Eli Ully and Company Lafayette , lndlana Alternative Monitorin g Potltlon During the autop urg e period , rol li ng average ca lcu la t ions for the pollutants mon itored by the Ecochem system (HCI, CO , 0, , S0 2 , and NO , ) w i U be frozen (similar to when the system Is In calibration mode) . Once the autopurge period i s complete and data i s ava il able ( approx i mately 5 minutes), rolli ng average ca l culations will be unfrozen . Th e app roximate 5 - minute time period when the Ecochem is offt l ne due the autopurge shou l d be considered excused downtime. 3.3. 4 . 3 PM and HWC MACT Metals Rolling Average Calculations during Ecochem CE MS Dally Calibration and Ongoing Quality A ssu rance Audits The stack moisture content measurad by the Ecochem i s used to calculate the dry stack nowrate. The dry stac k ft owrate Is used to determi ne the roll ing average va lue of the PM e mission rate In tenms of mgldsan. In addition, the PM CEMS and the Mufti..Metals CEMS use the stack 0, conce n tration to c:oneot measured stack data to 7% oxygen . Since both the stack moisture cont ent and stack 0, concen tration will be u navaila ble when the Ecochem Is bei ng ca li brated, Whe n perform i ng an ACA, or when the probe Is being purged Wh il e burning hazardous waste , th e rolling average calculations of the HWC MACT metals and PM emission rates will be froze n during these periods . This i s in addition to freezing the rolli n g average va l ues of the constlluents measured by the Ecoche m CEMS (HCI , CO, 

## o, , S0 2, a n d NO , (See Sectio n 3.3.4.1 ). Specifically , the r olling averages for t he Mu lti- Metals and PM CEMS wil be frozen once three consecutive 1 5-mi nu te average valUes are unavailable in a one hour block avera ge period due to calibration or ACA of th o Ecoche m, o r autopurge of the Ecochem stack probe. In addition , U ll y**w~ l**  cons id er the time perio d the rolli n g averages are fro zen as excused downtime . 3.3.5 Backup to the HCI CEMS Lilly wal monitor operating parameter lim its defined i n Sectio n 1209 of the HWC MACT when the i ncinerator I s In parametri c mode . Details of the specific operating limits are provided i n the NO C. Li ll y wU I in corpora te delay s When trans i tioning from the CEMS mode of operation to the parametric mode o f operation . Specifically , once the HCI CEMS is unavailable, the ccntroj system will automatically switch to the parametric modo of operation . Ro lling averages, related to the Air Pollution Control System ( APCS), will not start until the system h as bee n under the parametric mode of operation for 10 minu tes . Th i s 1 <Hninute time period will allow Lilly time to make any adjustments to the APCS to bring the system to within the respective operating parameter limi ts. In addition. up to four hours will be allowed before restarting constit u ent feed rate roll i ng averag e opera ting parameter limits in order to c l ear the solid feed conveyor system . (Lilly wi ll use Its best efforts to avoid in t roducing ·new" waste streams from th e six ' infeed" conveyors to the fina l "merge· conveyor that leads to the ki l n f eed chute durin g this four hour period . However, duri ng initia l CEMS mode operation periods the r e will be practica l limita tions to this criterion beceuse few waste streams wiU have been burned.) Feed rates will be maintained nom i naly stable or historically tower than when operating in CEMS mode. If the CEMS mode of operation is still not 

### 52 Rev . 7 .0 

### VES009400Eli U lly and Company Lafayette , Indi ana Alternative Moni torin g P etit i on

ava i lable after fou r hours , the tra n s i tion to parametric mode will be compl et ed an<! on l y waste with known composition w ill be processe d In the incin erator so that co n sliluent feed ra te operat i ng para m ete r limits 

### can be computed .

3 , 4 JUSTI F I CATION FOR REQUEST FOR ALTERNATIVE MON ITOR IN G METHOD T he HWC MACT fina l rule ( 4 0 CFR 63 Subpart EEE ) did not mandaiG the 

### use of CEMS fol parameters o ther tha n CO, h ydroca rbon, o xygen , a nd pa rt i c ulate matter. (Use of a part i c u late matt er CE MS Is defemed until EPA promulgaiGs P M CEMS performance specifications and operational requ ireme n ts). However, as stated in t he Septembe r 30, 1 999 prea m b l e lo the HWC MACT , 64 Fed . Reg. 52925, the E PA has a strong pref e ren ce f or the use of CE MS for demonstration of com pl ia n ce w ith em ission standar ds. The reg ulatory p re f erence fo r CE MS aver the u se of process operating lim i ts is based on the CEM S direct measure of HAPs or surrog ate HAPs I n t he stack gas, 

### a hig h degree of ce rta in ty r egard i ng compliance with lhe em i ssion standards , and provision of bauer comp l iance information to tile public . Th e EP A therefore encourages u n its li ke Li ll y's to us e C E MS I n th e m anner proposed I n this petition as an alternative to the HWC MA CT ma n dated process param e ter C(l()ti n u ous mon i tori ng o f 40 CF R 6 3 . 1 209. This Alternative Mon i toring Petition i n d udes perf ormance specifications and qual ity ass uran ce requ i reme nts fo r ea ch C E MS. T h e use of the PM , m u l ti-m eta l s and HC I CEM S is a s ig ni ficant Investment that l illy h as vol untari ly undertaken In o rde r to receive cena i n regulatory ince n tives. Sucn regulatory incentives a l lowed t o f aciliti es us i ng al ternative C E M S are ou tl i ned in th e preamble to the Septemb er 30 , 1999 final HWC MACT rul e. The inoentives i ncl u de r el ie f from the operatin g parame te r li mits presa i be d In Section 1209 of th e HWC MACT and re l ief from sampling and analyzing the waste feed streams for asll , merrury , SVM , LVM , and HCVCI, . See T able 1 fo r th e o pe rat i ng and emissi on**ll ~s**  t hat a p ply while the a lt e rnative CE MS are operating . Provid i ng incentives is a key factor for facil ities voluntarily operating alternative CEM S and encou r age s th e development and Implemen tati on of ne w and em erg i ng CEMS .

53 Rev . 7.0 

### VE S00 940 1Ell Lilly and C ompany Lafayette , Indiana Alternative M onitoring Petition

U ALTERNATIVE MON ITORI NG CANDIDATES UNDER 63 . 1209(g) Lm y has prepared this section ollhe alternative mon i to ring petition under Section 63. 1209(g) ol lh e HWC MAC T to r equest r elief from certain operating paramete r r equirements .

4 . 1 STACK GAS FLOWMETER DAJL Y CHEC K AND AUTOPURGE Sect ion 6.2 of th e Append i x to t he HWC MACT allows fac U l ti es to bum hazardo u s w aste for a ma><lmum o f 20 minu tes while calibrating !he CO and oxygen C E MS . N o comparable provision exists in !he HWC MA CT rule for routine checks o f pa ra meter CMS that mon ito r oper atin g da ta . However. the G eneral Provisions allow such routine checks to occur during normal operation ( 4 0C FR part 63 . 8 (c)) . Ully wm perform daily routine ch ec k s of lhe s ta ck gas fl ow meter wh il e burn i ng haza rd ous waste. In addition. the probe tip 

### on the fl owmeter monitoring !he stack gas flow rate may be purged appr oxi mately once per day while hazardous w aste I s being bu rned. P urging I nvolves directing compressed ai r throug h the pro be Into the stack for a short period of time to p revent buildup of SOl ids in the probe . The pu r ge pe ri od will las t approximat e l y 5 m in utes. Pur g i ng the stack probe i s neile ss ary for pre ve ntive m a intenance reasons and is recommended by the manufacluret due to !he types o f wa s t es bu rned in the soli d liq ui d l ncl netatio n system. Duri ng t he dally checks and auto pu rge perio d s, the stac k gas ftow rate roiling aVetage cat cu lali ons will be frozen. O nce d ata is available. rolling average calcu l ations wi ll be unfroze n . Specif i ca lly , the first available o n e-m i nute avet ' age va l ue following the autopurge perfod wtll ba added to the most recent 59 on e-minute average val ues pri or to free zing th e rol ling ave rag e ca l c u lalio n s.

4.2 COMBUSTION GAS FLOW RATE OPERATING PARAM ETE R LIMIT The stack moisture content measured b y the E rochem is used to calcul ate the dry stack now rate in terms of dscf / m l n . Th e dry s taCk fiowrate hou rty ro ll ing average is compared to the H WC MACT maxi mum combustion gas ftowrale lim il T he stac k moistute con tent wiU be unavaU able wh en t he Ecochem is being ca librated. perf orming an ACA . o r the Ecoche m prob e i s be lng pu rged. Therefore , t he romng average calculations of the combustio n gas flowrat o will be fr oze n during th ese eve nts. I n**add~ lon** **.** Lilly will c onsider the time pe riod the ro Uing a verage Is froze n as excused downti me .

54 Rev . 7 . 0 

## VES009 402Ell Lilly and Company Lafayette , Indiana Alternative Monitoring Petition 4 . 3 C ALC ULA TION Of ROLLING AVERAG E S WHEN ALL ONE-MINUTE AVERAGE VALUES ARE NOT AVAILABLE Lilly r equests tha t the ca l cu l ation of the one hour rolling a verage v a l ues be al lowe d to continue provided t h at 95% of the On<H11inu te data va lues, I n terms of the apptieable l i mit, are ava il able Q . e . 57 m i nutes for a n hourly roUing ave rage an d 68 4 m i n utes for a 1 2-l'l our r ol l i ng average) . Correspond i ngly , histo rical storage o f the data will be cons i dered complete proVIding that 95 % o f the va lues h a ve been captured . Purge and catibr.ltlon times are excluded from the 95 % calculation. T h i s re quest is bas e d on r esponse to a commen t on t he Apri l 20 , 2004 prop os ed HWC MAC T ru l e . Alth oug h , EPA was unable to ma ke the change in th e fina l HW C MACT ru l e s i gned September 14 , 2005 , the agency stated th a t it u nderstands th e need for such l angu a ge and has r eco mmen ded tha t sources us e the p rovis io n s of 63 . 1209{g) to request t his al ternative monitori n g approach .

55 Rev . 7 . 0 

## VES009403Ell L ill y and C om p a ny L a f ayet te , I n d ia n a Alternative M onit ori ng Petition

5 . 0 A LTE RNATI V E M O N ITORI NG P ETIT I O N AP P ROVA L Pursuant to Section 63 8(1)( 5 ) of the Genera l PIO\Iisio n s. lhe Adminis trator will prov ide noti fi cation of ttle appro val o r i nte n ti o n to d i sa pp ro v e reque s ts ma de unde r Section 63 . 8(1) of t he General Provisions with i n 30 days of rece i pt ot the application . and wi1h l n ;lQ days after receipt of a n y suppl e mentary i n formation t ha t i s su b m itt ed . Sectio n 6 3 .1 209 (g){1 )( iii)( C ) s tates tha t th e ti m i ng for app ro val of requ ests under §63 . 1209(g) is tha t the Administrator will provide notification of the approval 

### or intention t o disapprove the a pp l ica tion wittll n 

### l1Q days o f receip t o f the appl icatio n . a nd w it hin 60 d ays a ft

er rece i pt o f any supp le mentary inf ormation that is s u bmitted . Howeve r , U l ly would welcome comments at lhe agency ' s eartiest conven i ence sinoe the a Hem ative mooi t oring iss ues I d en tified i n this ap pl i cati o n affe ct syste m des i gn and in s t rum e n t p rocu r e me nt a ct iviti es . te s t plann i ng. co nt rol system configuration , and completion of MACT compliance plans .

56 Re v . 7 . 0 

## VES0 0 9404Ell Lilly and Company Lafay ette , Indi ana AltemaUve M oni torin g Pet ition

6 . 0 RELEVANT REFER . ENCES 1 . Performance Speci fi cati on 11 - Speci fi cations and T e st Procedu res for Pa rticulate Matter Continuous Emission Moni1ori ng Systems at Stationary Sources, 40 CFR Part 60, Appendix B , Janu a ry 12 , 2004. 2. EPA Draft Guidance Documents on P M CEM S, provided to Eli 

### u ny and Compa ny by EPA Office of At Quality P lan ning and Stan dards March 3 , 2005 . 3. Procedure 2 · Qua lity Assura nce R e q uirements lor Pa rticul a te Matt er Conti nu ous E miss i o n M onhoring Systems at Stationary Sources , 4 0 CFR Part 60. Appendix F , January 12, 2004 . 4. Draft Method 301 E valuation of cand i date Conditional Methods , Coope r Environme ntal Services, L LC .. Vo l u m e I, Ju ne 10 , 2005 • X-<ay Based Fiher Methods ( X F M ) • MuiU· Meta l s I nst rumental Analyzer Procedure ( XACT-IAP) • Qua n titative Ref e rence Aerosol Generator (Q AG ) 5. Draft Standard Operating Procedure for Generating a Quantitative Mu l ti..-netals R eference Aero sol w ith the CE S QAG, Cooper Environmenta l Services , L LC .. Draft Method 301 Evaluation of candidate CondiUonal W.ethods Volume II , Appendix C , J une 9 , 2005 6. Draft Performance Specification YY : Speciflcalioos and Test Procedures lor X -ray Fluo resce nce Based**Mult eta** **s** Continuous E mission Monitoring Systems a t Stationary Sources. Cooper En vironmental Services , UC ., D raft Method 301 Eval uatio n of candid a te Co ndi tiona l Meth od s, Vol u me II , Appendi x F , J u ne 8, 2005 7. Draft Proced ure Z: Quality Assurance Requ i rements for 

## x .. ay Fluorescence Based Multi-metals Con ti nuous Emiss i on Mon itori ng Systems at S t ationa ry S ou rces, Coope r En vi ro nme ntal Servlces. 

## u c .. Draft Method 301 Eva l uation or Candidate Conditional Me thods , Volume II, Appendlx F. June 9, 2005 8 . Draft De termln alioo or Meta l Emi ss io ns fro m Stat i onary Sources U si ng Fi lters and So l i d Sorbe nts with X ·ray Fluorescence Analysis , Cooper Environmental Services, LLC . , Draft Method 301 Ev

aluation of C and idat e Co nd i tio na l Methods . Vo l ume II, Appendix B, J une 10 , 2005 . 57 Rev . 7 . 0 

## VE$009405Ell Lilly and Compan y L a f ayett e, In dia na All e m allv o M onitor1ng Pet ition 9 . Standard Operating Procedure for Ge nerating a Quantitative Multi-Meta l s R eference Aerosol with the CES OAG , Cooper En vi ronmenta l Services. LLC ., June , 2005 . 10. Performance Spe cifi cation 2 · S pe ci fications and Test Proced u res tor S02 and NOx Continuous E m ission Monitoring Systems i n Stationary So u rces, 40 CFR 60 Appendix B . February 2000 . 11. Performa n ce SpecifiCat i on 4A • SpecifiCations a nd Test Procedures for C8rtlon Monoxid e Co ntinuou s Emission Mo nito rin g S y s tem s i n Stationary Sources , 4 0 CFR 60 Appendix B , February 2000 . 1 2. Perfonnance Specification 4 B • SpecificaUons and Tes t Procedures fo r Carbon Monoxide a nd O xygen Conti nuou s Em i ssion Mo n itoring Systems i1 Stationary So urces , 40 CF R 60 Ap pe ndix 8 , Sep tem be r 30, 1999 . 1 3 . Appen d i x to Subpart EEE o f Pa rt 63- Quality As surance Procedures lor Co ntinuou s Emissions Monitors Used for Hazardous Waste Combustors , 40 CFR 63 Subpart E E E , September 30, 1999. 1 4 . Perfonnance Specificatio n Z : S pecificatio ns and Test Procedures Fo r Hydrogen Ch l oride (HCL) Conti nu ous Em ission Monitoring Systems At Stationary Sources , Eli Li ly. November 2005 . 15 . Proced u ra DO: Qua fi ty Control and Qua li ly Assurance Requirements lor Hydrogen Chloride ( H CL) Con ti nu ous Em i ss i on Mo n itoring Sysiem s At Sta tionary So urces , Eli Lilly , N ovembe r 2005.

58 Rev . 7.0 

## VES009406

## VES009407 . pdf

# Appendix A

Total Particulat e Ma ss C ontinuou s Emi s sion M onitoring Sy stem Supportin g D o cum e nts

Ve r sion 1. 0 

### Novembe r. 2 005



## VES009407

### Tabl e of C ontents I . Perf onnance Specijjcatioo II - Specifications and Test Procedures for Particulate Matte r Continuous Emi ssion M onitoring Systems at Stationary So urc es, 40 CF R Part 60, Appendix B , 

### January 12, 2004. 2. Procedure 2 - Qual ity Assurance Require m e nts for Part i c ulate Matter Con ti nuous Emi ssio n M onitoring Systems at Stat ionary Sources, 40 CFR Part 60, Appendix F, J an uary 12,2004. 3 . EP A Draft Guidance Documents on PM CEMS, provided to Eli Lilly and Company by EPA Office ofAir Quality Planning and Standards March 3, 2005. a. Precis ion and Bi as Guidance b. Procedure 2 Audits c. P rocedure 2 Routine Checks d. PS II Example Calculations e. PS II Sprea dsheet E xample 

### f . R elative Calibration Audit Dala E valuation g. Stratification Procedure



## VES009408

## VES009409 . pdf

# Appendix B X-ray Fluorescence Based Multi-Metals Continuous E mi ss ion Monitoring Sy stem S upporting Documents

Version 1.0 

### No n mber, 2005



## VES009409

### Ta b le o f Conte n ts 

### 1. Draft Method 30 I 

### Evaluation of Candidate Co n ditional Methods , Cooper Environmental Services. LLC ., Volume I , June 10,2005. a. X-ray Based filter Methods (XFM) 

### b. Multi-Metals Instrumenta l Analyzer Procedure (XACT-IAP) c . Quantitative Ref erence Aerosol Generator ( QA G) 2. Draft Performance Specification YY: Specifications and Test Procedures for X-ray Fluorescence Bas ed Mult i-metals Continuous Emission Monitoo ·ing Systems at Stationary Sources, Cooper Environmental Services, LLC., Draft Method 30 I Evaluation of Candidate Conditional Methods, Volume U. Appendix F, J une 8, 2005 3. Draft Procedure Z: Quali ty**As.~urnnce** 

### RequirementS for X-ray Fluorescence Based Multi-metals Continuous Emission Monitoring Systems at Stationary Sources, Cooper**Envirorun~ntal** 

### Services , LLC .. Draft Method 301 Evaluation of Candidate Conditional Methods, Volume U, Appendix F , June 9, 2005 4 . Draft Dctenninati on of Melal Emissions from Stationary Sources Using Filt ers and Solid Sorbents with X-ray Fluorescence Analysis, Cooper Environmental Services , LLC., Draft Method 30 1 Evaluation of Candidate Conditional Methods, Volume II, Appendix B, June I0, 2005. 5. 

### Standard Operating Procedure for Generat ing a Quantitative Multi-Metals Reference Aerosol with the QAG, Cooper E nvironmental Services , LLC ,. June 2005



### VES009410

# VES009411 . pdf

# Candidate Conditional Method ZZ: Determination of Metal Concentration in CES ' Xact C E MS Stilling Chamber U sing Filters and Solid Sorbents with X-Ray Fluorescence Analysis

Prep a red by: Cooper Environm en tal Services , LL C IOIRO SW Nimbus B l vd Suite J6 Ponl a nd , O reg on 9 7223



### R e'\<i s ion 1.0 Jun e, 2005

VES00941l

# Candidate Condition alMethod ZZ: Determination of Metal Concentration in C ES ' Xact C E MS Stilling Chamber U sing Filters and Solid Sorbents with X-Ra y Fluorescence Analysis

Draft June 23, 2005

Pr e p ar e d f or U.S . Environmental Pr otecti on Agency 

### Research Tr iangle Park, 

### NC



### Prq1ared by: J. A . Cooper , B . E . .Joh n sen, 

### K. P etterso n , C. A. Ya n ca, M. Nakanishi, 0 . Barth, S. Fry



## VES009412

### Coo p er En• ironmeotal S ervi «S, L L C 10 1 80 SW Nimb us B lvd Suit e J6 P

o rtland , Orego n 97223



## VES0094 13

# Candidate Conditional Method ZZ: Determination of Metal Using Filters and Solid Sorbents with X-Ray Fluorescence Analysis

P rep ared**=- --~=--**  Date:

_ _ _ D ouglas C . Ba r th, Environmental S cie,nti s t P repared by: Date: __ _ Cay A. Yanca, E nvi ronmental S cie ntist Prepared by: Date: __ _ Krag Pette r son , Environmental Scienti st R eviewed b y: Date: __ _ Bru ce E. Johnsen , Q A Mana g er Approved b y: Date :

_ _ _ J ohn A. Coo per, Dir ector



## VES009414

### E xec u tive S umm ary Eli Lilly and Company (Lilly) operat es 

### a waste incineration system located at the Tippecanoe Laboratories in Lafayette , In diana. This incin erator system inc ludes an Xac t multi-metals continuous emissions morut()ring syste m (Xac t-CEM S, manufactured by Cooper Environmental Services.LLC) fo r demonstrating attainment with the Hazardou s Waste C ombustor MACT for sem i -vo latile meta l s, low-volatile metals, and mercury emissions . Lilly must co nduc t an 

### initial pe rformance eva luati on test as well 

### a s quarterly and annual audi ts to assure the accuracy oft h e reported resul ts f ro m the CE MS . LiUy has proposed the use of 

### a NI ST-traceabl e reference aerosol gen erator fo r relative accuracy and lin eariry determinations. 

### lu addi tion , Lilly 

### is al so proposing the 

### u se of 

### a new sampling and analy sis reference metho d for metals to assure the accumcy ofthe spiked reference aerosol. This appendix. de scribes 

### this new sampling an d analysis method used in Me thod 301 

### tests described in th e body of this report and proposed for the above noied i rutial pe rformance evalu ati on test and annual audits of LiUy's Xact-CEMS. Thi s new method is an X-ray Based F

ilter Method (XI'M) tlla t drdws a repre s entat ive sampl e of i n ci nerator emi ssions from the Xact -CEM S st illing ch amber t hrough a serie s o f reactive a nd non - re active !ilters . The filter depo s its ar c non-destructively analy z ed 

### by X-Ray Flu ore scen ce (XRF) 

### to de termine metal c oncenlrlltions in the filter 

### deposits. Metal concentration s 

### in th . e 

### emissions are 

### calc ulated b y dividing the vol u me of samp led 

### flue gas i n to th e metal m ass measu red by 

### XRF. This meth od i s applicable to the measurement of chromium (Cr), arsenic (As), cadrruum (Cd), 

### mercury (Hg), 

### and lead (Pb)) 

### in emissions from Lilly's h a zardous waste 

### incinerator. Ald10ugb til e 

### X F M is op timi z ed for the se elements, it is applicable to other elements in cluding : ''anadiu m (V), manganese (Mn), 

### ir on (Fe) , nickel (Ni) , copper (Cu) , 

### zi nc (Zn), s ilver (Ag), 

### antimony (Sb), barium (Ba) , th alliu m (TI) , t in 

### (Sn), bismut h (Bi), cobal t (Co) 

### a nd sel enium (Se). The XFM can quantify flue gas concentration s ranging fro m les s than 0.2 to over 2000**~g/dsc m.** 



### Page i 

### ofi 

## VES009415

### Tab l e of C ontents Executi ve Summary ...... .. ... .. .. ...... . . ... . ... .. . . ...... .... ..... ..... . . ... ... ... .. ... . .. . ........... .. .. . . ...... .. . . ..... ....... .. i**i~t** of Symbols .. .. ........ ... ......... . ....... .. ........ .. .......... . ..... .... .... . ... .... ..... ...... ... ..... ...... . ... .. ... . . ........ iv 

### List of F igures .... .. ......... ... .... . .......... ... ..... . . .... . .............. . ............ . ................ .... ....... . . .. .. ..... . . . ..... .. 

### v 1.0 Method Summary ..... . ... ... .. . . ........... .. ...... . . . ........ ... ..... . .. .. ............................................... I 1.1 Principl e .... ... ........................... . ...... ..... ..... .... ....... .. ........................ . ............. . ......... I 

### 1.2 A pplicability ..... . ... .. . . . ..... . .... . . . .... . .... . ......... . . . ... ..... .. . . .. .. .. .. . . .... . .. . . . . .... . ... . . . ... ... .. . ... 

### I 1.3 

### Cautio ns . . ... . ..... . .. . . .. .. . . ........... .. .. .... . ... . ...... ... .... . ... . ... ... . ........... .. ........ ... ....... .. ........ I 2.0 Definitions and Abbreviations ....... . ........ .. ... ..... . ... ..... .... .. .. ...... .. ...... .. ... ..... . .. ... .. . ... . ...... 2 

### 3.0 Sa fety .. ... . .. .. ... . .... . .... ...... ... ...... . .... . . . .. . ...... . ......... . . . .... .... . .. ... ......... . ...... . .. .. .. . ... .. .. ... .. ...... 

### 2 4 . 0 Apparntus . . . .............. . . . ....... . ..... .. ... ...... .... .. ......... . ............ . .. .. ......................................... 2 

### 4.1 Overview .. . ........ ... ........ . ................... .. ................. ..... .. ........ . .. . ... .. .. . .. . . . . ... . .. . ... ... . . . . 

### 2 4.2 Extrac ti on assembly . ... . .... .... . ... . ... .... ...... .... .. . . ....... . . . . . .. . ..... . . . ..... .. . . .. .... .. .. . . ..... ... ... 

### 3 4.3 

### Extrnction flow control module .... ... ......... . .......... . ..... ..... ........ . ............................. 3 4.4 

### Dilution flow control modul e ..... ... .... .. ... .. .. . . ..... .. . .... .. .... . ..... . .. . . .. ... . . . . . . . ... . . . ... . ..... . 3 4 . 5 

### Sa m

ple filter ho ld er assembly .. ... ............... ... . ..... .. ..................... .. .... .. .. . ................ 3 4 . 6 

### Sample 

### flow control module .. .... .... .. ........ .... ................ ..... ...... .... ...... . ........ ..... ...... 3 5.0 Reagents and Standards ...... ... ....... . . ... .. ...... ...... .. . .... ... ...... .. . . ...... ... . . ..... .... ..... .... .... ........ 4 5.1 Filter ca Sll ette .... .. . ................... .. ....... .... ...... .. ....... .... ..... ............... .... .. .. ........ .. .... .. .. 4 5 .2 Desiccant ..... . ... . ......... .. .. .... .. . . . ..... .. ....... .... ......... .. ... .... . . .. . ..... .. . . . .. ...... . ......... . .. .... ... 

### 5 5.3 XRF standards ... .. . . ...... . ......... . ........ . ..................... . .... . . .. . ........ . .... ..... ...... .... .. ......... 

### 5 

### 6 .0 Pre- sample P reparation . . .. .. .... .. .... . ......... . . .... . . .. . . ............. .. .. .... ....... ... ..... ...... .... . .......... . . 

### 5 6.1 Te s t pr ep aration ..... . .. . .... . . . .. ..... ...... .... . .. ..... .. . .... ...... .... .. . . .. ..... .. .. . .... .. . .............. .. ... 5 

### 6.2 Pre-test 13bora to

ry preparation .. .... ..... ........ .. ...... .. . ... .. ... . .. ...... . . ... ... . .. .. ... .. . .. . .... ... .. 

### 5 6.3 S ample train preparation .. ....... . ....... . .. ..... .. . .. ........ ..... .. .. .. ....... . .. ........ . .... .. ... ....... . .. 

### 5 7 . 0 

### Sa mpl e Collectio n ... ......... . .......... . . ..... . ......... .... ..... ... ......... . ..... ....... ..... ... . .. . .......... . . .. .... . 6 7 . 1 Filter 

### h older lea k check ............................................................................... .. ........ 6 7.2 Setting tot al fl ow 

### n eedle valve ... .... . ........ . .... ... ..... .. ........ . ....... .......... .. ........ ... ...... .. 6 

### 7. 3 F ilt er temperature range ...... ...... ...... ..... . ..... ... ... .. ...... .. .. .. . .. .. . .. .. .. . ... ... . .. .... ..... . . .. . . .. 6 7.4 Evaluation of 

### samp l e meter accuracy .. .... ..... ...... ..... .... .... ...... ..... .... ...... ...... .. ...... .. 

### 6 7.5 

### Filter c asse tte instal la tion ................ ... ........ .. ................ ... ....... .... .... .. ...... .... .. ......... 7 7 . 6 Sampl in g . .......... ... .. . .. .......... . ... ... .. ............. . ... .... ....... .... ... . .. .... .. ...... . ......... . .. .. ........ 7 

### Pa ge ii ofv 

### V ES00941 67 . 7 Sample recovery . . . . ... ... . ..... ........ ... .... . .......... . .. . .. .. .. .. ..... .. . . .. ........ . ...... . . .. ... . ............ 7 7.8 Post- test Checks . . .... .. . . ... . ....... .. . .. . ... .. ........ .. . . ................. ....... .. . .......... ........ . .. ........ 7 8.0 S ample R e covery , Handling a.nd Pres e rvati on ... . . . . .......... . ... . .. ... . . ........... .. . . .. . . . . . .. ...... . .. 7 9. 0 Elementa l Analysis .. . . ... . .... . ... .... ........ .. ..... .. . .. .. .. . .. . ... . . .. . ... .... . . . ... .. . . .. ... . . .... . .. . .. ....... . . . . . . g 9 .1 Analysis .. . . .. .. . ........ . . .. . . . . .... .. ... .... .. .. .......... .. .. ....... .. . ....... ... .... ..... ..... . ... ............ ... .... 8 9. 2 Ca lib ratio n . . . .. . ..... ... .. . .. . .... .. . .... . . .... . ...... ... . . . .. .. . ... .. .. . . .. ...... .. ....... .. ... . ....... . ..... . . .. . . . .. 8 10.0 Calculations . . ... .... ... . .......... . . . ... .. .... . .... . .. ........ .. .. .. .. . ... . ..... . ..... . . . ... ................. ... .. ... .... ... .. 

### 8 10. 1 

### Fl ow Correction F a

ctor .... .. . .. . . .. .. .. ... ..... .. .... .......... ..... .......... ............. ........ ............ 8 10 . 2 

### XFM Measured A e ro sol Concentra tio n ... . . ..... . ..... . ....... . . .. .................... .. . . .. .. .... .. .. 

### 9 1 1 . 0 Q uality Con trol ........ .. .. ..... .................... .. ......... ........ .......... .. ..... .. .............. ..... .. .. ........... 9 11.1 Sam p ling ................................ .. .... .. .............................. .. ....... .. .............. .. ........... .. . 

### 9 

### I 1.2 A na lysi s ..... ........... ... ............. .. .. ... ..... .. .... .. . .. ... .. .... ............ . ........... .. .......... ....... .... .. 

### 9 12 . 0 Method 

### P erformance . ....... ... .. ... ........ .. . . ............................. . ... .. ................... . .. . . . ... . ..... .... 9 12. 1 Range ......... ... ..... . ..... ........... ...... .. . . .... ..... . .. .. . ........ .... ... . .. .................... .... .. ........... 10 

### 12 . 2 Det ection L imits .. ... ..... .... ....... .... ...... . . ... . . . ... ...... . .. .. .. .... ... ..... . .. . ........... . .. ...... . .. . ... 

### I 0 1 3. 0 Pollution Prevention. ......... ......... . ... .... . ...... ..... .......... ... .. .... ....... .. .... ..... ..... . . .... .... . ........ 1 0 1 4 . 0 Waste Management . .. ... .. ............ . ..... .. ................. .. .. . ..... ..... ......... ............ . .. .... . ......... ... 10 15.0 Ta bles an d Fi gures ... ...... .. ............................. . .... .... .. . .. .... . . . .. . .. ........ .... .. ..... .. ....... ... .... . I0 16.0 R eferences ............................... .. .... ... ......... ..... ............ ... .... .. .. . . . .... ...... ... . .. .. ....... . .. . . ..... 17

Page iii ofv 

## VES009 4 17

### Li s t of Sym bo ls**c,~m t**  

# • Con centration of the 

### ; •h analyte in the emission measured by the XFM 

### M, l'11'£ • XRF-detennined mnss of the;"' analyte on the PTFE filter M,fll!o- ? . 

### XRF-dot e n ni ned mas s o f 

### the 

### ;•h aua l yte on the reactive filter (RE0 -7 ) 

## v

: TJJ a 

### Total volume (emission plus di lut ion) sampled by 

### the XFM 

### Vfn' Q 

### Volume of dilution air drawn through filt ers of 

### t h e XFM



### Pag e iv ofv 

## VES009418

### List of Figu r es F

igure I Flow diagram of the sampling train us ed in P hase I and ll 

### XFM validation tes ts . .. 12 Figure 2 : Sample train componen ts used in Phas e I and U XFM validat ion tests ..... .... .. . ... .. . 1 3 Figure 3: E x plo ded view of 

### the extraction assembly ... .... ... ................. ...... ............. .. .... .. .. ...... 14 Figure 4 : 

### Sc hematie diagram of the extraction flow cont rol module. ....... ..... .... .... ...... ........ .. 14 

### Figure 5: Schematic diagram ofthe dilut ion fl ow control modul e ........ .... .... ....... .... .. ...... ...... 15 F

igure 6 : 

### Exploded and assemb l ed v iew of t he sample fi l ter h older... ........ .. ........ ... .... ...... .... 15 

### F i

gure 7 : 

### Schematic diagram oflbe sampling flow control module ........................... ... ......... 16

1112'9Jl(ltQ! 3:45PM 

### Page v ofv 

## VES009 4 19

### 1.0 M ethod S umm ary 1

.I Prin c iple 

### A representative samp le of flue gas 

### is drnwn from an 

### Xact CEMS 1 

### stilling chamber through a 

### cassette containing PTFE 

### and reactive filters. The e lement:; in particulate matter (PM} 

### are deposited on the 

### PTFE filter while the vapor phase elements are trapped on the reactive filter. The elemental mass 

### in each filter deposit is determined by X - Ray FluoreS(;ence (XRF} 

### using E PA 10 

### Compendium Meth od 3.3 1

. 

### Metal conce ntrat i ons in stilling chamber flue gas 

### are calcu Ia

### ted by 

### dividing the volume of the flue 

### gas sampled int o the eleme ntal m ass measured by 

### XRF. 1.2 A pp licability 

### This method is applicable to the measurement of metal aerosol concentrlltions in the 

### XactCEMS 

### stilling chamber. 1 .2. 1 

### Analytes 

### This method is applicable to Antimony (S b), Arsenic (As), 

### Cadmium (C d), 

### Chromi um (Cr), 

### Coba lt (Co), L ead (Pb ), Ma . nga.nese (Mn), Mercury ( Hg ) , Nickel (Ni) , and Selenium (Se) and is generally appropriate for eleme n ts wit h atomic number f1om about 13 (A I ) 

### through 92 (U) 

### as n oted in 10 

### Compendium Method 3.3. 

### This sampling melhod is also applicable to Beryllium (Be), if measured wi th 10 

### Compen dium Method 3.4l 

### after non -dest ru ctive XRF 

### analysis . 

### 1

.2.2 lmer ferences 

### There are no kn own flue gas components in their typical concentrlltions !hat interfere wilh sample collection . E lemental interferences 

### a re addressed in 

### 10 Compendium Method 

### 3. 3 2 • 

### 1 . 2.3 Concentration Range 

### Th e appl ic able concent ration ran ge o f th is method is from less tban 0.2 

### l! g/dS(; m (Table I) 

### to ov er 

### 2000 l!gldscm. 1 . 3 Cautions 

### This melhod does 

### not include all of !he specifica tions essential to its performan ce. Some material i s inc o rporat ed by reference . Therefore, to obtain reliable res ults, persons using this method should have a thorough knowledge of at least E P A Methods 1 4 

### and 

### 2 5 

### and EPA 10 

### Compend iu m Method 3.3 2 •

I 1/29 / 2005 XFM f(lf X a.et.. CEMS SOP VI 

### Page I of 17 

## VES009420

### 2 . 0 D e f mit io n s a nd Abb r e , • i a ti ons Accura cy : The agreement between an experimentally determined value and the true va lue. Ae , roso l : A suspension of solids aod/or liquids in a 

### gas. A o aJyte: A species (c l ement, metal, etc . ) of interest in an analytical method. D etectio n Limit: l11c lowes t concen trntion of 

### an e lemen t that can reliably be distinguished from 

### a zero concentration. Int erferan t : A substance other thao the analyte that 

### causes an undesired po s itive or negative outp u t. NJ S T: U. S. Department of Commerce , National institute ofStandards and Technology , Gaithersburg, 

### MD 20899 Uncerta inty : An i ndication ofthe degree of reli a bil ity of a value usually expressed statistically (probability) as 

### a multiple of the standard deviation of 

### a set of measurements . Unless otherwi s e stated, th e unc e rtainty in a mean value of a series of measurements w i ll be the**~"tandard** deviation . 

### In the case of values based on calculations, the unconuinty in the value is equal t o the propaga ted uncerta inty based on the uncertainties in the parameters used in the calculations. 

### 3. 0 S af ety This method involves the measurement of hazardous materials and the operation of equipment with th e potential to cause bodily harm. This test method does not address appropriate safety 

### and health practices associ ated witb its use . It 

### is tl1e res ponsibilily oftbc user of this test method to establish appropriate safety 

### and health plans prior to perfonning thi s method. 

### 4 . 0 A pp ara tu s l11e sample collection a pparntus used for thi s method is described in the fo llowing subsection. The equipment required for the XRF analysis of the filters is specified in 10 Compe n dium Method 3 . 3 2

. The sample collection equipment consists of the following five major components (Figure I 

### and figure 

### 2) : • Extraction assembly • Ext raction flow control module • Dilution flow control module

1112912005 XFM rar**act ~EMS**  SCW V I Page 2 of 1 7 

## VES009 42 1

### • Sa mple filter h ol der assem bly • Sample flow control module 4.2 Extraclio11 assembly 

### The extraction assembly (Figure 3) i s usec.l to d raw flue gas from t he Xa ct**~'tilling** 

### chamber d1rough the extra ction plate via the extraction fl o w control mo dul e (S ub section4.3) . A 

### sul>- sam ple o f t h is flow is drawn fro m the 

### elt tra ctio n a ssembl y through the p robe p late by t he sample fl ow control modu le (Subsection 4.6) . A 

### dilution pla te is directly downstream of the 

### probe pla te and the s tack g as sample is diluted and mixed with CDA 

### prior to passing through th e filter holder (Sub sec tio n 4 . 5). 4.3 Extraction flow control modul e 

### This module (Figure 4) 

### uses a n eductor to draw flue gas through the extraction assembly. The flow rate is controlled by n 

### standard industrial pressure regulator with gauge and 

### powered by com pressed C D A. The fl ue gas is then filtered, dried , and denuded of corro sive m at eri11l before it is elthausted back into the stilling chamber . 4.4 Dilution flow comrol module 

### The dilution flow contro l module (Fig ure 5) 

### dries, c leans , co ntrol s, meas u res and totalizes the flow 

### of dilution gas. 

### C lean , dry, compressed air is further dried in this module before it is u sed to d il ute the sampl e flu e gas. TI1 e dilu tion gas flow and pre ssure are con tro ll ed with a regulator, pre ssure gaug e and 

### a needle val ve. The fl o w rate i s measured by a mass flo w meter (D - MFM) . A 

### dilution flow integrator (D FI) 

### totalize s the output from the 0 - MFM 

### and reports the total vo lum e of d ilu ti o n air that has been udded t o the gas strea m. 4. 5 Sample filt e r hold e r as sembly 

### TI1e s ample filte r holder assembly (Figure 6) is used to 

### trap particulate and vapor phase 

### m

etals in the emission s ample . Two filters are con tained within 

### a 37 

### mm polypro pylen e filter cassette inside th e ftlter holder. The first ftlter 

### is non-reactive 

### PTFE fi lter and is 

### used to tmp patticulate phase metals . The seco nd filter is a reactive filter that collects vapor p hase metals 6

. 

### Downstream of the fi lt ers, a thermocoup le provides temperature information to en s ure. that the filters re main within the ir opt imal temperature range of 

### 100• to 

### 1 80" F. This assembl y includes a 

### qu ick di sconnect f or usc 

### with l ea k 

### cbccks . 4 . 6 Sample jluw c:untr ul m odu le 

### This module (Figure 

### 7) con trols the fl ow rate of diluted flue gas tl1r0ugh the filt ers and measures th e total sample flow. 

### After passing**tl~rou gb**  

### t11e fil ters, the gas 

### i s dried an d corrosive species 

### removed prior to detennining the dry 

### gas flow rate with a 

### mass flow me ter. 4. 6.1 Desic:c: anl Dtyer 

### D owns tream of the filler hold er, 

### a d esicc ant dryer i s used to remove mo ist u

re pri or to fl o w measuremcnL The XFM 

### reports concentrations as mass per dry 

### s t an dard vo lume. li1291200S, XFM 

### ror Xx1..CEMS SOP V I 

### Pag e3ofl7 

### VES009422

### 4.6.2 Corrosive Trap Following the desiccant dryer , the diluted flu e gas is drawn through a corrosive trap designed to remo ve corrosive flue gns species. 

### 4 .6.3 Total Flow MFM The total mass flow meter (T- MFM) measures the total flow (I -2 dslpm) passing through t he 

### filters. Thi s flow meter produce s 

### a 4- 20 

### mA s i gna l which is read and to tali zed by the total fl ow integrator (TFI). Th e total sampl e volume is 

### calculated by subtracting the dilution vo lume fro m tbe total volume. 

### 4.6.4 Vac tnnn 

### Ga.uge A 

### vacuum gauge cap able of reporti ng 

### a va cuu m between 

### 0 and 29 

### in . Hg is used to ensure that a vacuum can 

### be maintained 

### in the 

### XFM during leak check s . Monitoring of th i s gauge during sample co llection prov ide s cont i nuin g qu ali ty assurance of vacuum and 

### filter integrity. 

### 4

.6.5 Needle Valve A 

### needle val ve is u sed 

### for f ine control of the total flow rate during sampling. GeneraUy , litt le adjustment of the needle valve is necessary after the initial adjustment to achieve the de sired flow . 

### 4 .6. 6 1\vo - way Valve A 

### manual two-way valve located just upstream of the vacuum pump is used to perform pre

### sample l eak checks. This valve can al so 

### be used as a 

### course flow ad j us tment to regulate lhe tOtal flow passing through the filtec. 

### 4.6.7 Vacuum Pump A 

### diaphragm vacuum pump is used to 

### pull the emi ssion and 

### dilution gas sample through the filters . Tbe fil tered, clean ed and dried gas samp le that p asses through the pump is then returned to the stack . 

### 5 . 0 M a te ri als, Reagents and S t a ndard s S. I Filte r cas sette On e 37 nun diameter PTFE (Teflo7 

### or equ ivalent) and one 37 nun di ame ter RE0 - 7 8 

### filter fo r trapping particulate and vapor phase metals are 

### required by this method for each run. 

### Th e two filt ers sh ou ld b e pre-loaded into 

### a l abel ed 37 mm diameter fi lter cassette in a clean , dry environment prior to the test 

### run . Filter cassettes should be 

### stored in 

### a l abel ed Petri dish before and after samplin g. Page4 of 17 

## VES009423

### 5.2 Desiccant The XFM sample dryer requires an indicating desiccant (Agilent Silica Gel Grade 40 9 

### or equival ent). A 

### sing l e dryer canridge may be used for multiple runs as long as the desiccant remains below the removal capacity specified by the manufacturer. 5

. 3 XRF 

### standards 

### XRF thin-film standards for metals of interest s hould be used to 

### calibra te the 

### XRF prior to operation according to 

### IO Method**3.~** 

### Standards should have a known 

### mass per 

### area ()Jg/cm') to within five percent. 

## 6 . 0 Pre-sa mple Pr e pa ration 6. I 

### Test pr epa ration The complexity of this method is such tltat, in order to obtain reliable results, both testers 

### and analysts must be trained and experienced with the test proced ures, including source sampling; sample handling; safety equipment and procedures; analytical calculations; repo rt ing ; and the specific procedura l descri ptions throughout tllis method. 6.2 Pre -test 

### laboratory preparation Check filters visu ally against light for irregularities, !laws, or pinhole leaks. Prior to shipping, load one upStream PTFE 

### filter and one downstream RE0 - 7 

### fllter for each run 

### into a labeled filter cassette and place into a labeled Petri dish for transport. Provide one loaded filter casset1e for 

### a QA field blank . Before each series of tests , the now rates for both 

### the total flow an d the dilution flow integrators s h ould be 

### checked against a 

### certified NIST-traceable meter. The 

### flow reading on the integrator s hould be within five percent of the reading on the certi'fied NIST traceable meter. 6.3 

### Sample 

### rranz preparation 6

. 3. 1 

### Sample flow rates 

### and samp/1! time 

### Sample and dilution flow rates may range from 0.5 to 1.0 s lpm, but should not vary by mor e than ten percent during a test run. Sample time should be between 10 and 50 minutes. 6.3.2 Extraction 

### assembly and dilutionflow mod11le leak checks 

### and s ampling rate The extraction and dilution assembly muSt be leak checked prior to mounting on the XactCEMS sampl i ng port. To perform this leak check, cap the port adaptor with a rubber Stopper and insert the extraction assembly plug (Figure 3). Connect the dilution line for compressed air to the dilution plate port and cap the 3f8"extrnctio n p late port. Pressurize the**a.~semb y**  

### to 5 

### psi and close the dilution flow shut-off valve. The gauge reading should be stable (±5%) for 30 secon ds . Following a successful leak check, remove the stopper and 3/ 8" cap nut. The 11 '29.1 2005 XrM for X.11e....CEMS sor V I Page 

### 5 of 17 

## YES009424

### extraction assembly and dilution line can now be moun ted on the Xact-CEMS stilling chamber sampling port The now from the Xact-CEMS stilling chamber through tbc extraction assembly should be**main~aine<.l** 

### in the range of 15-30 s l pm. The XFM extraction assembly temperature should be above 220 ° F. 

### 7 .0 S ampl e C olle cti o n 7.1 Filter h older leak chec k 

### A filt er bolder leak check must be perfooned ufter the filter cassette has been loaded in the filter holder. To pcrfomttbis check, sea l the fi l ter h older assembly with the filter holder cap 

### nut (Figure 6), tum on the pump and allow the vacuum to reach 15 in Hg . Close the sample Oow shut - off valve (Figure 4) , tum off the pump, and record t he initial pressure and the pressure after 30 seconds. To pass this check , the change in pressure must be less than five percent of the initial pressure. Disengage the sampli ng train quick disconnect to release the vacuum (figure 6) . 7.2 

### Setti11g total flow needle 1'(1/ve 

### The tota l fl ow rate (sample and dilution) that passes Urroug h the filter is controlled by a needle valve (Figure 7). 

### To determine the needle valve's initial set point, plaoe a loaded blank filter cas se u c into t he filter holder and l eak check as stated above. Ins tall the filter holder onto the extraction assembly, wlticb i s at openting conditi ons. Open the sample shutoff va lve fully and turn on the sam pl e pump. Set the needle valve so that the T-MFM reads the desired sampling rate. Then close the shut-off valve and turn off the pump. For each s ample run , the shut-off valve wiU be used to start 

### the sampling now while the needle valve should be used to make minor flow adjustments as needed after the sampling has started. 7

.3 Filter temperature range 

### Since filter holder temperature can in crease at 

### the start 

### of tbe run , it 

### is recommended that the filter temperature be maintained at about 140 °F before sampling begins and should not exceed ISO • F at any time during sampling. 7

.4 EvaluatiOil of sample meter acc uracy 

### Prior to the firs t run , the accuracy of the T - MFM should be checked using a NIST-traceable flow meter nod stack 

### gas. Mount the filter bolder containing a filter cassette , attach the N'ISTtraceable flow meter to the sample flow outlet, tum on the sample pump , open the ball valve and allow stack gas to pass through the filter , T -MFM and NIST - traceable meter. Compare the T-MFM value t o the NlST flow m eter. Th e values shou l d be within tive percent. Ifthey differ by more than five percent, a correction shou ld be made using the fonnula in Section I0.1. Disconnect the NIST flowmeter and pl ace a new filter cassette in 

### tbe fil ter holder before starting the fmt sample run.

1 1 129

1 200S XFM fo r X

a ct

<EMS SOl• V I 

### Page6 of 17 

## VES0094257.5 Filter casselte installatiOII 

### For each run, fill out the XFM Fi eld Darn Sheet (Tnble 2) , iden tifyin g the date , run, opemtor, XFM module !.0. no., and fil t er J.D. numbers , and date, time, and o the r data for 

### the tes t run. I nsert fil t er cassette into the filter holder and conduct a filter holder leak check. 7.6 Sampling 

### Pr

i or t o s ampling , zero th e total fl ow integrator. At a time 

### co ncurrent with the srnrt of an Xact samp le run, start the XFM sample pu mp. open the ba ll valve , and recor d the initi al dilution volume and 

### stan time . Sample for 10 to 50 minutes , recording tempcrarures, pressures, an d volumes every five minute s. Use t h e dilution and total flow n eed le valves t o e nsur e that the fl ow rates are constant and monitor the filter tempera ture t o en s ure tha t it remains below 180"F. When sampling is complete, close the shut-off valve, tum off the vac uum pump and immediately record the di lution vol um e, t o tal volu me and sample run end lime on the wo r k

.sbeet. Not e: It 

### i s recommen ded tha t a post-rest sample flow leak chec k n ot be conducted since the test may c ompr omise the sample collec t ed on the fi lter. 7. 

### 7 Sample r ecovery 

### After removing the filter ho l der from the extraction ossembly,**disa.~semb e**  

### t he filter ho l der and remove the filter cassette. Return the filter cassette with filters to the original Petri dish, and seal tbe dish with tape. Do n o t separat e the PTFE and reactive fi lters from the filter cassette. Document any abnormalities on tbe filter and s hip to tbe appropriat e laboratory for a

naly sis. 7.8 Post-tesr Checks 

### The follow in g checks need to be made after the last t es t run i s comple t e and before p acking the equipment for return shipment. 7

. 8.1 F low Agreement Ch eck 

### Calibra t ion ofthe dilution an d total mass flow meters should be checked following the same procedure as in s ubsection 7. 3 . 7.8.2 E.waction assembly a11d dilurionjl<nv module assembly leak checks 

### The extraction**a.~embly** 

### and diluti on flow module l ea k chec k s hould be perf o nned acco rdin g to tbe sa me procedures found in subsection 6.3. 

### 8. 0 Sam pl e Recovery , Handling a nd Pr eservatioll Open the fil ter casse ttes in a clea n wor k area and note th e co nditi on of the fi lt ers. Carefully remove the filters from th e fil ter cassettes ao d pla ce eac h filter sampling sid e up in a separa tely labeled Petri slide . Filters should be stored in 

### archives at temperatures less than**11~!~\C** b Xacc.CEMSSOPVI 

### Pa ge 7 of 17 

### YES009426

## s•c. Th e filters remain in archives until they are scheduled for analysis . Following XRF analysis tbe fillers may be re turned to storage and analyzed again at a later date or they may be submitted for analysis for beryllium (Be) 

### according to the procedures outlined in Co mpend ium Method 

### 10 3 .4. 

### 9 . 0 E l em e ntal 

### Analys is 9.1 Analysis 

### TI• e analytical procedures are similar to those in Compendium Method 

### I0-3.3 2 

### "Standard Operating Pr oced ure for the X-Ray Fluorescence Analy sis of PM 2.s Deposi ts on Teflon Filters". Thes e methods address the ap plication of energy dispersive X-ray fluorescence spectrometry (E DXRF) 

### to the d ete nn i n ati on of 

### elemental coinposition of particulate matter depo sits on filters. 

### 9.2 Calibration The X-ray fluorescence analyzer is calibrated using thin film standards of a k.nown concentration (usually in 

### 11g/crn'). 

### Potential manu f.1crurers of thin fihn 

### standards are listed in Compendium Method 

### 10- 3.3 For 

### each e lement, a calibrati on sensitivity f actor is 

### obtained by dividi ng the x-ray intensity (counts/sec ./ rnA) by the concentration ofthe standard ( 11glcm'). 

### Generally these s tandards 

### are larger than the area of the exciting X - ray beam 

### while the XFM d eposition spot i s smaller than the 

### beam. For this reas on , a 

### thin film t o spot ratio must be 

### estab li s hed during calibration. This thin film to spot ratio is det e rmined empirically by using a 

### single s tandard of a 

### known concentration with the same area as 

### the XFM 

### deposition spol This ratio is determined for each analys is condition and is applied to each elemen t in that analy si s condition . 

### 10. 0 Ca l cu l ation s JO . J Flow Correctio n Fa c t o r B efor e each series of tests , the n ow rates for both the total integration 

### and the dilution integrator should be check ed against a certified NIST- t raceable meter. The n o w reading o n the integrator ( FFJ) 

### should be within five p ercent of the 

### reading on the certified 

### NIST traceable meter ( 

### F,.,., ) and recorded 

### in the field notes. lf 

### they ar e not w ithi n five percent, the noted di ffe ren ce mu st be used to calcu late a correctio n fac tor ( CF,) as defined below: Equation 1

llll9! 200..S XFM for X11ct-C£MS SOP V I 

### Page 8 

### of 17 

## VES009427

### 10.2 XF M Measured Aerosol Concentr at

ion The XFM-d e tennined con centration of tb.e fiv e MA C T me tals in the samp led flue g as is based on a measurement of the metal mass depos ited o n the 

### XFM fil ters and the samp le volume that passed throug h the filters. The 

### XRF analysis re s ults yield the rnetul masses in 11& of each 

### reported metal per filter. The 

### total sample vo lu me is 

### determined b y s ubtracting the dilution volume from the total vo lu me . These paramet ers are used 

### in Equation 2 

### to calculate th e concentrat i on of each analy t e a s shown below : 

### M l'f'FP. 

### M 'E()...' c ,..X FJI 

### = I 

### + I I y. rF>I _ y XFU , d 

### E quaoo n 2 

### Where: 

## C

t"' "**~** 

### Con ce ntrati on of th e i'h analy te in the emission measured b y the 

### XFM ( 11g / d scrn) M 

# ;m =**XRF~erennined** 

### mass of the ilh 

### anal)'le on the 

### PTFE filter (11 & ) 

### M , R£o-' = 

### XRF«tennined mass of the i 111 

### analyte o n the reactive filte r 

### (REO- 7; 11&) 

## v; ...., 

## = Total volume (e mi ssion plus dilution) sampled by the 

### XFM ( dscm ) 

# V /" " = 

### V o lume ofdi lution air dra w n through filters o f the 

### XFM (dscm) 

### 11 . 0 Quality Control 1/

. 1 Sampling 

### The sampling quality control requirement• in c lude p erf onning all necessary lea k c h ecks and checking the flow readings again s t a NlS T traceabl e s tandard . Th e foll owing is a lis t ofall n

ecessary sampling q uali ty control procedures . I . 

### EXtraction assembly leak check ( See 

### sub section 6.3) 

### 2. Di lution assembly leak c heck (See subection 

### 6.3) 3 . Sample filter holder assembly leak check (See**sub.~ection** 

### 7 . 1) 4 . 

### Flow calibration check (See subsect ion 

### i .3) 

### 11.2 Anal y.tis 

### Quality conrrol 

### and assumnce procedures 

### are perfonned 

### in accordance with Compendium 10 -3.3. 

### 12.0 Method Performanc e

11/29 !lOOS XfM (Or**Xaet...C~ ;;** **MS** SOP V I 

### Page 9 of 17 

## VES0094 28

### I 2.1 Rtmge The applicable concentration rnnge is from less ihnn 0.2 1•g/d scm to over 2000 jl g/dscm. 

### I

2.2 DeJection 

### Li mil s The interference free 

### detection limits ut the 95% confidence levelr ......! o ..

k .. ork • • • •dl•"'· 

### are given in Tobie I 

### a$Sum i ng a sampling rate of0 . 7 sl pm and a sampling time of30 minutes. Actual meihod d e tectio n limi ts are 

### based on actual source sampling and analyti cal r esults. If required , the method**in- 1ack**  

### detecti o n limits can be i mproved over t ho se shown in Table I 

### by eith er increasing the 

### stack gas volume sampled , the sample t ime, or 

### XRf analytical time. Inc reasing ihe volume sampled by a factor of two results in a corr esponding two fo ld in crease in the detection limits . 

### XRF detection limits improve with the s quare root of the analysis time. 

### 1 3.0 P o lluti on P r even tio n The exhaust from the s ample flow module is 

### vented to the otmosphere after pas sing thro ugh lhe sampling 

### filters, dryer 

### and corrosive gas denuder . There are n o reagem solutions generated in thi s method. 

### 14.0 Was t e Manage ment Sample lilters are 

### arch ived for one year and !ben disposed as non-hazardo us waste . 

### 15.0 Tab l es an d F i g ure s Table }· 

### XFM D etection LimitsEnM llool;m >tk not defi n ed. Element Symbol Analytica l In -sta c k

. {l!l!ISJ)Otl lualdscm) . Antimony Sb 23 . 0 2 . 20

Arsenic As 1.3 0 . 1 2 Cadm i um Cd 13. 0 12 Chrom iu m Cr 1.3 0.12

Cobalt Co 1 . 3 0.12 Lead P b 1 .7 0. 1 6 Manganese Mn 1 .3 0 . 12

Mercury Hg 2 . 1 0.20

Ni ckel N i 0 .8 0.08 Selen i um Se 1 .3 0.12

S ilve r 

### Ag 8 . 4 0.80 

### Page 1 0 of 

### 1 7 

## VES009429Da te R un N o . Opem tor(s): XFM Mod ul e No . PT F E F il te r No . RE0-7 Fi t ter N o. Pre-test Filter EvaJ . Leak Chec k Posl-test Filte r Ev. 

### Ext Time Te mp .

" F

NOTES : Table 2. XFM Fi eld Data S h eet 

## XFM FIELD DATA SHEET Start Time Stop T i m e A) !nit. Tot. Vol. (Oil. A ir) B) Final Tot. Vol. ( O i l . A i r) C) 0 11. Air for Test (B-A) D) I nitia l Total Vo l. E ) Final TOOl! Vol. F)Total Test Vo l. (E·D) G) Net Sample Vet (F-C) Filter Samp. Oil. F low Dll . Ext Flow Flow Temp . Flow Flow Vac . Pres. V a c .

• F lite rs l iters in . Hg in. H g in. Hg

ll fl 9.'200.S Xllol for Xx•<EMS soP VI 

### Page II of 1 7 Ext. Dr i er Flow Pres. Pres . ln . Hg ln. Hg



## VES009430Extraction Assembly Filter Holder Assembly



## . 

# """**[J ~;**  i

## xtracti~**!!~~** con1 r oJ1

### ~

# l~**~** .. 

# -----

Dilution Flow Control M

od ule """ Sample Flow Control 

### + Modu l e

# ~= 

# :J**J** Fia ure l Flow diag ram of the sampliug tra iu u sed I n Ph ase I a u d II XFM valldation 

### tes ts.

ttl29/lOCH XFM 

### r.,. x..o.ca.ts 

### sor v1 !'age 1 2 o f 17 

### VES0094 3 lOlk.I OOn F1ow**Co tr~**  Mod\le**,-- ----** **-- ---** **---- ----** **-------·~~**

Extmcdon FlOw COn1rQI Moc:f\MJ**-- --** **-- -------** **M·-- -----** **~--- ---~**  

## ' ' ' ' ' '

# ------**---- --** **---- --** **--- oe** **:s;; ~**  . '**~».- ...**  

## •**~·** 

## ' ' ' 

### ' 

## """' '

.......... O"JAt : 

### ' 

# -- : 

## '--- - - ---- -- · ---- - ----- ----- - -- -- -- ---' Figure 2 : S ample tra in co mpo n e n ts u sed in Pbas<> I an d ll X Fi\'1 validadon tes ts.



### Page 1 3 ofl7 

## VES00943 2

# - 

# -- £ •1Nrl•lfl**Aurni ~**  

# ...

......... 

# - -

.... 

# - ••• Oiknloo 

# ....... Figure 3: Exp loded view of the e xtra c tlou assembly.

0..**~** 

# - Figur e 4: Schematic diagram of the extraction now control module.



### Page i4ofi 7 

## VES009433, .--:;;n__ - 

# ... 

# ....... r. r.-:: ...



# .. ...,., FigureS: Sc hemati c diag ram of tbe d ilution flow cont ro l m odule.**PWI:! Wa!l** **~** 

# 0**T~** CamtiC R l ncl 

### I

# Rl**;:Cf** 

# I 

# I ....,.;,:...,..

Figure 6: Ex:plod ed and assemb led vi ew o f th e sa m ple filter bol d er.

11'29r.OOS XFM I(" X ...

-CEMS soP V I Page 1 5 of l7 

## VES009434

# ·- 

# -**~r======:::;tr=! ~**  

# -

__ ..r.,



# - - - ll!lfll fl tr,.. Vo. -wm**~C\'lle** llall y 111111 .,. Ncu Ollop: Vd w \ '.rw fiM¥ 

### Figure 7: Schemati c 

### diagram or 

### the sampling Dow control 

### m od ul e.

Page 16 of 17 

## YES009435

### 16.0 R e f ere nc e s Xact-CEMS. X- ray Bused Continu o us Emissions M onitoring System for M ulti - Metals. Manufactured by Cooper Environmental Services, LLC. Po rtl and , O il 

### www.cooperenviron.meotal.com. 2 EPA Compendium of Met h ods for t he Detennination of Inorganic Compounds i n Ambient Air. June, 1999. Compendium Method 10-3 . 3 Detem1ination of Metals in Ambient Particulate Motter Using X-Ray 

### Fluorescence (XRF) 

### Spectroscopy . EPN625/R96/010a. 3 

### EPA Compendium of Methods for the Determinatio n of Inorganic Compounds in Ambient Air. June, 

### 1 999 . Compendium Method I0-3.4 Determination of Metals in Ambient P articul a te Matter Using Inductively Coupled Plasma (ICP) Spectroscopy . EPN625/R-9 6/ 010a. 4 EPA Method I. 

### Sample and 

### Velocity Traverses for Stationary Sources. 

### 5 E P A Method 

### 2 . Determination of Stack Velocity a n d Vol umetric Flow Rnte (TypeS Pitot Tube) . 6 

### NIST. Na t ional Institute of Standards and Techoclogy. Gaithersburg , Md. 

### www.NJ ST. gov. 7 Teflo Filter. 2003. Manufactured by Pa ll Life Sc iences Laboratory Filtration and Separation Catalog. pp.30-3l . 8 REO- 7 . 

### Manufactured by Cooper Environ menral Services, L LC . P ortland, O R . 

### www . coopercnvironmeotal.co•n. 9 

### Agilent D ryer . Manufacturered by Agilent technologic . Found on the web at: 

### h

t tp://w w w.cbem .agi l cnt. com

l l/29f2003**l** (or X•1.CEM S SOP V I Page 17 

### of 17 

## VES009436

# VES009437 . pdf

# App e ndix C

H ydro gen C hloride (HC L ) C ontinuou s Emi ss ion Monitoring System S upporting Do c uments

V

e rs i o n 1.0 

### November , 2· 005



## VES0 094 37

### Table o f Con toots I. Perfonnance Specification Z : Spec ification s and Test Procedures For Hydrogen Chloride (HCL } Con tinuous Emissi on Monitoring S ys tems At Stationary Sources, El i 

### LiUy, November 2005. 2. Procedure DD: Qu ulit y Control and Qualit y Assurance Requirements for H

ydrogen Chlorid e (HCL) Conti nuous Emission Monitoring Systems At Stat ionary Sour ces, Eli Lilly, November 2005.



### VE$009438

# VES009439 . pdf

# Appendix D

Miscellaneous Performance Specifications and Quality Assurance Procedures Supporting Documents

Version 1. 0 N

o vember , 2005



### VES009439

### Ta b le 

### of Con t e. n«s I. Perfonnance Specification 2 - Specifications and T&-t Procedures for S02 and NOx Co ntinuous Emi ssion Monitor ing Systems i n Sta t ionary Sources, 

### 40 CT'R 60 Appendix 

### B , February 

### 2000. 2. Perfonnance Specification 4 A - Speci fications and Te st Procedures for Carbon Monoxide Continuous Emission Monitoring Systems in Stationary Sources, 40 

### CFR 60 Appendix 

### B, Febru ary 2000 . 3. 

### Performance Specification 4 B- 

### Specifications and Test Procedures for Carbon Monoxide and Oxygen Continuous Emiss ion Monitoring Systems in 

### Stationary Sources , 40 

### CFR 60 Appendix B , September 30 , 1999. 4. Appendix to Subpart EEE of Part 

### 63 - Quality Assurance Procedures for Continuous Emissions Mon itors Used for Hazar dou s Was t e**Combtl~tors,** 

### 40 CFR 

### 63 Subpart BEE. September 30, 1999



## VES009440

# VES009441 . pdf

## VES009441

# PERFORMANCE SPECIFICATION Z: SPECIFICATIONS AND TEST PROCEDURES FOR HCI CONTINUOUS EMISSION MONITORING SYSTEMS AT STATIONARY SOURCES

Revision 1 . 0 N ovember , 2005



## VES009442EXECUTIVE SUMMARY This periormance specification describes the criteria that a hydrodlloric acid (HCI) confinuous e m i ss i on monitori ng sys te m (C EM S) must meet to be co nsid e red va li d for EPA com pli ance a nd/o r other regu l ata<y applicaUons . Each HC I CEMS must meet the cri teria for accuracy . slability, and lnslrume nta l respO nse la id out I n th i s documen t. I n ad diti on, each H CI CEMS must meet the installatio n requi re m ents In P S - Z .



## VES009443TABLE OF CONTENTS 1.0 USING PERFORMANCE SPECIFICATION Z ....... ... . ....... .... ............. ... .. . .............................. 3 1. 1 WHAT IS THE PURPOSE A N D APPLICABI L ITY OF PER FORMA NCE SPEC IFICA T I ON Z? ................................ . ....... ... ... ...... .. . .. ... .... .. . ......... . .... ... .... ... .... .. .... .. 3 12 WHAT WIL L BE DISCUSSED I N PS-Z ? ................. ......... .......... .... .. ..... ........ .... .. ............ 3 1.3 WHAT ARE THE INSTALLAT IO N AND PRE-PER FORMA N C E SPEC I F I CAT ION T EST REQU I REME N TS? ...... . ... ..... .. .. ....... ....... . ... ...... .. .... ... ..... .. ... .... .4 1 .4 WHAT SPECIA L DE FI NIT I ON S APP L Y T O P5-Z? .. ..... ....... .. .. ... .. ... ........ .. .. ... ............... 5 2.0 I NTERFE R ENCES , SAFETY , AND EQU I PM ENT REQU IRE ME . NTS ...... ............... ...... ....... 8 2.1 WHAT D O I NE ED TO KNOW TO ENSUR E THE SAF ETY O F P ERSONS US IN G PS·Z? ............. ... .. ... ........... ............. .. ... ... ...... ...... . .. .... .. ............... .. ..... . ................. 8 2 . 2 WHAT EQUIPMEN T AND SUPPLIES DO I NEED? .... ..... .. .......... .. ................... .... ......... 8 2 .3 WHAT R E GENTS AND STAN DARDS DO I NEE D? .................. .. ................... .... ........ ... 9 3.0 P E RFOR MAN CE EVALUA TI ON PROCEDURES AN D REPORT ING ...... ........... ..... . ........ . 10 3.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPEC IF I CAT I O N TE STS AND WHAT IS REQU I RED TO P E RFORM THE TESTS ? ................... ........ ... 1 0 3.2 HOW DO I R EPOR T THE RESULTS OF THE I N IT I AL P ER FORMA N CE SPEC I FICAT IO N T E ST? ................. .... ......... .. ....... .. .. .... .. ............... . .. ........... . ...... .... ..... . 13 4 . 0 PERFO RMANC E CRIT ER I A AND CALCULATIONS ...... .............. ............ ........... ......... ...... 15 4 . 1 WHAT ARE THE P ERFORMANCE CR I TERIA FOR M Y HCI CE MS ? ... .. ...... .... ..... .. ... 15 4.2 WHAT CALCULATIO NS . EQUATIO NS, AND DATA ANALYSE S ARE N EE DED? ....................... .... ............... .. ............ ... .... ... . .... ......... ... .. ... ......... . .. . .......... ..... . . 16 5 . 0 O THE R REQU I REMEN TS A N D I NFORMAT IO N .. . ... ....... .. ............ .. . .... .............................. 23 5 . 1 W HAT QUAL ITY CO N TROL MEA S URES AR E R EQUIR ED? ............ . ............. ... . .... ... 23 5 . 2 WHAT CAL . IBRA T I ON AND STANDARD I ZATION PROCEDU RE S MU S T I P ERFO RM ? ............. ..... .. .......................... ............... .. ..... .. ......... ............ ....... .......... ....... 23 5 .3 WHAT POLL UTION PREVENTION PROCEDUR E S MU S T I FOLLOW? ( R ES ERVEDj . ............. .. . .... ....... ........ . ...... . .. .. .. ... .. . ...... .. ........ .. ... ........... .... .. .. .... .... ........ .23 5.4 WHAT RE FE RENCE TAB LE S AND FI GURES AR E RELEVA NT T OPS · YY? .. ..... ....... ... ..... ......... .. ..... ...... ............. ........... ERROR I BOOKMARK NOT DEFINED . 6.0 R ELEVA N T RE FERENCES ....... ............. ...... . . .. ....... ............ ... . .... ......... .. . . .. . .... ........... . ....... .26 T able 1. Performa n ce Spe aftcatloo Test Calibration Gas Ranges Figu re 1 . Dyn a m i c Sp iki ng Overview

jj 

## VES0094441 . 0 US I NG PERFORMANCE SPEC I F I CATION Z 1 . 1 WHA T I S TH E PURPOSE AND APPLICAB I LITY OF PERFORMANCE SPEC I FICATION Z ? The pu rpo se of Pe rforman ce Speci fica t i on Z ( P S - Z) I s to estab li sh the Ini tia l parform a nce r eq u i reme n ts f o r eval uati ng the acceptability of a HCI CEMS. Such applications may include , ( 1 ) Instrument. method o r p rocedu r e ca li b ration, and (2) evalua tion 

### or certificatio n for l nKial acceptance. 1 . 1 . 1 Ap pli ca ti on T his specification is for eva l uating the acceptabft ity o f a HC I C EM S a t the time of Ins tallatio n and du rin g pariocfic quality assurance checks . PS - Z applies to you if you win be using a HC I CEMS to demonstrnte comp li ance wi1h a regulatory HCI 

### or HCII CI 2 emissio n standa rd . 1.1 .2 Meas u rement Capabilities The HC I CEMS musl be capab le of measu ring HCI ooncentrn ti ons In the units of the applicable slandard or in u n its that can be conv erted to u n its 

### or th e a pplicable standard . 1 . 1 . 3 Oth er Monitori ng I f your H C I CEMS I s capab le o f r e portin g th e HCI conce ntr atio n I n the units of th e e xisti ng reg ul ation, no add itional monitoring Is necessary . If your HCI CEMS does n ot report concentrntions , In the un Ks of the e xisting s ta ndard . tha n o th er mon ito r ing (e.g., oxyg en . temperat ure , and pressure ) are necessary to convert the units r epcrted by you r CEMS to the units o f the standard . 1 . 2 WHAT WI LL BE DISCUSSED IN PS - Z? P S-Z covers two basic topics : (1) the i nstrum e nt req u ire m ents for an HCI CEMS and (2) the requirements that each H CI CE M S mus t meet during th e performance spec i fiCatio n test. 1.2 . 1 Instrument R equirem e nts T he HCI CEMS must be able 

### to accurately report concentrations of HCI in stack effluent . II may do so by extracti ng a represe ntative s a m ple (path o r poin t sam p li ng may be used if tha sample I s r e p rese ntative) of stack effluent and ana lyzing the effluent to provide an output proportiona l 

### to the HCI concentrntion. T he CE MS ope rating range (zero to span) shou l d encompass the re s ponse o f 111e HCI CEMS f or all expeded HC I oonceotrations, l ncludillg the app l icable emission llm iL T he CEMS must h ave a system respo n se time that is less than or equa l to two minutes. F i na l ly , the i nstrument 

### or operator must be able 

### to perform daily c alibratio n d ri ft t ests, quarterty ca li b ration error tests, and a nnu al accuracy t ests . 3 

## VES0094451.2 . 2 Performa nc e Spe<:lficatlon Tut The pu rpose o f the performance spec ifiCation test i s to es ta blish t h e accuracy . prec is ion , bias , and system response time of the HC I CEMS. Sped llcally, the following wil l be either tesled o r doCumented as part of t he perfomlance specificat ion test requirements l i sted In Sections 3.0 and 4 .0 of this document (1) data recorder sca l e, (2) daily ca ll bra lion d ri ll, (3) i nsta ll ation and measu r ement locatio n , (4) cali bra tio n drift 

### test (5) calibrallon etTOr lest ( 6 ) system response time , (7) slralificallon test , ( 8) ace<Jracy determination. 1 . 3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE SP ECIFlCA 110N TEST REQ UI REMENTS ? 1 . 3.1 I nstallatio n R equ l re men ta The sampDng l ocation of the HCI CEMS shoUld be downstream of all pol l ution control equipment at a position where t he HC I concentretion is d l recUy representa t ive or ca n be corrected so as to be representative of total emis s ions from the station ary SOUI'Ce . It is reco m mended that the sampl i ng location be at least 

### two eq u ivalent diameters downstream of the nearest contro l delltces, point of pollution ge n eration, bend, o r other point at which a change in pol lu tan t concentrati o n or flow dist urbance may oce<Jr . The sampling location i s also recommended to be at least a hal f equiva l e nt diameter upstre am from the ex haust or control device . The equ ivalent diameter Is calculated according 4 0 CFR Part 60, Append ix A, M e thOd 1 , Section 2.1 1 •**E~ er**  point or path sampling may be used. For point sampl ing the measuremenl poin t shoUld be no less t h a n 1.0 meter from the stac k or du ct wal l or l ocated over the ce ntroida l a r ea ol the slack or d u ct 

### aoss section. For a path samp l i ng CEMS the effective measu r ement path should be (1) totally w i th in the in ner area bounded by a line 1.0 meter from the stack or duct wan , or (2) have at teasl 70 percent of the path within the Inner 50 percent of the stack d i ameter or d u ct cross section, or (3) be centrally located over any part o f the centroida l area . The sample collecti o n and in strumental analyzer portions ol your HCl CEMS may be l ocated any distance f ro m th e samp li ng point provided the transmission effic ienc y from t h e sam pli ng poi nt to t he sample collection point can be determined and meets tha criteria ouUined later In this performance specification . It Is also recom m ended t hat t he sampl i ng probe for the H Cl CEMS be located a t point without strati fiCat ion (section 3.1 . 5) .

4 

## VES0094461 . 3 . 2 R e fe re nce M ethod Mea sur ement Location Yo u must select, as app rop riate, an a ccessible reference me tho<l (R M) measurement poi nt at l east two equivalent diameters downstream fro m the nearest contro l device, the point o f po ll utant generation , or other point at which a change I n t he pollutant conce ntration or emission rate may occur, and at least a half eq u ival en t d i am eter u pstream from the effluent exha ust or cont rol d e vice . Whe n po llutan t concentration changes are due solely to**d~uent** leakage (e.g., air heater leakages) and po[lutants and dil uents ar e si multaneous ly measur e d a t the sa me locat io n , a h a lf diameter m ay be used i n l ie u o f two equ i va l ent d i ameters . The CEMS and RM locations need not be the same . If dynamic spi k i ng is emp l oyed to determine the sys tem accuracy , bias, an d p recision, the spi k i ng of the calibration gas m u st encompass the sampl in g system of the HCL CEM S. 1 .3. 2.1 Refe re nce M e thod T raverse Poi nts Seled traverse points that assure acquisition of representative samples over the stac k or duct crosssection . The m i n im u m req uire ments a re es fo l lOWs : Establish a "measurement li ne" that passes throogh t he ce n troidal a rea and in the d i rectio n of any expected stratification. If this lin e i nte rfe res w ith the C EMS me asurements. displace the line up to 30 em (12 ln.) ( or 5 percent of the equivalent diameter ol the cross s ection , whichelfe( i s l ess) from the cen tro ldat area. Loca te thr ee traverse poi niS a t 1 6.7, 50 .0 , and 83.3 percent of the measurement Hne. If the measurement l ine I s longer than 2.4 me ters (7 . 8 ft) and pollutant stra ti ficatio n is not expected, the thr ee t raverse po ints may be located o n the t i ne at 0.4 , 1.2. and 2 . 0 meter,; from the stack o r duct wall . This option must no t be used after wet scrub bers or a t poi nts w h ere two stream s wHh differe nt pol lulant concentrations are combined . Other traverse points may be se l ected , provided that they can be shown to the satisfaction of th e Adm i nistra tor to provide a rep resentati ve sample over the stack or d u ct cr06S section. Conduct all necessary RM tests within 3 em (1 . 2 in . ) o f the traverse points, b ut n o doser than 3 em ( 1 .2 i n . ) to t he stack o r duct wall .

1.4 WHAT SPEC IAL DEF I N ITIO NS APPLY TO PS-Z? Calibrat ion Drift : The d ifference i n th e CEMS ou tput re ad i ngs from th e es tabl i shed reference value after a stated period of operation during which no unschedul ed mai nte n an ce o r ad justm ent took place . Calibration Error : T he mean differe nce between the concen tra tion in d icated by the CEMS a nd the known concentration gooera ted by a calibration source at three l evels wtlen the entire CEMS, I nclud i ng the sampl i ng interface is challenged . A CE test I s pe rf ormed to doc u me nt the accuracy and linea r i ty of the CEMS 

### over the entire measurement range . 5 

## V ES009447Ce nt r old aJ Are a: means a concentric area tha t is geometrically si m ilar to the s tac k or d u ct cross sect ion and Is 

### no greater than 1**percent~** the stack Of duct cross-sectional area . Continuous Em i ss io n Monitoring System : mea n s the t o tal equi pm en t req uired fOf t he det ermination of a gas concentration Of emission rate . The sample Interlace , pollutant analyzer, diluent anal)l2er , and data reco r de r a re th e m ajor subsys tems o f the C E M S . Correlat i on Coeffic i ent : d e term i nes the extent of a finear relationship between 

### two fie l d s over a given period o f U me . Data Recorder : The portion of the C EMS that provi d es a record ol analyzer o u tp ut, nags wh ich I ndicat e normal operation , and ft ags indicating abnormal operation . The data recorder may record other pertinent d ata suc h a s effl u ent fto w rat es, and vario us I n strumen t temperatur es . D il uent Analyz er: means that portion of the CEMS that senses the diluent gas (i . e . 0,) and generates an o utpu t pro po rtiona l to the ga s concent rati o n . Dynam i c Spiki ng : a procedu r e used 

### to document the accuracy, precision, a nd b i as of the moni toring s ystem b y qua ntita t ively spikin g a c ertifi ed g as I n to th e poll utant gas stream. Hlgh· l evel drift: means the absolute difference between a high-level ca l ibration gas and the monitOf r esponse. i n un ij s o f the app lica bl e s ta ndard. Inst rument Me asurement Range : The range of HCI concentrations the i nstrument can reliably measure from th e l owest ooncent ratio n to th e h ig hest.**lnte~pt: va** **ue~** the Y variable when the X variable is equal to zero . L i n ear Regres sion : e meth o do l og y us ed l o fl nd a formu l a th a t can b e us ed to re l a t e two varia b l es that are**llnea~y** related . Path Sampling CE M S : A CEM S t hat sam ples the s ource e ffl uen t a l ong a path grea t er than 10 perce nt o f the equiva l ent di ameter of the stac k Of d uct cross secti on. Po i n t Sa mpl ing CE MS : A C EM S t h at samples t he so u r ce e ffl u ent a t a s in gle poin l 6 

## VES009 44 8P ollutant Analyze r. means that portion of the CEMS that senses the poiiUianl gas and generates an outp ut proportional to tho gas concentra tion . Relative Accuracy (RA) : means the absolute mean difference between the gas concentration or em i ssion rate determ in ed by th e CE MS an d the valu e determined by the Reference M e th od (R M) , pl us the 2 . 5 peroent error confidence coefficien t of a senes of tests. divided by the mean of the RM tests or the applicable emission li mk. Response n me: The time interval between the start of a step change in the system input and when the po ll utant ana lyzer output reached 95% of the fin al value . Sample Interface: The portion of the CE MS u sed for one or more of the fo l lowing : sample**acq<Jis~ion,** sa m pl e transport, sample conditio n ing, or protection of the mon itor from the effects of s tack gas. Slope: The rate of change of Y relaUve to the chang e in X . Stratification : means th e c ha nge In eff l ue n t concen t ration i n a duct, over time when compa ri ng a reference measuremen t (ce ntroid of duct) to traversed sampllng concentrations . Zero drift means the absolu te difference between a higt>-level cal i bration gas and th e monitor response, In un i 1S of the appfi cab!e standard .

7 

## VES0094492.0 INTERF E RENCES , SAFETY , AN D E QU I P M E NT REQUIRE M ENTS 2.1 WH AT DO I N E ED T O K NOW T O E N S URE T HE S A F ETY OF P E RSO N S US I N G P 5-Z? People using PS · Z may be exposed to haZardous material , ()!lef8tiona l hazards , and hazardous site conditions. P S - Z does not a ddress a ll the safety Issues associat ed with**~s** use . I t is your respons i bility to e n sure the safely or persons using PS · Z. Some he l p fu l refe r ences may incl ud e the CE M S manua l . tha CEMS manufacturer , other reference methods , and**oo-s e**  safety regu l ations . 2.2 W H AT E QU I P M E NT AN D SUP PLI ES DO I N EE D ? 2. 2 . 1 E quipm en t for the C E M S 1 . S a mp l e Ext r action S y s t em: This portio n of th e CE MS must pr e sent a sam pl e o f source efflue nt to the sampling modul e t hat is d i r ecdy rep r ese ntallva or can be co rrected so as to be repres e ntative of source . Tha sample extraction system lyp l cally consists or a sample probe and a heated umbilical li n e. 2. Pre ssure Regul a ti o n Module : Tha p r ess u re regulati o n module is desig n ed to remove bot h free partiwlates and water-sol u ble aerosols from dhe gas stream prior to analysis by the sampling module . Th i s m odule also p rovides a samp l e gas to t ha a n alyzer at a constant pressure (optio n al) . 3 . A na lysis module : Tha portion of the CEMS that quantitates stack gas concentrations of HCI. 4 . Dil uent M odu l e : This portion o f the CE M S quantifies stack gas con cen t rellons or oxygen or CO, . For systems with a multi-<:omponen t analyzer , the same analyze r quantif18S the concentration of all measured anaJ ytes. 5. Syst e m Con1roller : T h is porl ion of the CEMS provides co n trol of the analyzer , samp l e probe . pressure regulatio n mod u le and the sample lntertace . 6. D a t a recor der: Yo ur HCI CEMS must be ab l e to re co rd H CI conce nt re fl ons and Instru men t stat us signals (flags). 2 . 2 . 2 E q u i pm e nt Speciflcat.l o ns The CEMS data recorder output rang e must Include zero and a high-leve l value . Tha rang e of tha data recorder and tha meas u rement range of th e HC I CEMS wi ll De documented . Tha h igh-level value is c h osen by tha source owner or operato r and I s defi ned as follow s : 8 

## VES009450For an HC I CEMS i n slal l ed to measure contmlled emissioos or emissions lhat are i n C<Jmp l iaoce with an ap plicab l e reg u lati on , t h e high-leve l value s h ou l d be at l east 1.5 times the emission stan da r d l evel and encompass lhe HC I conoentralion l eve l s expected by the process. The CEM S design shou l d also al low the determination o f calibration drift at lhe zero and high -l evel va l ues . I n specia l cases , the Admin i strator may approve a single-point ca li bration-drift determination . 2 . 3 WHAT REGENTS AND STANDARDS DO I NEED ? 2 .3. 1 Refe rence Gases , Gas Co lis, or Optica l Filters See Tabl e 1 for r ef erence gas concentration ranges .

9 

### V ES0094513.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING 3.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPECIFICATION TESTS AND WHAT I S REQUIRED TO PERFORM THE TESTS? T he purpose of !he perfonnance specification t ests Is to detenn i n e the accuracy , precision, bias, and system response time of the HCI CEMS. 3.1 . 1 Protest Preparation Prior to the start of yo..- Initi al performance specification tests , you must be s ure that the HGI CEMS i s insta lle d according t o the specifica t ions l a i d 

### out in this documenl Alter installing the HCI CEMS, It i s recomm ended you use the C EMS for a period o f ti me to ram lilarlze yourself wi th its operation. It is also re commend that y ou conduct da ily c he eks o f the ze ro and high - l evel drift , co nduct a ca li bration e rror te st, and oondud a cal i brat ion drift check to verify that the i nstrument is functJonlng property . When yo u are confident that the l nsln.Jment is perform i ng satisfactorily**~** is time to prepare lor the perfonnance specification tests . 3 . 1.2 Data Recorder Scale Check The rang e or the d ata recorder and the measurement range or the HCI GEMS will be documented . The C EMS operating ra nge (zero to span) and t he range or t he da ta recorder should eocompass both the response of the HCl GE M S lor a ll exp ected HG t concen t rati ons and the applicab le emission Hm ll 3.1.3 Calibration Drift Cheek Th e HC L CEMS must perform a ca l ibrati o n ched< at least once per day . Certifie d gases must b e u sed to perform the ze r o and hi gh - l eve l d ri ft checks . All data wm ba recorded . 3.1 .4 Installation and Me asurement Location C he ek The Installation location o rth e HCL CEM S must adhere to sectio n 1. 3.1 or th i s document. In addition. the location of any re fe rence me thod testing must adhere to section 1 .3.2 of th is document. 3.1.5 S t ratification Test Th e strat if i cat io n test mu s t ba cond uc ted when the fa cili ty is ope ra Ung duri ng n orma l operation. The purpose ol this t est i s to ve rily that excess stratificat io n of the target poHutan t does not exist a t h e sampling point of the monhoring system . To detennlne whether effluent stratification ex ists . a d ua l p robe system shou l d be used to detennine the average effl u e nt concentration wh il e m easureme nts at each tr averse poi n t are baing made . On e p r obe, 10 

## VES009452located at the stad< or duct centroid , Is used as a statio nary reference point to indlcaie change in the efflue nt concentration over ti me. The second probe is used for sampl i ng at lhe traverse points specified in Method 1. The traverse points are sampled for five minutes at each poi nt. You may test for stratification at lhe HCI CE MS sampling point by usi ng either velocity tests as described in Method 

### t' , HCI conc<lntrations using Methods 26 or 26A, or an acceptable alte rnati ve (i.e. CO or Nox ) A m i nim um of 12 samp ling points will be use d , with 6 sa mpling poin ts along eac h of t he two trave rses . 3.1 . 6 Seven-day Calibration Drift Test The seven-day calibration drift test must be conducted when the facility is opera ting durtrlQ norma l operation . T he purpose of thi s test is to verify that the in strumen t operation I s stable. During the calibration drift test period you must determine the magnitude or the zero calibratio n drift and the high · level ca l ibration drift at least once eacih day. During the stability tests no adjustments or calibrations may be made to the GEM S. I f pe ri odic auto mat ic or ma n ual adj u stm en ts are made to the CEMS zero and high-level calibration sett i ngs . conduct the CD test immediately before these adj u stments , or conduct It In such a way tha t 111e CD may also be determ i ood. T ile calibretion drift wi ll be determined at the zero and high -level va l ue ol the HCI CEMS . Introduce to the CEMS the reference gases , gas ce fi s , or optical filters (these need not be certifK!d) for the zero and hi gh leve l va l ues . Record lila GEM S response and subtract lh ls va l ue from th e reference value. The calibration gas concentrations are provide d i n Table 1 . 3.1.7 Calibration Error The HCL CE MS will be cha l lenged three non-con secutive times with zero . mid· l eve l. and high - level certifi ed HCL gases (Tab l e 1). T he cylinder gases need not be EPA Protocol 1 gases. The calibration gases will be i njected i nto the sam p l e system as clo se to the samp li ng probe o utl et as practica l and will pass through all CEMS components used during nonna l mon itoring . The difference between lhe Instru me nt response and the reference va l ue (ce rt i fied gas) will be calcu l ated after each injection and the res ulting three difference s will be averaged to determine lhe CE at each measurement poi nt. 3 . 1 . 8 System Response T ime Introduce zero gas into the ana l yzer . When the system output has stabil ized (no chang e greater than 1 percent of fu ll scale fo r 30 sec) , introduce an upscale ca li bration gas and**wa~** for a stable va l ue . Reco rd the Ume (upscale response time ) requ i red to reach 95 percent of the final stable value. Next, rei ntroduce the zero gas and wah for a stable read i ng before record i r\Q the respon se li me (downsca le response time). Repeal the entire procedure lh ree lime s and determine lhe mean upscale and downscale response limes . The slower or l onger of the 

### two means is the system response time . 11 

## VES009453Canbration gas ranges lor the response time t est are provided in Table 1 . II using a multi-component analyzer. the response time can be based on any analyte measu red by the CEMS . 3.1.9 CE M S Accurac y The accuracy of the HCI CEMS shall be determined by pertonning either a relative accuracy determination or by dynamic spi k ing . 3. 1 . 9 . 1 Re l at ive Accuracy (RA) Conduct the RA test while the affected facility i s operating du ri ng normal operation, or as specified in an applicable s ubpart. The RA test may be cond ucted during the CD test period . Reference Met hods (RMl. Unless olherwlse specified In an applicable subpart or the regulations, Met hods 26 o r 26A, or thei r app roved a lternatives, a re the ref eren ce methods for HCI. Other r e f erence methods for moisture , oxyge n , etc . may be n ecessary . Sampfing Strategy lor RM Tests . Conduel the RM te sts In SUCh a way tltat they will yield rasulls represent ative of the emissions from the source and can be correlated to the CEMS data. It is preferable to conduct the dil ue n t ( i f app li cable), mo i sture ( II needed) , and pol l utant meas urements simu lta neous l y . However , dilue nt and moisture measurements that are taken within an hour o f the pol l utant measurements may be used to ca l culate dry pollutant concentration and emission rates. I n order to correlat e the CEMS and RM data properly, note the beginning and end of each RM test period of each run (Includ i ng the e•act time or day) on the C EM S chart record i ngs or other permanent record of ou tput. For I ntegrated samp l es make a samp l e traverse of at l east 21 minutes , samp li ng fo r an equal t i me at each traverse point . Number of RM Tests . Conduct a minimum of nine sets of ell necessary RM test runs . N OTE: M ore than ni ne sets or RM t ests may be performed . I I th i s o ption Is chosen, a maximum of three sets of the test resulls may be rejected so long as th e tota l n u m ber of test resu lts used to determine the RA Is greater than or equal to nine . However, al l data must be reported, incl uding the rejected data . Correl ation of RM end CEMS Data . Correlate the CEMS and the RM test data as to tlte time and duration by r.-st determin i ng from the CEMS f in al output (the one used for report i ng) the In tegrated average po llutant conce nt ration or emission rate for each poll utan t RM lest period. Consider system response ti me , n**mportan~** and confirm that the pair of resuHs are on a cons i stent moisture, temperature , and diluent concentration basis . Then , compare each Integra ted CEMS value against the corresponding averag e RM va l ue . I I the RM has an Integrated sampling technique, make a direct comparison or the RM results and CEMS I nteg rated average value . 12 

## VES009454Calculat e the mean difference be twee n th e R M and CEM S values In th e un its of t h e em ission standa rd , the standard deviation , the confidence coeff iCi ent , and the relative accuracy accord i ng to th e procedures In Section 4 . 0 . 3 . 1 . 9.2 Dynamic Spi ki ng D ynamic spil<. l ng can be used I n l ieu of the Re l ative Accuracy de term i nation as an allemalive method for d ocume nting the acc uracy , p ro<: l s l on , an d b ias of the HC I C EMS . F ig u r e 1 pro vides an ove rvie w o f the d ynamic s p iking arra ng ement. Co nduct the dynam ic s pikin g test wh il e th e affe ct ed fac il ity I s operatin g d u ring nonnal operation . W h il e th e HC I CE M S I s sam p li ng flue gas , H C I stan d ard gas Is i nt rod uced Into the HC1 CEM S sa m ple Interface by us ing a mass n ow oon t rolle r (o r eq u ivale nt device). The t arge t ratio of actua l flu e gas to th e HCI standard gas Is 9 : 1 , but must be kept at a m i n i mum ratio of 1 :1 . The HCI ooncenttation i s q u antitated b y th e HC I CEM S. O n e min u te averaged va l u es, in u nits o f p pm co rre ct ed t o d ry ness a n d 7% oxygen , a r e c ol l ected. All d ata s hould be arch ived . An element o f opportu n ity shall be used to calculat e the d i lu tion of the dynamica l ly spike d HC1 re ference g a s (re presents the a ctual H CL r ef e r en ce gas co nce n tration) . The eleme nt o f opp ort un ity is an analyle , which wo uld normally be pres en t i n the flu e gas at steady conce nt rations . E xamp l es of prospecti ve elements of opportunity wo u ld be 0, , N Ox , SO, , CO, , or moisture . This anelyle is measured . down sltea m o f the HCL CEMS, u s ing a ce rti f ied r efe r en ce CE MS . In acldltlon , a calibrated Lam i nar Flow Elemen t (flow as an e l e m ent o f op po rtuni ty) ca n be used as a s econdary in d i cator for calculati n g th e dynamically s piked HC I concentration ( represe n ts the reference HCI co n c e n trati o n ) . Wh ie the La min a r FlOw E l em ent Is ma i n ly for v erificati on of the d yn am i c s pi k i ng sys tem o peratio n, the use o f fl ow as a n e l e m en t o f opp ortu n ity can b e u sed to ca l cu l a te the concentrati on of the HC I dynam ic spike . I n a d dition , the t>a se li n e H C I concen tr a ti o n ( no rmal H CL con centrat i o n of !tie s t ac1< e ffluent wi tho u t HC L s p iki ng ) shal l ba determi ned . The l>ase! ine H CI concen tratio n is t>a s ed u po n a series of 10 , o n e-m i nute a

veraged d ata points. Bas el i ne dala mu st be collected i mmediately prior to e ach t est run . T h e data poi n t s m ust incl u de th e HC I co n ce ntration , ele m ent of opportu n ity ooncentra ti on (s) and th e llow r ecorded b y th e la mi nar fl ow ele m ent. II is rec om me n ded th at a sHe·speci fic s tanda rd operati ng p roce d u r e, f or the dynamic spiking exercise , be prepared and used as g u i dance for the dynamic spiking accuracy test

3 . 2 HOW 00 I REPORT THE RESULTS OF THE I NmAL PERFORMANCE SPECIFICATION TEST?

13 

## VES00945 5S u mmari ze the resuks of th e cal i bration drift . ca li bration error, response time , stratification, a nd accu racy tests in tabu l a r loon . Include a ll data shee l s. calcu l ations. and reco rds of CEMS measu re me nts necessary to substantiate the performanoe of the CEM S and any other devices or methods (e.g.. method 26A). The CEMS measurements shall be repo rted to the agency in units of ppmv . on a dry basis .

14 

## VES0094564.0 PERFORMANCE CRITERIA AND CALCULAT IO NS 4 . 1 WHAT ARE THE PERFOR M ANCE CRITERIA FOR MY HCI CE M S? You must demonstrale that your HCI CEMS has adequate preci sion , accuracy, system response time and dala reporting capabilities to determine if your facllay I s I n compliance with HCl emissio n s tandards or operat i ng perm n limits as specified I n appl i cabl e re gu lations or permits . You will d emon s t rate this capac ity by showing that your HCI CEMS meets the fol l owing performance cri teria. 4 . 1 . 1 Data Reeonler Seale The measuremen t rang e o f the HCL CEMS, and the dala recorder scale , roos t encompass the expected HCL co ncen trations 

### as we i as the applicable emission lim it. 4 . 1.2 Calibration Drift The dally zero and**hlgh~evel** calibration drift is 5% of the Instrumen t span . Zero and high - level ca librat ion drifts s ha ll be adj us ted, at a m ini mum, whe n ever the 24 - h ou r z ero drift exceeds the l imits of the calib ration d rift spec ification . T h e amoun t of exces s ze ro and**hlgh~evel** drif t meas u red at the 24-hour interval checks will be reco rded . Section 4 . 2 provides the equ atio ns for calculating th e zero an d hi gh· level cal i bration drills . 4.1.3 Installation and M easurement location T he installation r eq uirem ents and measurement location o f the HCL CEMS wi ll mee t the specifica tion s ouUined in section 3 . 1 . 1 and 3.1 . 2 of this document 4.1 . 4 Stratif i cation Test The stratifica tion i n th e slack or du e l, at t h e measurement locati o n , mu s t be less than or equa l to a 1 0 pen;ent between lhe avera ge conce n tration In the d u ct or s la c k and the concen tration at any po int more than 1.0 meter form the duct or stack wa lt . Section 4 . 2.2 provides the equation for calcu l ating the s tratification of the slack or d u ct . 4 . 1.5 Seven-day Calibration D r ift Test Criteria The dally zero and h i g h -l eve l drift each must b e l ess tha n 5 % of the Instrum en t spa n fo r seven consecutive days. See Section 4 .2.2 for the equations used to determ i ne the zero and h igh-level drift.

15 

## VES0094574 .1.6 Calibration Error Test The mean difference between the CEMS and the reference values, at all three test levels, must be no greater than 5% of span . See Sect i on 42 . 3 lor the equation u sed to determine the calibration error . 4 .1.7 Response Time T est The CEMS response time shal l not exceed 2.0 min to achieve 95 percen t of the final stable va lu e. II using a mu lti- component analyzer, the response time can be based on any analyte measured by the CEMS. 4.1.8 Relative Accu racy Tha RA ol the CEMS must not be g reater than 20% of the mean value olthe reference method (RM) test data, or not greater than 10% i n term s ol the em ission stan dard (ppmv, dry), or have an abso l ute diff e rence o f lass than 5 ppmv between the mean re f erence va lu e and the mean CEMS value . See Section 4 . 2 . 5 lor the equations used to determ i ne the relaUve aocuracy of your CE M S. 4.1.9 Dynamic Spiking Dynamically sp i k i ng may be used in li eu of a relative accuracy test as a means t o docum e nt the accuracy, precision , and bias of the HC I CE MS . The crite ri a lor the HCI dynamic spiking is : • The correlation coeffic ie nt r, must be greater than 0< equal to 0.90 • The slope must be 1 . 0 , +/ - 0 . 15 • The Interce pt must be e qual to or l ess than 15% of the Instrument s pan. See Sect i on 4 .2 . 8 lor equations to dete rm i ne the lin ea r correlation coefficient, the slope and the Intercept At a minimum, t h e data set must meet the correlation coeffic i ent. I f thl s I s not met, the d ynam i c spiking procedure must be rep ea ted until the corre l ation coefficient criteri a i s met. If the HCI CEMS has mel the correlation coefficient requirement , but does not meet either the slope , or i ntercept c:rltaria, a bias ex i sts and a correction factor must be app lie d to the HCI CEMS fo r data collection . The equations to determ i ne t h e corrected va lu e are provided in S ectiOn 4.2.6. 1. The correcti on factor must be app li ed to the H CI C EMS one-m i nu te a verage data until a 

### new dynamic spikin g procedure I nd i cates the specific bias no longer exlsts , or , a different correction factor ( bias) i s indicated . 4.2 WHAT CALCULATIONS, E QUATIONS, AND DATA ANALYSES ARE NEEDED? 16 

### VES0094584 .2.1 Arfth m etlc M ean Ca l c u l a t e th e arithmetic mean of a d a ta se t as fol lows :

- I "" X=- £... X I n (Equation 1) wher e: X 

## = Arithmetic mean n = N umber o f d a ta po in t s 

# "

' = Value 

## or each data point

4 . 2 . 2 Dail y U p scale and Zero Dr ift CD =( I R - A i l S) ' 100 ( Equ a tion 2 ) where : C D 

### = Percent cali bration dri ft (% ). R 

### = Re ference value of zero or hi g h leve l calibration gas introducecl lnto the moni t oring system (ppmv). A 

### = Ac tu al m on ito r respo nse to calibrati o n gas (ppmv), S 

### = Span of the instrumen t (ppmv).

4 .2 . 3 Calibration Error CE = ! <1,,.1 S l • t OO (E qua tion 3) where : CE 

## = Pe rcent ca l i bra ti on error(%) . d .., = Mea n di ff ere nce b etween CEMS respo nse and t he k n own r ef e r e n ce g as (ppmv) . S = Span of the m on ito r (ppmv). 17 

## VES00945 94 .2. 4 M oa n Di ff erence Ca lculate the arithmecic mean d i ffere nce as fol l ows : {Equati o n 4 )

where : ds 11o 

## = Arithmetic mean of differences 

### n = Numbe r of data sets di 

## = difference of each da18 set 

### And d. = x r- yr {Equation 5 ) where: 

### = Value at data set 

### x Value at data set y 4 . 2 . 5 Re lative Accuracy The RA l or the mon i tors will be ca l cu l ated using the least restrictive of equation 6 or equ ati on 7: RA = 

### {l d.,. l + I CC I J { Equation 6) or RA 

## = {( i d .,. I + I CC I )tTM.,.)"100 {Equation 7) where : RA = Relative accuracy, either percent o r p p mv o r % absolute, d .,. = Arithmetic mean of differ ences between va l ue measu r ed by the installed CEMS and the reference method , CC = Confidence coeff'&cl ent, 18 

### VES009460TM .,. • Avera ge va l ue measured by the reference test method mo n K ors. 4.2 . 6 Confidence Coefficient The confidence coeffici en t wi ll b e calcul a ted us i ng eq uadon 8 : CC 

### = lo. 9 ,. • (S.I (n")) (Equation 8) where : CC = Confidence coe ffi cien t , 

### to..n = t-va l ue obtained from Table 2. 1 i n P erformance Specification 2 , 4 0 CFR Part 60 Appe ndix B 4.2.7 Standard Deviation (of Differences) 

### S. = Standard deviation of differences measured betwee n the irlSi aOed CEMS an d the referen ce me thods cal<:ulated usi ng equatio n 8 : ( Equation 9)

where : n 

## = Number of va l ues In th is data sel

4.2.8 Dynamic Spiking To determ in e the re f erence value of HCL during a dynam ic spiking run : Opp - 

### post.,, , · HC1 .., = I - • 

### Ca/Gas + 

### BaselineHCI Opp - pr e.,, (Equation 1 0) Where: H CI ,.. = Re f erence HC I value f or run "X ' Opp-post,.. = average reference elem e nt of opportunity va lue during test ( downstream of spike) Opp -pre"" =average re fe re nce elemen t of opportunity value during test ( u pst ream o f sp i ke) 19 

## VES009461Ca i Gas**~** HC I ca li bratio n g as coocen t ratlon B

aseline HCI " C EMS HC I average base li ne va l ue Using data from each of the three test runs, perfonn a linea r regressioo of the CEMS HCI average values against the Reference HCl values us i ng the following equations given below: (Eq u at i o n 11 ) wh ere : The y i ntercept

= The slope The inte rcept is ca l cu l ated accordi ng to l he following equa tio n : (Equation 1 2) where :

I • 

# J= - I y, II l.t The slope 

## or the line i s calculated accord i ng to equation below: 

### • 

## L ( x

,- x ){

y

, - Ji)**b, =~-** **~~ --------**  

### " (Equation 13) 

### L: (x, - x)' 

# ,., The linear correlation coefficient i s calculated according to the follOwing eq u ation . 

### 20 

## VES009462

# ( i: (x, - .f)(y, - 

# n)' l l •l 

# ,. 

# - . " 

## })x , 

## -x( [ (y, - .W (Equation 14)

,... 1=- 1 4 . 2 . 8.1 Dynamic Spiking Corrected Values I f the HC I CEMS f ail s to meet both th e stope and i ntercep t c rit e ria. the following correct i on factor mu s t be app l ied to the on&-min ut e average HC I data : (Equat . lon 15) Where : 

# cc = corrected CEMS H C L ooneen tra tion y

1 = CEMS r eporte d HCL concentra t io n 

### bo 

### = the intercept of the least sq u ares line a r regression line

= the stop e of the l east squa r es li near re gression li ne

b ). If the HC I CE MS fa il s to meet the s tope criter i a , but meets the intercept criteria , the following correcti on factor must be a ppli ed to the onEHllinute ave r age H CI data : ( Equ atlon 16)

c) . If the HC I CE M S ta i ls to meet t he I n t ercept c rit eria , but meets th e s l ope c rit eria, the f ol lowing cor rect i o n factor m ust be appl ied to the**o~m nu** **e** average HC I data : (Equation 17)

2 1 

## VES0094634 . 2.9 Stratification The va lu e at each traverse poi nt are then compared to lhe average va lu e for all sampling points to determ in e the pe roent stratification us i ng the fo l lowi ng equation: 

### S "'IC -- C i•tOO % I (ll 'f: (Equation 18) where: S c percent stratification 

## c , = concentra ti on or ve l ocity a t samp li ng point I C.,.. ., ave rage concen tration or vel ocity at al l samp li ng po i n ts

22 

## VES0094645 .0 OTHER REQUIREMENTS AND INFORMATION 5 . 1 WHAT QUAUTY CON T ROL MEASURES AR E REQUIRED? Ongo i ng q ua lity co nt rol will i n clude da il y ca li bratio n d rift t est s, qu arterl y ca li bration erro r a ud ij s (abso l ute ca li braUon aud it ), and annua l acc u racy t est audits . Speci f iC procedu res and performance cri te r ia are inclu ded In Procedure DD: Quality Control and Qua li t y Assurance Requirements fo r Hydrochlo ric Acid Continuous Emission Moni toring Systems at Statio nary Souroes. 5 . 2 WHAT CALIBRATION AND S TANDARDIZA TI ON PROCEDURES MUST I PERFORM? Ref e r to yo u r CE M S owne r's ma nu a l and m an ufac tu rer to determ in e wh at calib ratio n a nd sta n dard iza tion procedures are requ i red f or your HCI C E MS. 5 .3 WHAT POLLUTI ON P REVEN TI ON PRO C E D UR E S MUST I FOLLOW? ( RESERVED)



### 23 

### VES009465Tab le 1 . P e rf o rmance Spe c ifi c a tion Test Calib ratio n Gas Ra ng es

HCI Calibration Gas Co ncentrations ' Te s t U n its Zero M i d .t. evel H i gh-Leve l Cal ibration Drift a nd %of Span 0-30 NA 50- 100 Respons e Ti me Test • Cal i brallon E rro r Test %of Span 0-30 30-50 50 - 100 Dynamic Spiking %of Spa n 0 - 50 25-75 50 -1 00

'A copy of the supplier's certificate of analys i s m ust be provided lor each gas cyli nder. Calibration gases do n ot need to be P rotoco l 1 gases . "If conducting the response Ume using a m ul ll-romponent analyzer , the respon se time test can be based on any measu red analyte .

24 

## VES009466Fig ure 1 . Dyn ami c Sp ikin g Apparatu s

Dynamic Spiki ng Apparatus So pi e Probe Heated line ins i de sample umbi lli cal Hoole umpl •ll n• l ueGas 

# l •He a ted Filter • Pruaure Control

•Lam i nar Flow E le ment HCL CEMS Cal i bntion Manifold (Mass 

### now met""' ) 900·1000 ppm HCL In N2

On Reference Co n di Uontt M an urement( 5 )



### 25 

### V ES0094676 . 0 R ELEVANT REF E RE N CES I. U nited State s . Environmenta l Protecti on Age ncy [ EPA). Te chnology Transfer NetW()(k. Emissio n Measurement Center . P r omu l gated Met hods . Metho d 1: Sample a nd Velocity Traverses for Stat i onary So u r ces . Wa sh in gton, DC : E PA ; 2004. Available : h ltp:l/www . epa . gov/llntemtlpromga telm-01.pdf v i a the Int ernet. 11 . United States . E n vironme nta l Prot ection Agency [EPA ) . Technology Transfer N etwork . Emiss ion Measurement Center . Promulgated Methods . Method 2 : De termi na tio n of Stack Gas Velocity and Vo lu metric Aow Rate . Washington , D . C : EPA; 2004 . Avaiable : hllpJ iwww . epa.gov/Hnlemclpromgate/m-02 pdf via th e lntemeL 111 . United States. E nvironmental Protec t ion Agency ( EPA ) . Tech nology Transfer Networ1<. Emission Meas ur eme nt Center . Perf ormance Spec i fications. Perfonnance Specification 

### 2· Specifications and Test Procedures for S02 an d NOx Contin uous Emission Mo n i to ring Syst ems in Stationary Sources, 40 CFR 60 Appendix B , February 2000 . Available : h t

tp : //www.epa . gov/llntemtlperfspec . html via the I nternet. I V. U nite d S t ates. Enviro nme n ta l Protection Age n cy (E PA) . Tec hn ology Transfer N etwork . Em i ss i on M eas u reme nt Center . Performance Specifications. Performance Spe c ifi ca tion 4A - Specifications and Test Procedur es for Carbon Monoxide Continuo us Em i ssio n Mo n itoring Systems ln Stationary So urces, 40 CFR 60 Append i x B , February 2000 . Ava il able: http·l/www epa . gov/Hn/emtlperfspec . html via the ln te mel V. Un i ted Stales . E n•ironmental PrO(ection Agency ( EPA). Tech nology Transfer Nelwotk. Emiss i on Measurement Center . Performence Specifications . Performance Specification 46 • Specifications and Test Procedures for Ca rbon Monoxide and Oxyge n Continuous Emiss i on Mon itoring Syst ems in Stationa ry Sources, 40 C FR 60 Appendix B, September 30 . 1999 . Avai l able : http : //www.epa.govltln/emc/perfspec . html via the tntemel

26 

## VES009468

# VES009469 . pdf

# Method 301 Evaluation of Candidate Conditional Methods X-Ray Based Filter Method (XFM) 

# Multi-Metals Instrumental Analyzer Procedure (Xact-IAP) Quantitative Reference Aerosol Generator ( QAG)

Prepared b y : Coop e r En v ir onm e n ta l Serv ices, LLC 

### 1 01 80 SW Nimbu s B lvd Suite J6 P ot11 aod , Or e gon 9 7223



### R evis io n 1. 0 J u n e, 2 0 05



## VES009 4 69

## VES009470

### Exe c uti ve S um mary A new metal emiss i ons measurement and validation s ystem has recent ly bee n developed that has t he potential to sign ificantly improve our understanding of m eta. l e mi ss i o ns from a wide mnge of source categorie s . Thi s system consists of: • A continuous e mi ssion monitoring sys t em (Xact-CEMS) • An ins trumen tal analyze r procedure (Xact- IAP) • A sampling and analys i s mcas urernetJt method (XFM) • A NlS T- traceabl e reference aerosol generator ( QAG) Th e measurement components of this system are 

### based on collecting a representative sample of stack gas on a chemically reactive filter (solid sorbent) that traps both particulate and vapor phase s of metals, followed by non-desuuctive X - ray fluorescence (XRF) analysis using procedures consistent with ambient measurements . This system is applicable to e lement s with atomic number ronging fro m 

### 13 (AI) to 

### 92 (U), and can m eas ure Be after nonde s truc tive XRF analy s is ifothe r a na lytical procedures are used ; it can pro v id e detcMion limits as low as 0 .1**rg/dscm** with 15 min u te t u

rn around times or lower det cc lio n limits with longer s amp ling and analysis times; a nd has de m o nstrated accuracies better than five percent and precisions better than three percent. These genera t ion and measurement componen t s 

### are ind epen dently traceable to NIS T : the QAO thr·ough proc edural traceability a nd sol u tion stan d ards , w h ile the meas u remen t metbods 

### are ana l yt ic a lly traceable tluough thin film standards and 

### NJST stand ard reference m a

te rials . A series of laboratory and fiel d tests have been conducted to demonstrate tha t the QAG, XFM and Xact-IAP components of thi s new system meet Method 30 I accurucy and prec ision requirements for conditiona l method 

### status. Each of the methods met the performance criteria outlined in the Method 30 I test plan. These criteria included the following : • F ilt e r natl os - percent of Cr and Pb trapped o n the 

### XFM front 

### PTFE mrer. Although this crit erion is not required by Met hod 

### 301, high percentages assure high particle t rapping efficiency. • Metal ratio s - ratio o f Pb-nonnal ized s olution conc entra t ion to Pb - normalized aerosol c oncentration. This c riteri on is a l so not required by Me thod 

### 301 1 but ratio s close to o ne assure high r e la t ive generation, tTllDSport and sampling efficiencies for all metals in clud i n g vapors . • Efficiency - percent ofNJST-traceable reference aero so l concentratio n 

### measured. A high percentage assur es h igh absolute generation, t ransport and sa mpli ng efficiencies. • B ias cor r ectl o n facto r - rotio of r eference to me asured aero so l con cen t ration . A value close to one indicates high method accuracy. • P r ecis i on - percent relative standard deviation d etermined from sequential measurements. A low percent value indicates a highly precise and stable syst em. 

### • Lin ea rity - correlation coefiic ien t (r) based on a regression analy sis of a p lot of measured versus reference aeroso l concentrat ion. Me lhod301 E\' al .: V I .O Page i ofxii 

## VES 009471

### These criter i a and their acceptance values are based primarily o n t h

ose in Method 3 0 1 an d w

e re defined in the 30 1 validat ion tes t p l an (Appendix A). D UI'in g these tests , five e lemen ts (As, 

### Cd, Cr, Pb. and Hg) were 

### spiked at concentrations ranging from blank t o abou t 1 20 11gldscm. Al l three (QAG. XFM, and Xact- I AP) indepe n den t approaches showed good 

### agreement over this wide range of concentrations , and all three methods met the required criteria for all five metals. These results are summarized in the following three tables for the QAG reference aerosol generator, and the XFM and Xact- IAP measurement approaches. The Xact - IAP table includes res u lts from all 192 Xact-IAP runs . Compari son of 

### QAG labora t or y r es ults with criter i a acce p t ance valu es . C

riteria No. 

### Runs F il ter Rati o (% F ro n t) Metal 

### Ratio (SoiJAer.) Efficiency(%) Predslon (%) Uneanty - C«r. Coer . { r) Acc o table >9 >98 0 . 9- 1 . 1



### >80 <10 >0 . 85 'XFW •od Xad resub bf,. the N!Ms. "Co nfii"TTWCC \Jiill'l hl epetV:lent tCP INif')W NtiJIS Results ' Met C r ite ria > 25 Yes > 99 Yes 0 . 95. 1 .01 Yes•

94 - 100 

### Yes <4 Yes 

### >0 . 99 Yes

C ompari s on of 

### XFM field t es t · r es ult s with c r iteria acc e ptan ce value s . Criteria No. 

### Runs Bias Corr. Factor Precision (%) linearity- Corr. Coef . ( r) 'Xrlol rt.Uta b' all M ¥cmeniS Acce able >9 0 . 80 . 1 . 2 <10 >0 .85 'Confltmt<l wiCh independen!K::P**an:s~PJaa ,..u** **e~** R e sutts• 26 0 . 94 . 0 .97 <3 >0.99 Mot Crltoria Yes Yes• 

### Yes Yes

Co mpari s on of Xact - IAP field te s t r es ults witb criteria a ccephmce**alu~ -s.**  Criteria Acco 

### table Results • Ma t Criter i a No. Runs >9 192 Yes Bias Corr. 

### F actor 0 .80 -1 .. 2 1.00-1 . 14 

### Yes Precision (%) <10 <3 Yes Linearity - Corr . Coef. ( r ) >0 . 85 >0.99 Yes**-x.cz.w,....~«** .. filriiJI!>etMtem 

### Many more test 

### runs than required by Met hod 30 I were c o nducted, and all of the data fro m th ese runs were 

### i nc lude d in this eva l uation. 

### The QAG and X FM tab l es shown below i ncl u d e re sults from all 26 XFM runs. Th e filte r and metal mtios lis ted for the QAG are bigh and indicate that t h e relat ive gen eration, transport and sampling efficien cies for all elements are within the experimenta l accuracy of I

### 00%. The efficiency, precision and Linearity values for the QAG are also all well within the acceptable range. In 

### the case of the XFM and Xact-IAP measurement Method 301**E".J. ~**  VI.O 

### Page ii of xii 

## VES009472m ethods, all of the cri teria were met and the values were sub s ta ntially with i n th e accep t abl e range . w hich in the cas e o f th e bias aod p rec i s i on were more restric t ive i n o u r tes t p l an than required b y M ethod 3 0 1 . T he h i gh co rr e l a tio n c oeffici en ts in dic at e high ly l in ea r metho ds . This high degree of linearity i s i ll us tru t:cd with the f ollowing f our represen t a tive plo ts of the X FM a n d Xac t- IAP measured val ue s versu s th e i ndependent QAG r e fer e n ce aeroso l conce ntration during l aboratory a nd fi e l d tests 

### at a haz ardous was t e i ncinern tor .**15 ~--------** **-- --** **-------- -,** 

0 C ADMIUM n*2 6

y • o.tts• - 0 . 1 34 R

2 • 0 .915 50 1 00 QAG Co ne (IJgldacm) 150**50 r-** **-- --** **-- ----** **-- --** **------ ~** 

0 MER C UR Y**•1~**

y s- O , t7 1 x • 0 . 542 R' • O . lt3 50 1 00 QAG Cone**g/docm )**  150 R epr ese ntative scatt e r plot s of XFM and Xa ct -L <\P m easure d c on centra tio ns ve rsu s QAG referenc e aer o sol conc e n trati o n s du r ing l a borator y v alldatl o n t est s o f the Q A G.

1 50 ,-----------------------.

y• 1 . 01k · U OS R'•t .t t1

### ~----**-- ------------** **-- ~**  0 50 100 1 50 QAG Co n<. (lll>'dscm ) 150 .- ----- -- ---- ---, 

### L

ead n:192

0 'r • O. tt 1x • 1.1 24 R' • O ..H2 

### so 100 QAG Cone . ( pg/doC0!1 ) 150 R e pr esentative s catter p l ots of 

### X FM and Xact- IAP mea sured**ro cc** **ntn~tl s**  v e rs u s QAG ref e renc e aeros ol co n ce ntrati o n s during fiel d validation te s t s or th e XFM und Xact-IAP. Tite XFM and Xact - lAP are m gged a nd rob ust met h ods that are a p plica ble to a w ide range of source s and e le ment s. B ecause these me thods include d ilut i on sam p ling tech n iques , they a re re l a ti ve ly insensi tive to mo s t s tac k 

### gas characte ristics ( te m p eratur e, moi sture , PM c o ncentrati on, and c hemi stry) a nd ca n be o ptimized fo r specific s tack cond itio ns by ad ju sting dil u tio n ratios, sampling 

### times , e tc.. . Their range of app licability has been de monstra ted b y resu lts fro m these tests as well a s o ther laboratory an d fi e l d tests over the pas t five y ears including relati ve accuracy testing using both Method**2~and** Outario Hy droJ reference met hods. Ex a mples of these field va lidat io n tes t re s ults are illustrated with the fo llowing two figu res . The plot o f l ea d sh ows a stro ng lin ear re l a t i

on s h ip between the Xact and M e thod 29 M

cdlOO 3 () L

6val . : V I.O Page ii i of xii 

## VES00947 3results up to 2,200 llg/dscm and had 

### a relative accuracy of4%. The 

### mercury plot shows a similar strong linear relationship between t he 

### XFM and Ontario Hydro reference method results 

### at concentrations dow11 to about l llg/dscm and bad 

### a relativ e accuracy of 

### 1 1%.

- 2,500 .,..--- - ----- -. E 

### :ill 2,000 

# 8 1,000**~** 500 Lead n= 1 1

y a 1.056x • 5 . 786 R 2 z 1 .000

# ~ 1 ,500 

# li

><**oc -~** **--... -~---l**  0 500 1 , 000 1 , 500 2 , 000 2.500 M2ll Cone . {llg/dKm ) 

### Mercury n=9 

# • y 

# =**908~** + 0 . 152 

### R' = 0 . 962 2 4 OH Cone. (IJ9/dscm) 6 Exampl es o f field valida tio n test r es ults at a Dlllnition s in cin era t or• (lef t) and at a coalfired utlli ty boll e r \\1th bagh ouse an d 

### NO , controls 5 (rig h t). These tests have included wet and d r y inc inerators , and wet and dry coa l -fi red uti lity boilers covering 

### a range of contmls including electrostat ic precipitators, scn1bbcrs and 

### NO, catalytic reduction controls . The XFM 

### and Xact- lAP are also consistent with mnbieot me:Jliurement metbods 6• 7and applicable to mo st of 

### tbe elements typically 

### measured ht the ambient environmen t. Thus, the recommended range of source categories for which the XFM and Xact-lAP are a pplicable includes fugitive and dueled emissions such 

### as those from hazardous, municipal, sewage and other incinerators; cement and lime kilns; s melt ers and mills; mineral processing , plating and boiler sources 

### using control technologies such 

### as bag bouse filtration. electrostatic precipitation , 

### scrubbers and 

### NO, controls. Also, this technology offers the following additional advantages: • Significantly shorter reporting times (As short as 15 minutes compared to 3 weeks) • Precise (<3%), accurate 

### (beuer than 5%), linear (r>0.99) and ver ifi able results due to non-destructive ana lys is • Minimal operator requirements • The methods 

### are safe and 

### easy to 

### u se and generate no hazardous**wa.~t e.**  The res ults from th ese tests as well 

### as results from previous field tests support 

### th e following conclusions. • The 

### QAG candidate reference aerosol generator is independent of its appli cation , met all ofthe required validation criteria, and should 

### be approved 

### as a NIST-traceable reference aerosol generator for compliance and other regulatory applications such 

### as initial certification and continuing quality assurance audits ofmulti - metals CEMS as well 

### as calibration and validation of metal measuremen t methods. 

### Page iv of xii 

## VES009474

### • The XFM and Xact-IAP candidate conditional methods for measuring me tal concentrations in 

### emissions from s t ationary sources met all of the required validation criteria; have demonstrated d1eir applicability to a range ofsource types, controls and stac k conditions; and shou ld be approved for general compliance and other regulatory applications suc h !lS 

### initia l certification and continuing quality nssuranee audits of multi-metals CEMS, emission compliance audits, trial bums , and other regulatory applications where stack gas metal emission measurement s from stat ionary sources are required.

Mcehod 10 I Enl. : V I . 0 

### Page vofxii 

## VES009475

### Ta ble o f Cont ents Execu tive S umm ary ........**~** 

### .. . .. . .. .. .... .. .. . .. .. ...... . .............. . .... . ..... . ........**~** 

### ... . ... . ...**~** 

### . .. . ..... . .............. I Appeod lces ............... .... .. .. .. . .. . .. . .. .. .... ... ... .. ............... . ............... .. ..... .... .. .. .. .... .. ... .. ................. vii i 

### Li s t o f Fig ures .. . ..... .. .... .. ..... . ..........**~** 

### ........ ... .. ... .. .. . .... .. ...... ................... .. ... .. ......... . ...**~** 

### . ..... .. .. .. . 

### i x Li st o f A b b r eviati on s .................. . .. .. . .. .. .. .. .. ....... .. .... .. .........................**~** 

### .... .. .... . .. ...... . .... .. .... . .. xi 

### 1 . 0 In tro du c ti on .. ... .. ........... .. ........ . ... - .........**~** 

### .....**~** 

### .... .. ...... .. ...... .. ........ ... .. . .. . ....**~** 

### ................ .. 1 What i s this report about? ... .... .. . .... .. . ...... .. . .. . .. ... . .. .. .. .... . .. .. .. . . .. ... .. .. . . .. .. . ... ... .... . ... ..... ... .. ... .. I 

### Why 

### are we concerned about metal emissions? ............................................ .. .. .. . .. ............ I 

### Why is the current metals measurement system inadequate'/ .. ...... . .. .. .. ........ .......... .... .. ...... I 

### What is 

### this new metals measurement system? .... .. .... . .................. ...... .... .... ............ .. ... .. . .. . 2 What are these candidate condi t ion al methods? ................ .. ............................................... 

### 2 Why 

### are the XFM and Xact- IAP candidate methods more appropriate than Method 29?. 2 W

h y are these methods i mportant to the EPA and other stakeholders? .................... ... . .. ... 3 

### How was d1e 

### perfoffilance of these methods evalua t e

d ? ........... .. ........ .. .................... ...... .. . 3 

### Where are 

### the results presented in this report'/ ................................................................... 3 

### 2 . 0 Appr oac h ...**~** 

### ..**~** 

### ........ .... .. .. .. .. .. .... ..... .. ..................... .. .. .. ..- ................ .. .... .. .. .. . .... ...... .... .. . 3 2.1 

### Overview ....... .. . .. . ..... . .. . . .. ......... . ...................... .. ................... . . .. . ... . ................ . .. . . ...... .. 3 

### 2 . 2 General Approach .. ...... ............. ...... . . . .. . .. .. ..... . . . . . ............ . .......... . ..... . .................. .... . .. 4 2.3 Method Indepen dence . . . .. . .. . .. . .. . . .. . ....... . ............ . ......... . . ........................ .. .. . .. . .. . .......... 

### 5 2.4 QAG Validation (Phase!) ........ .. ............................. .. ................................ ........ ......... 7 

### 2 . 5 XFM and Xact-IAP Valida t ion (P hase 

### IT) .. .. ........ . .. ..... ............. .. ............................ I I 2 . 6 Deviations fro m Test Plan ................... .. ............................ .. ...... .................. .. .. .. ...... 12 3. 0 

### Met h ods .. .. .. .. . .... .. .. .... . ........................................ . .... ..... .. .. .. .... .... .. .. .... .. ......................... 14 3.1 

### QAG Reference Aerosol Generator ................. .. . ....... .. ... .. ....................................... 1 4 

### 3.2 XFM Candidate Omditional Method .. . ................... .. ........................ .. .................... 18 3.3 

### Xact lnstrumental Analyzer Procedure ..... . .. . ..................................... .. .............. ...... 21 

### 4 . 0 Ca lc ulatio n s ..................**~** 

### .....**~** 

### ................... .. .. .. .. .. .. .. . . .. .. .... . ....................**~** 

### ....... ... .. .. .. .. .. . 2 4 4.1 Overview ....... . .. . ............... . ........ . .... ... ... . .. . .. ... . ...... . ..... . ........ . .. ... . ..... ............... . .... . .... 24 4 . 2 

### List of Symbols and Terms ........... .. .................................... . ............................. .. ..... 24 

### 4.3 QAG Reference Aerosol Concentration ............. .. ...... . ........ .. .......... . ....................... 26 4.4 XFM Measured Aerosol Concentra tion ...................... .. .... .. ..................................... 27 4.5 Xact·IAP Measured Aerosol Concentratio n .. .. .. .. ...... .. .. ...................... .. .................. 28 Me

l bod 301 Eval. : VI.O 

### Page vi 

### of xii 

## VES0094764 . 6 Validation Comparison Parameters .................. . ... ... . . .. .. . ........... . ...... . ................... .. . 2 8 4.7 O ther Comp arison Parameters .... . .................. .. .................. . .......... . .... . ... . ................. 33 5.0 Qualit y C ont r ol and Assurance .................................................................................. 35 5 .1 O verview ............... ...... .. ................. ..... . ... . .. . ............... . ........ .. .. .. .. . .. . ............ . .. . ..... . ... 35 5 . 2 QAG .......... . .. . ....................... .... . .. . . .. . . ............... . ......... . ..................... . .. . ... . ... . ....... . .. . . 35 5.3 XFM ............ . .................... . .. . .. . . .. .. .. . ... . ............... .. .. . .. . .. .. . . ............... ........ ...... . .......... 37 5.4 Xact-IAP . ........... . ...... . ....................... . ...... . .. . ... ............ . ............ .. .. . .. . .. .. ...... ........ . .... . 38 6.0 Re s ults and Di . scussio n .................................................... .. .. ...... .. ................................. 40 6.1 Overview ..... . ....... . ................... . ... . .. .. ... .... . .... . ....... . .. . .. . .. . .. . .... . ................. . .......... . ..... 40 6.2 QAG Validation .......... . . ..... . ................ . .. .. .. .. .. . .... . ........ . .. . .............. . ...... . .. . ............... 40 6.3 XFM and Xact-IAP Validation Overview .. . ...... .. ........ ........... . ...... .. .............. . ......... 48 6.4 XFM Validation ......... . ...... .. . .. . .. . .. . .......................... . .. . .................. . ...... . .. .. .............. . 50 6.5 Xact- IAP Validatio n ..... . .... .. .. .. .. . . .. . ..... . .. .. ...... . ...... . ...... . .... . .. . ......... ... . ... . ............ ..... 52 7 . 0 Rang e of Met h od Application ............. .. .. .. . .... .. .. . ............................. ..... ................. . .... 55 7.1 Overview . .......... . .. . .......... . ..... ..... . ....... .. .. .. .. . .................. . .. . .. . ....... . .. . . .. ..... . ........ .. ...... 

### 55 7.2 Criteria for Candidate Method Applicability .. .. ......... . ..... . ............... .... .................... 

### 56 7.3 Key Sampling and Analysis Features ...... .......... .. .......... ................ .. .. . .. . .......... .... .... 

### 56 7.4 Key Emission Characteristics ......... .. .. . .......... . ........... .. .... . ....... . .. . ...... . ........ . ..... . ...... 57 7.5 Filter Trapping Efficiency for Vapor Phase Metals .... . .. ... . .. ......................... . .......... 58 7.6 Applicable Concentration Range . .. . ............... ............. ................ .. ..... .. .. .. .......... . ... .. 62 7.7 Deposit S tability . ............. . ... .... ...... ......... .. .. . .. . ... .. .. . .. . ................. .... . .. . .. .. .. . ... . .... . ..... . 62 7.8 Moisture ............ . ............................. . ...... .. .. . ........................ . ............................. . .. . ... 63 7.9 Holding Tim es .. . ...... . ...................... . . .. . ... . ...... ......... . .. . .. . .. . .. . ....................... . .. .. ........ 64 7 . I 0 Applicable El emen ts .................. . .. . .......................... .. .. .. ........... .. .. . ........... .. .. .. ......... 

### 65 7.11 O ther Rel a t ed Tests .. .... . . .. . .. . ...... . .... .... ............... . ...... . ............ ......... . .. . ... . ........ . .. . .. . .. 65 7 . 12 Applicable Source Ca tegories .. ..... .... . ............... . .................................. .. .. .. ............. . 66 8.0 Concl usions and Recomm e ndations ................................................. . ...... . .................. 67 

### 9.0 Glo ss ar y ......... .. .. ........ . .......................................... . .. .. . .. .... .......... ............................ .. .. .. 68 10.0 R e fere nces ....................................... . ...... .. . ... ....................... .. .... ..... ................. . .. ........... 73

M

e thod 30 1 Eval : V I. O Page vii of xii 

### VES009477A ppen dix A : Appe ndix B : A

ppe ndix C: App en d ix D : A p pendix E : A

ppen dlx F :

Ap p en dix G: A ppendix H: A

pp e ndix 1 : A

p pen dix J: A pp e ndixK

A

ppe ndix M :

M¢thod 3 0 1 fvnl. : VI.O 

### App en d ices Draft Tes t Plan for Validating a Referen ce Procedure for Measuring tl1e 

### Concent ration o f Metals in Eli Lilly and Company's Hazardous Was t e Incinerator S ta ck Gas Determinatio n of Metal Emissions from Stationary Sources Using Filters and So lid Sorbents with X-Ray Fluorescence Analy sis Standard Operating Procedure fo r Generating a 

### Quantitative Multi· Metals Reference Aerosol with th e CES QAG Derennination of Metal Concentrations in 

### Emissions from Stationary Sources (Instrumental Analyzer Procedure ) Perfo!TIU\nce Specifications for a Quantitative Reference: Aerosol Generator Specifications and Test Procedure for X-Ray Fluorescence Based Multi-Metal s Co ntinuous Emissions Monitoring Systems a t Stationary Sou r ces Quality A ss urance Requirements fo r X-Ray Fluorescen ce Bused Multi - M eta l s Con tinuous Emissio ns Monitoring Systems at Stationary Sources QA Informatio n during Phase I QA lnfonnation during Phase 

### 11 Phase I 

### Test Data Phase 

### U Test 

### Data Calcu lations Used for Method 301 Validation Tests A

d d i tional 

### Daw in Support of Servi ce and 

### Range Extension of Candidate Methods Related Reports Produced by Cooper Environment al Services



### P

age viii of xii



### VES009 4 78

### List of 

### F i g u res Figure I: Schematic flow diagram illu$trat ing key aspects of the general validation procedure . .............. ..... . ... .. . .. . . .. ..................... ......... . .. . .... . . . ...... . ... . . ... . ........... ........................ .. . . .. 

### 5 Figure 2: Schematic representati on of key compone n ts ofCES' reference aerosol generation system............ . ... . . . . ............................ . ...... .. . . ...... . ..... . ............ . ...... . . . . .. . . .. .. . ........ ... . ..... . .. ... . . . .. . .. 

### 6 Figure 3: Flow diagram s howin g tb e experimental arrangement 

### used t o valida t e lbe QAG reference aerosol generator.... . ..... . ............. . ..... . .... . . . .. . ... . .. . . . .. .... . ...... .. ... ... . .. . ................ ......... . .. 

### 8 Figure 4 : Schematic representation of the experimental arrangement used in Phase i to validate the QAG reference aeroso l generator ..... .. . . . .. ......................... ... ........ ..... . ....... .......... . .. 9 Figure 5 : A. Schematic of flow throu gh QAG components. B. Overview ofthe set-up of QAG components. ...... ... .... ...................................... .... . ..................... . ....... .............................. 1 5 Figure 

### 6: Schemati c flow diagram of the sampling train used in Phase 

### I and [( XFM validation tests .. .... . .... ... .. .... .. . . ... .. . .... ...... . ..... ........... ... .. .. . .... . .. .. .......... ... . ................................ 

### 19 Figure 7: Photogtaph of the**a.~scmb ed**  port adaptor, extraction assemb ly and fil ter ho lder . . 1 9 Figure 8: Exploded schematic view ofXFM filte r holder with filter cassette. .. .......... . . .. ....... 21 Figure 9: Overview of Xact-IA I ' components and flow schematic......... .. ... . ............. ...... . ..... 23 Figure 

### 10: QAG so l ution mass loss rate during Phase !testing...... . .................... . .......... . ...... 

### 36 Figure 11: QAG solution mass lo ss rate during Phase 

### 11. ... . ........... . . .. . ... • .•

. . .. ..• .•• ••• .. •• . . .. .. .. • •. . 37 Figure 12: QAG-generated and XFM- and Xact-IAP-measured aero sol concentrations during Phase I tests ...... .. .............. .. ... ... . . .. ...... . . ............... .... ......... . . ........... .. .... ... .. .. . ... . ...... . ..... .. . ......... 4 1 Figure 13: Ratio ofXFM and Xact-lAP measured metal concentrations to t he QAG reference aerosol concentration.. . ... .................. ........ ............................................................ ............ ...... 4 2 Figure 14: Phase I QAG lineari ty plots 

### as determined by the XFM .. . ...... .. .. ... ........ .... . .......... 46 Figure 15 : Phase I QAG linearity plots as determined with the Xact-lAP ... .. ................ . .. .. ... 47 Figure 16: Comparison ofthe XFM and Xact- IAP measured concentra t ion s with the QAGs piked flue gas concentrat i ons during Phase lltesting . ....... .. .. .. . . . .. .. . . .. . . ... . ............. . . .. .... .. ..... 

### 49 F i

gure 17: Phase ll XFM linearity . .. ... ... ...... . . .. ........ . .......... .. . ... . ................... .. ..... . ....... ..... . . .. .. 51 Figure 18: Phase U Xact linearity . . ............ . . .. ............ . ... . .. .... ......... . .. . .......... ...... . ........... . . . ...... 54 fig ure 19 . Comparison ofHg concentrutions determined by XFM and Ontario Hydro reference method at a coal - fired power plant ... ...... .... .. . . ......... ..... ..... ....... .. . ......... . ................. 60 f i

gure 20 Plot ofXact - IAP concentration versus Reference Met hod 2 9 m easu red concentrations showing 

### excellent agreement over two orders of magnitude and a t concentrations in excess of 2,000 jig/ds cm ................ ..... .. . .. . ... . ..... . ........... . .................. . ........ 62 Figure 21. Plot ofPb concentrations determined by Reference Method 29 and the Xact.... .. 63 Figure 22: Comparison of results from laboratory XRF ana lysis io July , 2002 with Xact field test results from May 2002 re lative accumcy tests at a hazardous waste inc inerator ...... . .. .. .. 63 Medtoc1301 Eval : VI .O 

### Pag e ix of xii



### VES009479

### Li s t o f Ta bl es Table 1 : Overview of Phase I validation te s t schedul e ........................ ............ . ... . .... .............. 10 Table 2: Acceptance criteria for QAG ................................. .. ........................................ ....... .. II Table 3: Overview of Phase II validation test schedule........ . ................................................. 12 Table 4: Acceptance criteria for 

### Phase TT validation nfthe 

### XFM and Xact-JAP ............... .. .. 12 Table 

### 5: Comparison of surrogate and Phase 

### II Oue gas characteristic s ........................ .... .. .. 14 T able 6: QAG Emjss ion Rates for Phas e 

### 1 and 

### ll ... .... ........... . .. . .............. .. .................. . ........ .. 36 Table 7: Flowmeter evaluation durin g Phase 

### !. ........... . ...... . ........ .. .... . .................................... 38 Table 8: Flowme te r evaluation during Phase 11 ....................... . .. . ....... . ............... .......... . ...... . .. 38 Table 9: Upsca le and zero drift during Phase I ce sting........ .. .. .... ............ .. .... .... ............... . .. .. . 39 Table 10: Evaluation ofNIST thin-film standards by the Xact-IAP ...................................... 39 Table II: Upscale and 

### zero drift during Phase II testing ... .......... ................................. .......... 40 Table 12: Comparison of Average QAG reference aerosol concentrations with XFM and Xact-lAP average measured concentration s (f.lg/dscm) .. ... ..... .. . .. . ......... .............. ...... ....... ...... 42 Table 13: Lead an d chromjum measured on the upstreamPTFE filler as percent of total 

### XFM le

ad and chromjum (IJg/fdter ) ......... . .. . . ................. . ........... ... ........... . ... . ................................... 43 Table 14: QAG efficiencies determined during Phase I laboratory tests( % ) .... ..................... 45 Table 15: Summary ofQAG Phase I precision(%) ............. .. .......... ..................... ................. 45 Table 16 Summary of Phase I QAG validation results ........................................................... 47 Table 17 : Summnry ofXFM and Xact-IAP measun:d concentrations and QAG-spiked flue gas concentrations Phase li (IJg/dsem) ... ........................ .. ....... .......... ......................... ............ 49 Table 18 : Summary ofXFM Phase II b i as values for each metal tes ted (llg/dscm) . ............ . 50 Table 19 : Summa ry of Phase 

### TI XFM validation test criteria and results ............................ ... 51 Table 20: Comparison of Xact-IAP with QAO reference concentrat ions and bias (IJg/dscm) .

............................................ .......... ........................................ ........ .................................. . .. . ..... 53 Table 21 : Summary of Phase 

### TI Xact results ..................... ......... .................................... ........ 54 Table 22 : Comparison ofXact Phase 

## n results witb proposed PS- 10 criteria ........................ 

### 55 Tabl e 23. Li st of stack conditions for which Xact-IAP and XFM tests have been conducted 58 Table 24 . List ofte.•;t condil ions and ref erences used to evaluate method applicability.. .. .. . .. 6 1 Table 25: Recenl te sts ofXact and XFM on wet and dry stacks ..................... . ........... . .. . .. .. .. . 64 Table 26: Xact detection limits determined at Lilly's Tl49 incinerator ................. ... ...... ....... 66

Mctbod 30 I E vat. V1 . 0 Page xofxii 

## VES009480

### J.lg/m' 

### As Cd CEMS CES CFPP CFR Cr DAS 

### DQO DSCM DSLP EPA Hg HWC IAAP lAP 

### LVM M29 

### M 30 1 

### MACT MFC MFM 

### MM-CEM MRl 

### Pb PSlO QA QAG QC RA 

### List of Abbreviations Micro - grams per cubic meter Arsenic Cadmium Continuous Emissions Monitoring System Cooper Envirotm 1en tal Services LLC of Ponl and , OR Coal Fired Power Plant. Code ofFederal Regulations. Chromium Data Acqui;ition System Data Qua l ity Objectives Dry Standard Cubic Meters Dry 

### Standard Liters Per M inute United S tates Environmental Protection Agency Mercury Hazardous Waste Combustor Iowa Anny 

### Anmmnition Plant Instrumental analyzer procedure Low Volatile M etal s (arsenic, b ery llium, chromi u m) EPA Reference Method 29 EPA Reference Method 30 I 

### Maximum Achievable Control Technology Mass Flow Controller Mass Flow Meter Multi-metal Continuous Emission Monitor Midwest Research Institute, Kansas City, MO Lead EPA's proposed Performance Standard I0 

### for multi- metal CEMS Quality Ass u mnce Quantitative Aerosol Generator Quality Control Relative Accuracy Method 301 6\':ll. : VI.O 

### Page xi 

### of xii 

## VES009481

### RSD slpm SVM T BA D 

### USACERL VM 

### XCEM XFM XRF Zn 

### Relative Standard De viation (% 

### RSD equals precision) Standard Lite rs Per M in ute Semi-volatile metal s 

### (cadmium, lead) Tooele 

### Army Depot 

### U.S. Ar my Construction 

### Engineering Research Library Volatile M etals (mercury) X-ray based Continuous Emission Monitor X-ray based Filter M e th od X- Ray F luorescence Zinc**"lhOO** 30 I E w L: V I .0 

### Page xii 

### ofx ii 

## VES009482

### 1.0 Intr o du ction What is this report abow? This 

### report describes a n ew multi-metal s measurement and validation system. It a l so presents the results of tes ts demon s trating that each of the system components m eet the 

### U.S. Environmenta l Protection Agency (EPA) Method 

### 301 cri teria for conditional me th od s tatus. 

### The objectives of this report are to present and discuss these results in support of EPA's evaluation ofthis system, and obtain EPA acceptance of its components 

### as condit ion al methods. Wiry are we concerned abow m etal emissions? Air toxic metals hav e been associated with a wide range of environmental and human health effects including respiratory disorders, pulmonary disorders , and cancer. Recent findings 

### link air toxic metals with**in·\~vo** and in-vitro inflammatory responses u . As such, there is continuin g concern for potential health effects of metal air pollutants in c ludi ng such metals as Sb, As, Cd, Co, 

### Cr, Hg, Mn , Ni , Pb , and Se. The EPA is required to control emission s of toxic and hazardous air pollutants under the Clean Air Act Amendments of 1990 10 • U nder Sections 112(k) and 112(c) or the C lean Air Act, the EPA is also required to monitor the ambient air concentrations of these species to evaluate the e ffectiveness of its reduction strategies. For these reasons, th e EPA has d e v eloped an air toxics object i ve t ha t inc l udes an effort t o reduce air toxi c emissions and implement area specific control stra te g i es to roduce air toxic exposures by 2010 1 1 • However, our current understanding of metal emissions i s relatively poor, primarily because our current measurement technol ogy is inadequate. Why 

### is the 

### currenr metals mlUI.Sllreme/11 system inadequaTe? A metals emissions measurement system needs to be capable ofmeeting a range of practical requirements in addition to meeting such basic requirements as being accurate , precise, reliable and verifiable. Top among practical requirements is that the measurements should be timely and representative; that is the results need to be available within a time fiame adequate for decisions (hours to days) and representative oflong term emissions ( months to years) . However, the currently accepted reference measurement system consists of one method capable of only i nfrequent periodic measurements; i.e. EPA Reference McU1od 29 ( Method 29) . This method is considered inadequate and inapprop riate for current app lication s primarily because it is not a continuous emission monitoring system (CEMS) and therefore may not be adequ ately repr esentative of long tenn average emissions; bu t also because of its l ong reporting times, which are typically on the order ofseveral weeks or more . For example , to be effective 

### as a quality assurance tool for CEMS validation or trial bum applications, a reference method must provide results within hours of the time of sampling or at least by the next day 

### so as to allow time for adjustments prior to completing these tests. In addition, it is felt that for some metals Method 

### 29 suffers from accuracy 

### aod precision limitations'z. 

### u Method 

### 29 is also relat ive ly difficult and dangerous to 

### use, creates large quantities of Sect io n 1.0 Introduction Page 1 of40 

## VES009 4 83

### hazardous waste, recovered samples are difficult to ship in a post-911 environment, and the method is costly. In addition , Method 29 is not consistent with current ambient metals measurements and as such more like ly to have systematic biases relative to these ambient measurements. Because of the above noted limitatio ns of Met h od 29, candidate alternative methods are being proposed. What is this new metals measurement system? The currently proposed metals measurement system consists of two candidate conditional measurement methods, a m ulti-metal CEMS and a quantita t ive reference aerosol generator. The multi - metal s CEMS is not addressed in tl1is report. What are these candidate conditional methods? The two candidate cond i tional methods are based on collection of representat ive samples of particle and vapor phase metals on a reactive filter followed by 

### metal det ermination using Xray fluorescence (XRF) analysis. One is a method of collecting periodic samples by drawing stack gas through a series of filters contain ed in a sealed fi l ter cassette. In this X- ray based filter method (XFM), particulate phase metals are trapped on a non- reactive filter while vapor phase metals including mercury are collected on a chemically reactive filter or solid sorbent. Tbe concentration of metals in t he resulting filter deposits are non-destructively determined, either in the field or laboratory using XRF analysis following analytical procedures similar to those listed in EPA's Compendium Method 10-3.3 

### ("Det ennination of Metals in Ambient Particula te Matter Using X-Ray Fluorescence (XRF) 

### Spectroscopy in Compendium of Methods for the Determinat i on of Inorganic Compounds in Ambient Air , EP A/625/R96/0lOa, June I999.) 14 • 

### The stack gas concentration is calculated by dividing the XRFdetermined metal mass b y the volu me of stack gas that passed through the fi l ters. The other measurement method is an instrumental analyzer procedure (lAP) based on the collection of a representative sample ofparticles and gas phase metals on a reactive filter tape followed by determination o f metals with XRF analysis (Xact -IAP). The o ther component in t his syst em is a Quant itative Aerosol Generat or (QAG). The QAG generates a NIST-traceable reference aeroso l that can be used, in addition to its other applications, to challenge and evaluate the accuracy, precision and linearity of the measurement methods and is applicable to non-metal species as well as m etal species. 

### Wiry are the XFM and Xact-IAP candidate methods more appropriale than Method 29? These cand idate methods are more appropriate than Method 29 primarily because oftheir rapid analysis tum arowtd times, which can be as short as 15 minutes in the case of the X actIAP or two hours in the case ofthe XFM if a field- portable XRF analyzer is used. No t only do these methods meet the required tum around times , but they also provide better precision a

n d accuracy than Method 29 as the results reported in this document demonstrate, and their results can be independently veri fied because the analysis is non - destructive. In 

### addition, the met hods provide lower detection limits, require fewer resources, are safe and easy to u se, generate no hazardous waste and are based on well-established E PA analysis procedures t hat are consistent with EPA ambient measurement methods.

MCit.Od W I £ o llt: V l . O 

### Sec t ion 1.0 Introduction Page 2 of40 

## VES009484

### Wiry are 1hesc methods imporramto 1he EPA a11d o1her stakeholders? We currently have a poor understanding of metals emitted from the country's smoke stacks because of the absence of metal s CEMS, infrequent manual method measuremems. a nd substantia l uncertainty in bow well the se measurements represent emissions , operating conditions and a ssu mption s. The XFM, Xnct-IAP, and QAO caudidate conditional**m~thods** 

### offer the E PA more convenient and reliable tools for measuring and val idating metal emissions. This should make it easier for plant operators to 

### make more freque nt measurements, which will provide the EPA and other s takehold ers with a higher leve l of understand ing ofmetal emissio n s. In addition , this technology should mak e it eas ier 10 

### test and e valuate new measurement and contro l technologies by reducing cost barriers and by providing more timely results for engioeeriog evaluation and adjustments. Also , more timely resultS provided by these candidate methods during such tests as trial bums will 

### reduce the need for repeating these**test~** 

### due to extensive delays in receiving Method 29 resultS , which are typically not available until after the completion ofsuch tests. How was theperformance of these methods evaluated ? A two phased approach was used to evaluate and validate the aerosol generator and the filter based meas urement methods. Phase I was a laboratory study in which the accuracy, precision and linearity of the QAG was established and ruggedness test datu developed for the XFM and Xa ct-IAP . Phase II was a field study conducted to va lidate the measurement methods for applications to stack gases. In Pllase II, the v alidated QAO was used to generate a reference aerosol that was spiked into stack gas, which was su bsequently measured with the XFM and the Xact-IAP. All of th e valid data generated during these t ests were used in these method evalu a t ions, and far more measurements were taken than required by M etbod 30 I . That is, no valid results were excluded in our analysis, even though a subsL"Inrial number of resultS could have been omitted whi l e still meeting Method 30 1 requirements. Is 

### th is system applicable 10 

### other s ottr c

es and elements? This system is applicable to most emissions from stationary sources and a ll of the hazardous elements as well as all of the e lements measured in the ambient environment ; inc lu ding Be if it is measured with other analytica l methods after non-destructive XRF ana l ysis. Where ore 

### the results presented in this r e port ? This report presents a summary und discussion of the methods us ed and t est resulls. The detail s of the methods and results are presented in the appendices ofthi s report along witb field data sheets, NIST-trnceable cenificatious, sample ca lculations, all u nproce ssed data, etc. 

### 2.0 Approach 2. I 

### Overview The primary objectives of these tests were to validate the QAO as a reference aerosol generator and obtain EPA conditional method acceptance for the XFM and Xact - IAP. The 

# ""'""'"" ' "'" vo • Section 1.0 Introduction P age 3 of40



### VES009485

### objective of this sect ion is to descnl>e the gen eral approach used to generntc the supporting data. and discuss how this app roach compares to EPA Method 30 I requirementS and the approach propos ed in CES' test p lan (Appendi>t A). 

### 2. 2 General Approac h Ne i ther an appropriate reference method nor pe r formance audit material s were available to evalu ate the candidate conditional met hods. A s 

### s uch, a new appro<t c h w as req uire d to d e monstra te the prec i sio n and accuracy capabilities of the candidate met h ods. Although ti1 ere are 

### n umerou s standar d EPA ana lyti cal pro tocols a vailable that are NIST-tra cea ble, th e real limitation was i n the sa mpl e co ll ectio n p art ofthe sampl ing and**ana y~is**  

### procedure. A 

### key sampling issu e in th is case was 

### the need to verify s ample**c~ ll** **ection** 

### efficiencies to a 

### precision and accurac y consistent with the potential precision (<5%) and accuracy ( < 5%) believed to be attainable with the candidate methods. A two-phased approach was used in this case as schematically illustrated in Figure I . The first phase (Phase I) 

### consisted of l aborotory validation ofCE S' QA G, 

### while P h ase 11 

### was a field evaluati on te s t of the XFM a n d Xact-lAP using a ref erence aeroso l generated by the val idate d QAG . 

### The frrst step was th e deve lopme nt ofa QAG 

### capa bl e of em itting 

### a reference aerosol , which cou ld then b e validated in the laboratory us in g independent Nl STtraceable aerosol concentration mea s urements (Phase I) . 

### The QAG, 

### thu s validated in the laboratory, was then used in the fi e ld to 

### spike s tack gas with a reference aerosol of NISTtraceable con centration to challenge the candidate conditional measurement methods (Phase If}. 

### The success of this approach depended on several key f actors includ in g: • Independen ce oftbe NIST-tra CC'db le aerosol generation process 

### and the NJSTtraceab le aerosol measurement methods. • High level ofprecision for both the generator and the analytical method (about 2%). 

### • The resulting small bias between the generator and analytical method (<5%). • Th e magnitude of th e bias being on the same order ofmagnitude 

### as the expected uncertainty in 

### the b i as established through propagation oferrors in 

### bot h the generator and anal} 1ical m easu r e m ents. Although under these conditions, the "true" concentration of the generated aerosol was 

### "u nknown ", its concentration wa s kn own at least to an accuracy comparnblc to the degree of propagated e rror and independent me thod a greement or magnitude of the bias; 

### i.e., <.5%, 

### which is signi ficantly better than t h e c>t i sting me tals refere nce method. 

### 1110 resu lt ing QAG 

### co uld th us be used in tbe fi e ld with a h igh l evel ofconfidence that the ge ne rated reference aerosol concentration was NIST- traccable to an accura cy of 

### 5% or bener. The general 

### validation proced ure used is illustrated in the schematic flow diagram s hown in Figure I. As 

### noted above , 

### a k ey component of t his vali dation procedure 

### was the fact that the QAG 

### not only generated 

### an accurate , NlST-traceable aerosol ofknown composition, but the composition ofthe generated aerosol was 

### stable over periods ofseveral day s as documented with 

### the Xact- IAP and XFM performance during evaluation teSting. TI1i s documented

Melhod JOI £y&J. ; V I. 0 

### Sec t ion 2.0 Approach 

### Page 4 of40 

## VES009486

### aerosol stability allowed the determination of precision through the collection of replicate sequential samples ins t ead ofco ll ection of simultaneous samples using dual sam pling trains.

Phase t CES L abo rat ory CESAEROSO L /IJ r GENERA TIO N SYSTEM



# . High Acc u racy 

# - )(act 

### _, XFM 

### I • High Precision



### -·- - • High Long term Stability 

# . Mo as ured Precision and 

### " . Phase II Stablity Ully Stack Gas 

### Fig ure 1: Schematic D ow diagr am Illus tra ting key aspects of the gener al valida tion p roc edure. 

### 2.3 Method Independen ce Independence of the aerosol ge n e rati on and measw·ement methods is essentia l to th e approac h used to validate the QAG and s ubseq uently the XFM and Xact- lAP. This method ind ependence is schematically i ll ust . rntcd in 

### Fig u re 2. As 

### illlh""tratcd in this figure, the QAG generated aerosol concentration 

### is traceable to 

### NIST (Appendix C). 

### I n this 

### eliSe, all parameters used in the calculation ofthe aerosol concentration are NTST

### -rraccable including the concentration of the standard solution and the rate of solution 

### use.

Method JOL Eval.: VJ.O 

### Section 2.0 Approach Puge 

### 5 of40 

## VES0094 87

# NIST

QAG

Figure 2: Schematic represe ntation of key components of CES' referrnce aerosol generation system. 

### The aerosol generation process was eva luated with independent filter samples of the aerosol collected by the 

### XFM an d Xact- lAP, wlticb were 

### subsequently analyzed by 

### XRF using two sep arate X-ray spectrometers. (Appendices B 

### and D) 

### The XFM 

### and Xact-IAP parameters used to determine the 

### volume of aerosol sampled are 

### NIST traceable . (Appendix 0) In 

### addition, the 

### XRF parameters used 

### to detennine the mass of metal in the. filler deposit are traceable to NIST (NIST SRM 1832 and 1833, and gravi metrically NIST traceable tllin film standards) and are 

### independent of the aerosol generation process. These 

### generation and measurement methods are 

### clearly independent. Although further traceability or confinniug measurements should not be 

### required , additional measurements and routes to traceabil i ty 

### were established through independent laboratory inductively coupled plasma analysis (ICP) 

### of solution and filter samples as illustrnted in the lower ponion of the schema!ic illustration shown in 

### Figure 2. The resulting independent laboratory-determined elemental co ncentrations and elemental ratios confumed the standard solution concentrations used in**~!«bod** 301 E m: VJ.O 

### Section 2.0 Approach Page 

### 6 of40 

## VES009488the QAG. In addition, selected XFM Iiller samples were analyzed by ICP using on independent laboratory to confl!IJl th e metal deposit measurements made by the XRF analyzer. These independent, t hird party measurements were also used to co nf um the elemental concentrations, their ratios and their N!ST traceabi lity (See Appendix G) . It s hould also be noted that the XRF unulyzer used 

### to analyze the XFM filter s amp l es was a l so used in 

### an earlier EPA PM ,., speciation program in which numerous " round robin" type of quality ass u rance tests were conduc t ed and demon st

rated comparable results to two other independent laboratories 15

. Thus , not only are the aerosol generation and measurement methods clear ly independent, but tbere is a reasonable d egree ofindependent quality assurance between the XFM and Xact meusurement methods. In addition , s ince two different Xacts were used in Phase I and Phase IT testing (CES and Lilly Xacts) requiring rwo different calibrations, there is a reasonable degree of independence of these two sets ofXact measurements. As a result , when there is a high degree ofagreement between the generated aerosol concentration and the measured concentration, accuracy ofboth the genemtor and measurement methods are simultaneously validated within the degree of agreement because of the independence of their NIST traceability. The test procedures used for this va lidation report 

### were more rigorous and demanding than the procedures described in EPA M ethod 30 l. For example, the Met hod 3 0 1-bnsed evaluatio n procedures used h ere include additional linearity requirements as well as the Method 30 I precision and bias requirements. In addition, substantially more meas urements were made than were required and none of th e valid data was exclud ed from th e data analysis. 

### Also, bec ause of t h e mulli-clemental nature ofthe measurements, inter - elemental ratio requirements w ere added to acceptability criteria. 

### 2 . 4 QAG Va/idatwn (Phast! I) The experimental arrangement used to validate the QAG during Phase !testing is illustrated in the flow diagrams 

### in Figure 3 und Figure 4 (Details ofthe test and QAG are discussed in Appendices A and C) . The QAG comr'nents are illustrated on the right side of Figure 4 . It consists of a Collison - type nebuli zer 1 maintained at 

## o •

F to minimize water vapor loss from tbe NIST -traceable spike solution duriog nebulization and vapor-drop let equilibration. The spiking solution was circulated through 

### a l arge solution reservoir to minimize th e impact on solution concentration due to los s of water from evaporation. The rate ofQAG metal emissions was determined by measuring the sol ution use rate in grams per minute us detennined by a NIST - traceab l e balance and correct ing fo r vapor loss. The res ulting nebulizer-produced aerosol (about 

### J

### 5 lpm) passed into a sett ling chamber where li quid droplets greater than about 

### 20 ).lm in diameter sett led out of the gas flow and w e r e returned to 

### tl1e solution reservoir. The resulting size-selected aerosol was 

### then injected in to 

### a drying chamber maintained at about 300 ° F where it was d r i ed a nd diluted wit.h about 30 t o 50 lpm ofclean , dry laboratory air. The dry salt and metal vapor containing aerosol emerging from the QAG was diluted further with about 

### 20 to 

### 40 lpm of 

### make-up air. The 

### reference aerosol total flow was about 100 to 120 lpm, o.nd was moni tored with a NlST-traceable mass flow meter.

Mclhod301 Evst : VJ.O Section 

### 2 .0 Approach Page 7 of40 

## VES009489MAKE- UP AI

R rl

'--"" 

# . r---·· I Q

U

ANTIT ATIVE AEROSOL GENERA TOK (QAG) QAG

_ j AIR SOL UTION RES ERVOIR TO EXHAU ST 

## f TOT Al. F.LOW E XHAU ST

_ l')ANIFOLD ! Xact**AP**

XACf STILLING CHAMB ER 

# t I BYPASS 

# I I l

# --**O~ _j**  ! 

# h_**;;: \**  i i



# -- -,....---_:

# ··**··~ ;~** **~;** H .J XFM 

# 1- '**~: L** 

# ____ __ XACTMETALS

ANAL YZE R QAG VAL!DATION • Percent Transport • P b and Cr Filter R a tios • Elementa I Ratios B

ALANCE

## ~ SOLUTION I;**L----- --~** **·** US E RATE L_

_ _ __.J • Precision • Linearity Fi g ure 3: Flow diagram s howin g the expe rimenta l ar r a n gemen t u sed to validate the 

### QAG ref e r e nce aero sol ge ne r ator. 

### The QAG-generated r eference aero so l contained five metals, (As, 

### C.d, Cr, Pb, and Hg) representing the vola tile , semi-volatile and low volatility metal ca tegories as 

### defined in the Hazardous Waste Combustor (HWC) Maxi mum Achievabl e Control Technology (MACT) rule 17 • 

### Aerosol concen tilltions ranged f rom 20 to more than 1 20 l'g/dscm , spanning t he range oftheir MACT emission l imits. 

### This reference aerosol was directed from the 

### QAG to the top ofthe Xact stilling chamber through 2-incb diameter stainiess steel (SS) 

### tubing . About 99"/o 

### of the flow passed t hrough the t est apparatus and was filtered prior to flow meas urement . Le ss t h

an 

### l% of the reterence aerosol w ·as sampled from the s tiUing chamber by t he XactIAP (ab out 0.7 slpm). During XFM testing, almost 4 0% of t h

e sample fl ow was dillwn through the XFM p lenum and retu rned to the exl1a ust downstream of the stilling chamber. From this s ubflow, about I 

### lpm ofthe re f e rence aerosol 

### was sample.d and drawn throu gh the

MC1hod 30 1 E "a

l.: V J.O 

### Section 2.0 Approach Page 8 of40 

## VES009490Exhaust Aetoeol fi fiM

1 • liiiQ'I; • ' 

# D 

# · I[] i • 

# t-·

-- - ![I

• •

F ig ure 4: S chemati c repr esen tatio n of the e¥ J>erimental arrangement u sed in Ph ase I to validate th e 

### QAG r eference a e ro s ol ge n e rator. XFM filter cassette . The resuhing XFM fLiters were analyzed by XRF using EPA Compendium Method 

### 10-3 .3 for panicle deposits on filters while the CES Xact-IAP automatically reported metal concentmtion s every 15 minutes for the**dun~rion** o f the test. Typical test periods consisted of establishing a stable reference aeros o l fl ow through the Xact-JAP St i lling chamber and out the exhaust manifold. The concentration of this reference aerosol was stable to within a few percent during each series oft est runs as demon s trated by the Xact and QAG combi n ed preci s ion, which was typically on the order of2 to 4 

### % . The aerosol metal concentrdtion in the s tilling chamber was simultaneously sampled and measured by both the Xact and XFM, wbicb provided independent confirmat i on of the QAG reference aerosol con centration s. During I inearity evaluation tests, the aeroso l concentmtion was increased or decreased by changing t he spiking solution concentration. Phase I validation testing of the QAG was conducted at CES' l aboratory using spiked ambient air. During these tests, the QAG s piked five MACT metals (As. Cd, C r, Pb and Hg) at five concentration level s, in c luding a series ofblank runs, which were then compo.red to the measured concentrations reported by the CES Xact-IAP and the 

### XFM. During 

### Phase I , a total of26 

### XFM and 

### 148 Xact runs 

### were compared to the QAG reference concentrations ( Table 1 ).

MethodJOl**E-.~1.:** V I.O Section 2.0 Approach Page 9 of40 

## VES009491

### Table 1 : 

### Su mmar y o f QAG valida tion tes t sche dule. Nominal No m in a l No . o f Dat e Lev el for QAG Conc. 

### XFM No ofXact MACf R un s Run s Met a l )Jgl d scm Dec. 14-15,2004 Mid2 65 1 2 93 Dec. 16, 2004 Mid i 50 4 

### 13 Dec. 1 6 , 2004 Low 20 4 

### 12 Dec. 16, 2004 High 130 4 lJ 

### Dec. 17, 2004 Blank 0 

### 2 19

T o tal Ru n s 2 6 

### 148 The validation metrics or criteria used to establish the validity of the Q AG are li s t ed below: • Tran s port Efficie nc y: The calculated transport efficiency shall be greater than 80% for all elements. Since t h e NIST- traceab l e reference aerosol concen tration is totally independent from the NIST - traceable filter sampling and analysis method, t h

is criterion, if met, might be considered adequate t o establis h an acceptab l e efficiency c

orrection factor for the QAG. • Lead an d C r Filt er Ratio s: To ensure tha t t

he filters had adequate particulate trapping efficiency, less than two percent ofd 1 e Pb and Cr were perm itted on the XFM reactive filter downstream of the PTFE filter . This plus the assumed low volatil ity of these elemen ts wi ll assure a near 1 00% sample train trapping efficiency for these element s. This crit erion plus t he following criterion provide additional assurance that the trapping efficiencies for all of t he elements are near I 00%. • E le me ntal Ratios : As, Cd, 

### Cr, and Hg con c

e ntration ratios to lead measured in the aerosol sample must be 

### with in ± I 0% ofthe concentration rat ios i n the QAG so l ution . Meeting this crit erio n assures not only h igh trapping efficiencies but also high gen eration and transport efficiencies for aU of the elements including volatile elements. • Preci s ion : The QAG m ust have a precision, as measured by percent relative standard deviation (PRSD) , o f l

ess than I0% for each of the 

### e lements. This high precisio n c riterio n will enable sequential sampling of the candidate methods at each concentration level. • Li n ea rity: The QAG and both candidate tllter- based conditional methods shall have a correlation coefficient (r) that is greater than 0.85. This criterion show s that the QAG is linear over a wide range ofconcen t rations. These criteria and their acceptable ranges are summarized i n Table 2. Method 30 1 E\· :. 1 . : V 1 .0 

### Section 2.0 Approach Page 10 of40 

## VES00 9492

### T ab l e 2: Acceptan ce crit e ri a f or QAG . Criteria Measure No. Runs 

### Accep t abl e Ra ng e Filt er Rati o back to fron t rat io (Cr , PB) > 9 <0.02 Metal Ra ti o s o l u tion t o aero::>o l ratio > 9 0.9to I. I Efficie.ncy t·statistic > 9 < c ritical val ue o r efficiency faclor >9 'Between 0.8 and 1. 0 P r ecb i on percent of spiked cone . >9 < 1 0% L i

nea r ity cflrrcl ation coefficient > 9 >0.85 

### These criteria i nclude required bias (efficiency) and precision validat i o n paramelers from Method 30 I (bias or in thi s case efficiency and precision) and additional validation indicators relevant to these specific t ests: i. e. , fil t er ratio, metal ratio and linearity criteria. The acceptability ranges listed in 

### Table 2 were guided by values required by Method 30 I , Perfonnance Specifications I I and proposed Performance Specification 10, and are ei th er equal to those listed in these procedures or are more restrictive. 2.5 XFM and Xact - IAP 

### Validation (Phase ll) 

### The primary objective of Phase II testing was to val idate the XFM an d Xa c t-TAP wh ile sampl ing flue gas. Tite validity of these sampling and analysis methods was e valuated by comparing the Phase I validat ed QAG r efe rence aerosol concentration with the XFM a n d Xact-IAP measured concentrations . It 

### i s important t o note t h at a different Xact instnunent was used in Phase 11 than was used in Phase I. Followin g Phase I testing, the QAG was installed at a hazardou s was t e incinerator 18 

### and a ser ies of validation tests were conducted. During these tests, the QAG reference aerosol was spiked int o incinerator flue gas at fou r different concentration level s while an XFM samplin g train and X act -IAP w ere collecting sim u

ltaneous samples from the Xact still ing chamber . Tbe experintental arrangement was similar t o t hat used in 

### the laboratory with the primary difference that the reference aerosol was spiked into stac k gas instead of laboratory air. In addition, the Xact used in these field tests was different from the one used durin g the Phase I t ests at CES' l aboratory. Durin g Phase U, the QAG spiked five MACT m etals at four concentration l evels (Table 3) into about 35 slp m of flue gas while the XFM and Xact - IAP concurrently sampled the reference aerosol sp i ked stack gas. A total of 24 XFM and 192 Xact-IAP runs were completed during Phase 

## n t ests w hile the QAG was operating.

Section 2.0 Approach Page II of40 

## VES 00949 3

### T ab le 3 · Ov e r v iew o f Phase ll 

### valid ati o n te s t sch e dule

# . No m i na l No min:d Q A G No.of XFM No ofX a ct Da t e· Level Cone . R u ns Run s lll!f d sc m March 4 · 5, 2005 H igh l OR 12 45 March 6, 2005 Low 21 4 46 March 7 , 2005 Mid 45 4 37 M:rrch 8 , 2005 Blank 0 4 64

T ota l R u os 24 192 

### Validation criter ia used t o evaluate the acceptance of the XFM and Xact - IAP were similar to 

### those used 

### for the QAG in 

### Phase I and are li s t ed in Table 4. These criteria include bias , prec i s ion and l inearity ofthe measurement methods. The main difference was the omission of the filter and elemen tal ratio criteria, which were not relevant to Phase U testing. As was the case in P h as e I , the acceptabi lity ranges listed in T able 4 were guided by values req u ired by Method 30 1, Performance Specifica t ions 1 1 1 

### s and proposed Perfonnance Specification 1 

## <flO, and are either equal to t hos e liste d in these procedures or are more restrictive. Table 4 : Acce pta nce c r iteria for P has e II v alida tion o f th e XFM and Xact - I AP . Cr iter i a M easure 

### N o . Acc epta ble Ra n ge M easur e me nts B ias ! -statist ic >9 

### < critical val u e o r correction factor >9 

### B e twee n 0 . 8 and 1.2 Pr eci sion percent of emission limit >9 

### <10% L

inea r i ty correlation coefficient 

### >9 >0.85 

### 2. 6 Del'iationsfrom Test Plmt 

### The original draft 

### Test Plan was developed in the 

### fall of2004 to organize validation t esting of the XFM and can be found in Appendix A . During actual testing, there were fi ve significant deviations from this test plan. Why these dev i atio n s occurred and any potential impacts to 

### the resulting data 

### set are discussed b e low. • E v alu atio n o f th e Xact- IAP : The test plan proposed an approac h for validating the QAG and XFM, but it did not focus on the Xact-!AP as a separate Ins t rume ntal Analyzer Procedure. Following d iscussions with the EPA, the scope of the test was expanded to incl u de the Xact- IAP, followi n g the same validation criteria as the XFM . Both the XFM and the Xact- IAP are candida t e con ditional methods, but the Xact-IAP offers end-users more immedia t e feedback. For this reason, and since the same QAG data set could be applied to both a p

proaches, the test plan was expanded t o include v

alidation proce dures fo r the Xact-IAP. • Total C ap tu re : The origina l test plan propose d using a total capture approach to validate the QAG in Phase I. 

### The total capture approach, however, was t echni cally Method 30 1 E val : V I.O 

### Section 2.0 Approach Page 12 of 40 

## VES00949 4

### prob l ematic and was not used during the validation tests. Instead, the approach used was based on independent measurements of the resulting QAG generated aerosol concentration as described above. • Bla11k Run s: The original test plan called for injection ofwater for b l ank nms to determine XFM detection limits. During the course o f tes t ing, it was determined t h at pure water wou ld freeze in the QAG . For this reason, blank 5% nitric acid wa s spiked instead ofwater. These blank tests were conducted during both Phase I (five hours) and 11 

### (eight hours). This blank testing resulted in six XFM and about 100 Xact blank test runs. Although all five metal s reported blank concentrations ofless than one**~dscm** 

### for the XFM and the Xact- IAP, acrual detection limits were calculated using a much larger data set (Appendix K) and then compared to the blank runs as discussed i n Section 7 .11.2. • Pr ecisi on : T he precisions measured for the QAG, XF M, and Xact-IAP were based on the PRSD of the measured metal concentrations when the QAG was spiking at a constant rat e. The original test p lan called for calculation of precision as a percent of the emission limit, and tl1e results indicate that calculati n g precision in this manner would have met t h

e test plan precision criteria of 10% . However, since a range of concentrations were used to detennine linearity, a more demanding protocol using all of the data including the lowes t spiked concentrations was used tha t divided the s t andard dev iation at each concentration by the mean concentration at each spiked leve l. This latter approach is consistent with Method 30 1 : Equation 301-622 • 

### • Flue Gas Compo s ition: Phase 11 

### samples were collected when the incinerator was burning narurn l gas instead of waste. In the week prior to Phase ll testing, cracks were observed in a section of incinerator pip i ng that is exposed to pressures o f more than I 000 PSL These cracks p reclu ded the burning of waste during testing and, since i t was a two to thr ee month d elay before the pipes could be repaired , it was decided to conduct the t ests using narural gas rather than delay the tests. A comparison of the flue gas characteristics for Phase 

### 11 tests relative to 

### flue gas 

### characteristics duri n g surrog ate feed stock bum s condu cted in the Fall of2004 is 

### shown in Table 5. 

### In 

### general, the incinerator emissions produced w hil e bumin g narural gas in Phase II were very similar to those observed during the surrogate fe ed stoc k burns. Most major flue gas species such as 

### S02, 

### H2 

### 0, CO, and C()z, were found in the same or higher concentrations during Phase 

### 11 tests than in the surrogat e feed stock bum t ests in the fall of2004. T h e primary difference was a decrease of 64% in particulate concentrations du r ing P hase II tests . However, the impact of th i s parameter i s insignificant at these concentrations (less than I Omgldcsm @ 

### 7% 0 2), 

### and would not be s ignificant unless it were well over the permitted PM emission limits .

Section 2.0 Approach Page I3 of 40 

## VES009495

### T bl 5 C f 

### a e : 

### om p a n so n o s u rro2ate an d Ph II 

### f1 ase ls tl 

### u

e I!&S character cs. Cbetuical SuOTogate .TesiS Phas e II Ph aseD

Sp<cies F all 2004 Ma r ch 2005 Surrogote Rodo 

## s o b dry· (ppm) 

### NO ± 

### NO ND ± 

### NO**-~~~----** H C I , dry (ppm) 2.3 ± 1 .2 1.9 

# ,. 06 0.8 CO,, dry · (%) 8.3 ± 0.7 6.0 :i: 0 . 1 0.7 C O , dry (ppm) 8.4 :1: 1.9 1 3.8 ± 0. 7 1. 7 o , , dry(%J 9. 1 ± 0.9 11.4 ± 0.1 13

H , O (%) 9.2 ± 3.3 10.1 ± 0.4 1. 1 PM @7% 0 , 9.8 ± 2.8 3.5 ± 0.4 0.4

(m gt ds em) NO ., dr)' (ppm) 40.5 ± 10. 0 108.1 :i: 

## s.s 2.7 Flow (dscfm) 14196 ± 1096 9952 ± 423 0.7 

### 3 . 0 

### Metho d s 3.1 QAG Rejere11ce Aerosol Generator Th e reference aerosol used in these tests was gen erate d with CES' quantitative aerosol generator (QAG). T hi s aerosol was the primary reference source used to determine bias and precision capabilities of the candidate conditional multi-metals methods. The QAG provides a conti nuous reference aerosol whose analyte concentration is NIST- t raceable widt documented accuracy and preci sion. Ouce va l idated iu the laboratory during Phas e I testing, the QAG was used t o spike in ci n erator slack gas in the field during Phase ll 

### testing. Although the QAG has the abi lity to generate a wide range of analyte-containing aerosols, tbe only type used in the experiments described in this report were metal containing aerosols . The QAG generates its reference aerosol using t he following three basic steps: • First, an aerosol o f anal)1e solution droplets is 

### created using a nebulizer 1 6

. 

### • This is followe d by the separation and recirculation of large droplets using a settlin g chamber where the large droplets are removed while liquid and vapor phases are equi librated. • The third ste p consists of drying droplets smaller than**20~tm** 

### in diameter. Met h od J O

J £\•3.1 . : V I. O 

### Section 3.0 Methods Page 14 

### of40 

## VES009496

### The dried analyte-containing aerosol emission rate is 

### calculated from the analyte concentration in t h e nebulized solut ion, the solution droplet emiss ion rat e, and the total volume of nebul izing, drying and dilution gas used to crea te the resulting aerosol. Use of neb ulizers to generate quantitative aerosols is 

### typically limited by three key factors: • Th e magnitude and uncertainty of the water vapor emission rate lo st during droplet gen eration and equilibration • C h anging solution concentration due to evaporation of solution • Generation oflarge droplets, w hic h can represen t a significant fraction ofthe emitted mass and cou l d have low transport efficiency due to the large size of the resulting dried salt particles. These potential problems have been effectively eit h

er el iminated or mi nimized in the current model of the QAG by (I) 

### generating the droplet aerosol at 32° Fusing cooled water-saturated nebulizing air to minimize and quantify the evaporative component, (2) using a large solution reservoir to both 

### minimize the impact of changing concent ra tio n d ue to eva pOrdtiOn and to a

llow for measuremen t of tota l solution use rate, a n d 3) incorporation of a st illing chamber to separate and recycle large solution droplets. Key QAG 

### components are ill ustrated wid1 

### the schematic drawings shown i n Figure 

### 5. Quanl i l ll.liv.: Atr

CSbl i. 

### ::.. DJy in a <lamb" i. 

### ::.. Soollngl &:;uil i lx'ati.ng 

# """' "' " i. 

# I C

(IIIISI"" l )'pt Ncblll i ta 

## ·j

# · /'**~ ~**  Pucnp**~** i. 

# I lJ I !**COIII Y~oo**  Nt'buti:u: r S!.

nn(hlrd ---1' T(I'J'II'¢iWre A Nebl!llz a A i t Sol

utjon (' c. mtmUcd Coolrol 

# --,... } ( e b."lt h 

# " C ontrol S oJ u

t Xl

. u R

f.SefV olr 

### - · 

# __ , I tt ibt h**B~ '!_nC(<**  

### A. B. Ca""d Elubbl.<'f"

Eltt\'fllll 8 u

bbl

er

### g Figure 5 : A . Sc hemati c of flow t hro u g h QAG components. B. Overview 

### of the set- up of QAG c ompone nt s. MNl!od30 l Evo L : V l. O 

### Sect ion 3.0 Me t hods Page 

### 15 of40



### VES009497

### There are s ix major components of the QAG: • A reference solution control component is used to c i rculate the analyte-containing solution through the nebulizer and measure the total solution use rate . This component consists of a peristaltic pwnp, solution reservoir, balance, connecting tubing and a laptop used to record the balance re-ad ing every 1 5 

### seconds . • A 

### nebul izer air control component used to maintain and measure the flow, t emperature, pressure and saturation of air used in the nebulization process. This component uses compressed air at about 20 PSI-gage pressure to force air through the nebulizer. The nebulizing air passes through flow and 

### pressure regulators, an external b u bbler to sat urate the air at room temperature and then a second bubbler to assure that the nebu lizing air is saturated a 32° 

### F prior to entering the nebulizer. • A 

### temperature control component (ice bath) is used to control the t empe rature of the nebulizer air, the nebulizer and 

### the settling/equilibrating chamber at 32° F. • A 

### Collison- type nebulizer 1 6 

### component is used to create the solution droplet aerosol. It consi s ts oftbree major components: the nebulizer cup, the nebulizer and nebulizer nozzle as describe in more detail in Appendix C . The nebulizer cup contains the standard solution. This solution is con tinuously circulated from the nebulizer cup to an external reservoir to minimize the impact of vapor loss on solution concentration and to allow for det ermination of the solution use rate. • A 

### settling/equilibrating chamber component located just above the nebulizer component. Tite nebuliz er-generated aerosol i s directed into t his chamber where large droplets settle from the gas stream and the remaining droplets equilibrate with water vapor prior to enter ing dte drying chamber. The nebulization process creates a droplet spray con taining a wide range of droplet sizes . The largest droplets impact on the walls of the nebulizer cup an d are recycled. The smaller droplets are entrained i n the n ebulizer ai r flow and pass into the settling-equilibration cham ber. The functio n of the settling-equilibra t ion chamber i s to 

### remove and recycle all 

### droplets greater than 

### about 20 11m in diameter as well as 

### to assure droplet-vapor equilibrium at 32°F. Th us, the on ly drop l ets emitted into dte drying chamber have d i ameters less dtan 20 11m 

### and have been equi li brated**\\~th** 

### water vapor at 32°F. • A 

### drying chamber co m ponent with temperature and flow controls. In this chamber, the size-restricted and vapor equilibrated aerosol from the settling/equ ilibrating chamber is surrounded by dry air at about 300° F, wh ich i s used to dry the reference solution droplets p rior to being emitted from the QAG. The aerosol exiting the drying chamber consists of the transport 

### gas (air) , water and metal vapor and dried salt particles. The size of the salt particles is controlled by the ana lyte solution concentration, the design o f tlte settling chamber and the flow rat e of nebu lizer air. This aerosol i s the referen ce aerosol produced by the QAG. However, in t his ex p eriment, the aerosol was further d ilut ed with makeup air prior to being transported t o the Xact stilling chamber from which both Xact- IAP and 

### XFM samples were drawn. QAG efficiencies referred to in this report are combination generation Me:chod 30 1 E v<tL : V I , () 

### Section 3.0 Methods Page 

### 16 of40 

## VES009498

### (aerosol emitted from the drying chamber ofdte QAG) and 

### transport to the Xact stilling chamber. The QAG's generated aerosol concentration ( q<J.<G) 

### is process traceable to NIST through the traceability of its components (see Appendix C). 

### As demonstrated in Equation 1 

### below , the generat ed concentration is a functi on of t he solution standard concentration of the 

## ( c ;-

0 · ' c ) , 

### total flow rate (F,), 

### rate ofmass loss ofthe solution (R.,), 

### and rate of vapor Joss (R,). 

### Process traceability to NTST is esta blished by using instruments that are NIST-traceable (e.g. , calibrated with NIST standards) to measure these param eters and a solution with NTSTtraceable concentra t ions. The fmal product of the QAG is an aerosol containing dried salt particles and vapors of the ana l yte or analytes. The concemration of the analytes 

### in the aerosol and the concentration uncertainty are calculated from the QAG 's recorded operating parameters. T he eq uation for calculating the generated aerosol concentration is as follows:

c s- QAG**c~ -{)** **AG** 

# = , (R _ 

### R 

# J 1 

### F m v I Eq u ation 1 

### Where:**C~ -'** **G** = 

### Concentration of the i"' element in the reference



### ' aerosol generated by the QAG 

### c;..e-'c = 

### Concentra t ion of t h

e i 111 

### ele ment in lhe QAG 's NIST-traceable s olut ion 

### F, = 

### Total combined tlow of the nebulizer air, drying air and malceup air or stack gas /1.., 

### Total rate of solution m ass loss for the QAG, determined from the slope of a linear least squares fit of the reservoir mass data over the period of a test or series of tests 

### R, . 

## = Rate of vapor loss 

### from the reference solution , 

### as calculated 

### us ing th e following equation: Equ atio n 2 

### Where: 

### F, Plow of expanded nebulizer air in the QAG M , 

## = Mas s ofwater vapor io 

### a liter of saturated air at 

### 32°F Melh <>d 3 01 E val. : V1. 0 

### Section 3.0 Methods Page 17o f 40 

## VES009499