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# OAR Box 1338 Prepped by Ollie Stewart



### Document

Number: 

# 49 ) V-C- 1
Docket Number: 

# A-89-1 1

Printed 6/17/2008 1:48:07

PM Sheet 49 of 105P. 2 

# /4-89-/ I

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# V-c- /

'cJJJ-LLiXf ^ IM MAR- 7 199

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# SUMMAR YOF COMMENT S AN

D RESPONSE S FO

R METHOD S 2 3 AN

D 26P. 3

TABL E O F CONTENT S Pag e Chapte r 1
. Introduction ^ 1

4 Chapte r 2
. Summar yo f Change s Sinc e Proposa l 2 Chapte r 3
. Summar yo f Comment s an d Response s 3 Lis t o f Commenter sP. 4

/ •

LIS T O F ACRONYM S USE D CD D - Chlorinate d Dibenzo-p-Dioxi n CD F - Chlorinate d Dibenzo-p-Dioxi n 4 CF R - Cod e o f Federa l Regulation s EP A- Environmenta l Protectio n Agenc y G C - Ga s Chromatograph y HC l - Hydrochlori c Aci d HpCD D - Heptachloro-Dibenzo-p-Dioxi n HxCD D - Hexachloro-Dibenzo-p-Dioxi n MW C - Municipa l Wast e Combusto r M S - Mas s Spectrometr y NPR M - Notic e o f Propose d Rulemakin g NSP S - Ne wSourc e Performanc e Standar d OCD D - Octachlorinate d Dibenzo-p-Dioxi n OCD F - Octachlorinate d Dibenzofura n PCD D - Polychlorinate d Dibenzo-p-Dioxi n PCD F - Polychlorinate d Dibenzofura n PeCD F - Pentachloro-Dibenzo-p-Dioxi n Q A- Qualit yAssuranc e Q C - Qualit yContro l TCD D - Tetrachloro-Dibenzo-p-Dioxi n TCD F - Tetrachloro-Dibenzofura n TMQ L - Theoretica l Minimu mQuantificatio n Limi t



### nP. 5

Chapte r 1

INTRODUCTIO N O n Decembe r 20 , 1S89 , th e U.S . EP Apublishe d i n th e Federa l Registe r (5 4

4 F R 52190 ) Metho d 23 , "Determinatio n o f Polychlorinate d Dibenzo-p-Dioxin s and Polychlorinate d Dibenzofuran s fro mStationar ySources " and Metho d 26 , "Determinatio n o f Hydroge n Chlorid e Emission s fro mStationar ySources. " Thes e method s wer e propose d unde r th e authorit yo f Section s 101 , 111 , 114 , 116 , and 30 1 o f th e Clea n Ai r Act , a s amended
. Publi c comment s wer e solicite d a t th e tim e o f proposal
. T o provid e intereste d person s th e opportunit yo f ora l presentatio n o f data , views , o r argument s concernin g th e propose d tes t methods , a publi c hearin g wa s schedule d
a t 10:0 0 a.m . o n Februar y7 , 1990 " a t th e Researc h Triangl e Park , Nort h Carolina , bu t n o on e requeste d a hearing
. Th e publi c commen t perio d wa s fro mDecembe r 20 , 198 9 t o Marc h 5 , 1990
. Twelv e commen t letter s wer e receive d concernin g issue s relativ e t o th e propose d tes t methods
. Adetaile d discussio n o f thes e comment s hav e bee n carefull yconsidered , and necessar ychange s hav e bee n mad e i n th e propose d methods
.P. 6

Chapte r 2

SUMMARYO F CHANGE S SINC E PROPOSA L

METHO D 2 3 1 . Th e cleanu p procedur e fo r th e sampl e trai nha s bee nchange d t o requir e
mor e thoroug hrinsing . 2 . Th e optio no f wrappin g filte r sample s inaliuminu m foi l afte r collectio n ha s bee ndeleted . 3 . Metho d 2 3 ha s bee nchange d t o giv e th e teste r th e optio nt o choos e ga s chromatographi c colum nsystem s othe r tha nth e recommende dsystem , provide d tha t th e necessar y

resolutio nca nb e acheived . 4 . Th e concentration s o f th e calibratio nstandard s inTabl e 2 hav e bee n lowered . 5 . Th e metho d now

require s th e analys t t o includ e a loc k mas s an d a chec k channe l fo r th e mas s spectromete r durin g sampl e analysis .

METHO D 2 6 1 . Th e optio no f usin g a nin-stac k filte r ha s bee ndeleted . A heate d out-of-stac k filte r i s now required . 2 . Th e requiremen t fo r facin g th e samplin g nozzl e away fro m th e directio no f th e stac k ga s flow

ha s bee ndeleted .P. 7

Chapte r 3

SUMMARYO F PUBLIC COMMENT S AN D RESPONSE S

4 Metho d2 3 Commente r IV-D-0 1 1. 1 Comment : W e ar e dismaye dtha t ther e ar e s o man y mino r difference s betwee nthi s metho dan dth e samplin g an

danalytica l method s fo r PCDD s an d PCDF s foun dinEPA

publicatio nSW-84 6 "Tes t Method s fo r Evaluatin g Soli d Waste. " Th e proliferatio nof mino r difference s betwee nmethod s use dfo r th e
same contaminant s a t differen t source s wil l onl y lea dt o confusio ninth e fiel dan dinth e laboratory . Response : Ther e i s n o procedur e inSW-84 6 fo r measurin g PCDD' s an d PCDF' s b y hig hresolutio nmas s spectrometry , althoug hther e i s a metho dusin g low resolutio nmas s spectrometry . An y difference s i

nth e procedure s ar e generall y

a result o f th e differen t type s o f sample s o r source s t o whic hth e method s wil l be applied . W e hav e attempte dt o eliminat e al l unnecessar y differences . 1. 2 Comment : W e fee l tha t th e additio no f surrogat e standard s t o th e XAD- 2 resi ni s o f littl e valu e t o th e qualit y contro l program . Th e standard s
ar e adde di na singl e dose , befor e samplin g an dar e subjec t t o th e entir e samplin g run , whil e an y PCDD s o r PCDF s inth e emission s ar e adde dove r th e entir e samplin g period . Sinc e th e migratio no f th e PCDDs/PCDF s alon g th e resi ncartridg e woul dstar t whe nth e samplin g started , th e surrogate s woul d brea k throug hbefor e th e nativ e PCDDs/PCDFs . I t woul db e possibl e t o hav e a 5 0 percen t los s of surrogate s withou t havin g a 5 0 percen t los s of natives . I tP. 8

woul d als o b e incorrec t t o appl y th e collectio nefficienc y correctio no f th e resi nt o th e PCDDs/PCDF s foun d i nth e filte r catc han dth e rins e solvents . Any PCDOs/PCDF s los t fro m th e glasswar e o r filte r woul d b e collecte d b y th e resin . Sinc e al l portion s o f th e trai nar e extracte d an d combine d int o on e extract , i t i s no t possibl e t o appl y a correctio nt o jus t th e resi nresults . Sectio n7. 3 o f th e metho d doe s no t defin e wha t constitute s "isolate d surrogat e compounds " and i t i s therefor e no t clear whe nth e correctio nfacto r shoul d b e applied ^ Response : Inou r ow

ntestin g program , w e consistentl y showe d surrogat e recoverie s i

nth e allowabl e rang e o f 70-13 0 percent . Althoug hi t i s tru e tha t thi s migh t tes t overestimat e th e effec t o f breakthrough , w e believ e tha t any wel l controlle d samplin g trai nwil l sho w recoverie s i

nth e acceptabl e range . I f w e eliminate d thi s qualit y contro l check , w e woul d no t hav e any mean s t o determin e i f sampl e breakthroug hha doccurred . Whil e i t i s no t strictl y accurat e t o appl y

a collectio nefficienc y correctio nt o th e whol e sampl e base d solel y onth e recover y

o f materia l fro

m th e adsorben t cartridge , thi s i s offere d onl y

a s a noptio nan

d i s no t a requirement . Becaus e th e effec t o f thi s correctio nwoul d b e t o overestimat e th e PCDD's/PCDF's , an y sourc e tha t choos e thi s alternativ e an d stil l complie d wit hth e regulatio nwoul d b e spare d th e cos t o f a retes t withou t affectin g it s complianc e status . Thu s w e d o no t pla nt o chang e thi s qualit y contro l requirement . 1. 3 Comment : Th e us e o f methylen e chlorid e a s a rins e solven t i nth e fiel d (Sectio n4.2.4 ) shoul d b e droppe dform th e method . Methylen e chlorid e i s a suspecte d carcinoge nand it s us e inth e fiel d wher e prope r ventilatio ni s
no t alway s possible , i s hazardou s t o th e member s o f th e samplin g team . Whateve r smal l gain s i nrecover y

tha t ma y

b e mad e b

y usin g methylen e chlorid eP. 9

i nplac e o f a les s toxi c solven t suc ha s hexan e o r toluene , woul d b e los t i n
ananalysi s wher e anacceptabl e interna l standar drecover y i s 40-13 0 percen t
and goo d precisio nwoul d b e ±5 0 percen t onduplicat e samples . Response : We ar e inth e proces s o f investigatin g toluen e a s a possibl e alternativ e solven t t o methylen e chloride , bu t unti l w e ca ndetermin e tha t i t doe s no t affec t th e amoun t o f PCDD's/PCDF' s recovere d fro m th e samplin g trai n
w e canno t substitut e fo r th e solven t tha t wa s use d durin g th e collectio no f th e dat a t o suppor t th e regulation . 1. 4 Comment : Th e metho d shoul d als o requir e a fiel d blan k trai ntha t i s treate d identica l t o th e sampl e train s and analyze d alon g wit hth e samples . Response : Althoug hi t woul d b e a goo d ide a fo r th e teste r t o d o thi s a s par t o f a ninterna l qualit y assuranc e program , w e d o no t believ e i t i s
necessar y

t o requir e thi s a s par t o f th e complianc e tes t method . Fiel d blan k train s woul d onl y

demonstrat e tha t a positiv e bia s migh t hav e existe d durin g th e sampl e collection . Becaus e a positiv e bia s inth e fina l resul t woul d b e a disadvantag e t o th e sourc e ther e i s a ninheren t incentiv e t o preven t thi s
occurrence . 1. 5 Comment : Finally , ther e ar e apparentl y two typographica l error s in Tabl e 1 . Th e las t interna l standar d liste d shoul d b e 13 C 12 -l,2,3,4,6,7,8-HpCDF . Th e firs t surrogat e standar d shoul d b e 37 Cl 4 -2,3,7,8-TCDD . Response : Ther e wer e two typographica l errors . Bot ho f thes e hav e bee n corrected . Commente r IV-D-0 3 2. 1 Comment : Anothe r proble m associate d wit husin g dioxin/fura n emission s and Metho d 2 3 a s th e measur e o f organi c emission s no t addresse d in th e NPR M i s th e procedur e itself . Ther e ar e ver y few stac k samplin gP.1 0

organization s i nth e worl dthat hav e experienc e wit hth e method . Onl y a handfu l o f laboratorie s hav e th e GC/M S equipmen t necessar y t o perfor m

th e method . Th e bigges t problem , however , i s th e availabilit y o f standard s (laborator y

an dfield). ^ How

doe s EPA

pla nt o addres s thi s issue ? Wit ha
4 requiremen t fo r annua l dioxin/fura ntestin g onal l ne w an dexistin g MWC s (se e
commen t concernin g frequenc y o f testing) , ther e wil l b e majo r delay s i n securin g samplin g an

danalytica l contractors . How wil l thi s know

nproble m

be deal t wit hfro

m a complianc e standpoint ? Response : W e believ e tha t th e numbe r o f test s require dimmediatel y afte r promulgatio no f th e regulatio nwil l no t excee dth e capabilitie s o f th e availabl e samplin g an danalytica l laboratorie s an dtha t ther e wil l b e a n adequat e suppl y

o f labele dstandard s an daudi t samples . Th e ful l effec t o f th e testin g requirement s fo r the'ne w an dexistin g source s wil l no t b e fel t fo r abou t fiv e years . W e believ e tha t thi s i s adequat e tim e t o allo w fo r th e
necessar y

expansio no f testin g capabilities . 2. 2 Comment : If , however , EPA continue s t o advocat e th e currentl y propose dMetho d23 , EPA shoul da t leas t allo w functionall y

equivalen t method s and/o r equipmen t t o b e use dwher e comparabl e result s fo r tota l CDD/CD F level s
ca nb e obtained . EPA shoul drevie w

method s availabl e fro m th e Californi a DOH S
an dAR B an

dth e Ontari o MO E a t a minimu m befor e settlin g onth e curren t Metho d 23 . Fo r example , th e laborator y tha t develope dth e propose dMetho d2 3 (currentl y

existin g a s Metho d829 0 inEPA SW-846 ) use s th e DB- 5 colum nan dth e DB-22 5 colum

nfo r quantificatio no f al l isomer s includin g 2 , 3 , 7 , 8-TCDF , whil e Metho d2 3 call s fo r th e DB- 5 an dth e SP-233 1 columns . Response : Tester s alway s hav e th e optio no f requestin g alternativ e methods , bu t thi s i s no t th e appropriat e avenu e t o submi t suc hrequests .P.1 1

Request s fo r alternativ e method s shoul dbe submitte dafte r th e metho di s promulgated . Th e reques t shoul db e i nwritin g an dshoul dcontai nan

y supportin g data . EPA reviewe dothei^method s befor e beginnin g it s progra m t o collec t dat a
4 insuppor t o f a regulatio nfo r MWCs . Th e propose dMetho d2 3 reflect s th e procedur e use dt o colle'c t thi s supportin g dat a a s require db y law . Th e metho dha s bee nrevise dt o allow alternativ e ga s chromatograph y colum nsystem s provide dtha t th e use r ca ndemonstrat e throug hcalibratio nan d performanc e check s tha t th e column s wil l provid e th e necessar y isome r separation . 2. 3 Comment : I

nSectio n1 , a ne w

Sectio n1. 3 shoul db e adde dt o remin d th e user s tha t thi s samplin g metho deliminate s an y possibilit y

o f obtainin g a vapor/particl e distributio no f tota l CD/CD F o r an y o f th e isomer s o r congeners . Response : Sectio n1. 2 ha s bee nrevise dt o mak e i t clea r tha t Metho d2 3
canno t determin e a vapor/particl e distributio no f PCDD' s an dPCDF's . 2. 4 Comment : InSectio n5.1.1 , i t appear s tha t th e referenc e t o "th e concentrat e fro

m Sectio n5.1.2 " i s reall y fro m Sectio n5.1.3 . Response : Thi s i s correct . Sectio n5.1. 1 ha s bee nrevise daccordingly . 2. 5 Comment : I

nSectio n8.3 , Audi t Sampl e Availability , ther e i s
concer ntha t eve ni f request s ar e mad e i na timel y

manne r EPA

ma y no t be abl e t o kee pu

pwit hth e deman dt o provid e thes e an dthu s critica l financia l deadline s coul db e jeopardize dbase do ndelay s eve nbeyon dth e contro l o f EPA . We reques t tha t EPA

addflexibilit y

t o th e audi t procedur e t o preven t problem s befor e th e metho di s finalized .Response : W e believ e tha t th e numbe r o f test s require dimmediatel y

afte r promulgatio no f th e regulatio nwil l no t excee dou r abilit y t o provid e th e necessar y

audi t samples . 2. 6 Comment : Infectio n9 , EPA shoul dad

da sectio nt o codif y it s
curren t practic e offonlyllistingjnondetecte disomer s o r congener s an dno t includin g the m

inth e calculatio no f tota l CDD/CDF . I f nondetect s ar e t o b e counte da s th e detectio nlimit , a rethinkin g o f appropriat e emissio nlimi t i s inorder . Response : Sectio n9 ha s bee nrevise dt o clarif y tha t i t i s EPA' s inten t t o coun t "nondetected " result s a s zeroes . 2. 7 Comment : Th e fina l qualit y assuranc e rins e use s toluene . EP A state s tha t i t wil l continu e t o revie w toluen e fiel drins e qualit y assuranc e result s an

dma y chang e th e metho da t some tim e inth e future . A S OCDD/OCD F
ma y b e mor e solubl e i ntoluen e tha nmethylen e chloride , a chang e coul dresul t inquit e a differenc e intota l dioxin/furan--bu t no t inTEF's . EP A mus t validat e th e fina l metho donMWC s an destablis ha

nachievabl e limi t i nth e NSP S an dEmissio nGuidelines , regardles s o f samplin g an danalysi s methodology . Response : EP A

wil l revis e Metho d2 3 t o specif y toluen e a s th e rins e solven t onl y

i f th e tes t result s show tha t th e toluen e doe s no t mak e a significan t differenc e inth e tota l measure dPCDD' s an dPCDF's . Commente r IV-D-0 6 3. 1 Comment : Sectio n3.3.1 3 Basi c Alumin a Pre-activate dalumin a i s availabl e fro m manufacturer' s andca nb e use d
a s is , provide dblank s ar e fre e fro m interference s an

dcarry-over . Activatio n befor e us e shoul dno t b e a prerequisite .P.1 3

Response : Th e metho dha s bee nrevise dt o allo w th e us e o f activate d alumin a a s receive dfro m th e supplier . 3. 2 Comment : Sectio n3.3.1 5 Silic a Ge l Impregnate dwit hSulfuri c Acid . ^

4 I ncase s wher e greate r capacit y i s required , OxyChe m ha s successfull y substitute dcelit e fo r "silic a gel . OxyChe m suggest s tha t celit e shoul db e liste da s alternativ e soli dsuppor t inthi s step , providin g satisfactor y QA/Q C i s demonstrated . Response : Thi s i s no t th e appropriat e avenu e t o revie w request s fo r alternativ e methods . Request s fo r alternativ e method s shoul db e submitte d afte r th e metho di s promulgated . Th e reques t shoul db e i nwritin g an dshoul d contai nan

y supportin g data . 3. 3 Comment : Sectio n5.2: 2 Basi c Alumin a Colum n OxyChe m ha s successfull y

employe dth e us e o f solvent s othe r tha n methylen e chlorid e an dhexan e t o elut e PCDD s an dPCDF s from

th e basi c alumin a column . OxyChe m

suggest s tha t solvent s othe r tha nmethylen e chlorid e an d hexan e shoul db e allowed , providedacceptabl e QA/Q C i s demonstrated . Response : Se e respons e t o Commen t 3. 2 Commente r IV-D- 7 4. 1 Comment : We believ e we hav e a nalternativ e sampl e trai ncondense r configuratio nwhic hi s superio r t o th e on e describe di nMetho d23 . Th e condenser-adsorben t cartridg e ar e combine dina U-shape darrangemen t wher e on e
ar m o f th e Ui s th e condense r an dth e othe r i s th e adsorben t cartridge . Thi s allow s th e condense r t o b e submerge dinth e impinge r trai nic e bat hwhic h make s i t les s fragil e andeliminate s th e nee dfo r a Teflo nlin e betwee nth e filte r bo xan

dth e impinge r trai nallowin g a nal l glas s system .P.1 4

Response : Se e respons e t o Commen t 3.2 . 4. 2 Comment : Th e second modificatio ninvolve s th e us e o f a glas s extractio nthimbl e a s th e caniste r fo r th e samplin g train . Th e siz e o f th e caniste r i s suc htha t 4 0 gram s o f XAD- 2 resi nca nb e incorporated . Th e beaut y
o f thi s modificatio ni s tha t i t eliminate s al l handlin g o f XAD i nth e fiel d
an d i nth e laborator y

prio r t o extractio nan d analysis . Recover y o f XA D afte r
us e i s n o longe r a questio na s th e materia l i s no t transferre dprio r t o extraction . Th e standar d operatin g procedur e call s fo r remova l o f th e caniste r after use , wrappin g i t i nsolven t rinse d aluminu m foi l an

d storin g i t
a t 4° C unti l extraction . Fo r extraction , th e foi l i s remove d an dth e caniste r i s place d insid e th e soxhle t extractio ndevic e fo r extractio no f th e compound s
o f interest . Response : Se e respons e t o Commen t 3.2 . 4. 3 Comment : A

thir d modification , whic hi s mor e practic e tha n equipmen t oriented , involve s th e us e o f a backu p XA D caniste r periodicall y t o documen t th e captur e efficiency . Basicall y th e practic e involve s followin g th e primar y

caniste r wit ha second caniste r ever y thir d run . Th e caniste r i s extracte d and analyze d separatel y fro m th e res t o f th e samplin g train . Thi s dat a i s intende d t o demonstrat e th e collectio nefficienc y durin g th e tes t program . Collectio no f th e dat a ove r th e year s ha s provide d dat a t o bac k MM- 5 design . Response : Whil e thi s i s a goo d practice , w e believ e tha t spikin g th e adsorben t sample r wit hlabele d PCDD' s an d PCDF' s accomplishe s th e same result . Metho d 2 3 already

require s tha t th e adsorben t sample r b e spike d befor e eac h tes t run .



### 1 0P.1 5

Commente r IV-D- 8 5. 1 Comment : I nSectio n5 , no statemen t i s mad e regardin g th e cleanin g
o f laborator y

glasswar e use d fo r laborator y extractio nan

d cleanu psuc ha s tha t mad e in4.2.2. 2 regardin g th e samplin g equipment . Ar e th e variou s pipette s use d fo r chromatographi c column s pre-cleane d o r use d "out-of-box? " Response : Th e metho d ha s bee nrevise dt o requir e tha t al l glasswar e b e cleane d befor e use . 5. 2 Comment : InSectio n5.2.3 , i s a ste p missin g betwee nth e reductio n
o f th e volume t o 20 0 fil an d th e sampl e analysi s b y GC/MS ? Fo r example , i s th e sampl e take nt o a smalle r volume ? Shoul d th e 13 C U -1,2,3,4-TCD D an d 13 C IZ 1,2,3,7,8,9-HxCD D Recover y Standard s b e adde d jus t prio r t o analysis ? N o mentio no f Recover y

Standar d additio ni s mad e inMetho d 23 , bu t thi s ste pi s needed . Response : Th e metho d ha s bee nrevise d t o includ e th e additio no f th e Recover y Standard s jus t prio r t o analysis . Th e volume o f th e sampl e i s no t reduce d belo w

20 0 # 1 befor e analysis . 5. 3 Comment : InSectio n6.1.1 , wha t rang e o f injectio nvolume s ar e injecte d int o th e analyze r fo r initia l calibration ? Response : On e IL\

o f eac hth e calibratio nsolution s show ninTabl e 2 i s injecte d int o th e analyze r fo r th e initia l calibration . Th e metho d ha s bee n revise d t o clarif y

this . 5. 4 Comment : Th e purpose s o f th e TMQ L i s neve r explained . Wil l thi s b e use d t o calculat e detectio nlimit s fo r th e nondetecte d2 , 3 , 7 , 8 - substitute d isomers ? Ar e analyze r pea k area s o f height s use d fo r sample specifi c detectio nlimit s (fo r example , se e Metho d 8290) ? Calculatio no f detectio nlimit s shoul d b e addresse d inMetho d 2 3 s o tha t result s ar e
1 1P.1 6

consisten t from

laborator y

t o laboratory . Detectio nlimit s ar e nontrivial , sinc e the y

ar e ofte nuse dfo r ris k assessments . Response : Th e TMQ L ha s bee nremove dfro m th e metho dan

dreplace dwit h th e minimum

detectio nlimit . A nequatio nha s bee ninclude dinth e metho dt o
4 calculat e th e minimum detectio nlimit . 5. 5 Comment : Whe nreferenc e i s mad e t o Metho d5 , doe s thi s refe r t o th e stac k particulat e measurin g protoco l o r t o th e "Modifie dMetho d5 " dioxi n protocol ? Response : Al l reference s t o Metho d5 ar e t o th e Metho d5 in4 0 CF RPar t 60 , Appendi xA . Thi s i s a procedur e fo r measurin g particulat e matter . Commente r IV-D- 9 6. 1 Comment : W e suppor t th e developmen t o f standar dsamplin g an d analysi s procedure s fo r th e measuremen t o f polychlorinate ddibenzo-p-dioxin s
an dpolychlorinate ddibenzofurans . Uniform procedure s ar e neede dthroughou t th e Unite dState s t o provid e a reliabl e dat a bas e fo r (1 ) furthe r technica l analysi s t o guid e technolog y development , an

d(2 ) sounddecision s in regulator y

policy . Response : No respons e i s needed . 6. 2 Comment : Th e condensatio no f vapo r emission s prio r t o th e adsorptio ntra pi s critica l t o obtai nconsisten t an dreliabl e data . Response : W e believ e tha t coolin g th e ga s stream prio r t o it s reachin g th e adsorben t sample r i s critica l t o achievin g maximum collectio nefficienc y wit hth e adsorben t sampler . Metho d2 3 require s a condense r i nfron t o f th e adsorben t sample r t o accomplis hthis . W e believ e tha t thi s i s sufficient . 6. 3 Comment : A s note dabove , substantia l reduction s i nsamplin g an d analytica l costs , tha t don' t sacrific e dat a quality , ar e greatl y neede dt o (1 )
1 2P.1 7

provid e lo

w cos t complianc e testin g an d (2 ) promot e th e developmen t o f sufficien t dat a fo r technolog y development . Alternativ e analytica l technique s shoul d b e investigate d t o reduc e costs . Fo r example , analysi s technique s fo r tota l dioxin s an

d furan s (i.e. , th e basi s o f th e regulations ; tetr a throug h octa ) shoul d b e evaluate d a s analternativ e t o analyzin g th e variou s homologue s separately . Response : Se e th e respons e t o Commen t 2.2 . 6. 4 Comment : Th e limit s o f th e capabilitie s o f th e propose d tes t metho d (EPA

23 ) ar e greatl y

needed . Mos t othe r standar d EPA tes t method s hav e discussion s o f (1 ) detectio nlimits , (2 ) accuracy , (3 ) potentia l interferences , (4 ) measuremen t repeatability , an d (5 ) sampl e stabilit y a s par t
o f Sectio n1 . Th e propose d EP A 2 3 doe s not . Th e determinatio no f thes e parameter s an

d associate d technica l discussion s ar e necessar y t o asses s th e appropriat e us e o f thi s tes t metho d an d th e validit y

and reliabilit y

o f th e resultin g data . Response : Th e metho d describe s how eac hlaborator y

ma y calculat e it s
ow ndetectio nlimits . Ou r tes t method s d o no t generall y repor t accurac y

dat a becaus e i t i s no t usuall y possibl e t o asses s th e accurac y o f emissio nsamplin g methods . Th e metho d ha s bee ndesigne d t o eliminat e interference s b y usin g ga s chromatography

t o separat e th e compound s o f interes t fro m othe r compound s befor e measurement . Precisio nmeasurement s hav e no t ye t bee nperforme d o nth e method . A

statemen t abou t maximu m storag e time wil l b e adde d t o th e method . Commente r IV-D-1 0 7. 1 Comment : Th e Californi a Ai r Resource s Boar d (ARB ) ha s formall y adopte d tes t method s fo r determinin g PCDD/PCD F (ARB Metho d 428 ) an d HC l (ARB Metho d 421 ) i

nemission s fro

m stationar y

sources . Th e difference s betwee nth e
1 3P.1 8

Californi a adopte dmethod s an dth e EP A propose dmethod s ar e no t substantial . Th e applicabilit y

o f AR B Metho d42 8 doe s no t exclud e th e applicabilit y o f EPA Metho d23 . Fo r municipa l wast e combustors , th e sourc e matri xrender s EPA Metho d2 6 andAR B MethocM2 1 effectivel y identica l i nresults . 4 W e reques t tha t th e EP A accep t th e us e o f th e AR B adopte dmethod s in Californi a t o satisf y EPA' s propose dstandar do f performanc e fo r municipa l wast e combustors . Thi s woul dobviat e th e nee dfo r duplicat e testin g t o satisf y bot hstat e (o r local ) an dfedera l requirements . Thi s simplifie s administration , an

dreduce s th e burde no nth e applicant . Response : Whil e w e woul db e happ y t o revie w

request s fo r alternativ e procedures , thi s i s no t th e appropriat e avenu e t o submi t suc hrequests . Request s fo r alternativ e method s shoul db e submitte dafte r th e metho di s promulgated . Th e reques t shoul db e i nwritin g an

dshoul dcontai nan

y supportin g data . 7. 2 Comment : Sectio n5. 3 o f th e propose dEPA Metho d2 3 require s tha t th e SP-233 1 colum

nb e use dt o quantif y onl y 2,3,7,8-TCDF . Thi s i s differen t from :
a . AR B Metho d42 8 whic hrequire s tha t th e concentratio no f 2,3,7,8 - substitute dtetr a t o hexachlorinate dPCD D an dPCD F isomer s b e calculate dfro m th e result s o f th e analysi s o f th e sampl e extrac t onth e SP-233 1 column .

b . SW-84 6 draf t Metho d829 0 whic hrequire s tha t th e concentratio n
o f al l 2,3,7,8-substitute dtetr a t o hexachlorinate disomer' s othe r tha n 2,3,4,7,8-PeCD F b e calculate dfor m analysi s o

nth e SP-233 1 column . Th e propose dMetho d2 3 doe s no t allow th e quantitatio nmetho d require db

y AR B Metho d428 . Thi s quantitatio nmetho di s base donth e advic e
o f contrac t laboratorie s tha t hav e evaluate dth e AR B method . W e sugges t tha t
1 4P.1 9

languag e b e adde d t o EPA Metho d 2 3 t o allo

w quantitatio no f th e 2,3,7,8 - substitute d isomer s o nth e SP-233 1 confirmatio ncolum na s lon g a s th e analytica l laborator y document s th e isome r specificit y o f tha t colum

nwit hth e prope r calibratio nprocedure s an dperformanc e checks . « Response : Metho d 2 3 ha s bee nrevise d t o specif y tha t al l isomer s othe r tha n2,3,7, 8 tetra-chlorodibenzofura n(TCDF ) b e measure dwit ha DB- 5 colum n
an d tha t th e 2,3,7, 8 TCD F be measure d wit ha DB-22 5 column . Th e metho d wil l als o allow

th e teste r th e optio no f usin g othe r colum nsystem s provide dth e teste r ca ndemonstrat e throug hcalibratio nan d performanc e check s tha t th e column s wil l provid e th e necessar y isome r separation . 7. 3 Comment : Analysi s b y HighResolutio nGC/Mas s Spectrometr y EPA' s Metho d 2 3 require s analysi s b y hig hresolutio nga s chromatograph y

(HRGC)/hig hresolutio nmas s spectrometr y (HRMS ) wherea s AR B Metho d 42 8 allow s th e us e o f eithe r HRGC/HRM S o r HRGC/lo w resolutio nmas s spectrometr y

(LRMS) . Thi s i s a choic e tha t th e AR B metho d allow s th e teste r t o mak e base d o

nth e targe t detectio nlimit s fo r th e metho d an dth e typ e o f
sourc e t o be tested . AR B staf f ha s foun d tha t a t som

e source s othe r tha n municipa l wast e combustors , suc ha s uncontrolle dhospita l wast e incinerators , PCDD/PCD F concentration s ar e highenoug htha t LRM S migh t b e th e preferre d analytica l method . Response : Tester s alway s hav e th e optio no f requestin g alternativ e methods , bu t thi s i s no t th e appropriat e avenu e t o submi t suc hrequests . Request s fo r alternativ e method s shoul d be submitte d afte r th e metho d i s promulgated . Th e reques t shoul d be inwritin g an d shoul d contai nan

y supportin g data .



### 1 5P.2 0

EPA reviewe dothe r method s befor e beginnin g it s progra m t o collec t dat a insuppor t o f a regulatio nfo r MWCs . Th e propose dMetho d2 3 reflect s th e procedur e use dt o collec t thi s supportin g dat a a s require db y law . 7. 4 Comment : ARB^ s Metho d23 8 interna l standar drequiremen t differ s 4 fro m Metho d2 3 onl y

inth e requiremen t fo r low resolutio nmas s spectrometry . Fo r low resolutio nmas s "spectrometry , AR B Metho d42 8 require s onl y on e PCD F interna l standard , 13 C-2,3,7,8-TCDF , compare dt o fou r fo r hig hresolutio nmas s spectrometry . Thi s wa s dictate db y th e limitation s o f th e LRM S method . I f Metho d2 3 i s revise dt o allow lo w resolutio nmas s spectrometr y a s a noption , thi s limitatio nshoul dbe addressed . Response : Becaus e th e metho di s no t bein g revise dt o allo w th e optio n
o f low resolutio nmas s spectrometry , i t i s no t necessar y t o chang e th e numbe r
o f interna l standards . 7. 5 Comment : Sectio n7. 4 o f Metho d2 3 state s tha t th e toluen e rins e
mus t b e analyze dseparatel y fro m th e othe r rinse s an dmateria l collecte dfro m th e samplin g train , an dtha t th e result s o f thi s analysi s mus t no t be include d i nth e estimat e o f tota l PCDD/PCD F collecte db y th e samplin g train . AR B Metho d428 , onth e othe r hand , require s a benzen e o r toluen e rins e whic hmus t be include dinth e estimat e o f tota l PCDD/PCD F collecte db y th e samplin g train . AR B Metho d42 8 migh t giv e a highe r PCDD/PCD F estimat e o f th e concentratio no f th e same ga s stream tha nEPA

Metho d23 . Nevertheless , th e AR B ha s retaine dthi s requiremen t i nth e propose damendmen t t o Metho d42 8 (Attachmen t III ) a s measure s t o contro l PCDD/PCD F emission s i nCaliforni a hav e alread y bee nestablishe do r propose dbase dondat a obtaine dwit hthi s versio n
o f Metho d428 .



### 1 6P.2 1

Response : Thi s requiremen t affect s onl y th e Ne w

sourc e Performanc e Standar dfo r MWC s an dan y Stat e regulation s base dondat a collecte db y EPA . I t woul dstil l b e appropriat e fo r th e CAR B t o us e th e amende dversio no f Metho d42 8 t o enforc e Sfat e regulation s base do ndat a obtaine dwit hth e 4 revise dMetho d428 . Commente r IV-D-1 1 8. 1 Comment : Specification s fo r th e samplin g prob e hav e bee nomitted . Althoug hi t ca nb e surmise dtha t th e prob e shoul dbe o f th e same materia l a s specifie dfo r th e samplin g nozzles , materia l specification s fo r th e prob e shoul dbe included . Response : Specification s fo r th e prob e wer e no t omitted . They wer e include db

y referenc e t o th e prob e specification s fo r Metho d5 . 8. 2 Comment : I t ha s bee nou r experienc e tha t mos t testin g firm s performin g dioxin/fura nsamplin g programs , purchas e precleane dresi n cartridge s fro

m laboratorie s tha t wil l subsequentl y perform

th e sampl e
recover y an danalyses . Thes e cartridge s mus t be sen t t o th e clien t an d returne dvi a appropriat e carrier . Althoug ha chai no f custod y for m ma y accompany

thes e cartridges , the y ar e expose dt o contamination . I t i s ou r opinio ntha t EPA

shoul daddres s thi s potentia l proble m b y requirin g tha t a certifie dfield/tri pblan k accompany th e cartridge s an

dbe analyze dinth e
same manne r a s th e sampl e t o determin e i f th e sampl e cartridge s wer e subjecte d t o contaminatin g atmospheres . Response : Se e respons e t o Commen t 1.4 . 8. 3 Comment : Th e Departmen t ha s successfull y use da vacuum

desiccato r i nlie uo f th e dryin g colum narrangemen t fo r dryin g o f th e adsorben t followin g



### 1 7P.2 2

th e cleanin g procedure . Coul d EPA conside r thi s techniqu e a s analternativ e i f a laborator y

i s no t equippe d wit hth e dryin g colum napparatus ? Response : Se e respons e t o Commen t 3.2 . Commente r IV-D-1 2 9. 1 Comment : We hav e observe d tha t th e preparatio no f AX-2 1 column s
ca nb e ver y

critica l t o th e succes s o f th e clean-u p procedures . I n particular , i f no t properl y packed , AX-2 1 fine s ca nen d u padherin g t o th e wall s o f th e colum

no r sometime s was hthroug hth e glas s woo l plu g and ge t int o th e sample . Thi s problem ca nb e prevente dthroug hth e additio no f a celit e plu g onth e fina l exi t en d o f th e column . Response : Th e metho d ha s bee nrevise d t o allow thi s option . 9. 2 Comment : W e hav e als o observe dtha t som e o f th e highe r congener s
ar e difficul t t o elut e fro m th e AX-2 1 andsugges t a large r volume o f toluen e b e use d i

nth e fina l elutio nt o insur e adequat e recovery . Fro m a safet y standpoint , i t woul d b e preferabl e t o eliminat e th e us e o f benzen e i nth e (1:1 ) benzene/ethylacetat e elution . W e hav e found tha t toluen e ca nb e use d a s
a substitut e fo r benzene ; however , th e elutio nprofile s shoul d b e confirme d
an d necessar y

adjustment s mad e i

nth e volume o f th e fraction s befor e th e solven t switc hi s incorporate d int o th e method . Response : Se e respons e t o Commen t 3.2 . 9. 3 Comment : Metho d 2 3 specifie s th e us e o f a nSP-233 1 colum nfo r th e isome r specifi c determinatio no f 2,3,7,8-TCDF . By th e usua l standar duse dfo r definin g an

d demonstratin g isome r specificit y fo r 2,3,7,8-TCD D (2 5 percen t valle y separatio no f 2,3,7,8-TCD D from th e know

ncloses t elutin g isomer s t o b e demonstrate d dail y

usin g th e appropriat e colum nperformanc e isome r mi x standard ) th e SP-233 1 colum ncoul d no t b e considere d isome r specific . Throug h

1 8P.2 3

informatio nobtaine ddurin g th e metho ddevelopmen t wor k conducte di nth e EPA/Pape r Industr y

Cooperativ e Dioxi nScreenin g Study , NCAS I wa s abl e t o identif y critica l isomer s require dt o demonstrat e th e 2,3,7,8-TCD F isome r specificit y

o f a DB-225. ^ .Thes e isomer s an dth e ga s chromatographi c condition s 4

- require dfo r th e isome r specifi c determinatio no f 2,3,7,8-TCD F ar e presente d i nNCAS I Technica l Bulleti nNo . 551 . Sinc e thi s colum nha s bee ndemonstrate d t o b e isome r specifi c fo r 2,3,7,8-TCDF , i t shoul db e incorporate dint o propose dMetho d2 3 an dal l reference s t o th e us e o f th e SP-233 1 fo r isome r specifi c determinatio no f 2,3,7,8-TCD F shoul dbe change daccordingly . Response : Se e respons e t o Commen t 7.2 . 9. 4 Comment : Althoug hno t demonstrabl y isome r specifi c b

y th e criteri a generall y

accepted , th e SP-233 1 i s considere dt o com e th e closes t t o generatin g isome r specifi c dat a fo r severa l 2,3,7,8-substitute dpent a an dhex a CDD/CDF . Therefore , thi s colum nshoul dcontinu e t o b e include di nth e procedur e an

dshoul db e recommende dfo r us e ingeneratin g mor e specifi c o r selectiv e dat a o

ncertai n2,3,7,8-substitute disomers . Response : Se e respons e t o Commen t 7.2 . 9. 5 Comment : Th e metho dspecifie s a nionizatio npotentia l o f 7 0 ev . Som e o f th e mos t commonl y use dinstrumentatio nfo r hig hresolutio nGC/M S PCDD/PCD F analyse s us e io nsource s especiall y

designe dfo r hig hsensitivit y fo r PCDD/PCD F compounds . Thi s wa s i npar t accomplishe db y usin g a lowe r ionizatio npotentia l (betwee n30 t o 4 0 ev ) t o minimiz e fragmentation , thereb y retainin g al l th e charg e wit hth e molecula r ion s whic har e use dfo r identificatio nan

dquantitation . B

y specifyin g a fixe dionizatio npotential , n o improvemen t i nth e qualit y o f th e dat a woul db e expecte dandanoveral l los s i nsensitivit y

woul dresult . Th e metho dshoul db e modifie dt o specif y

1 9P.2 4

electro nimpac t ionizatio nbu t shoul dno t specif y a specifi c ionizatio n potential . Thi s woul d b e inkeepin g wit hother publishe d o r draf t high resolutio nM S PCDD/PCD F procedures . Response : Th e metho d ha s bee nrevise d t o delet e th e voltag e specificatio nfo r th e ionizatio nsource . 9. 6 Comment : Th e metho dspecifie s acceptabl e recover y range s fo r th e interna l standard s bu t allow s tha t i f th e criteri a ar e no t met , th e dat a woul d b e considere d acceptabl e i f th e interna l standar d signa l t o nois e rati o wa s greate r tha no r equa l t o 10:1 . A minimu m S/ N rati o o f 10: 1 woul d b e a usefu l QA/Q C criteri a i

nan d o f itsel f an

d w e recommen dtha t i t b e incorporate d int o th e metho d fo r al l analyses , bu t a nacceptabl e S/ N rati o canno t b e use d t o compensat e fo r poo r recoveries . I f th e losse s occur durin g th e extractio n procedure , th e recover y o f th e interna l standard s canno t totall y correc t fo r thes e losse s sinc e i t i s currentl y impossibl e t o insur e (o r demonstrate ) tha t th e interna l standard s distribut e themselve s i nth e matri xexactl y

lik e th e nativ e analytes . Thus , recover y o f th e Interna l Standar d ca noverestimat e nativ e analyt e recovery . Th e isotopi c dilutio nprocedur e ca nadequatel y and accuratel y

correc t fo r losse s whic hoccu r durin g th e clean-u p procedures . Fo r thes e reasons , analyse s wit hunacceptabl e interna l standar d recoverie s shoul d b e rejecte d a s unreliable . Response : Th e metho d ha s bee nrevise d t o limi t acceptabl e recoverie s o f interna l standard s t o betwee n4 0 and13 0 percen t fo r th e tetra - throug h hexachlorinate d isomer s an d betwee n2 5 and 130 % fo r th e highe r hepta - an d octachlorinate d homologues . 9. 7 Comment : Thes e sam e concern s appl y

t o th e us e o f th e surrogat e spik e recoverie s t o correc t fo r lo w recover y

efficiency . Unti l i t ca nb e
2 0P.2 5

unambiguousl yestablishe d tha t th e surrogat e spike s exactl ymimi c th e nativ e analytes , the ycanno t b e use d t o correc t fo r lo wrecoveries
. Response : Se e respons e t o Commen t 1.2
. 9. 8 Comment : Althoug h allowin g a mas s spectromete r resolutio n a s lo w
a s 8,00 0 ma yimprov e sensitivity , th e generall yaccepte d minimu mresolutio n fo r a "hig h resolutio n MS " procedur e i s 10,000
. Thi s i s intende d t o minimiz e potentia l fals e positive s o r mis-identifications
. I n keepin g wit h thi s generall yaccepte d standard , a minimu m M S resolutio n o f 10,00 0 shoul d b e specified
. Response : Th e metho d ha s bee n revise d t o defin e hig h resolutio n mas s spectrometr ya s havin g a minimu m resolutio n o f 10,000
. 9. 9 Comment : I n orde r t o monito r fo r drif t i n th e resolutio n o r tun e
o f th e mas s spectrometer , monitorin g o f a loc k mas s chec k channe l i s generall y require d i n hig h resolutio n M S PCDD/PCD F protocols
. Instrumentatio n suitabl e fo r us e i n Metho d 2 3 shoul d b e capabl e o f performin g thi s QA/Q C function
. Sinc e thi s provide s adde d assuranc e o f th e instruments ' performanc e a t th e tim e o f analysis , monitorin g an d reportin g a loc k mas s chec k channe l shoul d b e require d i n th e procedure
. Response : Th e metho d ha s bee n revise d t o requir e settin g a loc k mas s
an d monitorin g a chec k channel
.

Metho d 2 6 1
. Commente r IV-D- 2 1. 1 Comment : W e strongl ysuppor t EPA' s adoptio n o f io n chromatograph y fo r chlorid e io n detectio n a s par t o f Metho d 26
. Thi s analytica l technolog y i s clearl yth e metho d o f choic e fo r thi s typ e o f determinatio n becaus e o f th e
2 1P.2 6

hig hdegre e o f specificit y an dlinearit y

whic hi s easil y

attaine dusin g a numbe r o f commerciall y availabl e instruments . Response : No respons e necessary . 1. 2 Comment : W e ftrge th e Agenc y t o develo pqualit y

contro l sample s fo r 4
. voluntar y

use , simila r t o th e meta l an dorgani c qualit y

contro l sample s distribute db

y th e EPA' s Cincinnati , Ohi o office . Response : Qualit y

contro l sample s fo r Metho d2 6 ar e currentl y unde r developmen t an

dwil l b e mad e availabl e inth e future . Thes e sample s wil l b e availabl e fo r voluntar y practic e an

dinvalidatin g Metho d2 6 analyse s whe n makin g complianc e determinations . 2 . Commenter s IV-D-2 , IV-D- 5 Comment : W e ar e concerne dtha t Metho d2 6 a s propose dma y b e pron e t o significan t interference s fro m fin e particulate s presen t insome emissio n
sources . W e ar e particularl y concerne dtha t th e metho dcurrentl y ha s n o wa y
o f detectin g particulat e breakthroug hinth e filter . Thi s woul dresul t ina significan t erro r i f particulat e chlorid e salt s ar e present . A determinatio n
o f th e variou s catio nconcentration s inth e impinger s suc ha s NH 4 + , Fe 2+ , Fe 3+ , Al 3+ , Ba 2+ , Ca 2+ , K + , Mg 2+ , an dNa + shoul db e don e t o verif y whethe r breakthroug hha s occurred . Run s havin g catio nlevel s significantl y abov e baselin e level s o r greate r tha n1 0 percen t o f th e CI " concentratio nshoul db e considere dinvalid . Th e presenc e o f an y o f thes e cation s woul dindicat e th e likel y penetratio no f th e filte r b y volatil e o r fin e particulat e salts . Th e metho dshoul dals o b e modifie dt o mor e clearl y indicat e circumstance s wher e thes e interference s woul dprohibi t th e us e o f th e method . Response : Th e specifie dMetho d2 6 filte r use s a ma t configuration . Th e
ma t configuratio nshoul dpreven t fin e particulat e matte r from penetratin g th e
2 2P.2 7

filte r (se e respons e t o commen t 6.1) . Th e specification s describin g th e filte r hav e bee nclarifie dt o emphasiz e thi s poin t an deas e concer nabou t particulat e penetration . W e d o no t fee l an^impinge r analysi s t o determin e filte r breakthroug hi s
4 necessar y

fo r cation s o f non-volatil e chlorid e salts , suc ha s calcium chlorid e (CaCl 2 ) , tha t woul db e expecte dinemission s from municipa l wast e combustors . Filte r penetratio nb

y mor e volatil e particulat e chlorid e salts , suc ha s ammoniu m chlorid e (NH 4 C1) , ma y occu r whe ntestin g source s suc ha s cemen t kilns . However , th e metho dwa s no t develope dfo r us e a t cemen t kilns , an d thes e source s wil l b e grante da waive r fro m th e hydrochlori c aci d(HCl ) testin g requirements . 3 . Commenter s IV-D-2 , IV-D- 5 Comment : W e objec t t o Metho d2 6 bein g use da t cemen t kilns . Dat a show s th e unlikelihoo do f emission s containin g HC l du e t o backgroun dlevel s o f variou s cations . Chloride s detecte db y th e metho dresul t from volatil e chlorid e salt s suc ha s NH 4 C 1 an dothe r salt s instea do f HCl . Althoug hth e metho dstate s tha t volatil e chlorid e salt s ar e obviou s interferences , suc ha statemen t ha s no t prevente dvariou s Stat e regulator y agencie s from

requirin g thi s metho dfo r testin g cemen t kilns . Thi s seriou s interferenc e proble m shoul db e clearl y

an dfull y acknowledge dfo r cemen t kiln s s o tha t industr y wil l no t b e hel dhostag e b y th e Agency' s inabilit y t o develo pa metho dfo r measurin g regulate demissions . Propose dMetho d2 6 ha s no t bee nthoroughl y evaluate dan

dvalidate dfo r us e onth e broa dclas s o f municipa l wast e combustor s t o b e regulated . W e recommende dtha t th e metho db e limite d t o device s fo r whic hi t ha s bee nvalidate d- municipa l wast e incinerators .



### 2 3P.2 8

Response : Th e metho dwa s no t develope dfo r us e a t cemen t kilns ; therefor e th e qualit y o f dat a obtaine db

y samplin g thi s matri xwit hMetho d2 6 i s unknown . Cemen t kiln s tha t qualif y a s MWC s wil l b e grante da waive r fro m th e HC l testin g requirements . 4 . Commente r IV-D-1 0 Comment : Propose dMetho d2 6 use s a 0.1 N sulfuri c aci dsolutio nt o absor bHC l selectivel y an davoi dfre e chlorin e (Cl 2 ) interferenc e i f presen t inth e stack . Th e metho di s otherwis e ver y simila r t o Californi a Ai r Resource s Boar d(ARB ) Metho d421 . Sinc e Cl 2 ga s i s theoreticall y negligibl e inincinerato r flu e gas , an dno experimenta l evidenc e i s availabl e t o show tha t Cl 2 interferenc e commonl y exists , w e believ e bot hmethod s wil l produc e indistinguishabl e result s whe nincinerator s ar e tested . Therefore , th e correctio nfo r Cl 2 i s unnecessary . We reques t tha t EPA accep t th e us e o f AR B Metho d42 1 t o satisf y th e HC l testin g requirement s a t MWC s t o obviat e th e
nee dfo r duplicat e testin g t o satisf y bot hStat e an

dFedera l requirements . Response : Th e Agency , a s well , i s no t priv y t o experimenta l evidenc e showin g Cl 2 ca nb e presen t i nMW C emissions . However , w e d o fee l tha t Cl 2 migh t b e presen t unde r certai nconditions . T o minimiz e th e interferenc e in thes e cases , w e fee l th e modifie dabsorbin g solutio ni s warrante dove r adoptin g AR B Metho d421 . 5 . Commente r IV-D-1 1 Comment : Th e titl e o f propose dMetho d2 6 implie s tha t i t i s appropriat e fo r al l stationar y

sources . Thi s i s no t th e case . Metho d2 6 wa s researched , developed , an

dteste da t MWC s an di s designe dt o captur e HC l init s gaseou s form . Th e metho duse s a constan t samplin g rat e anda samplin g nozzl e positione di nth e downstrea m directio nt o preven t a positiv e bia s from CaCl 2
2 4P.2 9



### from lim e injectio nsystem s typicall y installe donMWCs . Hydrochlori c aci d doesn' t reall y

lik e t o b e HC l gas , i t woul drathe r b e anHC l aerosol . Propose dMetho d2 6 effectivel y eliminate s th e possibilit y o f measurin g thi s aerosol . I t i s ou r opinio ntha t EPA ha s overlooke dsource s whic hma y hav e particulat e andvapo r form s o f HC l whic hwoul dnecessitat e samplin g isokineticall y

i nth e conventiona l Metho d5 mode . r^\ y Response : W e agre e tha t Metho d2 6 i s applicabl e onl y t o municipa l wast e combustors . Th e metho dtitl e doe s no t specificall y mentio nMWC s t o allo w

a broade r applicatio nt o othe r source s tha t ma y requir e HC l testin g inth e future . Th e CaCl 2 

### from

contro l device s wil l no t b e a ninterferan t whe nth e specifie dfilte r i s use d(Sectio n2.1. 5 o f th e method) . W e agre e tha t isokineti c samplin g ma y b e preferre dove r samplin g a t a constan t rate . W e hav e compare dMetho d2 6 an dMetho d5 , samplin g isokinetically , a t a

nMW C an dfoundtha t th e two method s gav e th e same results . However , a t othe r MWC s wher e th e HC l aeroso l ma y hav e a large r aerodynami c diameter , isokineti c samplin g ma y giv e highe r HC l result s tha n Metho d26 . Therefore , w e ar e continuin g t o asses s th e metho dinthi s respec t
an dar e evaluatin g anisokineti c samplin g metho dfo r futur e use . 6 . Commente r V-D-1 2 6. 1 Comment : Th e filte r medi a specifie dinth e propose dmetho di s Pallfle xTX40H17 5 o r equivalent . Thi s filte r i s constructe do f PTF E ona glas s fibe r suppor t an

di s 2 5 percen t glas s fiber . Th e filte r medi a use din th e developmen t o f thi s method , a s reporte dinth e reference ddocument , wa s Schleiche r an

dSchuel l #41-01510 . Thi s filte r i s compose do f PTF E ona polypropylen e support . Inligh t o f report s tha t HC l ca nb e los t onglas s fibe r filters , th e us e o f Pallfle xTX40H17 5 medium ma y no t b e appropriate . 2 5P.3 0

Additionally , w e sugges t tha t instea d o f specifyin g th e filte r mediu mb ybran d
name , th e metho d shoul d specif yfilte r efficienc yand acceptabl e material s o f construction
. Response : Th e Pallfle x TX40H17 5 filte r wa s selecte d becaus e i t i s i n a
ma t (a s oppose d t o a laminate ) configuratio n an d contain s th e maximu mamoun t
o f Teflo n consisten t wit h thi s configuration
. Th e los s o f HC l du e t o adsorptio n o n th e glas s portio n o f th e filte r shoul d b e minima l whe n th e purgin g procedur e specifie d i n th e metho d i s used
. W e fee l tha t specifyin g a
ma t configuratio n i s a mor e effectiv e mean s o f eliminatin g fin e particulat e matte r fro mpenetratin g th e filte r tha n specifyin g a DO P o r othe r efficienc y rating
. Th e filte r specification s hav e bee n revise d t o clarif ythi s poin t and t o allo walternativ e brand s tha t ar e constructe d o f acceptabl e materials
. 6. 2 Comment : Th e metho d state s tha t eithe r an in-stac k o r an out-of

stac k filte r ca n b e used
. However , a n out-of-stac k filte r and filte r holde r
wer e no t evaluate d durin g th e metho d developmen t studies
. W e sugges t tha t th e metho d b e evaluate d usin g a n out-of-stac k filte r and filte r holde r t o addres s th e followin g questions : First , ho wmuc h HC l i s los t i n th e out-of-stac k filter , whic h expose s mor e surfac e are a o f th e glas s fibe r i n th e filte r t o th e sourc e ga s tha n th e in-stac k filte r method ? Second , wha t woul d b e th e impac t o f usin g large r filter s and filte r holder s whic h ma yb e require d fo r
source s wit h hig h particulat e matte r concentrations ? Third , wha t i s th e effec t o n HC l o f th e glas s fri t use d i n a glas s o r quart z filte r holder ? Response : W e hav e specifie d a n out-of-stack , instea d o f a n in-stac k filter , t o minimiz e th e possibl e los s o f HC l du e t o moistur e condensation
. Also , w e hav e specifie d a Teflo n o r quart z filte r holde r (a s oppose d t o glass ) t o minimiz e HC l losses
. ATeflon , no t a glas s frit , shoul d b e use d t o suppor t
2 6P.3 1

. ' * th e filter . Th e impac t o f usin g large r filter s an dfilte r holder s shoul db e negligibl e i f the y

ar e constructe dmostl y o f Teflon ; thi s i s especiall y tru e sinc e th e samplin g system upstrea m

fro m th e firs t impinge r i s purge dwit h stac k ga s prio r t o sampling . W e hav e clarifie dth e specificatio nfo r th e filte r an

dfilte r holder . * 6. 3 Comment : Th e descriptio no f th e filte r location s presente di n Sectio n2.1. 5 appear s t o b e incomplete . Response : Thi s ha s bee nclarified . 6. 4 Comment : I

nth e metho devaluatio nrepor t reference di nth e proposal , ther e ar e no dat a o nsampl e recover y

throug hth e complet e samplin g syste m excep t fo r spike dfiel dsamples . Spikin g fiel dsample s wil l no t revea l constan t losse s o f HC l (i.e. , losse s whic har e no t concentratio ndependent) . Sampl e recover y

shoul db e determine dthroug hth e complet e sampl e trai nusin g alternativel y

a nin-stac k an

da nout-of-stac k filter . Thi s wil l indicat e whethe r an

y HC l i s los t t o reactio nwit halkalin e particulat e matte r collecte d
o nth e filter . Thes e test s shoul db e conducte dusin g cylinde r ga s mixe dwit h humidifie dai r rathe r tha t dr y air . Response : Ther e i s evidenc e (interna l memo o nresult s o f recen t laborator y

experiments ) whic hindicate s tha t th e los s o f HC l t o alkalin e particulat e matte r i s small , i f any . Ther e i s als o evidenc e inth e ope n literatur e whic hindicate s tha t some HC l i s lost . T o minimiz e th e significanc e o f an

y bia s du e t o reaction s o f HC l wit hparticulat e matte r collecte do

nth e filter , w e hav e specifie da minimu m samplin g tim e o f on e hour .



### 2 7P.3 2

• ' « ' 'a * « .
LIS T O F COMMENTER S

Docke t Numbe r A-89-1 1 Docke t Item-Numbe r Commenter/Affi1 i atio n IV-D- 1 ^ . Thoma s M . Allen , Directo r Divisio no f Ai r Resource s New Yor k Stat e Departmen t o f Environmenta l Conservatio n 5 0 Wol f Roa d Albany , Ne w

Yor k 1223 3 IV-D- 2 Davi dGossman , Presiden t Gossma nConsulting , Inc . 45W96 2 Plan k Roa d Hampshire , Illinoi s 6014 0 IV-D- 3 Davi dB . Sussman , Vic e Presiden t Ogde nMarti nSystems , Inc . 530 1 Eisenhowe r Avenu e Alexandria , Virgini a 2230 4 IV-D- 4 . Ric hStafford Denver , Colorad o 8020 9 IV-D- 5 Dougla s Y . Ma c Iver , Manage r Environmenta l Engineerin g Southdown , Inc . Citicor pCenter , Suit e 240 0 120 0 Smit hStree t Houston , Texa s 77002-446 8 IV-D- 6 Timothy J . Yagley , Environmenta l Chemis t Occidenta l Chemica l Corporatio n Occidenta l Chemica l Cente r 36 0 Rainbo w

Boulevar dSout h Niagr a Falls , Ne w

Yor k 1430 2 IV-D- 7 JohnT . Kane , Jr. , Manage r Ai r Qualit y

Engineerin g Keyston e Environmenta l Resources , Inc . 300 0 Tec hCente r Driv e Monroeville , Pennsylvani a 1514 6 IV-D- 8 Jea nM . Czuzw a Babcoc k & Wilco x 156 2 Beeso nStree t Alliance , Ohi o 4460 1


### 2 81 '.•'. • •*
. P.3 3

IV-D- 9 IV-D-1 0

IV-D-1 1

IV-D-1 2

IV-D-1 3 Joh nZin k Compan y Georg e Lew , Chie f Engineerin g Evaluatio nBranc h Monitorin g an

d Laborator y

Divisio n Ai r Resource s Boar d 110 2 Q Stree t Sacramento , Californi a 9581 2 Be nA . Brodovicz , Chie f Divisio nof Technica l Service s an d Monitorin g Burea uof Ai r Qualit y Contro l Commonwealt ho f Pennsylvani a Departmen t o f Natura l an d Economi c Resource s Harrisburg , Pennsylvani a 17105-235 7 JohnE . Pinkerton , Progra m Directo r Ai r Qualit y Nationa l Counci l of th e Pape r Industr y fo r Ai r an

d Strea m Improvement , Inc . 26 0 Madiso nAvenu e New York , Ne w

Yor k 1001 6 Bria nMurphy Privat e Citize n



### 2 9

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