locatio n b e a t leas t tw o equivalen t

diameter s downstreamo f th e neares t contro l devices , poin t

o f pollutio n generation , bend , or

othe r poin t a t whic h achang e i n pollutan t concentratio n o r

flow disturbanc e may occur . Th e samplin g locatio n i s als o recommende dto b e a t leas t tw o equivalen t

diameter s upstrea

mfro mth e exhaust . Th e equivalen t diameter i s calculate d accordin g 4 0 CF RPart

60 , Appendi x A , Metho d1 , Sectio n 2.1' . Eithe r poin t o r pat h samplin g may b e used . Fo r poin t samplin g the measurement poin t shoul db e n o les s than 1. 0 meter fro mthe stac k

o r duc t wal l o r locate dove r

th e centroida l are ao f

th e stac k

o r duc t cros s section . Fo r

apat h samplin g CEM S th e effectiv e measurement

pat h shoul db e (1 ) totall y withi n th e inne r are abounde db y a lin e 1. 0 mete r fro mth e stac k

o r duc t wall , o r (2 ) hav e a

t leas t 7 0 percent

ofth e pat

h withi n th e inne r

5 0 percent

o f th e stac k

diamete r o r duc t cros s section . Th e sampl e collectio n an dinstrumental analyze r portion s o f

you r XR Fmulti-metal s CEM S ma y b e locate dany distanc e fro mthe samplin g poin t provide dthe transmissio n efficienc y fro m the samplin g poin t

t o the sampl e collectio n poin t ca n b e determine dan dmeet s th e criteri aoutline dlate r

i n thi s performanc e specification . I t i s als o recommende dtha t th e samplin g prob e fo r

you r multi-meta l CEM S b e locate da t poin t withou t stratification . Yo u ma y tes t

fo r stratificatio n a

t th e propose dCEM S samplin g poin t b y usin g eithe r P M (a s outline di n PS-11) , velocit y test s as describe di n Metho d2 2 , o r metal s concentration s usin g Metho d2 9 or an acceptabl e alternative .

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 2 of 21.3.2 Sampling Requirements You r multi-meta l CEM S shoul dsampl e fro mthe sourc e a t aflo w rate whic h i s withi n 1 0 percent

o f tru e isokinetic . I f

you r multi-meta l CEM S doe s no t maintai n a n isokineti c samplin g rat

e yo u mus t

us e actual site-specifi c dat ao r dat afro masimila r installatio n to prov e to us , the State , and/o r loca l enforcemen t

agenc y tha

t isokineti c samplin g i s no t

necessary . 1.3.3 Pre-Test

Preparation Requirements and Suggestions Prio r to the initia l performanc e specificatio n tes t yo u nee dto ensur

e tha t you r multi

metal CEM S datalogge r accuratel y record s emission s level s a s wel l a s signal s (flags ) tha t indicat e bot h norma l an dabnormal operation . Prio r t o star t o f the seve n da

y stabilit y tes t

th e dail y drif

t measurement s (upscal e an dzer o values ) shoul db e monitore dto ensur

e tha t the instrumen t

i s operatin g i n a

n appropriate an dstabl e manner . W e recommen dtha t yo u us e you r

XR Fmulti-meta l CEM S fo r asufficien t lengt h o f tim e t o becom e comfortabl e wit h it s operatio n prio r to th e star

t ofth e initia l performanc e specificatio n test . 1.4 What

special definitions apply to PS-YY? Calibratio

n Drift : Th e differenc e i n th e CEM S output reading s fro mthe establishe d referenc e valu e afte r

astate dperio do f

operatio n durin g whic h n o unschedule dmaintenanc e o r adjustmen t

too k place . Cycl e Time : Th e tim e betwee n whe n the stack ga s first come s i n contac t

wit h the concentratin g medi aan dwhe n the concentratio n valu e fo r tha t sampl e i s reported . Dat a Recorder : Th e portio n o f th e CEM S tha

t provide s arecor do f

analyze r outpu t includin g meta l concentrations , flags whic h indicat e norma l operation , an dflags indicatin g abnormal operation . Th e dat arecorde r ma y recor dother

pertinen t

datasuc h a

s effluen t

flow rates , andvariou s instrument temperatures . Diluen tmodule : Th e par

t o f the CEM S i n whic h an

y diluen t i s adde dan dmeasured . Drif tCalibratio

n Standard : A standardcontainin g aconstant amoun t o f meta l use dto establis h th e drif

t i n the x-ray fluorescence modul e response . Emissio n Limit : Th e emissio n limi t fo r asingl e metal i s equal to th e maximu mamoun t allowe dunder

th e applicabl e regulatio n fo r it s categor

y assumin g al l o f

th e other metal s i n it s categor y were no t

present . Elemen to f Opportunity : A n element tha t i s present

i n the stac k

effluen t an dca n b e use dt o establis h transpor

t efficiency . Instrumen

tMeasuremen

tRange : Th e rang e o f

meta l concentration s th e instrumen t can reliabl y measure fromthe lowes t concentratio n t o the highest . Th e instrumen t measuremen

t rang e ma y b e differen t

fo r differen t metals . I f

th e upper

en do f the measurement

rang e i s

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 3 o f 3mor e than fou r

time s the emissio n limit , th e upper limi t doe s no t nee dto b e definitivel y established . Pat h Samplin

g CEMS : A CEM S tha

t sample s the sourc e effluen t alon g apat

h greate r than 1 0 percent

o f th e equivalen t

diameter o f the stac k o r duc t cros s section . Poin tSamplin

g CEMS : A CEM S tha

t sample s the sourc e effluen t a t asingl e point . Non-Quantitativ

e Spiking : Th e proces s o f introducin g a

n unknow n amoun

t o f metal o r metal s int o th e effluen t

o r sampl e stream . Quantitativ

e Spiking : Th e proces s o f introducin g aknow n amount metal o r metal s int o the effluen t or sampl e stream . Percen tRelativ e Bias : Th e differenc e between areferenc e valu e an dthe CEM S measure d valu e divide db y the referenc e value . Referenc

e material : A material o f know n valu e use dt

o chec k th e calibratio n drif

t o f you r XR Fmulti-meta l CEMS . Sampl e Interface : Th e portio n o f th e CEM S use dfo r

on e o r more o f the following : sampl e acquisition , sampl e transport , sampl e conditioning , o r protectio n ofth e monito r fro mthe effect s o f

stac k gas . Samplin g module : Th e portio n o f an x-ra y fluorescenc e base dmulti-meta l CEM S tha t trap s the metal s an ddeliver s the mt o the XR Fmodule . Spiking : Th e proces s o f introducin g metal s int o the effluen t strea mo r the samplin g stream . Transpor

tEfficiency : Th e percent o f metal tha

t i s transporte dfro mthe sampl e prob e t o a poin t a s clos e a s possibl e t

o the samplin g module . Upscal e Drift : Th e upscal e drif t i s the differenc e i n th

e reporte dvalu e fo r

the upscal e referenc e fro mit s valu e a t the las t calibration , divide db y the valu e a t th e las t calibration . It i s use dt o monito r

the stabilit y o f

th e x-ra y fluorescenc e analysis . X-Ra y Fluorescenc

e (XRF) Module : Th e portio n o f a n XR Fbase dmulti-meta l CEM S whic h identifie s an dmeasure s metal masse s o r concentration s usin g x-ra y fluorescence . 

### XR F Multi-Metal

s Continuou

s Emissio n Monitorin

g Syste m (CEMS) : Al l o f

the equipment

require dfo r

determinin g meta l concentration s usin g x-ra y fluorescenc e as a n analytica l technique . Th e syste mma y consis t o f severa l majo r

subsystem s includin g but not limite dto the followin g the sampl e interface , the x-ra y fluorescenc e module , diluen t module , datarecorder , samplin g modul e an dvolum e measurement module . Zer o Drift : Th e zer o drif

t i s the differenc e i n the CEM S reading s fo r the zer o referenc e fro m thei r value s afte r

th e mos t recent calibration , divide db y the emissio n limi t fo r eac h element .

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 4 o f 4

### 2. 0 Interferences , Safety, an d Equipmen

tRequirement

s 2.1 Are there any potential interferences for

my XRF

multi-metal

CEMS? There ma y b e interference s arisin g fro mthe x-ra y fluorescence analysis , th e trappin g media , o r fro mcondensatio n i n the effluen t gas . Chec k

wit h you r

multi-meta l CEM S manufacture r t o fin dout

more about

potentia l interferences . 2.2 What

do I need to know to ensure the safety of persons using PS- YY? Peopl e usin g PS-Y Y ma y be expose dt o hazardou s material , operationa l hazards , an d hazardou s site conditions . PS-Y Y doe s no t addres s al l the safety issue s associate dwit h it s use . It i s you r responsibilit y t o ensur

e the safety o f

person s usin g PS-YY . Som e helpfu l reference s may includ e the CEM S manual , th e CEM S manufacturer , other referenc e methods , an don-sit e safety regulations . 2.3 What

equipment

and supplies do I

need? 2.3.1 Equipment

for the CEMS 1 . Sampl

e interface : Thi s portio n o f the CEM S mus t

present asampl e o f

sourc e effluen t t o th e samplin g modul e tha

t i s directl y representativ e o r ca n b e correcte ds o a

s to b e representativ e o f source . T o accomplis h this , the sampl e interfac e ma

y contain , amon g other

things , heater s o r

heatin g systems , an d dilutio n air . 2 . Samplin

g module : Th e samplin g modul e mus t collec t an dtra p al l th e analyte s o f mteres t fro marepresentativ e sampl e o f stac k effluen t withou t significan t loss . Th e trappe danalyte s the n mus t b e presente dto the XR Fmodule . 3 . XR F module : Th e XR Fmodul e use s x-ra y fluorescence to determin e the mas s o r concentratio n o f

metal capture db y the samplin g module . 4 . Volum

e measuremen

tmodule : Thi s portio n ofth e CEM S measure s th e volume o f

sourc e effluen t

fro mwhic h th

e meta l analyte s were capture di n th e samplin g module . Thi s volum e alon g wit h the datafro mthe XR Fto determin e concentratio n o f

sourc e effluent . 5 . Diluen

tModule : I f

you r multi-metal s CEM S use s adiluen t suc h a s ai r o r nitroge n i t

i s adde dto th e effluen t sampl e an dmeasure dusin g the diluen t module . 6 . Qualit

y assuranc

e an d qualit y contro l materials : You r

multi-meta l CEM S mus t posses s th

e necessar

y equipment

t o perfor mdail y upscal e an dzer o checks . You r

multi-meta l CEM S mus t als o posses s the equipment to perfor ma dail y chec k

ofth e sampl e volum e a t norma l sampl e flo w rates . 7 . Dat a recorder : You r

XR Fmulti-meta l CEM S mus t b e abl e to recor dmeta l concentration s an dinstrumen t statu s signal s (flags) . Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 5 o f 52.3.2 Other Equipment

Needed for the Performance Specification Test PS-Y Y doe s no t

specif y al l th e equipment

an dsupplie s necessar

y fo r th e performanc e specificatio n tests . Some o f thi s informatio n i s include di n th e applicabl e referenc e method s (e.g. , Metho d2 9 o r an acceptabl e alternative) . 2.4 What

regents and

standards do I

need? 2.4.1 Zero Drift

Reference You r multi-metal s CEM S mus t includ e astandardfo r

th e measurement

o f th e dail y zer o drift . Thi s referenc e shoul dproduc e aCEM S respons e indicatin g th e absenc e o f metals . I f

thi s i s no t

feasibl e thi s standardshoul dproduc e avalu e betwee n zero an d 20 % ofth e emissio n limi t fo r a t leas t tw o element s measure db y you r XR Fmulti

metal s CEM S whe n the instrument i s operatin g appropriately . 2.4.2 Upscale Drift

Reference Th e referenc e fo r

the upscal e drif

t chec k shoul dgenerat

e arespons e fo r

a t leas t on e metal fro meac h conditio n use di n th e XR Fanalysis . Thi s respons e mus t b e a t leas t 8 0 percent o f th e emissio n limit . 2.4.3 Volume Drift

measurement

device Durin g the initia l performanc e specificatio n tes t th e volum e measurement mus t b e compare do n adail y basi s agains t a n interna l volume o r

flo w measurement

device . Thi s volum e o r

flow measuremen

t devic e mus t

b e calibrate dindependentl y o f th e sampl e volum e o r

flo w measuremen

t devic e an dmus t

b e a s accurate o r

mor e accurate tha n the sampl e volum e o r flow measurement

device . 2.4.4 X-ray Fluorescence Calibration Check Standards You r XR Fmulti-metal s CEM S mus t includ e amean s o f

checkin g the x-ra y fluorescence calibratio n agains t an externa l standard . NIS T traceabl e thi n film standard s ar

e a n exampl e o f

asuitabl e x-ra y fluorescence calibratio n chec k standard . 

### 3 . 0 Performanc

e Evaluation Procedure s an d Reporting 3.1 What

is the purpose of

the initial

performance specification tests and what is required to perform the tests? Th e purpos e o f

th e initia l performanc e specificatio n test s i s t o detennin e th e bias , precision , stability , an dcycl e tim e o f you r multi-meta l CEMS .

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 6 o f 63.1.1 Pretest Preparation Prio r to the star

t o f you r initia l performanc e specificatio n test s yo u mus t b e sur e tha t you r CEM S i s installe daccordin g to th e specification s lai dout i n thi s document . Afte r installin g you r

XR Fmulti-metal s CEM S w e recommen dtha t yo u us e th

e CEM S fo r

a perio do f tim e t o familiariz e yoursel f wit h it s operation . W e als o recommen dtha t yo u conduc t dail y check s ofth e zer o an dupscal e drif t to verif y tha t the instrument

i s functionin g properly . Whe n yo u ar e confiden t

tha t th e instrument

i s performin g satisfactoril y i t

i s tim e t o prepar

e fo r th e initia l performanc e specificatio n tests . 3.1.2 X-ray Fluorescence Calibration Check I f you r CEM S measure s mor

e metal s fo r

complianc e purpose s than wil l b e evaluate d durin g the CEM S accurac y testin g describe dlate r i n thi s document

yo u mus t

perfor ma calibratio n chec k

o f the x-ray fluorescenc e modul e fo r thes e additiona l metals . Durin g th e calibratio n chec k

yo u mus t

challeng e the x-ra y fluorescenc e modul e wit h astandard o r standard s fo r

eac h meta l measure db y you r XR Fmulti-meta l CEMS . Eac h metal mus t b e measure da

t leas t thre e time s an dthe erro r i s calculate daccordin g t o Equatio n 1 3 fo r

eac h measurement . Th e averag e erro r o f the thre e measurement s mus t b e les s tha

n 10 % o f

the calibratio n standard' s valu e fo r eac h metal , i f

no t you r CEM S may no t

b e properl y calibrated . Th e x-ra y fluorescenc e calibratio n chec k ma y occu r a t anytim e durin g the initia l performanc e specificatio n test. . 3.1.3 Stability - The 7-day Calibration Drift Tests Prio r t o th e star

t o f th e accurac y tes t

yo u mus t

perfor macalibratio n drif t tes t fo r a perio do f a t leas t seve n days . Th e purpos e o f thi s tes t i s t o verif y tha t the instrumen t operatio n i s stable . Durin g the calibratio n drif t tes t perio dyo u mus t

determin e th

e magnitud e o f

the zer o calibratio n drif t (as calculate di n Sectio n 4.2.9) , th e upscal e calibratio n drif

t (a s calculate di n Sectio n 4.2.8) , an dth e volume (o r flow) drif

t (calculate dusin g Equatio n 14 ) a t leas t onc e eac h day . Durin g the stabilit y test s n o adjustment s o r

calibration s ma

y b e made t

o the CEMS . Th e result s o f th e stabilit y tes t mus t b e reporte dalon g wit h the result s ofth e accurac y tests . 3.1.4 CEMS

Accuracy Th e accurac y o f

you r XR Fmulti-meta l CEM S ma y b e determine dusin g on e o f th e followin g fou r

options . 1 . Optio n A : Linearit y tes t o f th e entire CEM S 2 . Optio n B : Linearit y tes t o f th e XR Fan dsamplin g module s separatel y fromthe sampl e interface . 3 . Optio n C : Relativ e bia s tes t ofth e entire CEMS . 4 . Optio n D : Relativ e bia s tes t o f the XR Fan dsamplin g module s separatel y fromth e sampl e interface . Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 7 o f 7There ar e als o several option s fo r generatin g th e metal s tha t wil l b e analyze db y you r multi-meta l CEM S including , metal s tha t ar e generate da

s aby-produc t

o f nonna l stac k operation , quantitativ e spiking , an dnon-quantitativ e spiking . Regardles s o f the generatio n optio n yo u choos e yo u mus t b e abl e to produc e concentration s fo r some o f the analyte s o f

interes t a t 8 0 t o 120 percent

o f the emissio n limit . Al l o f the CEM S and referenc e metho dmeasurement s mus t b e conducte dwhil e samplin g flu e gas . Yo u d o no t

nee dto tes t

ever y meta l tha

t you r CEM S measures , however , yo u mus t generat e a t leas t on e meta l fro meac h category o f metal s measure db y you r CEM S fo r th e accurac y tests . Fo r

instance , i f

you r XR Fmulti-metal s CEM S measure s semi

volatile , lo w volatile , an dhig h volatil e metal s yo u mus t tes t a t leas t one meta l fro m eac h o f thos e categories . (Lo w volatil e metal s may als o b e use dt o verif y th e capture efficienc y an ddetectio n o f non-enumerate dmetals) . Yo u mus t als o prov e tha

t th e X R Fmodul e i s properl y calibrate dt o measure th e element s tha t ar e not bein g measure ddurin g the accurac y tes t b y followin g the procedure s describe di n Sectio n 3.1.2 . Th e tes t

requirement s fo r

eac h optio n ar

e explainedbelo w an dsummarize di n Tabl e 1 .

• Linearit

y Tes tRequirement

s (Option

s A an d B) : Th e bia s an dprecisio n o f you r XR Fmulti-metal s CEM S ma y b e determine db y checkin g the linearit y o f th e instrument

respons e ove r

aserie s o f

concentrations . I f

quantitativ e spikin g i s used , the n the concentratio n o f th e aeroso l i s paire dwit h areporte dCEM S concentratio n acquire da t the sam e time . Eac h datapoin t i s then plotte dwit h th e spike dconcentratio n o n th e X axi s an dthe reporte dCEM S concentratio n o n th e Y axis . I f

either non-quantitativ e spikin g o r stac k b y produc t

i s used , the n th e reporte dCEM S concentratio n i s plotte do n the Y axi s versu s th e concentratio n reporte db y metho d2 9 o r asuitabl e alternative . Linea r leas t square s regressio n analysi s i s the n use dto fi t the dat apoint s to a line . I f yo u challeng e onl y the XR Fmodul e an dthe samplin g modul e th e slop e o f thi s line , whic h i s an indicatio n o f the accurac y o f

you r XR Fmulti-meta l CEMS , i s require dt

o b e betwee n 0.8 5 an d1.1 5 fo r eac h metal . Th e coefficien t o f correlatio n mus t

b e greate

r tha n 0.9 0 an di s a

n indicatio n ofth e precisio n o f you r multi-meta l CEMS . Finally , the intercep t o f thi s bes t fit lin e mus t b e les s tha n 20 % ofth e applicabl e emissio n limit . I f yo u challeng e the entir

e CEM S syste man dd o no t

mee t the slop e o r

intercep t criteri ayo u mus t

appl y a correctio n facto r

accordin g t o the procedure s i n Sectio n 4.2.12 . Yo u are , however , stil l require dt o hav e acorrelatio n coefficien t o f 0.9 0 o r greater . T o perfor mth e linearit y tes t yo u mus t

b e abl e t o generat e a t leas t thre e concentratio n level s fo r on e meta l fro meac h clas s o f metal s (hig h volatile , lo w volatil e an dsemi-volatile ) measure db y you r CEMS . Th e thre e level s mus t incorporat e a

t leas t atw o fol dconcentratio n chang e an don e leve l mus t b e betwee n 8 0 an d12

0 percen t o f th e emissio n limit . Yo u ma y acquire ablan k sampl e i f yo u wish , either

b y samplin g ambient

air , o r b y operatin g the sourc e i n suc h awa y tha

t metal s ar

e no t produce d(e.g. , burnin g onl y natural gas) . A t

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 8 o f 8leas t thre e measurement s ar

e require da

t eac h concentratio n leve l an datota l o f 1 5 measurement s ar

e require doverall . Yo u may make additiona l measurements , however , yo u mus t repor t al l th e results . I f

yo u ar e no t usin g quantitativ e spikin g yo u mus t mak e 1 5 correspondin g measurement s usin g metho d2 9 or

asuitabl e alternative . W e recommen dusin g due l train s fo r the referenc e metho dmeasuremen t to identif

y an dscree n th e referenc e metho ddata fo r imprecisio n an dbias . Additiona l requirement s fo r eac h ofth e tw o linearit y tes t option s ar

e outline d below . Yo u ma

y als o want

to refe r to figure s 1 throug h 8 fo r guidanc e o n whic h optio n t

o choose . 

### Optio n A : Tota

l CEM S Linearit

y In optio n A th e entir

e CEM S syste mi s challenge ddurin g the linearit y tests . An y on e o f

th e thre e method s o f

metal s generatio n may b e use ddurin g th e test . Some ofth e testin g requirement s associate dwit h metal s generatio n ar e outline d belo w 1 . Metal s generate da

s aresul t o f stac k operatio n I f metal s fo r

th e tes t ar e generate da

s aresul t o f stac k operatio n yo u mus t measur e th e concentratio n ofth e metal s i n the stac k usin g metho d2 9 or

a suitabl e alternativ e an dcompare the value s wit h thos e reporte db y you r CEMS . W e recommen dusin g dua l referenc e metho dtrain s t o scree n the referenc e metho dfo r

precisio n an dbias . 2 . Non-quantitativ e spikin g Yo u may either

spik e non-quantitativel y int o the stac k or duc t itsel f o r int o th e transpor

t syste ma

s clos e as possibl e t o the sampl e probe . I f yo u spik e int o the sourc e yo u mus t measur e th e concentratio n i n the sourc e usin g metho d2 9 o

r asuitabl e alternative . Thi s measurement i s the n compare dt o th e resul t o f you r CEMS . I f

yo u choos e t o spik e int o th e transpor t lin e yo u mus t measur e th e concentratio n immediatel y downstreamo f th e spik e poin t wit h ametho d2 9 o r

asuitabl e alternativ e an dcompare tha t measuremen

t wit h th e concentratio n reporte db y you r CEMS . 3 . Quantitativ e Spikin g Yo u may spik e aquantitativ e aeroso l directl y int o the sourc e o r int o th e transpor t lin e as clos e as possibl e to sampl e probe . Eithe r way th e know n spike dconcentratio n i s compare dwit h tha t measure db y th e CEMS . 

### Optio n B : Linearit

y forSamplin

g an d XR F Module

s Onl y I n optio n B onl y th

e samplin g an dXR Fmodule s o f you r mult i metal s CEM S ar e challenge dwit h alinearit y test . Yo u mus t als o complete atranspor t efficienc y tes t

alon g wit h the linearit y test . Th e procedure s fo r perfomiin g a transpor t efficienc y tes t

ar e describe di n sectio n 3.1.5 . Th e procedure s fo r optio n B associate dwit h eac h metal s generatio n optio n ar e liste dbelow . 1 . Metal s generate das aresul t o f stac k operatio n

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 9 o f 9 

### VE S 00069 6I f metal s concentration s fo r the accurac y tes t

ar e generate da

s aresul t o f stac k operatio n yo u mus t

measur e the concentratio n o f

th e metal s a

s clos e as possibl e to th

e samplin g modul e usin g metho d2 9 o r asuitabl e alternativ e an dcompare the value s wit h thos e reporte db y you r CEMS . W e recommen d usin g dua l referenc e metho dtrain s to scree n the referenc e metho dfo r precisio n an dbias . 2 . Non-quantitativ e spikin g Yo u may either

spik e non-quantitativel y int o th e stac k o r duc t itsel f o r int o the transpor

t system . Eithe r

wa y yo u mus t

measur e the concentration s o f

th e analyte s a

s clos e a s possibl e to the samplin g modul e an dcompare tha t concentratio n wit h tha

t reporte db y you r

mult i meta l CEMS . 3 . Quantitativ e Spikin g Yo u mus t

spike a t alocatio n as clos e a

s possibl e t o the samplin g modul e an d compar e th e know n spike dconcentratio n wit h tha t reporte db y you r

CEMS .

• Relativ

e Bia s Tes tRequirement

s (Option

s C an d D) : There ar

e tw o relativ e bia s option s available : on e tha t challenge s the entire CEM S an don e tha t challenge s th

e samplin g an dXR Fmodule s separatel y fro mthe sampl e interface . Eithe r

optio n require s a

t leas t 1 2 CEM S measurement s b e made a t a concentratio n leve l 8 0 t o 12 0 percent o f the emissio n limi t

fo r ameta l fro m eac h categor

y o f metal s analyzedb y you r XR Fmult i meta l CEMS . I f yo u ar e no t usin g quantitativ e spikin g yo u mus t als o hav e a

t leas t 1 2 correspondin g run s o f metho d2 9 o r

asuitabl e alternativ e a

t thi s concentratio n level . W e recommen dusin g dua l train s fo r the referenc e metho dt

o scree n th e dat afo r imprecisio n an dbias . Additionally , fo r

a t leas t on e meta l measure da

t the emissio n limi t

o r fo r a surrogat e metal tha

t ca n b e measure db y you r CEM S (suc h as iron ) yo u mus t tes t th e CEM S a

t thre e differen t

concentratio n levels . Thes e thre e level s mus t incorporat e a

t leas t atwo-fol dchang e i n concentratio n an don e o f th e level s mus t b e between 8 0 an d120 percen t o f the emissio n limi t

(the concentratio n o f th e emissio n limi t

fo r th e surrogate metal i s equa l t o tha t fo r the metal measure d b y you r CEM S wit h the highes t emissio n limit) . Yo u ar e require dt

o obtai n a

t leas t thre e measurement s a

t eac h concentratio n leve l an dar e require dto hav e a tota l o f a t leas t 1 2 measurements . Yo u mus t repor t the result s o f

al l measurements . Th e relativ e bia s i s a n indicato r

o f accurac y an dshoul db e calculate dusin g equatio n 5 fo r eac h element . Also , th e percent relativ e standar ddeviation , whic h i s a n indicato r o f precision , shoul db e calculate dfo r each meta l Ifyo u challeng e the entire CEM S syste man dyo u d o no t mee t the tes t criteri a yo u may appl y acorrectio n facto r to you r CEM S data . Calculat e acorrectio n facto r fo r eac h metal i n th

e relativ e bia s test

accordin g t o the equatio n foun di n sectio n 4.2.13 . I f

yo u challeng e the samplin g andXR Fmodule s separatel y fro mth e sampl e interfac e yo u ma y no t appl y acorrectio n facto r t o the data

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 0 o f 1 0 

### VE S 00069 /fro mthe relativ e bia s test , yo u may , however , appl y acorrectio n facto r t o the result s o f the transpor

t efficienc y test . Fo r

the meta l tha

t wa s spike dove r several concentration s yo u mus t perfor mlinea r

leas t square s regressio n analysi s o n the data . Th e correlatio n coefficien t fo r thi s fi t mus t b e bette r tha n 0.90 . Thi s i s t o demonstrat

e tha t the instrumen t

respons e i s vali dove r

it s applicabl e range . I f the criteri afo r

thi s tes t i s me t the n the correctio n factor s ar e assume d t o b e vali dove r

th e rang e o f

the instrument . Optio n C I n accurac y tes t

optio n C the entire CEM S i s subjecte dto arelativ e bia s test . Th e option s fo r

metal s generatio n an dth e associate dspikin g an dreferenc e metho drequirement s ar e the sam

e a s thos e fo r

Optio n A under

the linearit y tests . Optio n D I n accurac y tes t

optio n D onl y th e XR Fan dsamplin g module s ar e subjecte dt o arelativ e bia s test . Th e option s fo r metal s generatio n an dthei r associate d spikin g an dreferenc e metho drequirement s ar e the sam

e a s thos e fo r

Optio n B . Yo u ar e als o require dto perfor matranspor t efficienc y test . 3.1.5Transport

Efficiency Test Yo u mus t

perfor matranspor

t efficienc y tes t

i f yo u hav e onl y challenge dthe samplin g andXR Fmodule s durin g th e accurac y test s (option s B an dD) . An y one ofth e fou r method s describe dbelo w ar e vali dway s o f

determinin g percent

transpor t fo r you r multi-metal s CEMS .

• Particulat

e Matte r (PM) : I n thi s approac h particulat e matte r i s measure d concurrentl y i n tw o locations , (1 ) i n the stac k effluen t strea ma s clos e a s possibl e t o you r

multi-metal s CEM S sampl e interface , an d(2 ) a t apoin t i n th e transpor t syste ma

s clos e a s possibl e t o the samplin g module . Yo u ma y us e an y standardreferenc e metho dto measur e P M includin g Metho d5 , Metho d5i , o r Metho d1 7 (4 0 CF R60 , Appendi x A) 3 ' 4 ' 5 . Particulat e matter mus t b e generate d b y operatin g th

e source . Yo u mus t

acquir e a

t leas t 1 2 paire dconcentratio n measurement s (eac h pai r consist s ofth e measurement made a s clos e as possibl e to the sampl e interfac e andthe measurement mad e a s clos e a s possibl e t

o th e samplin g module . Th e percent transmissio n i s calculate dfo r each pai r

usin g equatio n 6 an dthe overal l percent transmissio n i s determine db y calculatin g the averag e o f

al l twelv e runs . • Elemen

to f opportunity : Alternatively , transpor t efficienc y can b e detennine d usin g asurrogat

e metal suc h as iro n o r

zin c tha t i s commonl y present

i n stac k effluent . Metho d2 9 (4 0 CF R60 , Appendi x A) 6o r asuitabl e alternativ e ca n b e use dt o measur

e the meta l concentratio n i n the stac k effluen t strea mas clos e a

s possibl e t o th

e sampl e prob e an da

t apoin t i n the transpor

t syste mas clos e as possibl e t o the samplin g module . Also , i f you r XR Fmulti-metal s CEM S i s

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 1 o f 1 1capabl e o f measurin g the element

o f interest , yo u ma y compare th e measure d concentratio n o n the CEM S wit h tha t measure di n the stationar y sourc e usin g the referenc e method . Transpor t efficienc y i s calculate dusin g equatio n 6 . Yo u ar e require dt o mak

e a t leas t twelv e paire dconcentratio n measurement s t o determin e the mea

n transpor

t efficiency . • Non-quantitativ

e spiking : A n aeroso l containin g asurrogat e meta l o r

ameta l analyte ca n b e spike dnon-quantitativel y int o the stac k o r duc t ga s strea mo r int o the transpor

t syste mas clos e a s possibl e t o the samplin g probe . Th e concentratio n o f

the spike dmetal i s measure db y metho d2 9 (4 0 CF R60 , Appendi x A) 5 o r

asuitabl e alternativ e as clos e as possibl e to th e CEMS ' sampl e prob e an db y another

Metho d2 9 o r

asuitabl e alternativ e as clos e a s possibl e to th e samplin g module . Ifyo u spik e directl y int o the transpor t lin e yo u mus t mak e you r upstreamconcentratio n measurement as clos e a

s possibl e t

o the spike locatio n an dyou r

downstreammeasuremen t a s clos e a s possibl e to the samplin g module . I f

you r XR Fmulti-metal s CEM S i s capabl e o f measurin g th e spike dmetal , yo u may compar e it s reporte dconcentratio n wit h th e i n sourc e metal s measurement

o r wit h th e upstreami n transpor

t lin e measuremen

t t o calculat e transpor

t efficienc y accordin g t o equatio n 6 . Yo u ar e require dto mak e a t leas t twelv e paire dconcentratio n measurement s t o determin e the mean transpor t efficiency .

• Quantitativ

e Spiking : A n aeroso l containin g asurrogate meta l o r ameta l analyte ca n b e spike dquantitativel y int o th e stac k o r duc t ga s strea mo r int o th e transpor t syste ma

s clos e as possibl e to the samplin g probe . Th e concentratio n ma y be measure do n the CEM S o r b y usin g metho d2 9 o r

asuitabl e alternativ e a s clos e a s possibl e t o the samplin g module . Thi s measurement i s the n compare dwit h th e know n concentratio n ofth e spike daeroso l t o determin e th e percent transport . 3.1.6 Dual Train Requirements Ifyo u us e areferenc e metho d(eg. , metho d2 9 o r 5i ) durin g th e linearity , relativ e bias , or transpor t efficienc y test s i t

i s recommende dtha

t yo u us e dua l train s t

o scree n the referenc e metho dfo r

bia s an dimprecision . 3.1.7 Cycle Time Requirements Th e cycl e tim e fo r

you r XR Fmulti-metal s CEM S shoul db e n o greate r tha n one-thir d o f the averagin g perio dfo r the applicabl e standard . Durin g al l phase s o f the performanc e specificatio n tes t includin g th

e CEM S mus t

us e the sam

e cycl e tim e a s wil l b e use ddurin g day t o da y operation . 3.2 How do I

report the results of

the initial

performance specification test? Summariz e the result s o f the calibratio n drif

t an daccurac y test s i n tabula r form . Includ e al l dat asheets , calculations , an drecord s o f CEM S measurement s necessar y to substantiat

e th e performanc e o f

the CEM S an dany other device s o r

method s (e.g. , metho d29) . Th e CEM S

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 2 o f 1 2measurement s shal l b e reporte dto th e agenc y i n unit s o f ug/m 3 o n adry basis , correcte dt o 20°C . 

### 4. 0 Performanc

e Criteri a an

d Calculation

s 4.1 What

are the performance criteria for my XRF

multi-metals CEMS? Yo u mus t

demonstrat

e tha t you r XR Fmulti-meta l CEM S has adequat e stability , precision , accuracy , cycl e tim e an ddat areportin g capabilitie s t o determin e i f you r facilit y i s i n complianc e wit h metal emissio n standard s o r operatin g penni t

limit s as specifie di n applicabl e regulation s or permits . Yo u wil l demonstrat e thi s capacity b y showin g tha t you r X R Fmulti-meta l CEM S meet s th e followin g performanc e criteria . 4.1.1 7-day Drift

Check Criteria - Stability Upscal e Drift : Th e upscal e drif t a s calculate di n sectio n 4.2. 8 mus t b e les s than 15 % o f the origina l calibratio n valu e o f th e upscal e referenc e eac h da y fo r seve n consecutiv e days . Zer o Drift : Th e zer o drif

t a s calculate di n Sectio n 4.2. 9 mus t b e les s than 20 % o f

th e emissio n limi t

each day fo r

seve n consecutiv e days . Volum e o r Flo w Drift : Th e volum e o r flo w drif

t as calculate di n Sectio n 4.2.1 1 mus t b e les s then 20 % o f

th e ful l scal e valu e o f

th e flo w o r

volum e measuremen

t devic e eac h da y fo r seve n consecutiv e days . 4.1.2 X-Ray Fluorescence Calibration Drift Criteria Fo r eac h metal measure db y you r multi-meta l CEM S fo r complianc e purpose s the x ra y fluorescenc e calibratio n drif t mus t b e les s tha

n 10 % o f

the valu e o f

the standard . (Note : yo u ar

e not require dto calculat e the XR Fcalibratio n drif t fo r thos e metal s use d durin g th e bia s andprecisio n testing) . 4.1.3 Relative Bias Criteria - Accuracy and Precision Th e relativ e bia s o f

th e instrumen t

mus t b e les s tha

n 15 % an dthe relativ e percent standarddeviatio n (RSD ) mus t b e 10 % o r

les s i f yo u challeng e the XR Fan dsamplin g module s o f

you r CEM S separatel y fro myou r transpor t system . I f

yo u challeng e you r entir e CEM S andi t

doe s no t meet the abov e relativ e bia s criteri ayo u mus t appl y a correctio n facto r

t o the result s reporte db y you r CEMS . Th e correctio n facto r i s calculate dusin g th e equatio n i n sectio n 14.2.13 . Also , th e correlatio n coefficien t fo r a leas t square s linear

regressio n fit

o f the meta l tha

t wa s spike da

t thre e differen t concentratio n level s mus t b e greater

than 0.90 . Thi s i s t o hel p assur e tha t th e correctio n facto r

i s applicabl e ove r

the rang e o f

the instrument .

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 3 o f 1 34.1.4 Linearity Test Criteria Accuracy and Precision Ifyo u choos e to d o linearit y test s to determin e the accurac y an dprecisio n o f you r XR F multi-metal s CEM S the slop e o f th e leas t square s linear

fi t shoul db e betwee n 0.8 5 an d 1.15 . Th e correlatio n coefficien t mus t b e 0.9 0 o r

better an dth e intercep t

shoul db e les s than 20 % o f

th e applicabl e emissio n limit . I f yo u challeng e onl y th e XR Fmodul e an d th e samplin g modul e o f you r CEM S yo u mus t

meet th e abov e criteria . I f

yo u challeng e you r

entir e CEM S an dyo u d

o no t meet th e slop e o r

intercep t criteri ayo u mus t adjus t th e result s reporte db y you r CEMS , yo u mus t

however , stil l meet

th e correlatio n coefficien t

criteria . Th e correctio n facto r i s calculate daccordin g to the procedure s i n sectio n 4.2.12 . 4.1.5Transport

efficiency - Accuracy I f th e averag e transpor

t efficienc y i s between 9 0 an d11 0 percent , then n o correctio n fo r transpor t efficienc y need s t

o b e applie dt

o concentration s reporte db y you r XR F multi-metal s CEMS . If , however , you r averag e transpor

t efficienc y i s les s than 9 0 percent o r more tha n 11 0 percent

the n yo u mus t

us e acorrectio n factor . Yo u ma y us e you r transmissio n efficienc y tes t dat ato establis h acorrectio n facto r tha t woul dchang e th e reporte dCEM S concentration s fo r eac h meta l t

o avalu e tha

t woul dreflec t

100 % transmissio n efficiency . 4.1.6 Cycle time - Appropriate Reporting Th e cycl e tim e fo r

you r XR Fmulti-metal s CEM S mus t b e n o greate

r tha n one-thir do f th e averagin g perio dfo r

th e applicabl e standard . 4.2 What

calculations, equations, and data analyses are needed? 4.2.1 Arithmetic Mean Calculat e th e arithmeti c mean o f adatase t a s follows . 

### Equatio n 1 Wher e : x Arithmeti c mean n Numbe r

o f datapoint s Valu e o f eac h datapoin t

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 4 o f 1 44.2.2 Arithmetic Mean of Difference T o calculat e th e arithmeti c mean o f differenc e us e th e abov e equatio n substitute dfo r x. Wher e

D . _ (JCEMS _ R R M



### Equatio n 2 Where :

c cms =j^e concentratio n o f th e i t helement

as reporte db y the CEM S

R RM _concenn -atio n o f the i t helement

as reporte db y the referenc e metho do r

areso l 4.2.3 Standard

Deviation (of

differences) 

### Equatio n 3 Where : SDi = Th e standarddeviatio n o f difference s fo r

the i * element n = Th e numbe r o f dat apoint s di = Th e differenc e betwee n the concentratio n measure db y the referenc e metho do r

the concentratio n o f

th e referenc e aeroso l an dthe concentratio n reporte db y th e CEMS . 4.2.4 Percent

relative standard

deviation 

### SD Equatio n 4 PRSD, ==i x 10 0

R m Where : Rf M = Th e averag e o f the referenc e metho ddatase t o r the referenc e aeroso l concentratio n fo r the i t helemen

t PRSD, = Th e relativ e percent standarddeviatio n fo r

the i t hmeta l 4.2.5Relative Bias



### TM < = 

### lbif x10 0

### Equation s Ri

Specification s fo rXR F Base d Multi-Metal s CEM S (PS-YY ) Pag e 1 5 o f 2Wher e di i s th e mea n difference , Rf M i s th e averag e ofth e referenc e metho d dat ase t or the averag e aeroso l concentratio n fo r th e i t helement , an dPRBi i s the relativ e bia s fo r

th e i * element 4.2.6 Percent

Transmission PT =-VxlO O 

### Cf Equatio n 6 Where : Cf = Concentratio n o f the i t helement

a t th e stac k C-"'= Concentratio n o f th e i t helemen

t a t the samplin g modul e o r a s reporte db y th e XR Fmulti-metal s CEMS . PT. = Th e percent

transpor t o f th e i t helement Report the averag e percen t

transpor t (PT ) o f al l measurement s fo r

eac h element tha t wa s teste d(only on e element i s require dthoug h mor e ca n b e tested) . 4.2.7 Best Fit Line for Linearity Test Calculat e the linea r

correlatio n equatio n give n below . y = b 0 +b l x Equatio n 7 Where : b 0= Th e y intercep t b\ = Th e slop e Th e intercep t

i s calculate daccordin g to th e followin g equation . b 0 =y-b x x Equatio n 8 Where : 1 

# 2

> X n y Th e slop e o f

the lin e i s calculate daccordin g t o equatio n below .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 1 6 o f 3 01 ^ j ( x i -x)(y i - y )



### _ J^I Equatio n 9

Th e linea

r correlatio n coefficien t i s calculate daccordin g to th e followin g equation .

n ]T(x . -x)(y, -y) 

### 1 = 1 Equatio n 1 0 I ;= i /= i 4.2.8Upscale Drift Wceim _ja I 

### Equatio n 1 1 CZD . = —-xlO O Where : UD, = Th e upscal e drif t o f th e i * element

o n you r CEM S i n percent . jcemu = Th e measure( j CEM S respons e t o th e i l helement

i n the upscal e standard L" = Th e calibrate dvalu e o f the i t helement

o f th e upscal e standard

4.2.9Zero Drift 

### I Equatio n 1 2 ZD,. = ^—

—p^xlOO Cf ZDj= Th e zer o drif t o f th e i * element

o n you r CEM S i n percent jcemn _Tn e measure( j CEM S respons e t o the zer o standar dfo r the i 1 element L° = Th e calibrate dvalu e o f the i , helement

o n th e zer o standard Cf = Th e emissio n limi t o f th e i t helement 4.2.10X-Ray Fluorescence Calibration Accuracy

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 1 7 o f 3 0Wcem _jstd 

### I Equatio n 1 3 CA: —17-^x10 0

Lf Where : CA, = X-ra y fluorescenc e calibratio n accurac y U. m= Th e valu e o f th e standardreporte db y you r CEM S Lf - Th e know n valu e o f th e standard 4.2.11 Daily Sample Volume Check VD = \ Vcmr ~ Vm \ x10

0 Equatio n 1 4 FS Where : V D = Volum e drif t Vcemr=Sampl e ga s volume (o r flow ) measure db y th e CEM S volume chec k measurement

devic e V„, = Sampl e ga s volume (or flow ) reporte db y you r multi-meta l CEM S FS = Ful l scal e valu e o f the CEM S volum e (o r

flow ) measuremen

t devic e 4.2.12 Linearity Test

Correction Factors (Applicable only when the linearity test challenges the entire CEMS) 1 . Correctio n equatio n i f CEM S doe s no t

meet either the slop e or

the intercep t criteria .



### ~ ^ Equatio n 1 5 Where : Cf = correcte dCEM S concentratio n fo r th e 1 t h element y t = CEM S reporte dconcentratio n fo r the i t helement bo = the intercep t o f the leas t square s linear

regressio n lin e bi = the slop e o f

th e leas t square s linear

regressio n lin e 2 . Correctio n facto r

i f CEM S meet s intercep t

criteria , bu t

doe s no t mee t th e slop e criteria . Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 1 8 o f 3 0C, c =y,.-Z> 0Equatio n 1 6 3 . Correctio n facto r

i f CEM S meet s slop e criteri abu t doe s no t meet intercep t criteria . 

### Equatio n 1 7 4.2.13 Relative Bias Correction Factors



### j R 

### RM Equatio n 1 8 CF RB A N CEM

R RM Where : CFTM = Th e relativ e bia s correctio n facto r fo r the i t helement QCEM _

Tn e averag ereporte dconcentratio n o f th e CEM S fo r

the i element R f 4 = Th e averag e o f

th e referenc e metho dmeasurement s fo r the i t h meta l

4.2.14 Percent

transport

correction factor

D T

### lEquatio n 1 9 C F p r = = PT t Wher e CF^= Correctio n facto r fo r percent transpor t fo r th e i t helement PTj= Averag e percent transpor t fo r th e i t helement

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 1 9 o f 3 0

### 5. 0 Othe rRequirement

s an d Informatio

n 5.1 What

quality control

measures are required? Qualit y contro l measure s fo r a n XR Fmulti-meta l CEM S ar e addresse di n procedure Z "Qualit y Assuranc e Requirement s fo r X-Ra y Fluorescenc e Base dMulti-Metal s Continuou s Emissio n Monitors. " 5.2 What

calibration and

standardization procedures must I perform ? Refe r t o you r CEM S owner' s manual an dmanufacture r t o determin e wha

t calibratio n an d standardizatio n procedure s ar e require dfo r

you r multi-meta l CEMS . 5.3 What

pollution prevention procedures must Ifollow? [reserved] 5.4 What

waste management

procedures must

I use? A l l chemical s use dt o produc e areferenc e aeroso l o r i n performin g standardmethod s nee dt o b e dispose do f

properly . 5.5What

reference tables and

figures are relevant

to PS-YY?

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 0 o f 2 0

### Tabl e 1 . Initia l Performanc

e Speci i icatio n Test s an d Criteria Tes t Categor y Tes

t Tes

tRequirement

s Tes

tCriteria

Seve n Da y Stabilit y Zer o Drift Monito rzer o standar

d fo r 7 consecutiv

e day s unde r normal operating condition

s < 20 % drif tever y da y fo rseve

n consecutive day

s 

### Seve n Da y Stabilit y Upscal e Drift Monito rupscale standar d fo r 7 consecutiv

e day s unde r normal operating condition

s < 15 % drif tever y da y fo r seve

n consecutiv

e day s 

### Seve n Da y Stabilit y Flo w Drif t Monito rflo w drif tfo r 7 consecutiv

e days unde

r norma l operatin

g conditions < 20% drif tever y da y fo r seve

n consecutiv

e day s 

### Calibratio

n X-Ra y Fluorescenc e Calibratio n DriftChec k Tes ta standar d fo r eac

h elemen

t measure d fo rcompliance b y you r CEM S 3 time

s < 10 % drif tfo rever

y elemen

t measure d fo rcompliance b y you rCEM S



### Accurac y Optio n A Perfor m a linearit

y tes to n entir e CEM S • A tleas ton e meta l fro m eac

h categor y • Nee d a

tleas t3 concentratio

n level s whic

h include a 2 fol d cone , chang

e an d th e emissio n limi t • I f spiking , spik

e int o source , o r spik e int o transpor

tlin e a s clos e a s possible t

o th e prob e • Slop e = 0.8 5 t o 1.1 5 • r>0.9 0 • intercep

t< 20 % o f

emission limi t

• i f th e abov e criteri a ar

e me t the n n o correction • i f no tme tapply a correction (correlation criteri a mus tbe met )



### Accurac y Optio n B

• Perfor

m a linearit

y tes t o n samplin g module and XR F modul

e onl y • Determine transpor t efficienc y separatel

y • A tleas

ton e meta l fro m eac

h categor y • Need a

tleas t3 concentratio

n levels whic

h include a 2 fold cone , chang

e an d th e emissio n limi t • Spike o

rmeasur

e concentration

s wit h referenc

e method a

s clos e a s possible t

o th e sampling modul e Linearit y Criteri a • Slop e = 0.8

5 t o 1.1 5 • r>0.9 0 • intercep

t< 20 % o f

emission limi t • th e linearit

y criteri a mus

tbe me t Percen tTranspor

tCriteri a • 90<PT<11 0 • I f percen ttranspor

tcriteri a ar e no tme tappl y a correction facto r 

### Accurac y Optio n C Perform a relativ

e bia s tes t o n entir e CEM S • A tleas ton e meta l fro m eac

h categor y a t8 0 t o 12 0 percen

to f emission limi t • One othe

r meta l a t3 cone , level s whic h includ e a 2 fol d cone , chang e an d th e emissio n limi t • I f spiking , spik

e int o sourc e o r spike int o transpor

tlin e a s clos e a s possible t

o th e prob e Percen trelative Bias RB < 15 % %RSD < 10

% r> 0.9 0 fo rmeta

l wit h thre e fol d cone , chang

e • I f Criteri a no

tme tapply a correction facto r (correlation coefficien tcriteri a mus tbe met ) 

### Accurac y

Optio n D

• Perfor

m a relativ

e bia s tes to n sampling module an d XR F modul e onl y • Determine transpor t efficienc y separatel

y • A tleas

ton e meta l from eac

h categor y a t8 0 t o 12 0 percen to f emission limi t • One othe

r meta l a t3 cone , levels which include a 2 fol d cone , chang e an d th e emissio n limi t • Spike o

rmeasur

e concentration

s wit h referenc

e method a

s clos e a s possible t

o th e samplin g module Percen tRelativ e Bias Criteri a RB<15 % %RSD < 10

% r> 0.9 0 fo rmeta

l wit h thre e fol d cone , chang

e Percen tTranspor

tCriteri a • 90<PT<11 0 • I f percen ttranspor

tcriteria ar e no tme tappl y a correctio n facto r

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 1 o f 2 1

### Method s o f Metal s Generation fo r Accuracy Test

s

Quantitativ

e Spikin g Non Quantitativ

e Spikin g Stac k Operation Figur e 1 : Type

s o f metal s generatio

n availabl

e foraccurac

y tests .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 2 o f 2 2Quantitativ e Spikin g

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 3 o f 2 3Non-Quantitativ e Spikin g

Challeng e th e cniin c batc h Multi Mclal s System . N o independen t measur e o f transpor t efficiency . Y o u ca n challeng e th e samplin g modul e an d pollutan t analyse r portio n o f you rbutc h M M CiiM S separatel yrm m th e transpor t sy>tem , however , yo u wil l als o hav e t o determin e transpor t efficiency . No



# C Y o u ma yus e eithe r^"" V linearit ytestin g o r) relativ e bias . ^ / 

### Figur e 3 : Flo w char tfo rusin g non-quantitativ

e spikin g durin g th e accurac y tests .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 4 o f 24Metal s Generate d Durin g Stac k Operatio n

c d by . Ca n I generat

e 'concentration s a

t+/ - 20 % ofthe ' Emissio n Limi tfo r a meta l fro m

v cac h clas s o f

metal s mcasu i m y CEMS ? 

### Ye s N o

Yo u nee d t o us e a differen t melho d l o ceneral e metals .

N o • ( Yo u mus tus e relative bias .

Ye s

: :— \ Yo u ma y us e either linearit

y \ testing o r relative bias . J 

### Figur e 4: Flo w char tfo rusin g stac k operatio

n t o generat e metal s concentrations

. Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 5

### Transpor t Efficiency

1 

### r P M Measurmen

t Elemen to f Opportunit

y Figur e 5 : Specie

s availabl

e fortranspor

ttest s

Specification s fo rXR F Multi-Metal s CEM S (PS-YY )P M Measurnic m

Ye s 

# * Us e Metho d 5 , 5 i o r1 7 t o measur e P M cone , a

t (h o slac k an d a l you rCEMS . Calculat e transpor t efficiency .



### Figur e 6 : Procedur

e fo rpercen ttranspor

tusin g PM .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 7 o f 2 7 

### VE S 00071 4Compar e the concentratio n o n o r nea r th e CEM S wit

h the concentratio n measured a t th e stack . Calculat e transpor

t efficiency .

Y o u mus t establis h a correlatio n t o \ correc t fortranspor t efficiency . J

/ N o correctio n laclo ri s necessary . \ [ Yo u hav e complete d th e transpor t J V efficienc ytest . J 

### Figur e 7: Procedur

e forpercen

ttranspor

tdeterminatio

n usin g a n elemen to f opportunity

.

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 8 o f 2 8 

### VE S 00071 5. /Choos e Ncw \ N u \ Specie s J

Non-Quantitativ e Spik e

Selec t transpor t lin e o r N c * M Choos e Ne w Specie s Selec t I n Slac k o r H a * \ Choos e Ne w Specie :

. /ChooseNcw S Specie s J

Compar e th e concentratio n o n o rnea rth e CEM S wit h th e concentratio n measure d a t th e stack . Calculat e transpor t efficiency .

Y o u mus t establis h a correlatio n t o correc t fo r transpor t efficiency .

f N o correctio n facto ri s ^ ( necessary . Yo u hav e complete d V th e transpor t efficienc ytest . J 

### Figur e 8: Procedur

e o f percen ttranspor

tdeterminatio

n usin g spiking .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 2 9 o f 2 9 

### VE S 00071 65.6 What references apply to PS-YY? 1 . Unite dStates . Environmenta l Protectio n Agenc y [EPA] . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d1 : Sampl e an dVelocit y Traverse s fo r Stationary Sources . Washington , DC : EPA ; 2004 . Available : http://www.epa.gov/ttn/emc/promgate/m-01.pd f vi athe Internet . Accesse d Ma y 8 , 2005 . 2 Unite dStates . Environmenta l Protectio n Agenc y [EPA} . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d2 : Determinatio n o f

Stac k Ga s Velocit y an dVolumetri c Flo w Rate . Washington , D.C : EPA ; 2004 . Available : http://www.epa.gov/ttn/emc/promgate/m-02.pd f vi athe Internet Accesse dMa y 10,2005 . 3 . Unite dStates . Environmenta l Protectio n Agenc y [EPA] . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d5 : Determinatio n o f

Particulat e Matte r

Emission s fro mStationary Sources . Washington , DC : EPA ; 2004 . Available : http://www.epa.gov/ttn/emc/promgate/m-05.pd f vi athe Internet . Accesse dMa y 10 , 2005 . 4 . Unite dStates . Environmenta l Protectio n Agenc y [EPA] . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d5i : Determinatio n o f

Lo w Leve l Particulat e Matte r Emission s fro mStationar y Sources . Washington , DC : EPA ; 2004. Available : http://www.epa.gov/hwcmact/frhwc5.pd f vi a the Internet . Accesse dMa y 10 , 2005 . 5 . Unite dStates . Environmenta l Protectio n Agenc y [EPA] . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d17 : Determinatio n o f

Particulat e Matte r

Emission s fro mStationary Sources . Washington , DC : EPA ; 2004 . Available : http://www.epa.gov/ttn/emc/promgate/m-17.pd f vi athe Internet . Accesse dMa y 10 , 2005 . 6 . Unite dStates . Environmenta l Protectio n Agenc y [EPA] . Technolog y Transfe r Network . Emissio n Measuremen t Center . Promulgate dMethods . Metho d29 . Determinatio n o f

Metal s Emission s fro mStationary Sources . Washington , DC : EPA ; 2004 . Available : http://www.epa.gov/ttn/emc/promgate/m-29.pd f vi athe Internet . Accesse dMa y 18 , 2005 .

Specification s fo rXR F Multi-Metal s CEM S (PS-YY ) Pag e 3 0 o f 3 0 

### VE S 00071 7

# VE S 000718.pdf

# Procedur e Z : Qualit

y Assuranc

e Requirement

s fo r X-Ray-Fluorescenc

e Base d Multi-Metal s Continuou

s Emission Monitorin g System s a t Stationar y Source

s



# DRAF T Jun e 9 , 200 5

Submitte dto : Th e Environmenta

l Protectio

n Agenc y Researc h Triangl e Park , N C

Prepare dby : Coope r Environmenta

l Services

, LL C 1018 0 S W Nimbu s Blv dSuit e J 6 Portland , Orego n 9722 3

# Procedur e Z : Qualit

y Assuranc

e Requirement

s fo r X-Ray-Fluorescenc

e Base d Multi-Metal s Continuou

s Emission Monitorin g System s a t Stationar y Source s



# DRAF T Jun e 9 , 200 5

Prepare dby : 

### J.A . Cooper

, K . Petterson

, B.E . Johnsen

, C . A . Yanca, M . Nakanishi , D . Bart h

Prepare dby : 

### Coope rEnvironmenta

l Services

, LL C 1018 0 S W Nimbu s Blv dSuit e J 6 Portland , Orego n 9722 3

# Procedur e Z : Qualit

y Assuranc

e Requirement

s fo r X-Ray-Fluorescenc

e Base d Multi-Metal s Continuou

s Emission Monitorin g System s a t Stationar y Source s

Prepare d by : Date: _ Krag A . Petterson

, Environmenta

l Scientis t Reviewe d by : Date : Ca y A . Yanca, Environmenta l Scientis t Reviewe d by : Date : Bruc e E . Johnson

, Q A Manage

r Approve d by : Date : Joh n A . Cooper

, Directo r

### Executiv e Summar

y Procedure Z outline s th e continuin g quality contro l andqualit y assuranc e requirement s fo r

a n x-ra y fluorescence base dmulti-meta l CEMS . Procedure Z require s dail y check s o f

th e upscale , zer o andvolum e measurement drift . I t als o specifie s quarterl y check s o f th e x-ray fluorescenc e calibratio n an do f the volume measuremen t calibration . Finall y procedure Z require s tha t the entire XR Fmult i metal CEM S accurac y b e verifie do n a n annual basis .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e i o f i v 

### VE S 00072 1b 0 bi CA, Cf QCEMS QCEM CFf

7 CFTM Cf Cf C sm

d FS 

# A juemo

i f L u, n PT, 

### Lis to f Symbol s Th e y intercep t

o f the bes t fi t lin e Th e slop e o f

th e bes t fi t lin e X-ra y fluorescenc e calibratio n accurac y Correcte dCEM S concentratio n fo r th e i t helement Th e concentratio n ofth e i t helement as reporte db y th

e CEM S Th e averag e reporte dconcentratio n ofth e CEM S fo r th e i t helement Correctio n facto r

fo r percent transpor t fo r the i t helemen

t Th e relativ e bia s correctio n facto r fo r th e i l helemen

t Th e emissio n limi t

o f th e i t helement Concentratio n o f

the i t helement

a t th e stac k Concentratio n o f

th e i t helement

a t th e samplin g modul e o r a s reporte db y th e XR Fmulti-metal s CEMS . Differenc e betwee n tw o paire dmeasurement s Arithmeti c mea

n o f difference s Ful l scal e valu e o f

you r CEM S volum e (or

flow) measuremen

t devic e Th e calibrate dvalu e o f

th e i t belement

o n the zer o standard Th e valu e o f

the standardreporte db y you r CEM S Th e measure dCEM S respons e t o th e zero standardfo r

the i t helement Th e measure dCEM S respons e t o the i t helemen

t i n th e upscal e standard Th e know n valu e ofth e XR Fcalibratio n chec k standard Th e valu e ofth e i t helement o f the upscal e standard Numbe r o f datapoint s Th e percen t

transpor t ofth e i * element

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e i i o f i vPTi = Averag e percent transpor t fo r the i element PRBi = Percen t

relativ e Bia s o f

the i t helement Rf M = Th e averag e o f the referenc e metho dmeasurement s fo r the i t hmeta l PRSD, = Th e relativ e percen t standarddeviatio n fo r

the i' hmetal r = Th e correlatio n coefficien t SDi = Th e standarddeviatio n o f difference s fo r

the i t t lelement Vcemr= Sampl e ga s volum e (or

flow ) a s measure db y the CEM S volume chec k devic e VD = Volum e drif t V,„ = Volum e (o r flow) reporte db y you r multi-metal s CEM S UDj = Th e upscal e drif t o f the i t helement

o n you r CEM S i n percent . x = Arithmeti c mea n X, = Valu e o f eac h datapoin t Vi = CEM S reporte dconcentratio n fo r the i t helement ZD , = Th e zer o drif t o f th e i t helement

o n you r CEM S i n percent

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e ii i o f i v

### Table o f Content s Executiv e Summar

y i Lis t o f Symbol s i i Tabl e o f Content s i v 1.0 Usin g Procedur e Z 1 1. 1 Wha t i s the purpos e an dapplicabilit y o f Procedur e Z ? 1 1. 2 Wha t ar e the basi c requirement s o f Procedur e Z ? 1 1. 3 Wha t specia l definition s appl y to procedure Z ? 1 2. 0 Interferences , Safety , an dEquipmen t Requirement s 2 2. 1 Wha t interference s ar

e associate dwit h procedure Z ? 2 2. 2 Wha t do I nee dt o kno w to ensur e the safety o f

person s usin g Procedur e Z ? 2 2. 3 Wha t equipment

andsupplie s d

o I need ? 3 2. 4 Wha t reagent s an dstandard s do I need ? 3 2. 5 Wha t sampl e collection , preservation , storage , an dtranspor t procedure s ar

e relevan t t o Procedur e Z ? 4 3. 0 Qualit y Control , Calibration , an dStandardizatio n 4 3. 1 Wha t quality contro l measure s ar e require db y thi s procedure fo r m y multi-meta l CEMS ? 4 3. 2 Wha t calibratio n check s an daudi t procedure s mus t

I perfor mfo r

m y multi-meta l CEMS ? 4 4. 0 Calculation s 7 4. 1 Wha t calculation s an ddataanalysi s mus t I perform ? 7 4. 2 Wha t wast e managemen

t procedure s ar

e require dfo r

procedure Z ? 1 3 5. 0 Othe r

Requirement s an dInformatio n 1 3 5. 1 Wha t pollutio n preventio n measure s mus t I tak e whe n usin g procedure Z ? 1 3 5. 2 Wha t criteri aar

e necessar

y fo r m y XR Fmulti-meta l CEM S to b e i n contro l an d wha t d o I do i f

i t i s out o f control ? 1 3 5. 3 Wha t tables , diagram s an dflo w chart s ar e relevan t

t o Procedur e Z ? 1 6 5. 4 What reference s ar

e relevan t

to Procedure Z ? 1 8

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e i v o f i v

### 1. 0 Usin g Procedur

e Z /. 1 What

is the purpose and

applicability of

Procedure Z? Th e purpos e o f

Procedur e Z i s t o establis h the minimu mrequirement s fo r quality contro l (QC ) an dqualit y assuranc e (QA ) procedure s fo r x-ra y fluorescenc e (XRF ) base dmulti

metal s CEMS . Thes e quality contro l an dqualit y assuranc e procedure s ar e i n plac e t o ensur

e th e accurac y an dvalidit y o f the datareporte db y you r multi-meta l CEM S fo r emissio n complianc e purposes . Yo u mus t meet thes e minimu mrequirement s ifyo u pla n t o us e you r multi-meta l CEM S fo r

reportin g purposes , however , w e encourag e yo u t o develo p amore extensiv e Q A programo r t o continu e wit h suc h program s where the y already exist . An y XR Fmulti-metal s CEM S use dt o repor t t o us , th e state , o r

aloca l enforcemen t

agenc y mus t compl y wit h procedure Z immediatel y afte r the completio n ofth e initia l performanc e specificatio n tes t

outline di n Performanc e Specificatio n YY 1 . 1.2 What

are the basic requirements of Procedure Z? Procedure Z require s yo u to perfor mseveral drif t check s an daudit s whic h ensur e the accurac y o f

the datareporte db y you r XR Fmulti-metal s CEMS . Yo u ar e require dto , o n a dail y basis , recor dan dcalculat e zer o drift , upscal e drift , and , asampl e volum e drift . O n a quarterl y basi s yo u ar

e require dt

o perfor man XR Fcalibratio n audi t (XFCA ) an dasampl e volume audi t

(SVA) . O n an annual basi s yo u ar e require dt o execute either alinearit y audi t (LA ) o r arelativ e bia s audi t

(RBA ) and , i f

applicable , atranspor

t efficienc y audi t

(TEA) . Th e criteri afo r

passin g thes e audit s an ddrif t check s ar

e outline di n procedure Z . Procedur e Z als o summarize s th

e requirement s fo r

whe n an di f

you r CEM S fail s a

n audi t o r drif t test . Finally , Procedur e Z als o cover s th e requirement s fo r an dtimeline s associate dwit h period s whe n you r

XR Fmulti-metal s CEM S i s out o f control . 1.3 What

special definitions apply to procedure Z? Linearit y Audit : (LA ) A n assessmen t o f th e validit y ofth e origina l linear correlatio n o f you r CEMS . Referenc

e material : A materia l o f know n valu e use dto chec k the calibratio n drif

t o f you r X R Fmulti-meta l CEMS . Relativ e Bias : Th e differenc e betwee n areferenc e metho do r aeroso l concentratio n an dth e concentratio n recorde db y you r CEM S divide db y the concentratio n ofth e referenc e measurement . Relativ e Bia s Audit : (RBA ) A n assessmen t o f the bia s i n you r

CEMS . Sampl e Interface : Th e portio n o f the CEM S use dfo r

on e o r more o f the following : sampl e acquisitio n fro mthe stac k o r duc t effluent , sampl e transport , sampl e conditioning , o r protectio n ofth e monito r fro mth e effect s o f

stac k gas .

Qualit yAssuranc e fo rXR F -Base d Multi-Meta l CEM S (Procedur e Z ) Pag e 1 o f 1Sampl e Module : Th e portio n o f th e XR Fmulti-meta l CEM S tha t trap s the metal s an d deliver s the mt o th e x-ra y fluorescenc e module . Standar d Volum

e Audit : (SVA ) Thi s i s an evaluatio n o f you r XR Fmulti-metal s CEM S sampl e volum e measurement system . Thi s i s require di f you r CEM S use s avolum e measuremen

t t o repor t meta l concentration s an di s accomplishe db y comparin g the volume measure db y you r

CEM S wit h the volume measure db y an independentl y calibrate ddevice . Transpor

tEfficienc

y Audit : (TEA ) A n assessmen t o f the transpor

t efficienc y o f

the sampl e interfac e o f

you r multi-metal s CEMS . Thi s audi t applie s t o you r

XR Fmulti-metal s CEM S i f either th e RB A or

L A challenge donl y the samplin g an dXR Fmodules . Transpor

tSystem : Th e portio n ofth e CEM S tha t transport s arepresentativ e sampl e o f sourc e effluen t

fro mthe sampl e prob e t o th e sampl e module . X-Ra y Fluorescenc

e Calibratio

n Audit : (XFCA ) Thi s i s an evaluatio n o f ho w wel l th e x ra y fluorescence portio n o f you r multi-metal s CEM S ha s maintaine dit s origina l calibration . Thi s i s accomplishe db y challengin g the XR Fmodul e wit h astandar do f know n concentratio n fo r

eac h metal measure db y you r CEM S fo r

compliance . Th e analyze r respons e i s compare dwit h the know n concentratio n ofth e standard . X-Ra y Fluorescenc

e Module : Th e portio n o f a n XR Fbase dmulti-meta l CEM S whic h identifie s an dmeasure s metal masse s o r concentration s usin g x-ra y fluorescence. XRF Multi-Metal

s Continuou

s Emissio

n Monito

r (CEMS) : Al l o f

th e equipment

require d fo r determinin g meta l concentration s usin g x-ra y fluorescence a s a n analytica l technique . The syste mma

y consis t o f severa l majo r

subsystem s includin g the sampl e interface , th e x ra y fluorescenc e module , the volume measuremen t module , diluen t

analyzer , datarecorder , andsamplin g module . 

### 2. 0 Interferences , Safety, an d Equipmen

tRequirement

s 2.1 What

interferences are associated with procedure Z? There may b e interference s arisin g fro mth e x-ray fluorescence , th e trappin g media , o r

fro m condensatio n i n th e effluen t gas . Chec k

wit h you r

multi-meta l CEM S manufacture r t o fin d ou t more about

potentia l interferences . 2.2 What

do I need to know to ensure the safety of persons using Procedure Z? Person s usin g procedure Z ma y b e expose dto hazardou s materials , equipment , an d operations . Procedur e Z doe s no t purpor t to addres s al l ofth e safety issue s associate dwit h it s use . I t i s you r responsibilit y t

o establis h appropriate safety an dhealt h practice s befor e usin g thi s procedure . Yo u may consul t wit h you r

CEM S manua l and/o r

manufacture r

fo r precaution s specifi c to you r multi-meta l CEMS . I f

standardreferenc e method s ar e use dthe n yo u ma y als o consul t

th e appropriate referenc e method s to addres s safety concerns .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 2 of 22.3 What equipment

and supplies do I

need? [reserved ] 2.4 What

reagents and

standards do I

need? Referenc e material s fo r th e zer o an dupscal e drift s alon g wit h areferenc e measurement devic e fo r

the sampl e volume check . 2.4.1 Zero drift

reference Ever y XR Fmulti-metal s CEM S mus t b e equippe dwit h azer o referenc e tha t can b e checke do n adail y basis . Thi s referenc e shoul dproduc e aCEM S respons e indicatin g th e absenc e o f

metals . I f

thi s i s no t

feasibl e thi s standardshoul dproduc e avalu e betwee n zer o an d20 % o f th e emissio n limi t

fo r a t leas t tw o element s measure db y you r X R Fmulti-metal s CEM S whe n the instrument i s operatin g appropriately . 2.4.2 Upscale drift

reference Th e referenc e fo r

the upscal e drif

t chec k shoul dgenerat

e arespons e fo r

a t leas t one metal fro meac h conditio n use di n th e XR Fanalysis . Thi s respons e mus t b e a t leas t 8 0 percent o f the emissio n limit . 2.4.3 Sample volume or flow check I f you r XR Fmulti-metal s CEM S make s volum e o r flo w measurement s i t

mus t b e equippe dto perfor madail y sampl e volume check . 2.4.4 Sample volume audit standard I f you r XR Fmulti-metal s CEM S make s volum e o r flo w measurements , periodi c standardvolume o r

flo w audit s mus t

b e performed . A n independentl y calibrate d volum e o r

flo w measurement

devic e o r

standar dsuc h a s aDr y Cal ® i s require dfo r thes e audits . Th e standardmus t b e abl e to acquir e avolume o r flo w measuremen

t a t samplin g rate s typica l o f you r XR Fmulti-metal s CEMS . 2.4.5X-ray Fluorescence Calibration Check Standards You r XR Fmulti-metal s CEM S mus t includ e amean s o f

checkin g the x-ra y fluorescenc e calibratio n agains t a n external standard . NIS T traceabl e thi n fil m standard s ar

e a n exampl e o f

asuitabl e x-ra y fluorescenc e calibratio n chec k standard . 2.4.6 Reagents and

standards for

the Linearity Audits and Relative Bias Audits Yo u wil l nee dothe

r reagent s an dstandard s fo r the linearit y audi t

o r relativ e bia s audit . Th e regent s an dstandard s require dwil l diffe r dependin g o n ho w thes e audit s ar e performed .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 3 o f 32.4.7 Regents and

standards for

the Transport

Efficiency Audit Th e regent s an dstandard s fo r the transpor

t efficienc y audi t

als o depen dupo n ho w th e audi t i s performed . 2.5What

sample collection, presentation, storage, and transport procedures are relevant to Procedure Z? [reserved ] 

### 3 . 0 Qualit

y Control , Calibration , an d Standardizatio

n 3.1 What

quality control

measures are required

by this procedure for

my multi-metal CEMS? Yo u mus t

develo p an dimplemen t aquality contro l programthat , a t aminimu minclude s detaile dwritte n procedure s fo r al l o f the followin g activities . 1 . Procedure s fo r

performin g drif

t check s o n adail y basis , includin g bu t no t limite d to , zer o drift , upscal e drift , an dsampl e volume measurement drift . 2 . Procedure s an dmethod s o f adjustin g you r

multi-meta l CEM S i n respons e t o th e result s ofth e drif

t checks . 3 . Preventativ e maintenanc e o f you r XR Fmulti-metal s CEMS . 4 . Dat arecording , calculations , an dreporting . 5 . Procedure s fo r

require daudits , includin g transpor t efficienc y audit s (i f

necessary) , linearit y audits , an drelativ e bia s audits . 6 . Procedure s fo r

adjustin g you r

CEM S base do n audi t

results . 7 . A progra mo f

correctiv e actio n an dstac k operatio n procedure s i n cas e o f aCEM S malfunctio n an dan out

o f contro l period . Yo u ar e require dt o keep writte n documentatio n o f you r QA/Q C procedure s o n recor d an davailabl e fo r

inspectio n fo r

th e lif e ofth e CEM S o r unti l yo u ar

e n o longe r

subjec t to the requirement s o f

thi s procedure . Ifyo u fai l tw o consecutiv e audit s yo u mus t revis e you r QA/Q C procedures . 3.2 What

calibration checks and audit procedures must

I perform for

my multi-metal CEMS? 3.2.1 Daily drift

check procedures You r XR Fmulti-metal s CEM S mus t hav e the capacit y t o perfor meac h ofth e followin g check s o n a

t leas t adail y basis .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 4 o f 4• Zer o drift : Yo u mus t

chec k th e zer o drif

t to ensur e th e stabilit y o f

you r CEM S respons e t

o th e zer o drif

t reference . Th e zer o drif t mus t b e les s than plu s o r minu s 20 % ofth e emissio n limi t eac h day . Follo w you r CEM S manufacturer' s instruction s fo r

proper zer o drif

t chec k procedures . • Upscal

e drift : Yo u mus t

chec k th e upscal e drif

t to ensur e th e stabilit y o f

you r X R Fmulti-meta l CEM S respons e t o th e upscal e standard . Th e dail y upscal e drif t mus t b e les s tha

n 15 % o f

th e upscal e referenc e valu e determine d immediatel y afte r

the x-ra y fluorescenc e modul e ha s bee n calibrated . Follo w you r CEM S manufacturer' s instruction s fo r prope r upscal e drif

t chec k procedures . • Dail y volum e o r flow check : Yo u mus t chec k th e sampl e volum e o r

flo w measurement

to verif y th e accurac y ofth e volume measuremen t o n you r CEMS . Thi s volume chec k mus t b e done a

t th e norma l samplin g rat e fo r th e CEMS . You r

CEM S i s ou

t o f contro l i f

th e one da

y valu e exceed s 20 % o f th e ful l scal e o f

th e volum e o r

flo w measuremen

t device . Follo w you r

CEM S manufacturer' s instruction s fo r proper volume o r

flo w chec k

procedures . 3.2.2 Audit

procedures Audi t procedure s an dcriteri aar e liste dbelow . Thes e requirement s ar e als o summarize di n Tabl e 1 i n sectio n 5.3 . 1 . X-Ra y Fluorescenc

e Calibratio

n Audi t(XFCA) : Yo u mus t

perfor man XFC A onc e eac h quarter . T o perfor ma n XFC A yo u mus t challeng e the x-ra y fluorescenc e modul e o f you r multi-meta l CEM S wit h astandardo f know n concentratio n fo r

each metal measure db y you r CEM S fo r

complianc e purpose s an dcompare the valu e reporte db y th e CEM S wit h the know n valu e o f th e standard . I f

yo u wis h yo u may make onl y on e measuremen t o f astandardfo r eac h element . I f

you r multi-meta l CEM S fail s o n the initia l measurement yo u ma y mak e tw o mor

e measurement s o f

eac h standardan daverag e al l thre e measurements . I f

th e averag e CEM S respons e ove r the thre e measurement s deviate s b y les s tha

n 10 % fro mth e know n standardth e CEM S ha s passe dth e XFCA . I f

the averag e exceed s 10 % you r CEM S ha s faile dth e XFC A an di s out-of-control . Yo u mus t follo w th e procedure s outline di n Sectio n 5.2 . A n XFC A i s require donc e per quarter . Th e minimu mallowe dtim e betwee n eac h audi t i s tw o month s an dth

e maximu mallowe dtim e i s fou r months . 2 . Sampl

e volum e (o r flow ) audi t(SVA) : Yo u mus t

perfor masampl e volum e audi t o f you r XR Fmulti-metal s CEM S a t leas t onc e pe r quarter an dprio r

t o any linearit y or

relativ e accurac y audit . T o perfor ma n SV A yo u mus t independentl y measur

e th e volume o f

sampl e ga s extracte dfro mth e stac k o r duc t ove r the samplin g period . Yo u ma y make thi s measuremen t eithe r a t the inle t o r outle t o f you r CEMS . Yo u mus t

make volume measurement s durin g thre e differen t

samplin g cycle s an dth e measurement s mus t b e abl e t o make correction s fo r

moisture content

i f necessary .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 5 o f 5I f you r CEM S measure s flo w an dtotalize s tha t flo w to determin e volume yo u ma y perfor maflow audi t

instead . Yo u mus t

mak e flow measurement s durin g thre e differen t

samplin g cycle s an dfo r eac h samplin g cycl e yo u mus t make a t leas t 3 to 5 simultaneou s measurement s o f flow o n you r

CEM S an do n th

e independent

flo w measuremen

t device . Yo u mus t

calculat e th e erro r

fromeac h se t o f measurement s accordin g t o equatio n 6 an dthe n calculat e the averag e erro r i n th e flow durin g eac h samplin g period . Finall y yo u mus t calculat e th e averag e erro r

fromal l thre e samplin g period s an dthi s averag e mus t b e les s tha

n 10 % o f the independent

flo w o r volum e measurement

device . A sampl e volume audi t

i s require do n aquarterl y basis . Th e minimu mrequire d tim e betwee n eac h SV A i s a t leas t tw o month s whil e th e maximu mallowe d tim e betwee n audit s i s fou r months . Accurac y Audits : A s outline di n Performanc e Specificatio n Y Y i t i s acceptabl e durin g th

e initia l performanc e specificatio n tes t to asses s the accurac y an dprecisio n o f th e XR Fan dsamplin g module s o f you r XR Fmulti

meta l CEM S separatel y fro mthe sampl e interface . Yo u ma y als o d o thi s durin g th e Linearit y o r

Relativ e Bia s Audit s tha t ar e require dfo r

Procedur e Z . I f yo u choos e t

o challeng e th e samplin g modul e an dXR Fsystem s separatel y fromth e samplin g interfac e yo u mus t als o perfor maTranspor t Efficienc y Audi t (TEA) . I f

yo u challeng e th e entire XR Fmulti-metal s CEM S durin g th e Linearit y an dRelativ e Bia s Audit s yo u ar e no t require dt

o perfor ma

n independent

chec k o f th e CEM S transpor

t efficiency . Fo r

th e purpose s o f Procedur e Z yo u ar

e require dt

o perfor meither

alinearit y audi t

or arelativ e bia s audit , bu t

no t both . Yo u ar

e als o no t

require dt

o perfor mth e sam

e kin do f test s fo r th e audi t

a s were performe ddurin g the initia l perfonnanc e specificatio n test . Fo r

example , i f

alinearit y tes t

wa s performe ddurin g th e initia l accurac y tests , either arelativ e bia s audi t

o r alinearit y audi t

i s acceptable . Ther e ar e fou r differen t option s availabl e fo r

the accurac y audit s dependin g o n whether o r not alinearit y o r

relativ e bia s audi t

i s performe dan ddependin g o n whether o r not the entir e CEM S i s challenge db y th e audit . Th e audi t requirement s ar

e liste dbelow . Linearity A inlits Optio n A I n thi s optio n alinearit y audi t i s performe do n th e entire CEMS . Th e type s o f metal s generatio n an dthei r associate drequirement s ar e identica l to thos e fo r Optio n A i n performanc e specificatio n Y Y sectio n 3. 1 A 1 I f yo u do no t

mee t the linearit y criteri ayo u mus t appl y acorrectio n accordin g to th e procedure s outline di n performanc e specificatio n YY. 1 Optio n B I n thi s optio n alinearit y audi t i s perfonne do n th e samplin g an dXR Fmodule s o f the CEM S separatel y fro mthe sampl e interface . Th e type s o f metal s generatio n andthei r

associate drequirement s ar e identica l to thos e fo r

Optio n B

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 6 o f 6i n performanc e specificatio n Y Y sectio n 3.1.4. 1 A transpor t efficienc y audi t mus t als o b e completed . Relative Bias Audit Optio n C I n thi s optio n arelativ e bia s audi t i s performe do n the entir e CEMS . Th e type s o f metal s generatio n an dthei r associate drequirement s ar e identica l to thos e fo r Optio n C i n performanc e specificatio n Y Y sectio n 3.I.4. 1 I f you r CEM S fail s t o meet th e criteri ayo u mus t

appl y acorrectio n facto r accordin g to the procedure s i n performanc e specificatio n YY. 1 Optio n D I n thi s optio n arelativ e bia s audi t i s performe do n th

e samplin g an dXR F module s o f

the CEM S separatel y fro mth e sampl e interface . Th e type s o f metal s generatio n andthei r associate drequirement s ar e identica l t

o thos e fo r Optio n D i n performanc e specificatio n Y Y sectio n 3.1.4. 1 A transpor t efficienc y audi t

mus t als o b e completed . A n accurac y audi t

i s require do n a

n annual basis . Th e minimu mtim e betwee n successiv e accurac y audit s i s 9 month s whil e th e maximu mallowe dtim e i s 1 5 months . 3 . Transpor

tEfficienc

y Audi t(TEA) : Yo u ar

e require dt o perfor maTE A onl y i f yo u choos e to challeng e th e samplin g an dXR Fmodule s o f you r XR Fmulti

metal s CEM S separatel y fro mth e samplin g interface . Th e procedure s fo r performin g aTE A ar

e th e sam

e a s thos e fo r

determinin g th e transpor t efficienc y durin g the initia l performanc e specificatio n tes t an dar e outline di n Performanc e Specificatio n YY 1 . I f

th e transpor

t efficienc y o f

you r CEM S i s betwee n 9 0 an d 11 0 percen t

n o correctio n i s necessary . I f you r transpor t efficienc y i s les s tha n 9 0 percent

o r greate r tha n 11 0 percent

the n yo u mus t

establis h acorrectio n facto r accordin g t o th

e procedure s outline di n sectio n 3.1. 7 o f Performanc e Specificatio n YY 1 . Th e minimu mtim e betwee n successiv e transpor t efficienc y tests i s 9 month s whil e th e maximu mallowe dtim e i s 1 5 months . 

### 4. 0 Calculation

s 4.1 What

calculations and

data analysis must

1 perform? 4.1.1 Arithmetic Mean Calculat e th e arithmeti c mea n o f adat ase t as follow s 

### Equatio n 1 Where : x Arithmeti c mea n n Numbe r

o f datapoint s

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 7 o f 7 

### VE S 00073 1x , = Valu e o f eac h dat apoin t 4.1.2 Arithmetic Mean of Difference T o calculat e th e arithmeti c mea n o f differenc e us e the abov e equatio n substitute dfo r x . The n 

### Equatio n 2 

### di 

### — X; 

### - yi Wher e x an dy ar

e paire ddatapoint s fro mth e CEM S an deithe r the referenc e aeroso l o r

the referenc e method . 4.1.3 Da ily Zero Drift

\L c jemo -L]\ 

### Equatio n 3 ZD, = J-^-^xlO O H

Cf Where : ZD , = Th e zero drif t o f the i t helement

o n you r CEM S i n percent jcemo =measure dCEM S respons e to th e zer o standardfo r th e i element L] = Th e calibrate dvalu e o f th e i t helement

o n th e zer o standard Cf = Th e emissio n limi t o f th e i t helement 4.1.4 Daily Upscale Drift

\jcemu _ju 

### Equatio n 4 UD, = ]

— ^xlO O H L" Where : UD, = Th e upscal e drif t o f th e i t helement

o n you r CEM S i n percent . jcemu = T j j eAssure dCEM S respons e to th e i * element i n th e upscal e standard L! = Th e calibrate dvalu e ofth e i t helement ofth e upscal e standard 4.1.5Daily Sample Volume Check

V D

### = \

V 

### TM> " - V 

### "' \ x 10 0

### Equatio n 5 FS Where :

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 8 o f 8VD = Volum e drif t Vcemr= Sampl e gas volum e o r flow measure db y the CEM S volume or flow chec k

measuremen

t devic e V m = Sampl e gas volum e o r flo w reporte db y you r

multi-meta l CEM S FS = Ful l scal e valu e o f the CEM S volum e measurement devic e 4.1.6 Sample Volume Audit

Accuracy VA = V r 

### ~ V m 

### \ x 

### io o Equatio n 6 Where : V A = Volum e o r flow measurement

accurac y V r = Sampl e gas volume o r flow measure db y the independent calibrate dreferenc e devic e V,„ = Sampl e gas volume o r flow reporte db y you r

multi-meta l CEM S 4.1.7 X-Ra y Fluorescenc e Calibratio n Audi t Calibratio n \rcem TStdl

. . _ 

### A _ 

### A Equatio n 7 CA, = ]

- ^xlO O M

Lf Where : CA, = X-ra y fluorescence calibratio n accurac y Lf" = Th e valu e o f

the standardreporte db y you r CEM S Lf = Th e know n valu e o f the standard 4.1.8Relative Bias 

# TM ' = 

# | i x10 0 

### Equation s R. Wher e di i s the mea

n difference , R* M

i s the averag e ofth e referenc e metho d se t o r referenc e aeroso l concentratio n fo r the i t helement , an dPRBi i s the relativ e bia s fo r

the i t helement 4.1.9Transport

Efficiency

Qualit yAssuranc e fo rBatc h Multi-Metal s CEM S (Procedur e Z ) Pag e 9 o f 9 

### VE S 00073 3PT, =-VxlO O C 

### Equatio n 9 Where : Cf = Concentratio n o f the i t helement

a t th e stac k C-'" = Concentratio n o f the i t helement

a t th e samplin g modul e o r a s reporte db y the XR Fmulti-metal s CEMS . PT Th e percent transpor t o f th e i ' element Report the averag e percen t

transpor t (PT ) o f al l measurement s fo r

eac h element tha t wa s teste d(only on e element i s require dthoug h more ca n b e tested) . 4.1.10Linearity Audit - Least Squares Linear

Regression Calculat e th

e linear correlatio n equatio n give n below . y = b a+Z?,

x 

### Equatio n 1 0 Where : b 0= Th e y intercep t b\ = Th e slop e Th e intercep t

i s calculate daccordin g to th e followin g equation . b 0 =y-b l x Where : 1 "

1 " Th e slop e o f

the lin e i s calculate daccordin g t o equatio n below .

n

bi= M _ 

### Equatio n 1 1

Equatio n 1 2

Th e linea r

correlatio n coefficien t

i s calculate daccordin g to the followin g equation .

Qualit yAssuranc e fo rXR F -Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 0 o f 1 84.1.11 Standard Deviation (of

differences) SD, 

### Y.di 1 

### [Zdi 

### |

n n-\ 

### Equatio n 1 4 Where : SDi = Th e standarddeviatio n o f difference s fo r

th e i * element n = Th e number

o f dat apoint s dj= Th e differenc e betwee n th e concentratio n measure db y th e referenc e metho dor

th e concentratio n o f

th e referenc e aeroso l an dthe CEM S reporte dconcentration . 4.1.12 Percent

standard

deviation 

### SD Equatio n 1 5 PRSD, ==ixl0 0

R m Where : R m= Th e averag e o f th e referenc e metho ddatase t fo r th e i t helemen t PRSD

f = Th e relativ e percen t standarddeviatio n fo r

th e i * meta l 4.1.13 Linearity Test

Correction Factors (Applicable only when the linearity test challenges the entire CEMS) 1 . Correctio n equatio n i f CEM S doe s no t

mee t eithe r the slop e o r

the intercep t criteria . 

### QC _y-< ~ b 0

### Equatio n 1 6 Where :

Specification s fo rBatc h Multi-Metal s CEM S (PS-YY ) Pag e 1 1 o f 1 8Cf = Correcte dCEM S concentratio n fo r th e i t helement y, = CEM S reporte dconcentratio n fo r th e i * element bo = Th e intercep t o f th e leas t square s linear

regressio n lin e bi = Th e slop e o f the leas t square s linear

regressio n lin e 2 . Correctio n facto r

i f CEM S meet s intercep t

criteria , bu t

doe s no t mee t the slop e criteria . C 

### ?=yt-K Equatio n 1 7 3 . Correctio n facto r

i f CEM S meet s slop e criteri abu t doe s no t mee t intercep t criteria . 

### QC _ZL Equatio n 1 8 4.1.14 Relative Bias Correction Factors 

### Equatio n 1 9 CFTM - 1 -

R m Where : CF, m= Th e relativ e bia s correctio n facto r fo r th e i t helement C f m - Th e averag e reporte dconcentratio n o f th e CEM S fo r

th e i * element Rf 11 = Th e averag e o f

th e referenc e metho dmeasurement s fo r th e i t h metal 4.1.15Percent

transport

correction factor CF PT 

# = = L Equatio n 2 0 PT, Wher e CF, PT = Correctio n facto r fo r percent transpor t fo r th e i l l )element PTi = Averag e percent transpor t fo r the i t helement

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 2 o f 1 84.2 What waste management procedures are required for procedure Z? A l l chemical s use dto produc e areferenc e aeroso l o r i n performin g standardmethod s nee dt o b e dispose do f

properly . Pleas e consul t the appropriate referenc e methods . 

### 5. 0 Other Requirement s an d Informatio

n 5.1 What

pollution prevention measures must I take when using procedure Z? [reserved ] 5.2 What

criteria are necessaiy for my XRF

multi-metal

CEMS to he in control

and what do I do if it is out of control? 5.2.1 Required

Corrective Action for

Drift Checks and

Audits

• Dail y Zer o Drift : I f

the on e day drif

t exceed s 20 % yo u ar

e require dto reru n you r zer o drif t reference . I f

the XR Fmulti-meta l CEM S meet s the criteri a durin g the secon dtes t

yo u may continu e t o operate . I f the CEM S fail s t

o mee t th e zer o drif

t criteri aagai n the n i t

i s out o f control . It

i s recommende dtha

t yo u examin e th

e zero drif

t standardfo r

defects . Afte r

repair s t o the CEM S ar e complete dyo u ar

e require dto perfor ma

t leas t fiv e successfu l zer o drif t check s withi n a2 4 hour

period . Afte r

the fiv e check s hav e bee n successfull y complete dthe n yo u CEM S i s i n control . I f th e repair s were made t o the XR F modul e o f

the multi-metal s CEM S yo u ar e als o require dt o complete a n x-ray fluorescenc e calibratio n audi t (XFCA ) to verify the accurac y o f you r x-ra y fluorescenc e calibration . • Dail y Upscal e Drift : I f

the on e day drif

t exceed s 15 % yo u ar

e require dto retes t th e upscal e drif

t reference . I f

th e XR Fmulti-metal s CEM S meet s the criteri a durin g the secon dtes t

yo u ma y continu e to operate , however , i f the CEM S fail s th e secon dupscal e drif

t chec k i t i s out o f control . It

i s recommende dtha

t yo u examin e the upscal e drif t standar dfo r defects . Afte r

repair s t o the CEM S ar e complete dyo u ar

e require dt

o perfor ma

t leas t five successfu l upscal e drif t check s withi n a2 4 hour period . Afte r

the fiv e drif

t check s ar

e successfull y complete dth

e CEM S i s bac k

i n control . Again , i f

repair s were made to th e X R Fmodul e o f

th e multi-meta l CEM S yo u ar e als o require dto successfull y complete a

n x-ra y fluorescenc e calibratio n audi t (XFCA ) t

o verif y the accurac y o f th e calibration . • Dail y Sampl e Volum e Check : I f

you r sampl e volume o r

flo w drif

t exceed s 20 % i t ha s faile dthe dail y volum e chec k an dyo u mus t

perfor manother

dail y volume check . I f

the CEM S passe s th e secon dchec k yo u ma y continu e t

o operate . I f

you r CEM S fail s th e secon dtes t i t i s out o f contro l an dyou r

CEM S mus t b e repaired . Afte r

repair s hav e bee n mad e th e CEM S mus t

successfull y complete five sampl e volum e check s withi n a2 4 hou r period . Upo n successfu l completio n o f

th e five check s you r

CEM S i s bac k

i n control . I f

the repair s

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 3 o f 1 3were made to avolum e o r flow measuremen

t devic e yo u ar

e als o require dto successfull y complete asampl e volum e audi t (SVA) . • Quarterl

y Sampl e Volum e Audi t(SVA) : You r

XR Fmult i metal s CEM S i s out o f contro l i f

volum e (o r

flow) measure db y you r CEM S differ s fro mtha t measure db y the independent standardb y mor

e than 10 % percent . A failur e o f thi s audi t ma y indicat e tha

t repair s nee dto b e mad e to the volum e measuremen t system . Upo n completio n o f thes e repair s yo u mus t

perfor man dpas s another SVA . 

### • Quarterl

y X-Ra y Fluorescenc

e Calibratio

n Audi t(XFCA) : Th e respons e o f you r XR Fmulti-metal s CEM S mus t b e withi n 10 % o f

the standard' s valu e fo r eac h meta l measure dfo r complianc e purpose s b y you r CEMS . I f

you r CEM S fail s th e XFC A initially , reru n eac h standardtw o mor e time s an dtak

e th e averag e o f

the thre e measurements . I f the averag e CEM S respons e meet s the XFC A criteri ayo u ma

y continu e to operate , however , i f the CEM S fail s to mee

t th e criteri athen i t

i s out o f control . Afte r

the CEM S ha s bee n repaire dyo u mus t complete anothe

r XFCA . Upo n successfu l completio n o f the XFC A the CEM S i s bac k

i n control . 

### • Annua

l CEM S Accurac

y Test s Linearity A udit Optio n A (Linearit y audi t o f the entire CEMS) . Ifyo u challeng e the entir e CEM S syste m(includin g samplin g interfac e an dthe samplin g andXR Fmodules ) wit h alinearit y audi t yo u d o no t

nee dto appl y a correctio n facto r

t o you r CEM S datai f

i t meet s th e followin g criteria : 1 . aslop e betwee n 0.8 5 an d1.1 5 2 . th e correlatio n coefficien t equal to 0.9 0 o r

mor e 3 . a n intercep t

o f les s than 2 0 percent

ofth e emissio n limi t I f you r CEM S doe s no t

mee t th e slop e o r

intercep t criteri ayo u mus t

appl y a correctio n facto r

accordin g t o th

e procedure s describe di n Performanc e Specificatio n Y Y Sectio n 4.2.12. " You r CEMS , however , mus t stil l meet

the correlatio n criteria . I f you r CEM S fail s the linearit y tes t i t i s out o f control . Afte r

the necessar

y repair s ar e mad e i t mus t pas s alinearit y o r

relativ e bia s tes t

t o b e considere d bac k i n control . Optio n B (Linearit y audi t o f th e samplin g modul e an dXR Fmodul e onl y followe db y aTEA ) I f yo u challeng e the samplin g an dXR Fmodule s separatel y fro mthe sampl e interface , you r

XR Fmulti-meta l CEM S i s out o f contro l i f

th e linear leas t square s regressio n analysi s o f you r audi t datadoe s no t

meet the followin g criteri afo r

eac h o f the metal s measure db y you r CEM S fo r

complianc e purposes :

Qualif yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 4 o f 1 41 . aslop e between 0.8 5 an d1.1 5 2 . the correlatio n coefficien t equa l t o 0.9 0 o r

more 3 . a n intercep t

o f les s than 2 0 percen t

o f the emissio n limi t I f you r XR Fmulti-metal s CEM S fail s alinearit y audi t yo u mus t

make th e necessar y repair s t o you r

CEM S an dsuccessfull y complet e either arelativ e bia s audi t o r alinearit y audi t

befor e i t i s considere dt o b e bac k i n control . Yo u mus t

als o complete atranspor t efficienc y audi t

(TEA ) alon g wit h you r linearit y audit . Relative Bias Audit Optio n C (Relativ e bia s tes t o f the entire CEMS ) I f you r CEM S meet s the followin g criteri ai t ha s passe dth e relativ e bia s audi t andyo u do no t

nee dto appl y acorrectio n facto r to you r CEMS . 1 . th e percent

relativ e bia s (PRB) exceed s 15 % 2 . th e percent

relativ e standarddeviation(Pi?XD ) exceed s 10 % 3 . the correlatio n coefficien t (r ) fo r linearit y portio n o f

th e relativ e bia s audi t

i s les s tha n 0.9 0 I f you r XR Fmulti-metal s CEM S fail s t o mee t the relativ e bia s criteri ayo u may appl y acorrectio n facto r accordin g th e procedure s describe di n performanc e specificatio n Y Y Sectio n 4.2.13 1 . However , i f you r CEM S fail s to meet

eithe r th e percent

relativ e standarddeviatio n criteri ao r the correlatio n coefficien t criteri ai t i s out o f control . I f

you r XR Fmulti-meta l CEM S fail s arelativ e bia s audi t i t mus t successfull y compete anothe r linearit y o r

relativ e bia s audi t

to b e considere di n control . Optio n D (Perfor marelativ e bia s tes t o n the samplin g an dXR Fmodules ) You r XR Fmulti-metal s CEM S i s ou t o f contro l if : 1 . the percent

relativ e bia s (PRB) exceed s 15 % 2 . th e percent

relativ e standarddeviation(PicSD ) exceed s 10 % 3 . th e correlatio n coefficien t (r) fo r linearit y portio n o f

th e relativ e bia s audi t

i s les s tha n 0.9 0 Yo u mus t

successfull y complet e another RB A o r alinearit y audi t

befor e you r CEM S i s considere dt o b e i n control . Yo u mus t als o successfull y complet e a transpor t efficienc y audi t

alon g wit h the relativ e bia s audit . Transpor

tEfficienc

y Audi t(TEA) : A TE A i s onl y require di f yo u challeng e you r samplin g XR Fmodule s separatel y fro myou r sampl e interfac e (Option s B andD) . I f

the percent

transpor t i s betwee n 9 0 an d11 0 percent n o correctio n facto r i s necessary , however , i f the percent

transpor t i s les s tha

n 9 0 percen t

or greate r than 11 0 percent

the n yo u mus t

appl y acorrectio n facto r t o the result s reporte db y you r

mult i meta l CEMS . Th e procedure s fo r applyin g acorrectio n facto r usin g the equatio n i n Sectio n 4.1.15 . Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 5 o f 1 55.2.2 General out of control guidelines

• Ou to f contro l period : Th e out

o f contro l perio dbegin s immediatel y afte r th e faile ddrif

t tes t o r audi t an di s ove r

immediatel y followin g th e successfu l completio n o f

require dprocedure s associate dwit h th e failur e o f

th e audi t test . Durin g th

e ou t o f contro l perio dyo u ma y no t us e th e datagenerate db y you r X R Fmulti-meta l CEM S fo r complianc e purposes . • Reportin

g guidelines : Yo u mus t includ e i n you r

repor t to us , th e state , o r

loca l enforcement

agenc y the result s o f

th e faile daudi t

or drif t check , the correctiv e actio n tha

t wa s taken , an dth e result s o f th e successfu l audi t

o r drif t check . • Rule s governin

g auditin

g tim e periods : Th e X-Ra y Fluorescenc e Calibratio n Audi t (XFCA ) an dth e Sampl e Volum e Audi t (SVA ) ar

e require donc e a quarter . Tw o month s mus t pas s betwee n successiv e quarterl y audit s an dn o more tha n fou r month s may pass. . Th e Linearit y Audi t (LA ) an dth

e Relativ e Bia s Audi t

(RBA ) ar

e require do n a n annual basis . Successiv e LA s an dRBA s mus t b e separate db y a

t leas t nin e month s andn o more tha n 1 5 months . 5.3 What

tables, diagrams and

flow charts are relevant to Procedure Z?

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 6 o f 1 6

### Tabl e 1 : Continuin

g Q A Procedure

s forXR F Multi-Metal

s CEM S Tes t Frequenc y Tes

t Tes

tProcedure

s Passin

g Criteria Dail y Zer o Drif t Chec k zer o standar d an d calculat e drif t < 20 % drif t eac h da y 

### Dail y Upscal e Drif t Chec k upscal e standar d an d calculat e drif t < 15 % drif t eac h da y Volum e o r

Flo w Drif t Chec k flo w drif t an d calculat e drif t < 20 % drif t eac h da y



### Quarterl y X-Ra y Fluorescenc e

Calibratio n Audi t Tes t a standar d fo reac h elemen t measure d fo r complianc e b y you rCEM S ( 1 tim e pe r standard ) • < 10 % differenc e fo rever y elemen t measure d fo r complianc e b y you rCEM S • I f criteri a no t initiall yme t yo u ma ytak e th e averag e o f 3 measurement s 

### Quarterl y Sampl e Volum e

(o r Flow ) Audi t Volum e • Compar e CEM S volum e agains t a standar d durin g 3 samplin g cycle s • Averag e al l thre e Flo w • 3 t o 5 flo w measurement s wit h standar d an d CEM S pe rsampl e cycl e • Measur e i n 3 CEM S sampl e cycle s • Calculat e averag e differenc e betwee n CEM S an d standard s ove ral l measurement s <10 % differenc e fro m th e standar d



### Annuall y Optio n A Perfor m alinearit ytes t

on entir e CEM S • A t leas t on e meta l fro m eac h categor y • Nee d a t leas t 3 concentratio n level s whic h includ e a 2 fol d cone , chang e an d th e emissio n limi t • I f spiking , spik e int o source , o rspik e int o transpor t lin e a s clos e a s possibl e t o th e prob e • Slop e = 0.8 5 t o 1.1 5 • r>0.9 0 • intercep t < 20 % o f emissio n limi t • i f abov e criteri a i s me t the n n o correctio n • i f no t me t appl ya correctio n



### Annuall y Optio n B

• Perfon n alinearit ytes t on samplin g an

dXR F module s onl y • Determin e transpor t efficienc yseparatel y • A t leas t on e meta l fro m eac h categor y • Nee d a t leas t 3 concentratio n level s whic h includ e a 2 fol d cone , chang e an d th e emissio n limi t • Spik e o rmeasur e concentration s wit h referenc e metho d a

s clos e a

s possibl e t o th e samplin g modul e Linearit yCriteri a • Slop e = 0.8 5 t o 1.1 5 • r>0.9 0 • intercep t < 20 % oTemissio n limi t • th e linearit ycriteri a mus t b e me t Percen t Transpor t Criteri a • 90<PT<11 0 • I f percen t transpor t criteri a ar e no t me t appl ya correctio n facto r 

### Annuall y Optio n C Perfor m arelativ e bias tes t on entir e CEM S • A t leas t on e meta l fro m eac h categor ya t 8 0 t o 12 0 percen t o f emissio n limi t • On e othe rmeta l a t 3 cone , level s whic h includ e a 2 fol d cone , chang e an d th e emissio n limi t • I f spiking , spik e int o sourc e o rspik e int o transpor t lin e a s clos e a s possibl e t o th e prob e • Percen t relativ e Bia s • RB<15 % • %RSD<10 % • r> 0.9 0 fo rmeta l wit h thre e fol d cone , chang e • I f Criteri a no t me t appl ya correctio n facto r(correlatio n coefficien t criteri a mus t b e me t 

### Annuall y

Optio n D

• Perfor m arelativ e bias tes t on samplin g an

d X R F module s onl y • Determin e transpor t efficienc yseparatel y • A t leas t on e meta l fro m eac h categor ya t 8 0 t o 12 0 percen t o f emissio n limi t • On e othe rmeta l a t 3 cone , level s whic h includ e a 2 fol d cone , chang e an d th e emissio n limi t • Spik e o rmeasur e concentration s wit h referenc e metho d a s clos e a s possibl e t o th e samplin g modul e Percen t Relativ e Bia s Criteri a • RB<15 % • %RSD<10 % • r> 0.9 0 fo rmeta l wit h thre e fol d cone , chang e Percen t Transtror t Criteri a • 90<PT<11 0 • I f percen t transpor t criteri a ar e no t me t appl ya correctio n

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 7 o f 1 7 

### VE S 00074 15.4 What references are relevant

to Procedure Z? 1 . Performanc e Specificatio n YY : Specification s an dTes t Procedure s fo r

Batc h Multi

Metal s Continuou s Emissio n Monitorin g System s a t Stationary Sources . 2005 .

Qualit yAssuranc e fo rXR F Base d Multi-Metal s CEM S (Procedur e Z ) Pag e 1 8 o f