P. 1


# OAR Box 1392 Prepped by Ollie Stewart



### Document

Number: 

# 130 ) ll-A- 5 Docket Number: 

# A-94-5 2

Printed 7/7/2008 9:45:58 AM

Sheet 130 of 136E12
_ 

## ' / " ' • A-94-5 2

DRAF T REPORT : "PRELIMINAR

Y EMISSION S TESTIN G A T DO W CHEMICAL O

N JANUAR Y 4-5,1995 "

Prepare d by : Researc h Triangl e Institut e P.O
. Bo x 12194 Researc h Triangl e Park , N C 27709

I n cooperatio n with : U
. S
. Environmenta

l Protectio n Agenc

y Ai r an d Energ y Engineerin g Researc h Laborator y Researc h Triangl e Park , N C 2771 1

f'''7'!»h-f.f.'M ;

"#/.

. 

## RT I Projec t

No
. 5171-01 6
JANUAR Y 30 , 199 5P. 3



### TABL E O F CONTENT S 1. 0 INTRODUCTION 1 2. 0 OBSERVATIONS 1 2. 1 TES T SET-U P 1 2. 2 DA

Y 1 - HAN D LAY-U

P TES T 2 2.2. 1 Calibratio n gase s 2 2.2. 2 Total hydrocarbon analyze r trace s 3 2.2. 3 Background concentration s and end-o f ru n consideration s 3 2.2. 4 Mas s balanc e measurements 4 2.2. 5 Emissio n measuremen t result s 4 2.2. 6 Compariso n of

emission s (calculate d fro

mTH C analyzer measurements ) wit

h AP-4 2 emissio n factor s 5 2. 3 DA

Y 2 - GEL COA

T SPRAYIN

G TES T 5 2.3. 1 Duc t

flowrat e verification 5 2.3. 2 Samplin g syste

mleakag e consideration s 6 2.3. 3 Tota

l hydrocarbon analyze

r trace s 6 2.3. 4 Background concentrations , an d end-of-ru n consideration s 6 2.3. 5 Mas s balanc e measurements 6 2.3. 6 Emissio n measuremen t result s 7 2.3. 7 Compariso n o

f emission s (calculate d fro

mTH C analyzer measurements ) wit

h AP-4 2 emissio n factor s 7 2.3. 8 Gel coa

t overspra y observation s 8 2. 4 ALTERNATIV

E METHOD S O

F EXPRESSIN G EMISSION FACTOR S
. 8 3. 0 CONCLUSION S 9 4. 0 RECOMMENDATION S 1 0 

# m

i^P. 4



### LIS T O F TABLE S 1
. Parameter s fo

r han d layu p tes t 1 1 2
. Hand lay-u

p emissio n tes t

result s 1 2 3
. Parameter s fo

r gel coa t sprayin g tes t 1 3 4
. Ge l coa t spra y emission tes t

result s 1 4 5
. Emissio n factor s fo r han d lay-u p and gel coa

t spra y run s 1 5

LIS T O F FIGURES 1
. Sketch o

f mal e fabricatin

g mold , wit

h surroundin g flange 1 6 2
. Compariso n o f

Do w "CamiHe " compute

r versu s hand-recorded tota l hydrocarbo n analyze

r reading s 1 7 3
. Tota

l hydrocarbo n analyze

r trac e fo r han d lay-u p (hand-recorde

d values ) 1 8 4
. Cumulativ e mas s emissio n versu s tim e fo

r han d lay-u p ru n o f 1/4/9 5 1 9 5
. Gel coatin g emission s fo r ru n on 1/5/95 , a s recorded b

y Do w "Camille " compute

r syste m2 0 6
. Gel coatin g emission s fo r first 5 minute s of

ru n on 1/5/95 , a s recorde d b y Do w "Camille " compute

r syste m2 1 7
. Cumulativ e mas s emissio n versu s time fo

r gel coa t sprayin g ru n o f 1/5/9 5 2 2

APPEND K Comparison o f

recen t tes t result s to AP-4 2 emission factor s A- l



## * w >



# 3P. 5

1. 0 INTRODUCTIO N Mar k Banner visite d th e Do w Chemica l Compan y facility i n Freeport , Texa s o n Januar y 4-5 , 1995 , to observ e preliminary testin g o f emission s fro

m ope n mol d fabricatio n procedures . Th e purpose s o f

Mr . Bahner' s observation s wer e to witnes s th e tes tresults an d t o observ e and commen to n th e procedure s use d t o obtai n th e tes tresults . Th e testin g consiste d o f on e hand lay up ru n an d on e ge l coatsprayin g run . Thre e measuremen ttechnique s wer e used : 1 ) a tota

l hydrocarbo n analyze r (correspondin g to EP A Metho d 25A) , 2 ) intermittentsamplin g with a ga s chromatograph , an d 3 ) a mas s balanc e method . 2. 0 OBSERVATION S 2. 1 TES T SET-U P Fabricatio n procedure s (han d lay-u p an

d ge l coa tspraying ) wer e performed i n a ventilate d enclosure . Th e enclosur e wa s approximatel y 1 4 feetlong , 1 0 fee twide , an d 9 fee thigh . Th e side s o f th e enclosur e consiste d o f a woode n frame , ove r whic h plasti c myla r sheet s wer e stapled . Th e ceilin g o f

th e enclosur e wa s a larg e rectangular sheet-metal hood , wit h a n exhaus tduc ti n th e center . Tw o side s o f

th e enclosur e had singl e swingin g door s fo r personne l access , an d a thir d sid e ha d doubl e swingin g door s through whic h th e mol d coul d b e wheeled . Thre e side s o f th e enclosur e ha

d smal l (roughl y 1 foo tb y 2 feet) opening s atth e bottom , fo r inle tair . Fabricatio n occurre d nea

r th e sid e withou ta

n inle tai r opening . Withi n th e enclosure , tw o ai r register s wer e place d i n a manner suc

h tha tth e register s woul d directstream s o f recirculate d ai r fro

m nea r th e ceiling , dow n acros s th e face s o f th e mold . Thes e tw o ai r blower s wer e used to simulate ai r flow patterns i n typical productio n fabricatio n facilities . Exhaus tai r fro

m th e enclosur e wa s carrie d throug h a nomina

l 12-inch diameter duct , running parallel to th

e ceilin g o f

th e roo m i n which th e enclosur e wa s located . Samplin g probe s fo r a total hydrocarbon (THC ) analyzer , ga s chromatograph , and a n S-typ e pito ttub e (fo r velocit y measurements ) wer e inserte d int o th e duct . Outpu tfro m th e tota

l hydrocarbo n analyze r wa s fe d int o a Do w compute r system , and analyze d b y Do w "Camille " compute r software . Th e han d layup an

d ge l coa tsprayin g operation s wer e conducte d o n a mal e mold with three faces . Th e tota

l surfac e are

a fo r th e three face s wa s 3 0 square feet . I n additio n to th e thre e surfaces , a 9-inc h wid e flang e ra n around th e entire oute r perimete r o f th e mold . Overspra

y an d resi n run-of

f fro m the fabricatio n surface s wer e deposite d o n thi s flange . A sketc h o f th e mol d i s give n i n Figur e 1 . Th e mol d wa s mad e o f steel , an d place d o n a wheele d cart , suc h tha tth e botto m o f

th e mol d wa s approximatel y 1 foo tabov e th e floor . Th e tota l weigh to f

th e mol d an

d th e car twer e approximatel y 63 0 pounds . 

# HP. 6

Th e spra y equipmen tconsiste d o f a Bink s mode l B 5 pumpin g system , wit

h a car tan d boo m extensio n arm , an

d a Binks model 102-240 0 externa l mi x air - assiste d airles s spra y gun . Th e weigh to f

the complet e spra

y system (includin g cartan d boom ) wa s approximatel y 41 0 pounds . A platfor m floo r scal e wa s used to weig h bot h th e mol d an

d th e pumpin g system . Th e platfor m scal e ha

d a digita l readout, wit

h a maximu m reading o f 100 0 pounds , an

d a minimum reading o f

0. 1 pounds . During testing , i twa s observe d tha tth e scal e reading di d no talway s retur n to "0.0 " after a measurement. Instead , th e scal e mightreadin g 0. 1 o r "-0.P . Likewise , repeated measurement

s o f th e mold o r spra

y syste m migh tvar

y +/ - 0. 1 pound s from a give n value . 2. 2 DA Y 1 - HAN D LAY-U P TES T A tes tru n wa s mad e o f

han d lay-u p emissions . Th e han d lay-u p proces s involve d us e o f chopped stran

d fiberglas s mat

, to which catalyze d resi n wa s applied . Th e catalyze d resi n wa s applied wit

h a pain trolle r tha

tha d been dippe d int o a resi n bucket . After th e catalyze d resi n wa s rolle d ont o th e fiberglass mat , th e catalyze d resi n and ma twer e "rolle

d out " wit

h a metal rolle r t

o assure tha

tn o ai r void s existe d i n th e laminate . Mr . Bahner' s note s o n th e han d lay-u p ru

n indicat e a star

ttim e o f 13:07:0 0 (1:0 7 p.m.) . Th e note s furthe

r indicat e tha

ton e fac e o f

th e laminate wa s complete a t13:11:30 , a secon d fac e wa s complete a

t13:16:00 , an

d th e final fac e wa s complete d a t13:29:15 . Thi s represent s a tota l laminatio n tim e o f

2 2 minutes an

d 1 5 seconds . Thi s wa s followe d b y a curin g perio d o f approximately 10 0 minutes . Tota l hydrocarbon analyze r measurement s wer e stoppe d a t 15:13:56 , representin g a tota l elapse d tim e fro

m th e beginnin g o f

lamination o f

approximatel y 127 minutes . Tabl e 1 list s th e fabrication parameter s during th e han

d lay-u p test . 2.2. 1 Calibration Gases . Do w used fou r (non-zero ) calibratio n gases , and on e zer o gas . Th e calibratio n gase s wer e styrene , wit

h the balanc e in nitrogen . Th e fou r calibratio n ga s concentrations (i n part s pe r millio n (ppm) ) were : 1 ) 35 4 pp m (full-spa n gas ) 2 ) 28 3 pp m 3 ) 164 pp m 4 ) 10 4 pp m



# 5P. 7

Do w personnel note d th e tota l hydrocarbon analyze r respons e wa s no tcompletel y linear , becaus e a midrange ga s wa s abou t7 percen tabov e a linear calibratio n lin e (th e othe r thre e calibratio n gase s wer e withi n 5 percen to f a linea r calibration line) . Metho d 25 A include s a requiremen ttha

tinstrumen

trespons e b e withi n 5 percen to f linea r fo r al l calibratio n gases . Mr . Banne r state d tha

tthi s exceptio n t o Metho d 25 A shoul d b e note d i n th e tes tprotocol . 2.2. 2 Tota l hydrocarbo n analyze r traces . Mr . Banne

r recorded tota

l hydrocarbo n analyze r readings , S-typ e pito tprob e readings , an d comment s o n fabrication activitie s during th e han d lay-up test . Figur e 2 show s a compariso n o f emission s concentration s a s recorde d b y Mr . Banner, compare d t o emissio n concentration s recorde d b y th e Camill e compute r syste m (atth e tim e o f Mr . Bahner' s recordings) . Mr . Bahner' s recorde

d concentration s wer e based o n a full-scal e readin g taken t o b e 35 0 ppm . Th e correlatio n betwee n th e tw o concentratio n traces appear s good . Fo r th e approximatel y 8 0 reading s taken by Mr . Bahner , Mr . Bahner' s readings were , o n average , 9 percentbelo w th e value s recorde d b y th e Camill e system . I tappears , fro m Figur e 2 , tha

tther e ma

y hav e bee n a tim e differenc e betwee n th e Do w Camill e system an d Mr. Bahner' s han

d recordings . Specifically , i tappear' s tha tMr . Bahner' s recording were a fractio n o f a minut e late r tha

n equivalen tDo w Camill e readings . Therefore , th e actua l agreementbetwee n th e Do w Camill e syste m an

d Mr . Bahner' s recording s ma y b e muc h close r tha

n withi n 9 percent . Figur e 3 depict

s tota l hydrocarbo n analyze r emissio n concentration s recorde d b y th e Do w Camill e compute r system fo r th e entir e han d lay-up run . Figur e 3 include s notation s indicatin g th e tim e perio d whe

n lay-u p operation s wer e occuring , an d th e subsequentcurin g period . 2.2. 3 Backgroun

d concentrations , and end-of-run considerations . Non-zer o backgroun

d concentration s wer e observed o n bot h th e han d lay-u p an

d gelcoa t sprayin g tes tdays . Fo r th e han d lay-u p run , a backgroun d concentratio n o f

1.0 1 pp m wa s observe d i n th e fou

r minutes prio r t o th e star to f th e run . Thi s compare s t o a n averag e concentratio n o f

10.3 6 part

s pe r millio n ove r th e approximatel y 127 minute s o f

th e han d lay-u p run . Th e han

d lay-u p ru

n an d ge l coa tspra

y ru n wer e bot

h terminated befor e concentration s i n th e samplin g duc

treturne d to th e background concentration achieve d befor e th e testing . I twil l b e necessar y durin

g actua l testin g t o assur e tha

tmeasurement

s retur n t o pre-tes tvalue s prio r t o terminatin g runs , o r t

o accountfo r th e additiona l mas s tha

twoul d b e associate d wit h continuin g a run unti l measurement

s reac h pre-tes tconditions . Figure 5 show s a trac e o f cumulativ e emission s versu s tim e fo r th

e tota l hydrocarbo n analyze r o n th e han d lay-u p run . I

tca n b e see n tha

tth e curv e i s stil l increasing slightl y atth e en d o f the run .



# LP. 8

2.2. 4 Mas s balance measurements . Prio r t o th e han d lay-u p run , heavy-dut

y pape r wa s putdown unde r th e mol d t o catc

h an y resi n tha tdrippe d of f th e mol d durin

g th e laminatio n (han

d lay-up ) procedure . Mas s measurement

s for the han

d lay-u p ru

n wer e a s follows : 1 ) 7. 4 pound s (Mas s o f resi n used )
2 ) 640. 2 pound s (Mas s o f mol d plu s laminat

e plu s paper , afte r curing )

- 633. 5 pound s (Mas s o f mol d plu s paper , befor e lay-up ) 6. 7 pound s (Cure d resin o n mol d o r paper) 3 ) 7. 4 pound s (Mas s o f resi n used )

- 6. 7 pound s (Cure d resin o n mol d o r paper) 0. 7 pound s (Mas s loss , i.e. , styren e emitted ) Fro m thes e measurements , i twas clea r tha tth e measurement

s o f mol d mas s befor e an

d after lamination wer e problematic . If , fo r example , th e reading s o f the mol d mas s befor e an d after lamination wer e bot h take n t o b e accurat

e t o ± 0. 1 pound , th e calculate d cure d resi n o n th e mol d coul d var

y fro m 6. 5 pound s t

o 6. 9 pounds . Thi s woul d therefor e resul ti n a calculate d mas s los s o f

0. 5 pound s to 0. 9 pounds ; a ver y larg e range . 2.2. 5 Emissio n measuremen tresults . Tabl e 2 contain s comparison s o f th e calculate d han

d lay-up emission s fo r th e different measuremen

tmethods . Th e tota

l hydrocarbo

n analyze r produced th e lowes tcalculate d emissions . Th e gas-chromatograp h produce d higher calculate d emissions . Th e mass-balance metho d produced higher calculate d emission s tha n eithe r o f

th e directemissio n measurementmethods . Th e accurac

y o f th e thre e methods cannotb e definitivel y assesse d from thi s data . However , th e accurac

y o f th e mas s balanc e measurementmethod i s probabl y limite d b y th e repeatabilit

y the mol d mas s measurements , an d th e accuracy o f

th e ga s chromatograp h method ma y b e limited b y th e facttha tth e gas chromatograph doe s notsampl e continuously . Therefore , i tappear s tha tth e tota l hydrocarbo

n analyze r measuremen

ti s probabl

y th e mos taccurat

e measurement

.



# 1P. 9

2.2. 6 Compariso n o f

emission s (calculate d fro m TH C analyze r measurements ) wit h AP-4 2 emissio n factors . Tabl e 2 indicate s tha

tth e emissio n facto r fo r han d lay-u p (calculate d fro m tota l hydrocarbon analyze r data ) wa s measure d t o b e 17. 0 percento f availabl e styrene . Thi s valu e i s highe r tha

n th e AP-4 2 emissio n facto r o f 5 t o 1 0 percento f

availabl e styren e (fo r han d lay-u p o f a non-vapor-suppresse d resin) . I n fact , i f th e 7. 5 percentmidpointo f th e AP-4 2 emissio n facto r range i s utilized , th e rati o betwee n th e measure d valu e an d th e AP-4 2 midpoin ti s 2.27 . Thi s rati o i s comparabl e to th e ratio s foun d whe n comparin g othe r recen ttes tresult s fo r ge l coatin g an d spra y lay-u p wit

h AP-4 2 emissio n factor s (se e Appendix A) . 2. 3 DA Y 2 - GEL COA T SPRAYIN G TES T A tes tru n wa s mad

e o f ge l coatin g spra

y emissions . Mr . Bahner' s note s o n th e ru n indicate tha

tsprayin g starte

d a t11:28:29 . Th e to p fac e o f th e mold wa s spraye d fo r approximatel y 3 0 seconds . Thi s wa s followe d b y a paus e o f approximatel y 3 0 seconds . The n th e sid e fac e o f

th e mol d wa s sprayed fo r approximatel y 1 5 seconds . Thi s wa s followe d b y a paus e o f 5 seconds . The n th e frontfac e o f th e mol d wa s spraye

d fo r 3 2 seconds . Afte r a paus e o f 2 0 seconds , touch-u p spraying o f al l mol d face s laste d approximately 1 8 seconds . Thi s results i n a tota l spra y tim e o f 9 5 seconds , ove r a perio d o f 2. 5 minutes . Th e mol d wa s allowe d t o cur e fo r approximatel y tw o hours , until th e tota l hydrocarbo n analyze r wa s shutof f at13:31:57 , resultin g i n a tota l ru n tim e o f ove r 123 minutes . Th e tes tcondition s fo r th e ge l coa tsprayin g ru n wer e a s shown i n Tabl e 3 . 2.3. 1 Duc tflowrat

e verificatio n Prio r t o testing , Mar

k Bahne r mad e measurement s o f th e duc tdimension s an

d ai r flo w velocit y insid e th e duct . Thes e measurement s wer e made a ta singl e dampe r setting , correspondin g t o a nomina l flowrate o f

160 0 cubi c fee tper minut e (cfm) . A total o f

si x velocit y measurement

s withi n th e duc

twith a hot-wir e anemometer produced a n averag e ductvelocit y o f 205 8 fee tpe r minut

e (fpm) . A measuremen to f th e outsid e duc

tcircumferenc e produce d a valu e o f 3 8 3/16" . Thi s correspond s t o a n outsid e duc tdiameter o f

12.155" , an

d a n insid e duct diamete r o f

12.030 " (fo r a ductwal l thicknes s o f 1/16") . A duc

tvelocit y o f

205 8 fp m an d a n insid e diamete r o f

12.030 " results i n a calculate d flowrat e o f 162 4 cfm . Thi s i s i n clos e agreementwit

h a valu e o f

163 8 actual cubi c fee tper minut e (164 7 standar

d cubi c fee tpe r minute) measured b y Do w o n July 8 , 199 3 (se e Appendi x A) . Do w use d a single-poin tS-tub e prob e a s verificatio n tha tflo w insid e th e duc tremained constantduring testing . Mar k Bahne r recommende d tha tth e S-tub e readin g b e recorded frequently durin g testing , to assur e thatai r flo w remaine d constant . (Mr . Bahne r recorded value s durin g th e han d layu p testin g o f

0.5 6 ± 0.0 1 inche s o f

water . Thi s readin g i s compatibl e wit h a flowrat e o f approximately 160 0 cfm .

%P.1 0



### 2.3. 2 Samplin

g syste mleakag e considerations
. Do w personne l note d tha

t sampling syste

mleakag e test s ha

d bee n run immediately afte

r th e samplin

g syste mha d been installed
. Mr
. Banne r note d tha t sampling syste

mintegrit y coul d b e checked by closin g samplin g lines , an d observin g tha

t samplin g pressur

e wen t to zero . Thi s metho d woul

d als o verif

y tha t th e tota l hydrocarbo n analyzer

pum p diaphrag mha

d no t develope d aleak
. Verification tha

t th e samplin g syste

mdoe s no t

hav e in-leakag e assure s tha t samplin g syste min-leakag e doe s no t

caus e undermeasuremen

t o f emissions
. 2.3. 3 Tota

l hydrocarbo n analyzer

trace s A graph of

th e tota l hydrocarbo n analyzer

readings , a s recorde d by th e Dow "Camille " compute r system , fo

r th e ge l coa

t spraying ru n o f

1/5/95 , i s show

n in Figure 5
. Figur e 6 show s thes e reading s fo

r th e first 5 minute s only , and include s notation s o f th e sprayin g operation s bein g conducted durin g thi s time
. Bot h figures sho

w tha t th e emissio n rat e (exhaus t strea m concentration ) drop s of

f afte r sprayin g i s completed
. A n analysi s o f

Figur e 6 indicate s tha

t there i s atim e dela y of approximatel y 3 0 second s t o on e minut e between spraying episode s an d resultin g increase s i

n concentration s recorde d a t th e duct
. Thi s dela

y i s believe d t

o result fro m th e time s require d fo

r th e styren e plum

e t o trave l to th e samplin g point , an d th e time require d fo

r th e sample d ga s t o trave l to th e instrument
. 2.3. 4 Backgroun

d concentrations , an

d end-of-run considerations
. Non-zer o backgroun d concentration s were observe d o n bot h th e han d lay-u p an d gelcoa t spraying tes t

days
. Fo r

th e ge l coa

t spraying run , abackgroun d concentratio n o f 0.4 3 pp mwa s observed prio r

t o th e star t o f th e run . Thi s compare s t

o a n averag e concentratio n of 10.7 0 pp m ove r the approximately 123 minute s o f th e ge l coa

t sprayin g tes t

run . Th e han d lay-up ru

n and gel coa

t spra y ru n wer e bot h terminate d befor

e concentration s i

n th e samplin

g duc t returne d to th e background concentratio n achieve d befor e th e testing
. I t

wil l b e necessar

y durin g actua

l testin g to assur

e tha t measurement s retur

n to pre-tes t

value s prio r

to terminating runs , o r

t o accoun t fo r th e additiona

l mas s tha t woul d b e associate d wit

h continuing a run until measurement s reach pre-tes t conditions
. Figure 7 show s atrac e o f cumulativ e emission s versu s tim e fo r th e tota l hydrocarbo n analyze

r durin g th e ge l coa

t spraying run . I t

ca n b e see n tha t the curv e i s stil l increasin g slightl y a t th e end of

th e run . 2.3. 5 Mas s balanc e measurements . Prio r to th e ge l coa

t sprayin g run , heavy-dut

y paper wa s pu t dow n unde r th e mol d an d o n th e side s o f th e enclosure , t o catch an

y resin tha t drippe d of

f th e mol d durin g th e ge l coa

t spraying procedure
. 

# <{P.1 1

Mas s measurement

s for th e ge l coa tsprayin g ru n were a s follows : 1 ) 415. 8 pounds (Spra y rig, befor e spraying )

- 411. 9 pounds (Spra y rig, afte r spraying ) 3. 9 pounds (Tota l ge l coa tsprayed ) 2 ) 639. 3 pound s (Mas s o f mol d plu s ge l coa tplu s paper , afte r curing )

- 636. 2 pounds (Mas s o f mol d plu s paper , befor e spraying ) 3. 1 pounds (Cure d ge l coa to n mol d o r paper ) 3 ) 3. 9 pound s (Tota l ge l coa tsprayed )

- 3. 1 pound s (Cure d ge l coa to n mol d o r paper ) 0. 8 pound s (Mas s loss , i.e. , styren e emitted )
2.3. 6 Emissio n measuremen tresult s Tabl e 4 contain s comparison s o f th e calculate d ge l coatin g emission s fo r th e thre e differen ttes tmethods . Th e tota l hydrocarbo n analyze r produce d th e lowes tcalculate d emissions . Th e gas-chromatograph produce d highe r calculated emissions . Th e mass-balanc e metho d produced highe r calculated emission s tha n eithe r o f

the directemissio n measuremen t methods . Th e accurac

y o f the three method s canno tb e definitivel y assesse d from thi s data . However , th e accurac

y o f th e mas s balanc e measurementmetho d i s probably limite d b y th e repeatabilit

y th e mold mas s measurements , an d th e accurac

y o f th e ga s chromatograp h metho d may b e limite d b y the fac ttha tthe ga s chromatograp h doe s no tsampl e continuously . Therefore , i tappear s tha tth e tota l hydrocarbo

n analyze r measuremen

ti s probably th e mos taccurate measurement . 2.3. 7 Compariso n o f

emission s (calculate d from TH C analyzer measurements ) with AP-4 2 emissio n factors . Tabl e 4 indicate s tha

tth e emissio n facto r fo r ge l coa tsprayin g (calculate d from tota l hydrocarbo n analyze r data ) wa s measure

d t o b e 41. 2 percen

to f availabl e styrene . Thi s i s highe r tha n th e AP-4 2 emissio n facto r rang e o f 2 6 to 3 5 percento f

availabl e styrene . Othe r recen ttes t results hav e als o indicated ge l coatsprayin g emissio n factor s tha tare highe r tha

n AP-4 2 (se e Appendi x A) .



# 1 °P.1 2

2.3. 8 Gel coatoverspray observations . Afte r th e ge l coa tsprayin g ru n wa s completed , Mr

. Bahner performed a visua l inspectio n o f th e ge l coa tsprayin g patterns o n th e mold . I twa s note

d tha tth e ge l coa tdi d no tcompletel y cove r th e entir e portio n o f th e mol d withi n the are

a marke d off wit h masking tap e fo r coverage . Additionally , th e overspray o n th e 9-inch flang e surroundin g th e mol d wa s evaluated . Th e overspra y wa s found to b e relativel y heavy for th e insid e 2- 4 inche s o f th e flange, relativel y ligh t ou tto seve n inches , an

d virtuall y n o overspra

y was seen o n th e outsid e tw o inche s o f th e flange. Mr . Bahner judge d thi s t o b e muc h les s overspra

y (i.e. , a muc

h more careful sprayin g job ) tha n occurre d atproductio n facilitie s h e ha d visited . 2. 4 ALTERNATIV E METHOD S O F EXPRESSING EMISSIO N FACTORS Tabl e 5 present s tota

l hydrocarbo

n analyzer emissio n tes tresults fo r han d lay-u p an

d ge l coating . Thes e result s are expresse d a s emissio n factor s i n thre e differentforms : 1 ) Emission s a s a percentage o f initia l availabl e styren e (i.e. , emission s o f styren e i n pound s pe r 10 0 pound s o f initia l availabl e styrene) , 2 ) Emission s a s a percentage o f initia l resin mas s (i.e. , emission s o f styren e i n pound s pe r 10 0 pound s o f

initia l resin) , an

d 3 ) Emission s i n gram s pe r squar e mete r o f mold applicatio n surface . (Fo r thi s calculation , th e mold application surfac e wa s take

n to b e 3 0 squar

e feet. )

8 

# KP.1 3

3. 0 CONCLUSION S 1 ) Concentration s a s recorded b y th e Do w "Camille " compute r syste m are i n clos e agreemen t wit h measurement

s recorde d b y hand , indicatin g tha tther e ar e no programmin g error s i n th e Camill e compute r system . 2 ) Volumetri c flowrate i n th e exhaus tducta s measured b y RT I with a hot-wir e anemomete r i s i n clos e agreemen twit h flowrate measured b y Dow . Flo w appear s ver y stabl e ove r time . 3 ) Fo r bot

h han d lay-u p an

d ge l coa tspraying , emission s a s measured b y th e total hydrocarbo n analyze r wer e th e lowes to f th e thre e emissio n measurementmethod s evaluated . Ga s chromatograp h measurement s wer e higher , an

d mas s balance-base d calculate d emission s wer e highest . Thi s testin g di d notprovid e definitiv e result s o n whic h tes tmetho d wa s mos taccurate . However , th e ga s chromatograp h measuremen tmetho d provide d onl y intermitten t(no tcontinuous ) sampling , an d th e precisio n o f

th e scal e use d fo r th e mas s balanc e wa s probably no tsufficien tt o provid e highl y accurat e emissio n calculation s (se e conclusio n #4 , below) . Therefore , th e tota l hydrocarbo n analyze r ma y hav e bee n th e mostaccurat e measuremen

tmethod . Further evaluatio n o f th e accurac y th e tota l hydrocarbo n analyze r measurementmetho d i s recommended . 4 ) Th e precisio n o f

mass-balance d base d emissio n measurement s i s low , du e t o a scal e wit h a leas tsignifican tdigi to f

0. 1 pound , emission s o f les s tha n 1 pound , an

d scal e hysteresis . 5 ) Emissio n factor s a s calculate d from al l measurementmethod s wer e highe r tha n AP-4 2 fo r bot h han d lay-u p an

d ge l coa tspraying . Fo r han d lay-up , emissio n facto r calculate d from th e tota l hydrocarbo n analyzer/Camill e compute r emissio n measurementmetho d wa s 17. 0 percento f

availabl e styrene . Thi s compare s wit h a n AP-4 2 (198 8 revision ) emissio n facto r o f 5 - 1 0 percen tfo r han

d lay-u p o f

non-vapor-suppresse d resins . Fo r ge l coa tspraying , the emissio n facto r calculated from th e tota l hydrocarbon analyzer/Camill e compute r emissio n measurementmethod wa s 41. 2 percento f availabl e styrene . Thi s compare s with a n AP-4 2 (198 8 revision ) emissio n facto r o f 2 6 - 3 5 percen tfo r han

d lay-u p o f

non-vapor-suppresse d resins . Th e results o f

thi s preliminar

y testin g wer e i n genera

l agreemen twit

h othe r recen ttes tresult s (se e Appendi x A ) ma

tyiel d highe r emissio n factors tha n found i n AP-42 .



# IT-P.1 4

4. 0 RECOMMENDATION S 1 ) Prio r to forma

l testing , a preliminar

y experimen tshoul d b e conducte d i n whic h th e mas s balanc e metho d i s th e referenc e standar d (i.e . styren e evaporatio n fro m a stati c system , usin g a scal e wit

h increase d resolutio n compare d t o th e scal e use d i n thi s testing) . Thi s preliminar

y experimen twil l establis h th e accurac y o f tota l hydrocarbon analyze r and ga s chromatograp h emissio n measuremen tmethods . Th e tes twil l als o confir m ma tth e captur

e efficienc y o f

th e enclosur e i s nea

r 10 0 percent . 2 ) Durin g forma

l testing , i twil l b e necessar y t o verif y tha tbackground concentration s are lo w an d stabl e prio r to a tes trun . Further, i twil l b e necessary t o assur e tha tcurin g i s allowe d t o continu e t o th e poin ta

twhic h concentration s withi n th e exhaus tduc tretur n to pre-tes t conditions . 3 ) Future ge l coa temission s testin g should b e ru n wit h spraying t o th e outsid e edg e o f a tleas t on e sid e o f

th e mol d flange . Alternatively , sprayin g shoul d b e t o withi n 1- 3 inche s o f th e edg e o f severa l side s o f th e mol d flange. Thes e sprayin g situation s ar e probably mor e representativ e o f

condition s atmos tproduction plants . 4 ) I ti s recommende d tha

tsamplin g system leak check s b e performed a tfixe d interval s (dail y o r weekly ) durin g th e forma l testing . Lea

k check s wil l assur

e tha temission s ar e no tunder measured du e t o ai r in-leakag e int o th e samplin g line s o r instrument. 5 ) One method to increas e th e precisio n (accuracy ) o f th e mas s balanc e metho d i s t o us e a scal e wit h increase d resolution . Us e o f a scal e wit

h increased resolutio n (belo w 0. 1 pound ) shoul d b e investigated . Fo r example , RT I has identifie d a scal e (Mode l F150S) tha tca n measur e t o 33 0 ± 0.00 2 pounds , whic h can b e rente d from Sartoriu s Compan y fo r $10 0 pe r wee k (contactBob Youn g a t800-645-3108) . Anothe r scale , Mode l F300S , ca n measur e t o 66 0 ± 0.0 2 pounds , an d ca n b e purchase d from Sartoriu s fo r $4,195 . I f th e Mode l F150 S i s used , changin g t o a lighte r mol d woul d b e required . I f th e 63 0 poun d mol d i s required fo r generatin g baselin e emissio n measurements , a separat e compariso n o f th e mas s balanc e method wit h direc temissio n measurement

s migh tb e performe d wit h a lighte r mold .

1 0



# A>P.1 5

Tabl e 1 . Parameters for han d lay-u p test .
Facto r I Ambien tAi r Velocit y

1 Initia l Styren e Conten t Ge l Tim e

Laminate Thicknes s Valu e "Low " (nominall y 5 0 fee tpe r minut e acros s th e mol d surface) . "High " (4 2 percent) "Fast " (targeto f

1 5 minutes , t o b e achieve d wit h methyl ethy l keton e peroxid e Hi-Poin tj 9 0 catalyst , ata concentratio n o f 1. 5 E percent ) j "Thin " (on e laye r o f

1. 5 ounc e choppe d J stran d mat) . [

Additional Notes : 1 ) Ambien tai r temperatur e (a s recorde d b y Dow) : 68-7 0 degree s Fahrenheit .

1 1 

## i lP.1 6



### Tabl e 2
. Han

d Lay-up Emissio n Tes t

Result s

1 Measuremen

t I Metho d

Tota l Hydrocarbo n Analyze r (Dow "Camille " system ) Total Hydrocarbo n Analyze r (Mr.Bahner' s recorde d 1 measurements ) | Ga s Chromatograph B Mas s Balanc e Emissio n (Pounds )

0.52 8

0.48 3

0.61 1 

### 0. 7 Emissio n Facto r

(Percen t o f Availabl e Styrene )

17. 0

15. 5

19. 7 22. 5 Percent

Differenc e (fromtotal hydrocarbo n analyzer read b y Do w "Camille " system) No Differenc e 1

- 9

+ 1 6

+ 3 2

Note : AP-4 2 emissio n factor fo r non-vapor-suppresse d resi n i n han d lay-u p i s 5 t o 1 0 percen t

of availabl e styrene . 1 2



# 16P.1 7

Tabl e 3 . Parameter s fo r ge l coa tsprayin g test .
Facto r Ambien tAi r Velocit y
Initial Styren e Content 1 Ge l Tim e Ge l CoatThicknes s | J Spra y gun deliver y rat

e Valu e "Low " (nominall y 5 0 fee tpe r minut e acros s th e mol d surface) . "Low " (3 5 percent

) "Fast " (targeto f

1 0 minutes ) "Thick " (targetvalu e o f

2 4 mils ) "Fast " (targetvalu e o f

4 pound s pe r minute ) J

Additional Notes : 1 ) Gu

n type : Binks Mode

l 102-2400 , "externa

l mix" . 2 ) Spra

y system : Bink

s mode l B5 , with pum

p rati o o f 1 1 t o 1 (i.e . 10 0 psi g ai r pressure results i n 110 0 psi g flui

d pressure ) . 3 ) Ambientai r temperature : 68. 1 F (initial ) t o 69. 7 F (final) . 4 ) Ai r assis tpressure : 4 0 psi g (static ) t o 3 5 psi g (delivery) . 5 ) Pum

p ai r pressure : 50-5 2 psi g (static ) to 4 8 psi g (delivery) . Wit h a n 1 1 t o 1 pump , thi s woul d resultin ge l coa tfluid pressure s o f 550-57 2 psi g (static ) t o 52 8 psi g (delivery) .

1 3 

# IrP.1 8

Tabl e 4 . Ge l CoatSpra

y Emissio n Tes tResult s

Measuremen t Metho d Emissio n (Pounds ) Emissio n Facto r

(Percen to f Availabl e Styrene ) Percen tDifferenc e (from Total Hydrocarbon Analyze r rea

d b y Do w "Camille " system ) Tota l Hydrocarbo n Analyze r (Do w "Camille " system ) 0.56 3 41. 2 N o Differenc e

Gas Chromatograph 0.66 3 48. 6 + 1 8 Mas s Balanc e 

### 0. 8 58. 6 

### + 4 2

Note : AP-4 2 emissio n facto r fo r (non-vapor-suppressed ) ge l coa tsprayu p i s 2 6 to 3 5 percen to f availabl e styrene . 1 4



# A

### Tabl e 5 . Emissio

n factor s fo r han d lay-u p an d gel coa tspra y runs .

<c A O l 

### Ru

n Identificatio

n

Han d lay-u p (1/4/95 ) Ge l coa tspra y (1/5/95 ) Amoun

to f resin/gel coa

t applie d (pounds )



### 7. 4
3. 1 Initia

l Styren e Conten to f Resin/Ge l Coa t (percent )



### 42
3 5 Emissio

n (pounds , a s determine d b y TH C analyzer )

0.52 8
0.56 3 Emissio

n Facto r (a s determine

d b y TH C analyzer

) Percen to f availabl e styren e (i.e. , gram

s pe r 100 gram s o f initia l styrene ) 17. 0
41. 2 Percen

to f resin / ge l coa t (i.e. , gram

s pe r 100 gram s o f initia l resin/gel coat

)


### 7. 1
14. 4 Gram

s pe r squar e mete r o f applicatio n surfac e 

## 8 6 

## I
9 2

T J C O

### Figure 1 . Sketc h of mal e fabricatin g mol d wit h surroundin g flange .

_S > 0\

1 ) Tota l fabricatio n are a o n mol d equal s 3 0 squar e fee t

### Figur e 2 . Compariso n o f Do w "Camille " compute r versu s hand-recorde d tota l hydrocarbo n analyze r readings .

E Q . C <> • 3 

# s c U c o O -CAMILL E -HAN D

2 0 3 0 4 0 5 0 6 0 7 0 Elapse d Tim e 8 0 9 0 - 1 - 10 0 11 0 12 0

CAMVHAN D Char

t 1 T J

### Figur e 3 . Tota l hydrocarbo n analyze r trac e fo r han d lay-u p (hand-recorde d values) .

. 0 0

0 1 0 2 0 —••4 - 3 0 4 0 5 0 6 0 7 0 8 0 9 0 10 0 11 0 12 0 

### Sprayin g 

### Curin g Elapse d Tim e (minutes)

RANOHAXO.JU C V

### Figure 4 . Cumulativ e mas s emissio n versu s tim e fo r han d layu p ru n o f 1/4795 .

u.ou u

0.50 0 -$d(pounds3C3C/lassemittc3C0t3C3C

0 10 0 -

0.00 0 - 0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 10 0 11 0 12 0 13 0 14 0 15 0 

### Tim e elapse d (minutes )

1-*.« B Char t J r

o

### Figur e 5 . Ge l coatin g emission s fo rru n o n 1/5/95 , a s recorde d b y Do w "Camille " compute rsystem
.



# 8 E Q . Q. C o *« 3 C O h a 4-4 c <x> u c o 

## o U U - 1 o n 1 <i\i - 1 i n . 1 I U

o n . s u 8 0 - 7 0 6 0 - 50 - 4 0 - 3 0 - 20 - 1 0 - 0 - 

# i I 

# L 1 1 L 

# 1 T I 1 *T U "WP |

"' -^•^^trw*fm r

m 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 10 0 11 0 12 0 

# X " Sprayin g Curin g Elapse d Tim e (minutes )

OELSPdYJa C r oXL Concentratio n (ppm )

• n (5 * c © 

### tt 

### ? 

# § W. a a C D < Q
° - C D 

## < 5 . O ( A 

# II ' o c T 3 =• : 5 s c » C D r* 

### o o 

## 3 c < C D 3 C C D 3 , " • C D </ > C O 

# l a 

# P i o 3 CJ l C D O l

Q Z d

### Figur e 7 . Cumulativ

e mas s emissio n versu s tim e fo r ge l coa t sprayin g ru n o f 1/5/95 .



# 8 U.bU U -

A CA A u.ou u -

wi M.>*v\i

• • o c 3 O 

## 3 < u rt in n . tt 

### E in m « = 0 20 0 -

0 10 0 -

0.00 0 0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 10 0 11 0 12 0 13 0 14 0 15 0 

### Elapse d time (minutes )

1-6-9 8 Chwt lP.2 7



### Appendi x A Compariso n o f

recent tes t result s t o AP-4 2 emissio n factors
.



# IXP.2 8

Tabl e A contain s a comparison o f AP-4 2 emissio n factor s wit h emissio n factor s derive d fro m more recent(post-1990 ) testing . Th e emissio n factor s fro m recen ttestin g ar e a s calculate d b y Mar k Bahner , base d o n tes treport s tha tinclud e bot

h emissio n result

s an d dat a o n resi n and/o r ge l coatconsumption . Emissio n factors in Tabl e A ar e expresse d a s a percentag e o f availabl e (initial ) styrene . Fo r instance , th e AP-4 2 emissio n facto r for (non-vapor-suppressed ) ge l coa tsprayin g i s 2 6 to 3 5 percen to f

availabl e styrene . Thi s mean s tha ti f th e ge l coa twer e t

o initiall y contai n 10 0 gram s o f styrene , 2 6 t

o 3 5 gram s o f

styren e would b e emitted . I n additio n t o column s containing emissio n factors , Tabl e A als o contain s ratio s o f th e emissio n factors calculate d fro m testing t

o th e midpointAP-4 2 emissio n factor . Fo r example , th e midpointo f

th e AP-4 2 emissio n factor range for ge l coa tsprayin g i s 30. 5 percen to f availabl e styrene . Th e emissio n facto r fo r ge l coatin g calculate d fro m th e preliminar

y C F A/Do w testin g a

t Freeport , Texa s (Januar

y 4-5 , 1995 ) wa

s 41. 2 percent , a s i s documented i n thi s report. Th e rati o betwee n th e tes tresul tan d th e AP-4 2 midpoin

tfacto r i s therefor e 41. 2 divide d b y 30.5 , o r 1. 4 (rounde

d t o tw o significan tdigits) .

A - l



# 11

### Tabl e A
. Summar y o f Calculate d Emissio n Factor s (Expresse d a s Percentag e o f Availabl e Styrene ) 

### i

^ ^ Emissio n Facto r Sourc e

AP-4 2 Emissio n Facto r EPA/Souther n Researc h Institut e (SRI ) testin g a t

Eljer Plumbingwar e (no w Carolin aClassics)
. EPA/Radia n (RTP ) testin g a t Venetia n Marble , VA
. EPA/Radia n (RTP) testin g a t Genera l Marble , NC
. Radia n (Ohio ) testin g a t CORTEC , OH
. Preliminar y CFA/Do w testin g a t Freeport , T X (January 4-5 , 1995)
. Biso n Engineerin g testin g a t GE A Dynami c Fabricators , ID
. Ge l Coa t Sprayu p (NVS) ' 26-3 5
6 6

6 8

9 7

42/29 *

4 1

No t App
. Rati o t o

AP-4 2 Midpoin t 1. 0 2. 2

2. 2

3. 2

1.4/1. 0

1. 4

No t App
. Resi n

Sprayu p (VS) 2
3 - 9 1 6

No t App
. No t App
. No t App
. No t App
. No t App
. Rati o t o

AP-4 2 Midpoin t 1. 0 2. 7

No t App
. No t App
. No t App . No t App
. No t App . Resi n

Sprayu p (NVS) ' 9-1 3 No t App
. No t App
. No t App
. No t App
. No t App
. 2 4 Rati o t o

AP-4 2 Midpoin t 1. 0 No t App
. No t App
. No t App
. No t App
. No t App
. 2. 2 Han d

Layu p (NVS) ' 5-1 0 No t App
. No t App
. No t App
. No t App
. 1 7

No t App
. Rati o t o

AP-4 2 Midpoin t 1. 0
No t App
. No t App . No t App . 

### No t1 App . 2. 3

No t App .
1 ) NV S = Non-vapor-suppressed 2 ) V S = Vapor-suppressed 3 ) Emissio n facto r o f 4 2 percen

tfo r a "baseline " ge l coat , an d 2 9 percen

tfo r a "hig h performance " gel coatwit h a "fast " ge l time .