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# OAR Box 1168 Prepped by Ollie Stewart



### Document

Number: 

# 65 ) ll-A-3
Docket Number: 

# A-89-1 0

Printed 4/29/2008 11:23.18 AM

Sheet 65 of 131P- 2
.

I/O. * l '\ 

# &ER A Unite d State s Offic e o f Ai r Quality Environmenta l Protectio n Plannin g an d Standard s Agenc y Researc h Triangl e P=>* w r •>-»->

. . EPA-450/3-88-01 0 Octobe r 198 8
Ai r 

# Protocol s fo r Generatin g Unit-Specifi c Emissio n Estimates fo r Equipmen t Leak s o f VO C an d VHA P 

# A-89-1 0
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### PROTOCOL S FORGENERATINGUNIT-SPECIFI C EMISSIO N ESTIMATE S FOR EQUIPMEN T LEAK S O F VO C AN D HA P

U . S . Environmenta l Protectio nAgenc y Offic e o f Ai r an

dRadiatio n Offic e o f Ai r Qualit y

Plannin g an

dStandard s Emissio nStandard s Divisio n Researc hTriangl e Park, N C 2771 1

Octobe r 198 8P. 4

TABL E O F CONTENT S Sectio nPag e Lis t o f Figure s v Lis t o f Table s v i
GLOSSAR Y..vi i
FOREWOR D x i 1. 0 INTRODUCTIO N

.1- 1 2. 0 DEVELOPMEN T O F EMISSION ESTIMATE S .2- 1 2. 1 Introductio n2- 1 2. 2 Us e o f th e EPA' s Averag e Emissio nFactors . 2- 1 2. 3 Th e Leak/No-Lea k Approac h2- 4 2. 4 Applicatio no f Stratifie dEmissio nFactor s .. . 2- 8 2. 5 Lea k Rate/Screenin g Valu e Correlation s . 2- 9 2. 6 Unit-Specifi c Correlation s 2-1 3 2.6. 1 Generatio no f Mas s Emission s Dat a 2-1 3 2.6. 2 Developmen t o f Lea k Rate/Screenin g Value

Correlations . 2-1 5 2.6. 3 Statistica l Consideration s o f Lea k Rate/Screenin g

Value Correlation s 2-1 6 2.6.3. 1 Graphica l Compariso no f EP A vs . Othe r Correlation s 2-1 6 2.6.3. 2 Statistica l Compariso no f EPA vs . Othe r Correlation s 2-2 3 2.6.3. 3 Othe r Statistica l Analyse s 2-2 3 2.6. 4 Generatio no f Emissio nEstimate s 2-2 4 2.6. 5 Statistica l Consideration s fo r th e Predicte d

Emissio nEstimat e . . 2-2 4 3. 0 SOURC E SCREENING3- 1

3. 1 Screenin g Surve y Procedures . ... . 3- 1 3. 2 Monitorin g Instrumen t 3- 3 3.2. 1 Operatin g Principles an d Limitation s o f Portabl e VO C Detectio nDevice s . ...... . 3- 4 3.2. 2 Performanc e Criteri a an d Evaluatio nfo r Portabl e VO C Detector s 3- 5 3.2.2. 1 Respons e Facto r . 3- 7 3.2.2. 2 Respons e Time . . 3- 8 3.2.2. 3 Calibratio nPrecision . ......... . 3- 9 3.2.2. 4 Safet y

3- 9 3.2. 3 Monitorin g Device s Fo r Difficul t Situation s ... . 3-1 0

i nP. 5

TABL E O F CONTENT S (cont'd. ) Sectio nPag e

3. 3 Screenin g Procedure s 3-1 2 3.3. 1 Calibratio nProcedure s 3-1 2 3.3. 2 Procedur e fo r Screenin g Equipmen t 3-1 2 3. 4 Dat a Handlin g 3-1 9 3. 5 Calibratio nProcedure s Fo r Qualit y Assuranc e . 3-2 2 4. 0 MAS S EMISSION S SAMPLING4- 1

4. 1 Vacuu

m Metho d 4- 1 4. 2 Blow-Throug hMethod . 4- 6 4. 3 Sourc e Enclosur e 4-1 0 4.3. 1 Valve s 4-1 2 4.3. 2 Pump s an

d Agitator s 4-1 3 4.3. 3 Compressor s 4-1 4 4.3. 4 Flange s . 4-1 5 4.3. 5 Relie f Valve s 4-1 5 4. 4 Accurac y

Check s . 4-1 6 4. 5 Analytica l Techniques . 4-1 6 4.5. 1 Analytica l Instrumentatio n4-1 6 4.5. 2 Calibratio n4-1 7 4.5. 3 Analytica l Technique s fo r Condensate . ...... . 4-1 7 4.5. 4 Qualit y

Contro l fo r Analytica l Technique s 4-1 8 5. 0 REFERENCE S 5- 1 Appendi xA

- Referenc e Metho d 2 1 Appendi xB - Respons e Factor s Appendi xC - Calculation s o f Mas s Emissio nRate s Appendi xD - Lea k Rate/Screenin g Valu e Equation s Appendi xE - Selectio no f Sampl e Siz e fo r Flang e Screenin g Appendi xF - Determinatio no f Emissio nRate s fo r Defaul t Zer o Screenin g Value s Appendi xG- Developmen t o f a Defaul t Emissio nRat e fo r Equipmen t Tha t Doe s

No t Scree nAbov e th e Backgroun d Concentratio n

i vP. 6

LIS T O F FIGURE S
Figur e s Pag e 2- 1 Strateg y

fo r Estimatin g Emission s fro m Equipmen t Leak s 2- 2 2- 2 Modele drelationship-lea k rat e vs . OV A fo r valve s in ga s servic e . 2-1 7 2- 3 Log, Q lea k rat e vs . log, 0 OV A readin g fo r pum

pseal s 2-1 8 2- 4 Log, Q lea k rat e vs . log, 0 OV A readin g fo r valves-ga s servic e . . . 2-1 9 2- 5 Log, Q lea k rat e vs . log, 0 OV A readin g fo r valves-liqui d service . . 2-2 0 2- 6 Compariso no f SOCM I an d refiner y

lea k rat e correlations . ..... . 2-2 2 3- 1 Gat e valve s 3-1 4 3- 2 Globe valve s 3-1 5 3- 3 Lubricate dplu g valve . . 3-1 6

i 3-4 a Bal l valve 3-1 7 3-4 bButterfl y

valv e 3-1 7 3-5 a Wei r typ e diaphragm valv e 3-1 8 3-5 bChec k valve s ...... . 3-1 8 3-6 a Vertica l centrifuga l pum p3-2 0 3-6 bHorizonta l centrifuga l pump . . . 3-2 0 3- 7 Sprin g loade drelie f valve 3-2 1 4- 1 Samplin g trai nfo r baggabl e source s o f hydrocarbo nemission s usin g

a diaphragm . 4- 2 4- 2 Myla r plasti c sampl e ba g 4- 4 4- 3 Equipmen t require dfo r th e blow-throug hsamplin g techniqu e ... . 4- 7 4- 4 Ten t constructio naroundth e sea l are a o f a vertica l pum p4-1 1

wmmimmmP. 7

LIS T O F TABLE S

Tabl e Pag e 2- 1 Averag e Emissio nFactor s fo r Fugitiv e Emission s 2- 3 2- 2 Leakin g an

dNon-Leakin g Emissio nFactor s fo r Fugitiv e Emission s (kg/h r source ) 2- 6 2- 3 Estimat e o f "Uncontrolled " Fugitiv e Emission s fo r a Hypothetica l Cas e . 2- 7 2- 4 Stratifie dEmissio nFactor s fo r Equipmen t Leak s 2-1 0 2- 5 Estimat e o f Fugitiv e Emission s Usin g Stratifie dEmissio nFactor s

fo r a Hypothetica l Cas e 2-1 1 3- 1 Fugitiv e Emissio nSource s 3- 2 3- 2 Performanc e Criteri a fo r Portabl e VO C Detector s 3- 6 3- 3 Portabl e VO C Detectio nInstrumen t Performanc e Specifications . . . 3-1 1 3- 4 Exampl e Dat a Shee t 3-2 3 4- 1 Calculatio nProcedur e fo r Tente dLea k Rat e 4- 8
B- l Respons e Factor s wit h95 % Confidenc e Interval s Estimate d

a t 10,00 0 ppm

v Respons e B- l B- 2 Teste dCompound s Whic hAppea r t o b e Unabl e t o Achiev e an

Instrumen t Respons e o f 10,000 ppm v a t an y Feasibl e Concentratio nB- 7 D- 1 Predictio nEquation s fo r Nonmethan e Lea k Rat e fo r Valves , Flanges ,

andPum pSeal s i nSOCM I Processe s . D- 1

v iP. 8

GLOSSAR Y

Censore dsourc e - a sourc e whos e screenin g valu e i s know nt o b e abov e 100,00 0 ppm

v bu t whos e actua l screenin g valu e i s unknown . Emissio nfacto r - th e pe r componen t mas s emissio nrat e applicabl e t o population s o f sources , no t individua l componen t measurements . Inaccessibl e sourc e - a componen t whic hcanno t b e reache dbecaus e i t i s beyon dth e reac ho f a 6-foo t ladder . Lea k definitio n- monitorin g instrumen t readin g selecte da s th e trigge r valu e fo r initiatin g some actio nsuc ha s maintenance ; e.g. , 10,00 0 ppm v i s th e lea k definitio nuse db y EPA . Lea k frequenc y

- th e percentag e o f source s ( a particula r equipmen t typ e an d service ) determine dt o b e leakin g base dupo na chose nlea k definition . Lea k rat e - se e mas s emission s rate . Leakin g emissio nfacto r - th e pe r componen t mas s emissio nrat e associate dwit h th e populatio no f source s wit hscreenin g concentration s a t o r abov e th e lea k definition . Leakin g sourc e - a sourc e whos e screenin g concentratio ni s greate r tha no r equa l t o 10,00 0 ppmv . Mas s emission s rat e - th e quantit y o f volatil e organi c compound(s ) release dt o th e atmospher e i nterm s o f tota l mas s pe r uni t time . Monitorin g instrumen t - portabl e hydrocarbo nanalyze r meetin g th e performanc e specification s give ni nMetho d21 . Non-leakin g emissio nfacto r - th e pe r componen t mas s emissio nrat e associate d wit hth e populatio no f source s wit hscreenin g concentration s les s tha n th e lea k definition . Non-emittin g sourc e - a sourc e whos e screenin g valu e i s 0 ppmv ; a zer o emissio nrat e i s assumed . Non-leaking , emittin g sourc e - a sourc e whos e screenin g concentratio ni s greate r tha n0 ppm

v bu t les s tha n10,00 0 ppmv . Screenin g valu e - raw monitorin g instrumen t reading . Screenin g concentratio n- th e screenin g valu e (ra w instrumen t reading ) correcte db

y th e appropriat e respons e factor . Unsafe-to-monito r equipmen t - equipmen t tha t expose s monitorin g personne l t o animmediat e dange r whil e screenin g th e equipment .
vi iP. 9

EF = averag e emissio nrat e pe r sourc e EF , = averag e emissio nrat e pe r leakin g sourc e EF 2 = averag e emissio nrat e pe r non-leakin g emittin g sourc e X-, . = measure demissio nrat e fo r th e ithleakin g sourc e X 2 i = measure demissio nrat e fo r th e it hnon-leakin g emittin g sourc e X p= averag e measure demissio nrat e fo r non-leakin g emittin g source s N , = numbe r o f leakin g source s N « = numbe r o f non-leakin g emittin g source s N 3 = numbe r o f non-emittin g source s N = tota l numbe r o f source s (includin g inaccessibl e sources )
n , = numbe r o f bagge dleakin g source s np= numbe r o f bagge dnon-leakin g emittin g source s 2 s 2 = estimat e o f th e varianc e o f th e emissio nrate s o f th e non-leakin g emittin g source s
n 2

= £ (X 2 i - X 2 ) 2 /(n 2 - 1 )
y, . = measure demissio nrat e fo r th e it hleakin g sourc e y ? . = measure demissio nrat e fo r th e it hnon-leakin g emittin g sourc e / , . = predicte demissio nrat e fo r th e it hleakin g sourc e screene d 13 1 <100,00 0 ppm

v /, . . = measure demissio nrat e fo r it hcensore dsourc e lb i y , = averag e predicte demissio nrat e fo r leakin g source s y 2 = averag e predicte demissio nrat e fo r non-leakin g emittin g source s y , = averag e predicte demissio nrat e fo r leakin g source s screene d 1 3 <100,00 0 ppm

v y, . = averag e measure demissio nrat e fo r censore dsource s N . = numbe r o f leakin g source s screened , <100,00 0 ppm v 1 a N, . = numbe r o f censore dsource s n 1 h= numbe r o f bagge dcensore dsource s 'l b

= \ N 2 s , = varianc e o f th e predicte demissio nrate s o f th e leakin g source s

1

d 

### 1- 1 - s (y u

### - y 1 

### ) 2 

### /(N 1 

### - i )

v mP.1 0



### 'y z

Vi a varianc e o f th e predicte demissio nrate s o f th e leakin g source s screenin g <100,00 0 ppm

v N 2 

### £ (y 2 i 

### - y 2 

### ) 2 

### /(N 2 

### - i )
varianc e o f th e predicte demissio nrate s o f th e leakin g source s screenin g <100,00 0 ppm v N 

### l a

5 

### yl b 

### " f = 1 ( y 

### la i - *l. > /< N 

### i a- »

= varianc e o f th e measure d emissio n rate s o f th e censore d source s 'l b



### " -ftfolb l " *lb > ^ n 

### i b " *> •

Th e symbo l t i s th e valu e o f th e norma l deviat e correspondin g t o th e desire dconfidenc e probability . I f th e numbe r o f bagge dsources , n , i s greate r tha no r equa l t o 5 0 the nth e valu e o f t approache s 1.96 . I f th e sampl e siz e i s les s tha n50 , th e percentag e point s ma y b e take nfro

m Student' s t tabl e wit h(n-1 ) degree s o f freedom . Th e t distributio nhold s exactl y onl y i f th e emissio nrate s ar e normall y distributed . Moderat e departure s fro m normalit y

d o no t affec t i t greatly .

i xP.1 1



### FOREWOR D

Th e EPA' s protoco l fo r estimatin g equipmen t lea k emission s i s th e resul t o f detaile dinformatio ngatherin g an ddat a analysis . Th e protoco l wa s writte nt o provid e a thoroug hunderstandin g o f acceptabl e approache s t o generatin g proces s unit-specifi c emissio nestimates . I npreparin g thi s document , EPA

ha s encourage dindustr y expert s an

dtrad e associatio n representative s t o commen t onth e document' s content . Chie f amon g thes e contributor s ha s bee nth e Chemica l Manufacturer s Associatio n(CMA) , wh o ha s writte na guidanc e documen t simila r t o thi s EPA protocol .
Th e CM A documen t i s consisten t wit hthi s guide . Bot hdocument s presen t acceptabl e approache s t o generatin g emissio nestimates . Mino r difference s tha t exis t betwee nth e two document s shoul dno t affec t th e acceptabilit y o f th e emissio nestimates , provide dth e approache s t o generatin g acceptabl e emissio nestimate s ar e thoroughl y understood . Th e CM

A protoco l include s a provisio nfo r th e additio no f baggin g dat a fro m a singl e proces s uni t t o th e EPA correlatio ncurve s t o modif y th e lea k rate/screenin g valu e correlation . Whil e th e EPA agree s wit hth e technica l premis e tha t additiona l dat a coul dbe adde dt o th e existin g database , th e Agenc y believe s that , fo r practica l reasons , thi s approac hcoul dcreat e interpretatio nproblem s fo r contro l agencies . Therefore , th e Agenc y doe s no t suppor t thi s approach . Currently , EPA

i s workin g wit hCM

A t o expan dth e existin g databas e o f equipmen t screenin g an dbaggin g data . Ultimately , th e Agenc y wil l conside r th e additio no f th e dat a currentl y bein g collecte dt o th e existin g database . Thi s effor t ma y

provid e a bette r understandin g o f th e magnitud e o f equipmen t leak s an dappropriat e control s fo r them . Th e EPA wil l conside r appropriat e modification s t o thi s protoco l whe nadditiona l dat a collecte ddurin g thi s interi m perio dar e analyzed .

x iP.1 2

1. 0 INTRODUCTIO N

Th e purpos e o f thi s documen t i s t o presen t standar d protocol s fo r estimatin g mas s emission s fro m equipmen t leaks . Th e EPA' s interes t in developin g standar dprotocol s i s t o assis t state s an d industr y

inthei r effort s t o estimat e equipmen t lea k emissions . Emissio nestimate s ar e bein g develope dfo r a variet y o f purposes , includin g permitting , inventories , an d fo r th e Superfun dAmendment s an d Reauthorizatio nAc t (SARA) . Th e EPA previousl y

develope d equipmen t lea k emissio nfactor s inpreviou s wor k supportin g standards . Thes e factor s represente demission s fro m typica l facilitie s an

dwer e use dt o develo p industry-wid e emissio nestimates . Th e EPA' s standards-settin g proces s wil l continu e t o rel y upo nth e averag e emissio nfactor s fo r industry-wid e estimates . However , thos e estimate s d o no t yiel dth e accurac y

tha t facilitie s ar e lookin g fo r today ; therefore , ther e i s now a nee dfo r mor e accurat e emissio nestimatin g techniques . Recognizin g tha t th e significanc e o f ou r protocol s i s inprovidin g a consisten t approac ht o dat a collectio nand emission s estimates , EP A believe s ther e i s nee dfo r certai nminima l requirement s i nan y protocol . Ou r desir e i s t o develo pstandar dprotocol s fo r genera l us e ingeneratin g unit-specifi c emissio nestimate s fo r permittin g an dinventories . Thi s documen t describe s methodologie s th e EPA consider s appropriat e fo r developmen t o f uni t specifi c emissio nestimate s fo r equipmen t leak s o f organi c compounds : volatil e organi c compound s (VOC ) an dvolatil e hazardou s ai r pollutant s (VHAP) . Estimate s generate d usin g thi s protoco l woul d b e specifi c onl y t o proces s unit s (o r group s o f sources ) fo r whic ha nestimat e wa s made . EPA ha s mad e provisio nfo r extendin g suc hestimate s beyond th e limit s o f tha t grou po f sources . Fiv e method s fo r estimatin g emission s fro m equipmen t leak s fro

m a specifi c chemica l processin g uni t ar e include d inth e protocol : o Averag e emissio nfacto r method ; o Leak/no-lea k emissio nfacto r method ; o Three-strat a emissio nfacto r method ; o Applicatio no f EPA correlations ; an

d
o Developmen t o f ne w correlations .



### 1- 1P.1 3

The y rang e fro

m simpl y applyin g accurat e equipmen t count s t o th e EPA' s averag e emissio nfactor s t o th e mor e comple xprojec t o f developin g unit-specifi c correlation s o f mas s emissio nrate s an d screenin g values . Al l method s star t wit hobtainin g a naccurat e identificatio nan d coun t o f equipmen t t o b e include dinth e emissio nestimate . Th e equipmen t count s can simpl y b e use dwit hth e EPA' s previousl y develope d emissio nfactors . Th e nex t ste pi ncomplexit y

an drefinemen t i s th e us e o f a portabl e organi c analyze r t o fin dth e numbe r o f leakin g an d nonleakin g sources . Leakin g an d nonleakin g emissio nfactor s previousl y develope d b

y th e EPA ca nthe nb e applie d t o generat e th e emissio nestimate . A fina l refinemen t ina metho demployin g discret e emissio nfactor s i s tha t o f applyin g emissio nfactor s t o represen t thre e differen t range s o f screenin g values . Thi s ha s bee ncalle d th e stratifie d emissio nfacto r approach , o r th e three-strat a approach . Applyin g th e stratifie d emissio n factor s require s mor e rigorou s measuremen t o f organi c vapo r concentration s wit ha portabl e instrumen t becaus e actua l concentratio nreading s mus t be recorde dinstea do f notin g whethe r a piec e o f equipmen t i s classifie d a s leakin g o r no t leaking . Th e remainin g two method s mak e us e o f correlatio nequation s relatin g mas s emission s t o organi c concentration s measure d wit ha portabl e organi c analyzer . Th e EPA' s previousl y

develope d correlation s ar e offere d fo r use , an d finally , i f a proces s unit' s emission s ar e statisticall y differen t fro

m thos e represente db

y th e EPA' s correlations , provisio ni s mad e fo r developmen t o f correlation s specificall y fo r tha t proces s unit . Guidanc e an

drecommendation s ar e offere d fo r statistica l analyse s an d fo r gatherin g th e dat a require d t o execut e th e methods . Th e informatio ni s provide dinth e followin g majo r section s o f thi s protocol : o Sectio n2. 0 Emissio nEstimat e Development ; o Sectio n3. 0 Sourc e Screening ; o Sectio n4. 0 Mas s Emission s Sampling .



### 1- 2P.1 4

Sectio n2. 0 detail s th e type s o f dat a neede d fo r makin g emission s estimate s an dhow tha t dat a i s t o be applied . Section s 3. 0 an d 4. 0 offe r mor e detai l o n collectio no f dat a usin g a portabl e organi c analyze r an d usin g a techniqu e know na s "bagging, " i

nwhic ha

nenclosur e i s mad e around a potentia l lea k poin t an demission s ar e actuall y measured . Additiona l referenc e materia l i s include dinth e Appendices .

j ?



### 1- 3P.1 5

2. 0 DEVELOPMEN T O F EMISSION ESTIMATE S

2. 1 INTRODUCTIO N I nthi s section , fiv e method s fo r estimatin g VO C an d VHA P emission s fro

m equipmen t leak s inchemica l processin g unit s ar e described . Th e method s increas e incomplexit y an d inth e amoun t o f dat a collectio nan d analysi s required . However , al l fiv e method s requir e some dat a collection , dat a analysis , and/o r statistica l evaluation . Th e fiv e estimatio nmethod s an dth e option s availabl e fo r collecting an d analyzin g th e dat a ar e show nin Figur e 2-1 . A s th e flow char t shows , th e method s increas e inrigorousnes s an d complexity . Th e firs t method , th e averag e facto r method , i s th e leas t comple x an ddemandin g an

dth e las t method , developin g sit e specifi c correlations , i s th e mos t comple xan

ddemanding . Th e end produc t o f eac ho f th e procedure s describe di s a

nemission s inventor y fo r equipmen t leak s b y typ e o f equipmen t
an db y servic e (i.e. , ligh t liquid , gas , heav y liquid) . 2. 2 US E O F TH E EPA' S AVERAG E EMISSION FACTOR S Al l o f th e method s requir e a naccurat e coun t o f equipmen t component s b y typ e o f equipmen t an

db y service . Th e mos t basi c approac hfo r estimatin g emission s merel y

require s applicatio no f averag e emission s factor s develope d b y EPA t o th e equipmen t count s fo r th e unit . EPA' s averag e emissio nfactor s ar e show ni nTabl e 2-1 . Th e produc t o f th e emissio nfacto r an d th e numbe r o f equipmen t component s yield s th e emissio nrat e pe r sourc e type , an d th e emissio nrate s fo r al l sourc e type s ar e summe d t o generat e th e unit-specifi c emissio nestimates . Th e metho dEPA

use d fo r developmen t o f emissio nfactor s fo r individua l equipmen t lea k emissio nsource s wa s describe d inreport s onth e Petroleu m Refiner y Assessmen t Study . ' I nthi s study , "screening " dat a wer e gathere d usin g a portabl e organi c vapo r analyzer , an d mas s emission s wer e measure db y enclosin g individua l piece s o f equipmen t wit hbag s o r tent s an d measurin g th e organi c materia l emitted . Thes e dat a permitte dth e developmen t o f lea k rate/screenin g valu e correlation s an

demissio nfactor s fo r source s i npetroleu m refineries . 1 5 Subsequently , EPA

coordinate d th e SOCM I 24-uni t Study , a study o f 2 4 individua l chemica l proces s unit s representin g a cross-sectio no f th e SOCM I



### 2- 1

MBtP.1 6

Coun t Equipmen t Component s (b ytyp e an d service ) 

# 6 - Appl yAverag e Emissio n Factor s an d Composit e Tota l Emission s inventor ySectio n 2. 2

Conduc t Complet e Screenin g

Surve y (Respons e Facto rAdjustmen t

Optional ) 

# 6- Appl yLeak/N o Lea k Emissio n Factor s an d Composit e tota l Emission s Inventor ySectio n 2. 3


# oAppl yThre e Strat a Emissio n an d Composit e Tota l Emission s ^ Inventor

ySectio n 2. 4 

# 6 - 

# *n Adjus t Screenin g Valu e t o O V A/Methan e Forma

t

Ba g Component s fo rEac h Equipmen t Typ e an d Servic e

Develo p Individua l Correlation s

Compar e Statisticall y t o Existin g Correlation s

Appl yNe w Correlatio n an d Composit e Tota l Emission s Appl yEP A OV A Correlation s t o Screenin g Value s Abov e tri e Defaul t Zero Screenin g Valu e

Appl yDefault.Zer o Emissio n Rat e t o Screenin g Value s 8eio w th e Oefaul t Zero Screenin g Valu e

Inventory Composit e

Tota l Emission s Sectio n 2. S

InventorySectio n 2. 6



### Figure 2-1
. Strateg y fo r Estimatin g Emission s fro m

Equipmen t Leak

s

2- 2P J * J



### TABL E 2-1 . AVERAG E EMISSION FACTOR S FORFUGITIV E EMISSION S

Equipmen t Servic e Emissio nFacto r (kg/hr/source ) P.1 7



### Valve s

Pum pSeal s

Compresso r Seal s

Pressur e Relie f Seal s
Flange s
Open-Ende dLine s Samplin g Connection s 

### Ga s Ligh t Liqui d Heavy Liqui d
Ligh t Liqui d Heavy Liqui d
Gas/Vapo r
Gas/Vapo r


### Al l

Al l
Al l 0.005 6

0.007 1 0.0002 3

0.049 4 0.021 4

0.22 8

0.10 4

0.0008 3

0.001 7

0.015 0



### 2- 3P.1 8



### population , an

da six-uni t Maintenanc e Study . A s a resul t o f thes e chemica l proces s uni t studies , lea k rate/screenin g valu e correlation s an demissio n factor s wer e generate dfo r valve s ingas/vapo r servic e inSOCMI . Lea k rate/screenin g valu e correlation s wer e als o generate dfo r ligh t liqui dvalve s an dligh t liqui dpump s i nSOCMI , bu t industr y averag e emissio nfactor s wer e no t developed . 2. 3 TH E LEAK/NO-LEAKAPPROAC H Th e secondmetho doffer s some refinemen t ove r th e averag e emissio nfacto r method , thereby

allowin g som

e adjustmen t t o individua l uni t condition s an d operation . This metho dan dal l th e remainin g method s requir e screenin g o f al l equipmen t t o b e include dinth e inventor y usin g a portabl e analyzer . Equipmen t tha t i s dangerou s t o scree nma y b e omitte dfro

m th e se t o f equipmen t component s t o b e screened . Thei r emissio nrate s ma y b e estimate dusin g th e EPA' s averag e factor s presente dinTabl e 2-1 . Insulate dequipmen t ca nb e considere ddifficult-to-monito r equipment . Th e decisio nt o remov e insulatio nt o facilitat e screenin g i s lef t t o individua l judgement . I f insulatio ni s no t removed , th e insulate dcomponen t i s assume dt o lea k a t th e same rat e a s a simila r uninsulate dcomponent . Fo r flanges , a reduce dnumbe r o f component s ma y b e screened . Appendi xE describe s how

t o selec t th e sampl e siz e fo r flanges . I ncompilin g screenin g value s fo r us e inthi s techniqu e (o r an y o f thos e tha t follow) , a respons e facto r ma y

b e applie dt o correlat e th e screenin g value s measure dfo r th e chemica l i nth e lin e t o th e screenin g value s observe di ncalibratin g th e instrumen t t o anothe r chemical . Fo r a discussio no f respons e facto r adjustment , se e Sectio n3.2.2.1 . Th e leak/no-lea k approac ht o estimatin g emission s i s base donth e assumptio no f onl y

two emissio nrate s an dtw o population s o f equipmen t components : source s tha t "leak " (wit hscreenin g concentration s greate r tha n o r equa l t o 10,00 0 ppmv ) an dsource s tha t d o no t "leak " (wit hscreenin g concentration s les s tha n10,00 0 ppmv) . Th e basi s o f this approac hi s a s follows : whe na grou po f source s leak , the y lea k a t a certai nemissio nrat e onth e average . Similarly , a s a group , non-leakin g source s have , onth e average , a certai nmas s emissio nrat e

2- 4P.1 9

iB I associate dwit hthem . Thus , th e overal l emissio nestimat e fo r a populatio no f

emissio nsource s consist s o f tw o components : leakin g sourc e emission s an d non-leakin g sourc e emissions . Tabl e 2- 2 present s leakin g an d non-leakin g emissio nfactor s previousl y determine db

y EPA fo r equipmen t leaks . EPA generate d leakin g an d non-leakin g emissio nfactor s using : 1 ) emissio nfactor s generate d fro m empirica l screenin g distributio ndat a an d lea k rate/screenin g valu e correlations , 2 ) th e lea k frequencie s associate d wit hth e emissio nfactors , an d 3 ) th e percen t o f
mas s emission s associate d wit hth e leakin g sources . Th e detaile d procedur e fo r generatin g leakin g an d non-leakin g emissio nfactor s ha s bee npreviousl y 1 3 publishe dinth e "Additiona l Informatio nDocument " (AID ) fo r fugitiv e emissio nsource s o f organi c compound s an d i s als o describe di na documen t 1 6 entitle d"Emissio nFactor s fo r Equipmen t Leak s o f VO C an d HAP. " Th e applicatio no f th e leak/no-lea k approac hfo r estimatin g emission s i s show ni nth e followin g exampl e fo r a hypothetica l chemica l proces s unit . Tabl e 2- 3 present s th e dat a fo r thi s hypothetica l proces s uni t neede dt o appl y th e leak/no-lea k procedur e fo r estimating emissions . Th e firs t colum n show s th e numbe r o f source s i nth e proces s uni t b y sourc e type . Th e second colum nshow s th e numbe r o f source s wit hscreenin g value s greate r tha no r equa l t o 10,00 0 ppm

v (i.e. , leakin g sources) . Th e percentag e o f source s leakin g i s show ni nth e thir dcolumn . Th e emissio nestimate s fo r thi s hypothetica l proces s uni t ca nthe nb e compute dusin g th e leakin g an dnon-leakin g emissio n factor s inTabl e 2-2 . Fo r example , thre e o f th e 4 7 pum p seal s i nligh t liqui d servic e wer e foundt o be leaking . Usin g th e leak/no-lea k approach , th e emissio nestimat e i s generated : (0.43 7 kg/hr/source)(3 ) + (0.01 2 kg/hr/source)(47-3) , o r 1.8 4 kg/hr . Th e emissio nestimat e pe r sourc e fo r pump s i nligh t liqui d servic e coul dthe nb e compute d b y dividin g th e unit-specifi c emissio nestimat e b y th e equipmen t count . Th e las t colum ni nTabl e 2- 3 show s th e annua l emissio nestimate s b

y sourc e typ e fo r th e hypothetica l unit . Whil e thi s examplejllustrate s how tota l VO C emission s pe r sourc e typ e ar e calculated , a simila r procedur e ca nb e use d t o estimat e emission s fo r a particula r specie s i nth e line . Fo r example , conside r thi s same hypothetica l
cas e wher e th e ligh t liqui d pumpe d containe d 2 0 weigh t percen t o f Compoun dA .



### 2- 5

u*MMP.2 0



### TABL E 2-2 . LEAKIN

GAND NON-LEAKINGEMISSION FACTOR S FO

R FUGITIV E EMISSION S (kg/h r source )

Equipmen t

Valve s

Pum p Seal s

Compresso r Seals e
Pressur e Relie f Valve s Flange s Open-Ende d Line s Servic e

Gas a 

### LL b


### HL C



### L L H L

Ga s Ga s Al l Al l Leaking (>10,00 0 ppm ) Emissio nFacto r

0.045 1 0.085 2 0.00023 d

0.43 7 0.388 5

1.60 8 1.69 1 0.037 5 0.0119 5 Non-leakin g

(<10,00 0 ppm ) Emissio nFacto r

0.0004 8 0.0017 1 0.0002 3

0.012 0 0.013 5

0.089 4 0.044 7 0.0000 6 0.0015 0


### Th e leakin g an

d nonleakin g emissio nfactor s fo r valve s i ngas / vapo r servic e ar e base dupo nth e emissio nfactor s determine dfo r ga s valve s i nethylene , cumene , an d viny l acetat e unit s durin g th e SOCM I Maintenanc e Study . Reference s 8 an d 15 . LL - ligh t liqui dservice . C 

### H L - heav

y liqui dservice . Leakin g emissio nfacto r assume dequa l t o non-leakin g emissio n facto r sinc e th e compute dleakin g emissio nfacto r (0.0000 5 kg/hr / source ) wa s les s tha nnon-leakin g emissio nfactor .

e 

### Emissio nfacto r reflect s existin g contro l leve l o f 6 0 percen t foundinth e industry ; contro l 1 s throug hth e us e o f barrie r fluid/degassin g reservo1r/vent-to-flar e o r othe r sea l leakag e captur e system .

2- 6P.2 1



### TABL E 2-3 . ESTIMAT E O F "UNCONTROLLED " FUGITIV E

EMISSION S FORA

HYPOTHETICA L CAS E

Sourc e

Pum p Seal s Ligh t Liqui d Heav y Liqui d Valve s Gas/Vapo r Ligh t Liqui d Heav y Liqui d
Pressur e Relie f Va l Gas/Vapo r Open-Ende d Line s Compresso r Seal s Numbe r

Screene d

4 7 3

62 5 118 0 6 4

ve s 3 1 

### 278 4 Samplin g Connection s 7 0 Flange s 288 0 Numbe r Leakin g

3 1

1 9 1 3 0


### 1 9 0

- 

### 20 Percen t Leakin g

6. 4 33. 3

3. 0 1. 1 0


### 3. 2 3. 2 0

- 

### 0. 7 Compute d Emissio nEstimat e (pe r Source ) kg/hr/sourc e

0.039 1 0.138 5

0.001 8 0.002 6 0.0002 3

0.097 8 0.001 8 0.089 4 0.015 0 0.0003 2 Annua l

Emission s Mg/y r

16. 1 3. 6

10. 1 27. 2 0. 1

26. 6 

### 4. 5 3. 1 9. 2 8. 1

a 

### Base donvalue s fro

m Tabl e 2-2 , usin g E E = [LE F * PC L + NLE F * (100-PCL)]/10 0 wher e E E = Emissio nEstimat e (pe r Source )

LE F = Leakin g Emissio nFacto r NLE F = Non-leakin g Emissio nFacto r PC L = Percen t o f source s foundleakin g Thi s hypothetica l proces s uni t i s assume dt o be incontinuou s operation , s o i t operate s fo r 8,76 0 hour s pe r year . Batc ho r campaig nprocesse s ma y operat e fewe r hour s pe r year , s o th e annua l emission s woul db e prorate dt o accoun t fo r th e hour s th e equipmen t containe dth e chemical .

2- 7

IHS ! iuxiatP.2 2

Th e emissio nestimat e fo r Compoun d A fo r ligh t liqui d pump s i s compute d b y applyin g th e weigh t percen t (2 0 percen t i nthi s case ) t o th e emissio nestimat e generate dabove : (0.20)(1.8 4 kg/hr ) = 0.36 8 kg/hr . A s anothe r example , conside r th e hypothetica l cas e wher e th e ligh t liqui d pumpe dcontaine donl y 8 0 weigh t percen t VO C an d Compoun d A

accounte dfo r 2 0 percen t b

y weight . Th e emissio nestimat e fo r Compoun d A fo r ligh t liqui d pump s i s compute das : (0.2/0.8)(1.8 4 kg/hr ) = 0.46 0 kg/h r I nothe r words , compoun dA account s fo r one-fourt ho f th e tota l VO C emission s o f 1.8 4 kg/hr . A s before , emission s pe r sourc e ca nb e determine d b y dividin g th e estimat e b

y th e numbe r o f component s involved . Emissio nfacto r estimate s calculate di

nthi s manne r ma y

the nb e applie d t o th e equipmen t count s (wher e th e materia l inth e proces s lin e containe d 2 0 weigh t percen t o f compoun d A ) t o estimat e emission s o f compoun d A fo r tha t specifi c proces s unit . 2. 4 APPLICATIO N

O F STRATIFIE D EMISSIO N FACTOR S Anothe r approac ht o generatin g emissio nestimate s involve s a refinemen t
o f th e leak/no-lea k approac hdiscusse d above . Th e leak/no-lea k approac hi s base dontw

o emissio nrate s an

dtw o populations (i.e. , leakin g an d non-leakin g sources) . Th e stratifie demissio nfacto r approach , onth e othe r hand , i s base donsevera l populatio nan d emissio nfactor s spannin g severa l discret e screenin g valu e ranges . Screenin g value s i

nth e EP A SOCM I dat a bas e ar e distribute d widel y fro m 0 ppm v t o ove r 100,00 0 ppmv . Th e mas s emission s ar e correspondingl y distributed . Th e stratifie d emissio nfacto r approac hfo r estimatin g emission s segment s thi s distributio nint o discret e interval s t o accoun t fo r differen t range s o f screenin g values . Th e followin g range s ar e used :

o 0 - . 1,00 0 ppmv ; o 1,00 1 - 10,00 0 ppmv ; an d
o ove r 10,00 0 ppmv . Usin g dat a gathere ddurin g previou s EP A studies , emissio nfactor s fo r eac hscreenin g valu e rang e hav e bee ngenerated . Thes e stratifie d emissio n factor s represen t th e lea k rate s measure d durin g fugitiv e emission s testing .



### 2- 8P.2 3

Thei r developmen t incorporate d th e statistica l method s use d b y th e EPA in developin g othe r emissio nfactors . Th e emissio nfacto r fo r eac hdiscret e interva l i s presente dinTabl e 2- 4 b y equipmen t typ e an

d service . Thi s metho drequire s tha t screenin g o f al l equipmen t (excep t tha t whic h i s hazardou s t o screen ) b e conducte d inaccordanc e wit hmethod s describe di n Sectio n3 o f thi s report . Al l screenin g value s mus t b e recorde daccordin g t o th e applicabl e ranges . Then , a s wit hth e leak/no-lea k approach , th e tota l emissio nestimat e i s generate d b y applyin g th e numbe r o f component s ineac h screenin g valu e rang e t o th e appropriat e emissio nfacto r an d summin g eac h subtotal . A

nexampl e o f thi s procedure , show ninTabl e 2-5 , illustrate s ho w t o implemen t th e stratifie d emissio nfacto r approach . 2. 5 LEA KRATE/SCREENINGVALU E CORRELATION S Mathematica l correlation s offe r a nadditiona l refinemen t t o estimatin g emission s fro

m equipmen t leak s b

y providin g a continuou s functio nove r th e entir e rang e o f screenin g value s instea do f discret e intervals . Th e EPA ha s publishe dcorrelation s relatin g screenin g value s t o mas s emission s rates . A s show ninAppendi xD , ther e ar e fou r correlation s whic hca nb e applie d t o al l equipmen t type s an

dservices . Th e EPA' s correlation s ar e base d upo nOV A measurement s take nusin g Metho d 21 . Th e instrumen t wa s calibrate d t o methan e (se e Metho d21) . Screenin g valu e measurement s use d wit hthes e publishe d correlation s shoul db e inthi s sam e format . Fo r example , i f a TL V instrumen t calibrate dt o hexan e wer e use d t o gathe r screenin g data , th e dat a mus t be transforme dt o represen t measurement s gathere d usin g a nOVA , calibrate dt o methane , befor e usin g th e publishe d correlations . I f a detecto r fail s t o mee t Metho d2 1 specification s o r publishe d transformation s ar e no t available , a n instrumen t respons e curv e mus t b e develope d t o relat e screenin g value s t o actua l concentration s inth e appropriat e forma t (OVA/methane) . Developmen t o f thi s screenin g valu e correctio ncurv e shoul db e don e inth e laborator y befor e th e detecto r i s use dinth e field . Anothe r correctio nfacto r tha t ca nb e applie d t o Metho d2 1 an d non-Metho d2 1 instrument s i s th e respons e factor . Fo r man y compounds , th e instrumen t respons e i s non-linea r wit hincreasin g screenin g value . Interm s o f th e basi c leak/no-lea k approac hdescribe d ina previou s section , a singl e



### 2- 9P.2 4



### TABL E 2-4 . STRATIFIE D EMISSION FACTOR S FO

REQUIPMEN T LEAK S (kg/hr/source )

Sourc e
Compresso r seal s Pum p seal s

Valve s

Flanges , connection s Pressur e relie f device s Open-ende d line s Servic e
Gas/vapo r Ligh t liqui d Heav y liqui d Gas/vapo r Ligh t liqui d Heav y liqui d 

### Al l Gas/vapo r 

### Al l Emissio nFactor s (kg/hr/source ) fo r

Screenin g Valu e Ranqes , ppm v 0-1,00 0 1,001-10,00 0 Ove r 10,00 0

0.0113 2 0.0019 8 0.0038 0 0.0001 4 0.0002 8 0.0002 3 0.0000 2 0.01 H 0.0001 3 0.26 4

0.033 5 0.092 6 0.0016 5 0.0096 3 0.0002 3 0.0087 5 0.27 9 0.0087 6 1.60 8

0.43 7 0.388 5 0.045 1 0.085 2 0.0002 3 0.037 5 1.69 1 0.0119 5



### 2-1 0

_TABL E 2-5
. ESTIMAT E O F FUGITIV E EMISSION S USING STRATIFIE D EMISSIO NFACTOR S FO R AHYPOTHETICA L CAS E

Sourc e Numbe r Screene d Numbe r o f Source s Screenin g (ppmv )

0-1,00 0 1,001-10,00 0 Ove r 10,00 0 Compute d Emissio n Estimat e pe r Sourc e Type 8 pe r Sourc e (Kg/hr ) (Kg/hr/source ) Compresso r seal s Gas/vapo r Pum p seal s Ligh t liqui d Heav yliqui d Valve s Ligh t liqui d Heav yliqui d Flange s Pressur e relie f device s Gas/vapo r Open-ende d line s 4 7 3 1,18 0 64 2,88 0
3 1 27 8 3 2

1
1,02 0 6 3 2,60 0
2 5 23 6 1 2

1
14 7 1 16 0
5 3 3 2 0

1 9 0.29 8

2.2 0
3.3 7 0.42 7 0.074 5
3 1
3 0 1.77 6

0.48 5
2.8 1 0.0147 2 0.037 8

0.161 6
0.0023 8 0.0002 3 0.0007 6
0.108 7 0.0015 4

a Base d o n emissio n factor s fromTabl e 2-2 , wher e E E = (NL j * SEFj ) + (NL 2 * SEF 2 ) + .. . E E = Emissio n Estimat e NLj , NL 2 , etc
. = Numbe r leakin g i n 1s t rang e (0-1,000) , Numbe r leakin g i n 2n d rang e (1,001-10,000) , etc
. SEF, , SEF 2 , etc
. = Stratifie d emissio n facto r fo r 1s t range , stratifie d emissio n facto r fo r 2n d range , etc
. Compute d Emissio n Estimat e pe r sourc e = Compute d Emissio n Estimat e pe r Sourc e Type/Numbe r Screened
.P.2 6

poin t respons e facto r adjustmen t a t th e lea k definitio no f 10,00 0 pp m i s adequate . If , however , th e correlation s ar e t o b e used , th e bes t estimat e o f screenin g concentratio nove r th e entir e rang e i s needed . Therefore , a correctio nfo r non-linea r respons e mus t be made . Thi s ca nbe accomplishe di n th e laborator y

b y generatin g a respons e curve . Th e flow char t inFigur e 2- 1 show s a separat e treatmen t o f "zero " screenin g values . Th e functio ndescribin g th e correlatio no f lea k rat e an d screenin g valu e become s discontinuou s fo r zer o an dnea r zer o values . Th e correlatio nfunctio nmathematicall y predict s zer o emission s fo r zer o reading s onth e portabl e instrument . Empiricall y speaking , however , th e EPA' s dat a show s thi s predictio nt o be incorrect . Mas s emission s hav e bee nmeasure dfro m equipmen t showin g n o screenin g concentratio nabov e zero . Th e reaso nfo r thi s involve s th e detecto r accuracy . I nth e Refiner y

Assessmen t Study

mas s emission s correspondin g t o a screenin g valu e o f 20 0 pp m o r les s coul dno t be quantifie dbecaus e th e accurac y limi t o f th e detecto r wa s 20 0 ppm . T o handl e thi s discontinuit y

a t th e lo

w en do f th e correlation , th e EPA ha s derive da "defaul t zero " screenin g valu e ( 8 ppm ) an da nassociate dmas s emissio nrat e fo r th e screenin g value s betwee nzer o an dtha t defaul t zer o reading . Thes e "defaul t zero " value s an demissio nrate s show nbelo w wer e derive da s show ni n Appendi xF fro

m mas s emission s dat a gathere dinchemica l plant s an dth e publishe dlea k rate/screenin g valu e correlation s show ninAppendi xD :

Equipmen t Type/Servic e Valves , ga s Valves , ligh t liqui d Flange s Pump s an dal l othe r component s Thes e emissio nfactor s shoul db e applie d t o equipmen t component s screenin g betwee n0 an

d8 ppm . Th e publishe dcorrelation s woul db e applie dt o al l screenin g concentration s abov e 8 ppm . Th e tota l emission s estimat e fo r equipmen t leak s i s generate db y totalin g emission s estimate s fo r al l "defaul t
zeroes " an

daddin g tha t tota l t o th e tota l estimate s generate dusin g th e correlations . Appendi xGpresent s a nalternativ e methodolog y fo r generatin g unit-specifi c defaul t zer o emissio nrates .

2-1 2 "Defaul t Zero ' Screenin g Value , 

### 8 8 8
s 8 

### pp

m Zer o Screenin g

Valu e Emissio n Rat e (kg/hr/source ) 0.00003 3 0.00045 1 0.00009 3 0.00003 92. 6 UNIT-SPECIFI C CORRELATION S A proces s uni t ma y

develo pit s ow

ncorrelation s i f lea k rate s ar e statisticall y

differen t fro

m EPA' s rates . Th e step s involve d ingeneratin g a unit-specifi c emission s estimat e usin g correlation s develope d specificall y fo r tha t uni t are : 1 . Gatherin g o f mas s emissio ndat a an d calculatio no f mas s emissio n rat e (lea k rate) ; 2 . Developmen t o f lea k rate/screenin g valu e correlations ; 3 . Statistica l consideratio no f lea k rate/screenin g valu e correlations ; 4 . Applicatio no f lea k rate/screenin g valu e correlatio nt o th e empirica l screenin g data ; an d 5 . Predictio no f emissions . Thes e step s ar e discusse d individuall y inth e followin g sections . 2.6. 1 Generatio no f Mas s Emission s Dat a Afte r complete screenin g o f th e proces s uni t i s don e fo r al l sourc e type s (excep t possibl y

flanges) , selecte dsource s ca nb e bagge dt o measur e th e mas s emissio nrate . Th e source s selecte d fo r mas s emissio nmeasuremen t shoul db e rescreene da t th e time o f bagging . Th e mas s emissio nrat e determine db y baggin g an

dth e rescreenin g valu e ca nthe nb e use dt o validat e th e applicatio n o f EPA' s correlation s t o th e proces s unit . Alternatively , th e measurement s ca nb e use dindevelopmen t o f lea k rate/screenin g valu e relationship s fo r tha t specifi c unit . Th e screenin g valu e canb e affecte d b y th e portabl e screenin g instrumen t use dan

dth e ga s use d t o calibrat e th e instrument . Th e EPA lea k rate/screenin g valu e correlation s ar e base d ondat a gathere d usin g a nOV A instrumen t calibrate d wit hmethane . I f othe r instrument s o r calibratio ngase s ar e used , the nth e screenin g valu e shoul db e adjuste d(using theoretica l o r empirica l correctio nfactors ) t o b e equivalen t t o value s measure dusin g a nOV A calibrate d wit hmethan e prio r t o an y comparison s t o th e EPA equations . Instrumen t reading s abov e th e saturatio npoin t o f th e detecto r mus t b e bagge d t o quantif y th e emissio nrate . Th e amoun t o f lea k rat e testin g (bagging ) tha t shoul d b e don e depend s on th e objectiv e o f th e dat a collection . I f on e wishe s t o chec k th e fi t o f EPA publishe dequation s t o a particula r proces s unit , a s few a s fou r lea k rat e measurement s o f a particula r sourc e typ e ina particula r servic e ma y b e

2-1 3



## souP.2 8

,•• >

adequate . I f i t i s desirabl e t o develo pnew equations , 3 0 lea k rat e measurement s shoul db e obtained . Becaus e o f th e inheren t variabilit y o f lea k rate/screenin g data , i t i s difficul t t o detec t difference s betwee n correlation s wit hfewe r tha n3 0 dat a pairs . However , th e statistica l goa l i s t o generat e estimate s tha t ar e withi n5 0 percen t o f th e mea nvalue wit h9 5 percen t confidence . I f thi s statistica l goa l ca nb e achieve dwit hfewe r dat a pairs , the nfewe r dat a pair s ar e acceptable . Conside r a hypothetica l proces s uni t havin g a larg e populatio no f source s wit hscreenin g value s wel l distribute dove r th e range o f 0 t o 100,000 + ppmv . T o develo pstatisticall y vali dlea k rate/screenin g valu e correlations , mas s emission s dat a mus t b e collecte dfro m individua l source s tha t hav e screenin g value s distribute dove r th e entir e range . Fo r eac hsourc e typ e (i.e. , valves , pumps , etc. ) an

dservic e (i.e. , gas , ligh t liquid , etc.) , a random sampl e o f si xsource s shoul db e chose nfo r baggin g fro m eac ho f th e followin g screenin g valu e ranges : Screenin g Value Range (ppmv ) 1 - 10 0 10 1 - 1,00 0 1,00 1 - 10,00 0 10,00 1 - 100,00 0 > 100,00 0
I f th e maximu

m respons e o f th e screenin g instrumen t i s 100,00 0 ppmv , the n 2 0 o r al l (whicheve r i s less ) o f th e source s screene da t 100,00 0 ppm v shoul d b e bagged . I f si xsource s ar e no t availabl e ina particula r screenin g value range , additiona l source s fro m th e neares t rang e shoul db e tested . I f screenin g value s greate r tha n10,000 ppm v ar e no t foundinth e process , th e followin g fiv e group s ca nb e used : 1 - 10 0 ppm

v 10 1 - 30 0 ppm

v 30 1 - 1,00 0 ppm

v 1,00 1 - 3,00 0 ppm

v 3,00 1 - 10,00 0 ppm

v

2-1 4P.2 9

Simila r grouping s ca n b e develope di f al l source s i n th e uni t scree nles s than 1,00 0 ppmv . I f a statistica l determinatio ni s mad e tha t estimate s withi n5 0 percen t
o f th e mea nvalu e wit h9 5 percen t confidenc e ca n b e achieve dwit hfewe r tha n 3 0 dat a pairs , th e followin g baggin g strategie s ar e recommended : SCREENIN GVALU E TOTA L NUMBE RO F LEA KRAT E MEASUREMENT S RANGE (ppmv ) 4 8 1 2 2 0 1-10 0 2 2 3 4 10.1 - 1,00 0 1 2 4 1,00 1 - 10,00 0 1 2 4 10,00 1 - 100,00 0 2 2 3 4 > 100,00 0 2 2 4 Thes e grouping s an

d recommende dnumbe r o f source s ar e give na s guidelines . The y

ar e base do

n experienc e inmeasurin g lea k rate s an d developin g lea k rate/screenin g valu e equations . Othe r sourc e selectio n strategie s ca n b e use di f a n appropriat e rational e i s given . 2.6. 2 Developmen t o f Lea k Rate/Screenin g Valu e Correlation s Wit happropriat e mas s emissio ndat a an d screenin g values , lea k rate/screenin g valu e correlation s ca n b e generated . Least-square s regressio n analyse s ar e don e fo r eac hsourc e type/service , regressin g th e logarith m o f th e nonmethan e lea k rat e on th e logarith m o f th e screenin g concentration , accordin g t o Lo g (lea k rate ) = B +.B , Lo g (screenin g concentration) , wher e B , B , = mode l parameters . Al l analyse s shoul db e don e usin g logarithm s o f bot hth e lea k rat e an d screenin g concentration . Confidenc e interval s shoul db e calculate dfo r th e estimate dequatio n(Referenc e 19 , page s 28-31) . A scal e bia s correctio n facto r (Referenc e 20 ) i s require din transformin g th e equatio nin th e log-scal e bac k t o th e origina l units . A statisticia nshoul db e consulte d unles s on e i s familia r wit hthi s typ e o f analysis . Bagge dsource s whos e screenin g value s ar e know nt o b e abov e 100,00 0 ppm v bu t whos e actua l screenin g

2-1 5P.3 0



### value s ar e unknow

nshoul dno t be use dt o fi t th e regressio nlin e describe d above . Fo r thos e source s censore da t 100,00 0 ppm v an dwhic hwer e no t bagged , lea k rate s shoul db e estimate dfro m th e averag e lea k rat e fo r thos e censore d source s tha t wer e bagged . 2.6. 3 Statistica l Consideration s o f Lea k Rate/Screenin g Valu e Correlation s Th e predictiv e equation s resultin g fro m th e least-square s regressio n analyse s discusse dabov e mus t b e statisticall y evaluated . I f new correlatio nequation s ar e developed ; the y mus t b e show

nt o be i 

### statisticall y

differen t fro

m th e existin g correlation s develope ddurin g th e refiner y an dSOCM I studies . I f th e new correlation s ar e statisticall y differen t fro

m th e existin g correlations , th e new correlation s ma y

b e use di

n th e developmen t o f th e unit-specifi c emissio nestimate s fo r tha t specifi c clas s o f sources . I f not , th e EPA' s correlation s shoul db e used . Th e correlation s ca nb e compare dgraphicall y o r mathematically . 2.6.3. 1 Graphica l Compariso no f EPA vs . Othe r Correlations . I f enoug h dat a ar e collecte dt o develo pa proces s specifi c lea k rate/screenin g equation , the nthi s equatio nshoul db e compare dt o th e publishe dEPA equation . Th e EPA' s predictiv e equatio nshoul db e use dunles s th e equatio ndevelope dfo r th e specifi c proces s uni t i s foundt o giv e significantl y differen t estimates . Thi s compariso nca nb e don e graphicall y b y drawin g th e proces s specifi c equatio nona grapho f th e EPA equation . Figur e 2- 2 (fro m Referenc e 14 , pag e 66 ) i s a

nexampl e o f suc ha graph . A graphica l compariso nma y als o b e mad e b

y plottin g th e lea k rate/screenin g dat a fro m th e proces s ona log-scal e plo t o f th e EPA equations . Th e log scal e i s preferre ds o tha t linea r comparison s ca nb e made . Figure s 2- 3 throug h2- 5 (fro

m Referenc e 14 , page s 57-62 ) show suc hplot s o f th e EPA equations . Th e lea k rate/screenin g valu e measurement s use dt o develo pth e equation s ar e als o show nonth e plots . Thes e plot s wer e develope dfro m draf t version s o f th e correlations . Th e correlation s wer e refine dwhe ncensore d source s wer e include dinmodelin g th e lea k rate/screenin g valu e relationships . Onl y smal l difference s exis t betwee nth e ol dan dnew model s (se e Referenc e 8 , page s 14-18) .

2-1 6r o i C

O

. O

T 3 0.08
-

0.07
-

0.06
-

0 > 0.0 5 -

0.04
- ( 0 D C
c o C D

_ l

" O C D V. 0.0 3 -

0.02
-

0.01
-

0
- x / / / / y / / (95 % Confidenc e Limit s o f th e Mean ) /

T T T 20,00 0 40,00 0 60,00 0 80,00 0

Maximu m Screenin g Valu e (ppmv ) — i 100,00 0

Figur e 2-2

. Modele d relationshi p - lea k rat e vs
. OV

A fo rvalve s i n ga s service

.r o

• — • 0 0

• • • C

D

< - 9 C O CC -.rC C O C D

- J C D C C O c <m9 C D 

## s c z o 2 D ) O 1 -

- 1
-

- 2
-

- 3
-

- 4
-

- 5
- 

### T 

### 1. 5 Legend : o = 1 Observation s D = 2 Observation s A = 3-1 0 Observation s

o o

2. 0 

## T "

2. 5 3. 0 1 ^

3. 5 4. 0 4. 5 5. 0 5. 5 6. 0 

### Lo g Mea n OV A Readin g

Figur e 2-3

. Log 1 0 lea k rat e vs
. logi o 0V Areadin g fo rpum p seals

.0 - Legend : •= 1 Observation s
•= 2 Observation s A = 3-1 0 Observation s 0 = 11-1 4 Observation s

r o i vo < D

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### c r C O C D C D C C O JZ C B c o 

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• ••

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### • • ••

- 6 - —I — 1.2 5 1.7 5 2.2 5 2.7 5 3.2 5 3.7 5 4.2 5 4.7 5 5.2 5 5.7 5 

### Lo g Mea n OVA Readin g

Figur e 2-4

. Logj Q lea k rat e vs . logj 0 

### OV

A readin g fo r

valve s i n ga s service

.I

r o o C D

CO CC XL CO C D C D C C O

- C *-9 C D
C o C D O 0
-

- 1 -

- 2
-

- 3
- Legend : • = 1 Observation s
• = 2 Observation s A= 3-1 0 Observation s

- 5
-

- 6 0. 0 1. 0 1. 5 2. 0 " T " 2. 5 3. 0 T "

3. 5 " T "

4. 5 ~T ~ 6. 0 0. 5 4. 0 5. 0 5. 5



### Lo g Mea n OV A Readin g

Figur e 2-5

. Logi n lea k rat e vs
. log^ g OV A readin g fo rvalve s i n liqui d service

.A- i

I f th e point s fal l o n bot hside s o f th e lin e representin g th e equatio n an dar e withi nth e rang e o f dat a point s use dt o develo pequations , the ni t i s reasonabl e t o us e th e publishe d equation s fo r estimatin g emission s fro m th e process . Statistica l tests , suc ha s th e Wilcoxo nPaire d Replicat e Ran k tes t (Referenc e 21 , page s 401-403 ) ca n b e use d t o ai d i n th e decisio no f reasonablenes s o f th e equations . A s a n example , Figur e 2- 6 (fro m Referenc e 14 , pag e 79 ) show s tw o comparison s o f equation s develope d b y EPA fro m Petroleu

m Refinerie s t o th e SOCM I equations . Th e firs t compariso n(valve s i n ga s service ) show s th e refiner y equatio nconsistentl y estimate s greate r lea k rate s throughou t th e curve . Th e confidenc e limit s fo r th e tw o equation s d o no t overlap . Fo r thi s comparison , i t i s obviou s tha t differen t equation s ar e require d fo r th e tw o differen t type s o f proces s units . A secondexampl e o f graphica l compariso ni s show ni n Figur e 2- 6 fo r valve s i n light-liqui dservice . I n thi s cas e th e refiner y equatio nestimate s greate r lea k rate s tha nth e SOCM I equation , bu t th e refiner y equatio ni s withi nth e confidenc e band s fo r th e SOCM I equation . Th e SOCM I equatio nfall s below th e lowe r confidenc e band fo r th e refiner y equatio nfo r valve s screenin g greate r tha n30,00 0 ppmv . Th e compariso ni s no t a s clea r a s th e valve s i n ga s service . Sinc e ther e wer e abou t 30 0 dat a pair s use d t o develo p th e SOCM I equation , i t shoul dbe use d t o develo p estimate s fo r SOCM I units . Fo r comparison s o f proces s specifi c equation s t o th e EPA equation s ther e wil l usuall y

b e fewe r dat a set s use dt o develo p th e specifi c equations . Thi s wil l resul t in muc hwide r confidenc e band s fo r th e proces s specifi c equations . I f 3 0 pair s o f dat a ar e selected , th e uppe r confidenc e band shoul d b e les s tha na facto r o f two greate r tha nth e uppe r confidenc e band predicte d b y th e equation . Th e for m o f th e graphca n b e modifie dt o facilitat e th e compariso no f th e equations . I f mos t o f th e source s scree nles s tha n10,00 0 ppmv , th e equation s ca nb e graphe don a scal e fro m 0 t o 10,00 0 ppmv . Th e equation s ca n als o be graphe don a log-scal e t o mak e th e comparison s linear . However , th e scale-bia s correctio nfactor s woul d no t b e incorporate d i f th e comparison s ar e mad e i n thi s way . Therefore , thi s typ e o f compariso ni s no t recommended .

2-2 1

..PU,.—--""—-«—^TM—•^^^"•—"iii^^i^—^-^•—TMTM^ "P.3 6

if) n

_ j
C O a >

_ i

• o a > o •5 <x> a .

20,00 0 40,00 0 60,00 0 80,00 0

Maximu m TL

V Sniffe rReadin g (ppmv) Valves-Ga s 100,00 0

C O n

_ i J C ( 0 < D

_ l T 3 <0 ->m u

20,00 0 40,00 0 60,00 0 80,00 0 100,00 0

Maximu m TLV Sniffe rReadin g (ppmv ) Valves-Ligh t Liqui d
Dotte d line s ar e 90 % confidenc e bound s fo r th e "Refinery " mode l Dashe d line s ar e 95 % confidenc e bound s fo r th e SOCM I mode l Figur e 2-6 . Compariso no f SOCM I an d refiner y

lea k rat e correlations .

. 2-2 22.6.3. 2 Statistica l Compariso no f EPA vs . Othe r Correlations . A mor e forma l approac ht o comparin g lea k rate/screenin g valu e equation s i s t o us e statistica l test s t o compar e th e parameter s estimate d b y th e equations . Th e importan t parameter s o f th e lea k rate/screenin g valu e equation s (develope d o n a log-scale ) ar e th e following :

1 ) th e intercep t (Bo) ; 2 ) th e slop e (Bl) ; 3 ) th e standar d erro r (Se) . Statistica l test s fo r th e slop e an d intercep t ar e als o availabl e (Referenc e 19 , pag e 24-33) . Ninety-fiv e percen t confidenc e interval s fo r th e slop e an d intercep t wer e develope d fo r eac ho f th e SOCM I lea k rate/screenin g valu e equation s (Referenc e 8 , page s 24-25) . Fo r example , th e slop e o f th e equation s fo r valve s inga s servic e using th e OV A wa s estimate d t o be 0.693 . Th e 9 5 percen t confidenc e interva l fo r thi s slop e i s give na s 0.5 3 t o 0.85 . I f a slop e estimate d fro

m a particula r SOCM I proces s uni t i s withi nthi s confidenc e interval , the nth e EPA equatio nprovide s a reasonabl e slop e fo r a predictiv e equation . I f th e slop e estimat e i s outsid e th e confidenc e interva l fo r th e EPA correlation , th e confidenc e interva l fo r th e slop e estimate d b y th e unit-specifi c equatio nmus t be evaluated . Referenc e 1 9 indicate s ho w t o mak e thes e evaluations . A statistica l tes t t o compar e th e standar d error s fo r tw o equation s ca n be don e usin g a

nF-tes t (Referenc e 20 , pag e 3 1 o r Referenc e 21 , page s 111-116) . Sinc e th e standar d erro r i s th e ke y componen t o f th e scale-bia s correctio nfactor , thi s compariso no f standar d error s wil l als o serv e a s a compariso no f th e scal e bia s correctio nfactor s incorporate d inth e tw o correlations . 2.6.3. 3 Othe r Statistica l Analyses . Ther e ar e othe r type s o f statistica l analysi s tha t ca nbe use d inth e development , evaluation , an d compariso no f lea k rate/screenin g valu e equations . A Genera l Linea r Model s analysi s o f th e leak/rat e screenin g valu e dat a (Referenc e 20 , Chapte r 2 ) can b e use d t o develo p equation s an d t o tes t fo r differen t lea k rate/screenin g relationship s fo r differen t group s o f data . Thi s approac hwa s use d in Referenc e 1 4 (page s 51-53 ) t o evaluat e difference s betwee nth e cumene , ethylene , an

d viny l acetat e units .
2-2 3

sssaP.3 8

. A

2.6. 4 Generatio no f Emissio nEstimate s Th e generatio no f th e emissio nestimat e usin g correlation s develope dfo r specifi c proces s unit s make s us e o f th e empirica l screenin g dat a an d th e lea k rate/screenin g valu e correlations . Th e lea k rate/screenin g valu e correlation s ar e applie dt o th e screenin g dat a t o calculat e predicte d emissio nrates . Emissio nrate s ar e estimate d fo r al l emittin g source s (includin g thos e source s whic hwer e bagged ) by : Predicte demissio nrat e = exp [ B + B , lo g (screenin g concentration) ] x(scal e bia s correctio nfactor )
B an dB , ar e th e coefficien t estimate s eithe r publishe d b y EPA (Appendi xD ) o r develope dfro m a linea r regressio nanalysis , i f sit e specifi c correlation s ar e used . Th e result s presente di narithmeti c scal e ar e adjuste d t o represen t mea nemissio nrate s usin g th e scal e bia s correctio nfactor . Th e su m o f th e individua l predicte d lea k rate s represent s th e tota l mas s emissio nestimat e fo r a give ntyp e o f sourc e an d servic e bein g considered . A n emissio nestimat e pe r sourc e ca nb e derive db y averagin g th e tota l emissio n estimat e ove r th e numbe r o f source s i nth e distribution . 2.6. 5 Statistica l Consideration s fo r th e Predicte d Emissio nEstimat e Thi s sectio npresent s formula s fo r calculatin g th e 9 5 percen t confidenc e interval s fo r th e predicte d emissio nestimate . Fo r clarity , formula s fo r calculatin g th e emissio nestimat e pe r sourc e an d tota l emissio nestimat e ar e presente dalso . Definition s fo r th e formula s ar e presente d i nth e Glossary .
Fo r th e Averaa e Emissio nRat e Pe r Leakin g Sourc e (EE,) : N , 

### £ 

### Y EE , withou t censoring = i= l l i , N 

### i wit ha 9 5 percen t confidenc e interva l of :

EE , + ts v l 

## ( N l 

## i I / 2

2-2 4P.3 9



### EE, , wit hcensorin g = N 

### l a Y 

### l a + N 

### lb Y 

### l b,
wit ha 9 5 percen t confidenc e interva l of :

EE l±^^N la s al 2 + ^lb-l[N l b s ] 2 ) 1 / 2

N l n l b Fo rth e Averag e Emissio n Rat e Pe rNon-leakin g Emittin g sourc e (EF g ) :

EE , = i^ l Y 2 i , N 2 

### wit ha 9 5 percen t confidence interva l of :

: 

### 2 EE , ± ts 

### v 2 ( N 2 

### )'/ 2



### Fo r th e Averag e Emissio nRat e Pe r Sourc e (EE )

E E = ¥ E 

### 1 + N 

### 2 E E 

### 2 , N j + N g + N 3 

### - wit h9 5 percen t confidenc e interval s of :

E E ± t {[Nj S j F + [N 2 

### s y 2 

### ] > withou t censoring . I 2 

### + [N 2 

### s y 2 

### ] 2 

### } 1 / 2



### Tota l Emission s + N xE E (us e th e E E confidenc e limit s abov e multiplie db y N ) N j + N 2 

### + N 3



### 2-2 5P.4 0



### APPENDI XA REFERENC E METHO D 2 1P.4 1

MITKO D 21—DRnMIHATIO RO F VOUTO l OROAJII C COMPOUNDS LEAK

S 1. Applicability and

Principle. 1.1 Applicability. Thi s metho d applies t o th e determinatio n o

f volatil e organi c com

. poun d (VOC ) leak s from proces s equipmen t Thes e source s include , bu tare no tlimite d to . valves , fiance s and othe rconnection* , pump s an d compressors , pressure relief devices , proces s drains , open-ende d valve s pump an d compresso rsea l syste m degassin g vents , accumulato rvesse l vents , agitator seals , an d acces s doo rseals . 1.2 Principle. A portabl e instrumen tl a use d t o detec tVO C leak s from individua l sources . Th e Instrumen tdetecto rtyp e t s no t specified , bu ti tmus tmee tth e specifica
tion s and performanc e criteri acontaine d i n Sectio n 3 . A leak definitio n concentratio n base d o n areferenc e compoun d I s specified l n eac h applicabl e regulation . Thi s procedur e I s Intende d t o locat e and classif y leak s only , an d I

s no tt o b e use d u adirec tmeasur e of mas s emissio n rate s from individua l sources . 2 . Definition*. 2.1 Leak Definition Concentration. Th e loca l VO C concentratio n a tth e surfac e o f a lea k sourc e tha tindicate s tha taVO C emis
sio n (leak ) I

s present . Th e leak definitio n I s a n instrumen tmete rreadin g based o n aref
erenc e compound . 2.2 Reference Compound. Th e VOC specie s selecte d a s a n instrumen tcallbratlo a basi s fo rspecificatio n o f th e leak definitio n concentration . (Fo rexample : I f aleak defi
nitio n concentratio n I s 10,000 ppm

v s s methane , the n an y sourc e emissio n tha tresult s l n aloca l concentratio n tha tyield s a mete rreadin g of

10.000 o n a n instrument calibrate d with methan e woul d b e classified a s aleak . I n thi s example , th e lea k defini
tio n i s 10.000 ppmv , an d th e referenc e compoun d i s methane. ) 2.3 Calibration Oos . Th e VO C compoun d use d t o adjus tth e instrumen tmete rreadin g t o aknown value . Th e calibratio n gas I s usuall y th e referenc e compoun d a taconcentra tio n approximatel y equal t o th e leak defini
tio n concentration . 2.4 No Detectable Emiuion. Th e local VOC concentratio n a tth e surfac e o f aleak sourc e tha tindicate s tha taVO C emissio n (leak ) I s no tpresent . Sinc e background VO C concentration s ma

y exist , an d t o accoun t forinstrumen tdrif

tand Imperfectrepro ducibility , adifferenc e .between th e sourc e surfac e concentratio n an d th e loca l ambien t concentratio n i s determined . A differenc e based o n mete rreading s o f les s tha n acon centratio n correspondin g t o th e minimum readabilit y specificatio n indicate s tha ta VOC emissio n (leak ) i s no tpresent . (Po rex ample , i f th e lea k definitio n i n aregulatio n l a10.000 ppmv , the n th e allowabl e increas e in surfac e concentratio n versu s local ambi
en tconcentratio n woul d b e SO O ppm v base d on th e instrumen tmete rreadings. ) 2.5 Response Factor. Th e rati o o f th e know n concentratio n of

aVO C compoun d t o th e observe d mete rreadin g whe n meas ure d usin g a n instrumen tcalibrate d with th e referenc e compoun d specifie d i n th e ap plicatio n regulation . 2.t Calibration Precision. Th e degre e of agreemen tbetwee n measurement s of th e sam e know n value , expresse d s s th e relativ e percentag e o

f th e averag e differenc e be tween th e mete rreading s and th e know n concentratio n t o th e know n concentration . 2.7 Retponte Time. Th e tim e interva l fro m aste p chang e I

n VO C concentratio n a t th e inpu tof

th e samplin g syste m t o th e Um e a twhic h 9 0 percen to

f th e correspond in g final valu e I

s reache d a s displaye d o n th e instrumen treadou tmeter . I Apparatus. II Monitoring Instrument 3.1.1 Specifications. a . Th e VO C Instrumen tdetecto rshal l re spond t o th e compound s bein g processed . Detecto rtype s whic h may mee tthi s re quirementinclude , bu tar ano tlimite d to , catalyti c oxidation , flam e lonixatlo ainfra
red absorption , an d photolonlsatio a b . Th e Instrumen tshal l b e capabl e of measuring th e lea k definitio n concentratio n specified I

n th e regulation , c Th e scal e of

th e Instrumen tmete rshal l b e readabl e t o ± S pereen to f th e specifie d lea k definitio n concentration . d. Th e instrumen tshal l b e equippe d wit h apump ao tha tacontinuou s sampl e Is pro vide d t o th e detector . Th e nominal sampl e (lo w rat e shal l b e H t o 3 Uter s pe rminute . e . Th e instrumen tshal l b e intrinsicall y nfe toroperatio n i n explosiv e atmosphere s i s define d b y th e applicabl e UJ&A . stand ard s (e.g. . Nationa l Electrica l Cod e b y th e Nationa l Fir e Preventio n Association) . 3.1.2 Performance Criteria, a . Th e Instrumen trespons e factor s fo rth e indlvida l compound s t o b e measure d mus t b e les s tha n 10 . b . Th e instrumen trespons e tim e mus tb e equal t o o rles s tha n 3 0 seconds . Th e re spons e tim e mus tbe determine d forth e in
strumen tconfiguratio n t o b e used durin g testing . c . Th e calibratio n precisio n mus tbe equal t o o rles s tha n 1

0 percen to

f th e calibratio n ga s value . d . Th e evaluatio n procedure foreach pa ramete ri s given l n Sectio n 4.4 . 3.1.3 Performance Evaluation Requirement*. a . A respons e facto rmus tb e determine d fo reac h compoun d tha tI s to b e measured , eithe rb y testin g o rfrom referenc e sources . Th e respons e facto rtest s ar e required befor e placin g th e analyze rinto service , bu t d o no thav e t o b e repeate d a s subsequen tIntervals . b . Th e calibratio n precisio n tes tmus tb e complete d prio rt o placin g th e analyze rInt o service , an d a tsubsequen t3-mont h Interval s o ra tth e nex tus e whicheve rI s later . c . Th e respons e tim e tes ti s required prio r t o placin g th e Instrumen tint o service . I f a modificatio n t o th e sampl e pumpin g syste m o rflo w configuratio n i s mad e tha twoul d chang e th e respons e time , anew tes tI s re quire d prio rt o furthe ruse . 3.2 Calibration Oate*. Th e monitorin g Instrumen ti s calibrate d i n term s o f parts pe rmillio n by volum e (ppmv ) o f th e refer
enc e compoun d specifie d i n th e applicabl e regulation . Th e calibratio n gase s required fo rmonitorin g an d instrumen tperformance evaluatio n are azer o ga a(air . les s tha n 1 0 ppm v VOC) an d acalibratio n ga s l n ai rmix
tur e approximatel y equal t o th e leak defini
tio n specifie d l n th e regulation . I f cylinde r calibratio n ga s mixtur e are used , the y mus t b e analyse d an d certifie d by th e manufac
ture rt o b e withi n ± 2 percen taccuracy , an d ashel f lif e mus tb e specified . Cylinde r standard s mus tb e eithe rreanalyze d o rre place d a tth e en d o

f th e specifie d shel f

life. Alternately , calibratio n gase s ma y be pre pare d b y th e use raccordin g t o an y accepte d gaseou s standard s preparatio n procedure tha twil l yiel d amixtur e accurate t o withi n ± 2 percent . Prepare d standard s mus tbe replace d eac h day o f

us e unles s i tca n b e dem onstrate d tha tdegradatio n doe s no toccu r durin g storage . Calibration s may te performe d usin g a compoun d othe rtha n th e referenc e com poun d I f aconversio n facto rI

s determine d fo rtha talternativ e compoun d s o tha tth e resultin g mete rreading s durin g sourc e sur vey s ca n b e converte d t o referenc e com poun d results . 4. Procedures 4.1 Pretest

Preparations. Perfor

m th e in
strumen tevaluatio n procedure s give n in Sectio n 4. 4 if

th e evaluatio n requirements of Sectio n 3.1. 3 hav e no tbee n met .

A- lP.4 2

4.2 Calibration Procedures. Assembl e and star tup th e VO C analyze raccordin g t o th e manufacturer' s Instructions . Afte rth e appropriate warmup perio d an d zer o inter
na l calibratio n procedure , introduc e th e calibratio n ga s int o th e Instrumen tsampl e probe . Adjus tth e instrumen tmete rreadou t t o correspon d t o th e calibratio n ga s value . Non.—I f th e mete rreadou tcanno tte ad Justed t o th e prope rvalue , amalfunctio n o f th e analyze ri s indicate d an d correctiv e ac tion s are necessary befor e use . 4.3 Individual Sourc e Surveys . 4.3.1 Type I—Leak Definition Based on Concentration. Plac e th e prob e inle ta tth e surfac e of

th e componen tInterfac e wher e leakag e coul d occur . Move th e prob e alon g th e interfac e periphery whil e observin g th e instrumen treadout . I

f a n increase d mete r readin g t s observed , slowl y sampl e th e inter
fac e wher e leakag e l

aindicate d unti l th e m.Timn m mete rreadin g i s obtained . Leav e th e prob e inle ta tthi s maximu m readin g lo catio n fo rapproximatel y tw o time s th e in
strumen trespons e time . I f th e maximu m observe d mete rreadin g l agreate rtha n th e lea k definitio n I

n th e applicabl e regulation , record an d repor tth e result s a s specifie d I n th e regulatio n reportin g requirements . Ex ample s o f th e applicatio n of

thi s genera l techniqu e t o specifi c equipmen ttype s are : a . Valves—Th e moa

tcommo n soure e of leak s from valve s I

s a tth e sea l betwee n th e ste m and housing . Plac e th e prob e a tth e Interfac e wher e th e ste m exist s th e parkin g glan d an d sampl e th e ste m circumference . Also , plac e th e prob e a tth e interfac e of th e packin g glan d take-u p flang e sea tan d sampl e th e periphery . I n addition , surve y valv e housing s o f

multipar tassembl y a tth e surfac e of

al l Interface s wher e alea k coui d occur . b . Flange s an d Othe rConnections—Po r welde d flanges , plac e th e prob e a ttb e oute r edg e o f th e flange-gaske tinterfac e an d sampl e th e circumferenc e of th e flange . Sampl e othe rtype s of

nonpermanen tJoints (suc h a athreade d connections ) wit h asimi
la rtraverse . c . Pump s an d Compressor s Conduc tacir
cumferentia l travers e a tth e oute rsurfac e o f th e pum p o rcompresso rshaf tan d sea l Interface . If

th e sourc e l

aarotatin g shaft , positio n th e prob e Inle twithi n 1 c m of th e shaf tsea l Interfac e fo rth e survey . If th e housin g configuratio n prevent s acomplet e travers e of

th e shaf

tperiphery , campl e al l accessibl e portions . Sampl e al l othe rJoints o n th e pum p o rcompresso rhousin g wher e leakag e coul d occur . d . Pressur e Relie f

Device s Th e configura
tio n of mos tpressur e relief

device s prevent s samplin g a tth e sealin g sea tinterface . Po r thos e device s equippe d wit h a n enclose d ex tension , o rhorn , plac e th e prob e Inle ta tap proximatel y th e cente ro f th e exhaus tare * t o th e atmosphere . e . Proces s Drains—Fo rope n drains , pi^ . th e prob e inle ta tapproximatel y th e center o f th e are aope n t o th e atmosphere . p o r covere d drains , plac e th e prob e atth e su r fac e o f th e cove rInterfac e an d conductaat. ripheral traverse . f . Open-Ende d Line s o rValves—Plac e the prob e inle ta tapproximatel y th e cente ro f th e opening ; t o th e atmosphere . g . Sea l Syste m Degassin g Vent s an d Accu
mulato rVents—Place th e prob e inle ta tapproximately ; th e cente ro f th e openin g t

o th e atmosphere . h . Access ; Doo rSeals-Plac e th e prob e inle ta tthe'surfac e o

f th e doo rseal inter

fac e an d conduc taperipheral traverse . 4.3.2 Type II—"No Detectable Emission" Determin e th e loca l ambien tconcentra ! tio n aroun d th e sourc e by movin g th e prob e inle trandoml y upwin d an d downwin d a ta distanc e o

f > on e t o tw o meter s fro m tb e source . I f a h Interferenc e exist s wit h this determinatio n du e t o anearb y emission o r leak , th e loca l ambien tconcentratio n ma y b e determine d a tdistance s close rto ta t source , bu tl n n o caae shal l th e distance b t les s tha n 2f

tcentimeters . The n mov e tb s prob e inle tt o th e surfac e o f th e souree an

d determin e th e concentratio n described i n 4.3.1 . Th e differenc e betwee n thes e concentration s determine s whethe rther e ar e n o detectabl e emissions , Recor d and reportth t results a s specifie d b y th e regulation. Po rthos e case s wher e th e regulation require*
- aspeci f

l c devic e Installation , o

rtha t specifie d vent s b e ducte d o rpiped t o acontro l device , th e existenc e o f thes e condition

s shal l b e visuall y confirmed . Whe n th e regulatio n als o require s tha tn o detectabl e emis
sion s exist , visua l observation s and «"»p"i g survey s ar e required. Example s o f thi s tech niqu e are : (a ) Pum p o rCompresso rSeals—I f appUcable . determin e th e typ e of shaf tsea l Pre

form asurve y of

th e loca l are aambien t VO C concentratio n an d determin e i f detectabl e emiasion s exis ta s describe d above . (b ) Sea l Syste m Degassin g Vents . Accumu
lato rVesse l Vents . Preasure Relie f Devices
I f applicable , observ e whethe ro rnotthe applicabl e ductin g o rpipin g exists . Alas , determin e t f an y source s exis tI

n th e ductin

g o rpipin g wher e emission s coul d occu rprio r t o th e contro l device . I f th e required duct

in g o rpiping , exist s an d ther e ar e no soures

t wher e th e emission s coul d te vented to th s atmospher e prio rt o th e contro l device , then l tlapresume d tha tn o detectabl e rmlwtan s ar e present . If

ther e ar e source s l n th e ductin g o rpipin g wher e emission s coul d b s vente d o rsource s wher e leak s eould occur , th e ««wpnii g survey s describe d I n thi s para

grap h shal l te use d t o determin e I f detectabl e emiasions ! exist .

A- 2P.4 3

4,3.3 Alternative Screening Procedure. A screenin g procedure based on th e formatio n 0 ( bubble s i n asoa p solutio n tha ti s spraye d 0 n s potentia l leak sourc e ma y b e use d fo r thos e source s tha td o no thav e continuousl y movin g parts , tha td o no thav e surfac e tem peratures greate rtha n th e boilin g poin to r [es s tha n th e freezin g poin to f th e soa p solu tion , tha td o no thav e ope n area s t o th e at mosphere tha tth e soa p solutio n canno t bridge , o rtha td o no texhibi tevidenc e of liqui d leakage . Source s tha thav e thes e con dition s presen tmus tb e surveye d usin g th e instrumen ttechnique s of 4.3. 1 o r4.3.2 . Spra y asoa p solutio n ove ral l potentia l lea k sources . Th e soa p solutio n may b e a commercially availabl e lea k detectio n solu tion o rma

y b e prepared usin g concentrate d detergen tand water . A pressur e spraye ro r $ squeez e bottl e ma

y te use d t o dispens e th e solution . Observe th e potentia l lea k site s t o determin e i f

an y bubble s ar e formed . If n o bubbles ar e observed , th e sourc e I s pre sume d t o hav e n o detectabl e emission s o r leaks a s applicable . If

an y bubble s ar e ob served , th e instrumen ttechnique s of 4.3. 1 o r 4.3.2 shal l te use d t o determin e if alea k exists , o ri

f th e sourc e h u detectabl e emis
sions , a s applicable . 4.4 Instrument

Evaluation Procedures. A t tn e beginnin g o f

th e Instrumen tperform
anc e evaluatio n test , assembl e an d star tu p tn e Instrumen taccordin g t o th e manufac
turer' s Instruction s fo rrecommended warmu p perio d an d preliminary adjust
ments . 4.4.1 Response Factor. Calibrate th e in
strumen twith th e reference compoun d a s specifie d i n th e applicabl e regulation . Po r eac h organi c specie s tha tIs t o b e measure d during individual sourc e surveys , obtai n o r prepar e aknown standar d l n ai ra tacon centratio n d

f approximatel y 8 0 percen to f th e applicabl e lea k definitio n unles s limite d b y volatilit y o rexploslvlty . I n thes e cases , prepar e astandar d a t9 0 percen to f th e saturatio n concentration , o r7 0 percen to f th e lowe rexplosiv e Umi trespectively. In troduce thi s mixtur e t o th e analyse ran d recor d th e observe d mete rreading . Intro duc e ser o .sirunti l astabl e reading laob tained . Mak e atota l o f

thre e measurement s b y alternatin g betwee n th e know n mixtur e an d ser o sir . Calculat e th e respons e facto r fo reac h repetitio n an d th e averag e respons e factor . Alternatively , t

f respons e factor s hav e bee n pubUshed fo rth e compound s of inter
es tfo rth e instrumen to rdetecto rtype , th e respons e facto rdeterminatio n I s no tre quired , and existin g result s ma y te referenced . Example s o

f pubUshed respons e fac
tor s fo rflam e ionizatio n an d catalyti c oxi
dation detector s ar e include d l n Sectio n 9 . 4.4.2 Calibration Precision. Mak e atota l o f thre e measurement s b y alternatel y usin g zer o ga aan d th e specifie d caUbratio n gas . Record th e mete rreadings . Calculate th e averag e algebrai c differenc e betwee n th e mete rreading s and th e known value . Divid e thi s averag e differenc e b y th e known cali
bratio n valu e an d mutipl y b y 10 0 t o expres s th e resultin g caUbratio n precisio n a s apercentage . 4.4.3 Response Time. Introduc e zer o ga s Int o th e Instrumen tsampl e probe . When th e mete rreadin g ha s stabilized , switc h quickl y t o th e specifie d caUbratio n gas . Measur e th e tim e from switchin g t o whe n 90 percen tof

th e final stabl e readin g i s at tained . Perform thi s tes tsequenc e thre e time s an d record th e results . Calculat e th e averag e respons e tune . 5. Bibliography. 5.1 DuBose, D.A., and

G.E. Harris. Re spons e Factor s of

VO C Analyzer s a taMete r Readin g ot

10.000 ppmv fo rSelecte d Organ
i c Compounds . U.S . Environmental Protec tio n Agency , Researc h Triangl e Park . N.C . PubUcatio n No . EP

A 600/2-61-051 . Septem
be r1981 . 5.2 Brown , O.E., et

aL Respons e Factor s of VO C Analyzer s Calibrate d with Methan e fo rSelecte d Organi c Compounds . VS. Envi
ronmenta l Protectio n Agency . Researc h Tri
angl e Park . N.C . PubUcatio n No . EP A 600 / 2-81-022 . May 1981 . 5.3 DuBose, DA., et

al Respons e of

Porta bl e VO C Analyser s t o Chemical Mixtures , U.S . Environmenta l Protectio n Agency . Re searc h Triangl e Park . N.C . PubUcatio n No . EP A 600/2-81-110 . Septembe r1981 .

A-3P.4 4



### APPENDI XB RESPONS E FACTOR S
Thi s appendi xpresent s respons e factor s estimate d fo r a 10,00 0 ppm

v detecto r reading . Thes e respons e factor s wer e previousl y reporte din Reference s 4 an

d6 . The y

canb e use dt o determin e whethe r o r no t a concentratio ni s abov e o r below 10,00 0 ppmv . Th e respons e factor s ma y o r ma y no t b e accurat e a t othe r concentrations .P.4 5

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B- lTABL E B-l . RESPONS E FACTOR S WIT H 95 % CONFIDENC E INTERVAL S ESTIMATE D A T 10.00 0 PPM V RESPONS E (cont'd. )

0 0 r o CA

S No. «

109-73- 9 13952-84- 6 75-64- 9

123-72- 8 107-92- 6 109-74- 0 75-1-5 0

108-90- 7

67-66- 3 25167-80- 0

1 108-41- 8 95-49- 8 106-43- 4 95-48- 7 4170-30- 0 98-82- 8 110-82- 7 108-93- 0 108-94- 1 110-83- 8 108-91- 8

123-42- 2 Compoun d Nam e
Buty l amIne , N Butylamine , Sec Buty l amine , Tert Butylbenzene , Tert Butyraidehyde , N Butyrl c aci d Butyronltrll e Carbo n disulfid e Chioroacetaldehyd e Chlorobenzen e Chloroethan e Chlorofor m Chlorophenol , 0 - Chloropropene , 1 - Chloropropene , 3 - Chlorotoluene , M Chlorotoluene , O Chlorotoluene , P Cresol , O Crotona l dehyd e Cumen e Cyclohexan e Cyclohexano l Cyclohexanon e Cyclohexen e Cyclohexylamln e Oecan e Dlaceton e alcoho l Dlacety l D1chloro-l-propene , 2,3 - Volatlllt y Clas s

L L L L L L H L L L H L L L L L L L L L G L H L L L L L L L L L L L S L L L L LL H L L L L L L L HL H L LL L L Respons e

0.6 9 0.7 0 0.6 3 1.3 2 1.2 9 0.8 0 0.5 2

9.1 0 0.3 8 5.3 8 9.2 8 4.5 6 0.6 7 0.8 0 0.4 8 0.4 8 0.5 6 6.9 6 1.2 5 1.8 7 0.4 7 0.8 5 1.5 0 0.4 9 0.5 7 0.0 9 1.4 5 1.5 4 0.7 5 OV

A Facto r Confidenc e

0.53
. 0.58
. 0.58 , 0.89 , 1.07 , 0.38 , 0.40 , B 5.73 ,

0.32
. I 1.87 ,

5.19 , 1.72 , 0.61 , 0.72 , 0.45 , 0.42 , 0.52 , 0.70 , 0.82 , 1.10 , 0.39 , 0.65 , 0.97 , 0.42 , 0.42 , N 0.05 ,

0.96 , 1.25 , 0.56 , Interval s

0.9 8 0.8 7 0.7 0 2.2 0 1.6 1 3.1 4 0.7 4

16.2 0 0.4 7 26.4 0 20.0 0 27.2 0 0.7 3 0.9 0 0.5 1 0.5 5 0.6 1 1.4 5 2.2 4 3.7 1 0.5 8 1.2 0 2.7 6 0.5 7 0.8 6 >100.0 0 2.4 8 1.9 2 1.0 9 Respons e

2.0 2 1.5 6 1.9 5

2.3 0 10.7 0 1.4 7 3.9 2 5.0 7 0.8 8 3.9 0

18.3 0 0.8 7 1.2 4 0.9 1 1.0 6 1.1 7 4.3 6

0.7 0

7.0 4 2.1 7 1.3 8 0.1 6 0.9 8 3.2 8 1.7 5 TL

V Facto r

B

I I

P B I

I I B B

B

I 1 . Confidenc e Interval s

1.14
. 0.77 , 1.42 ,
0.96 , 6.53
. 0.62 , 1.87 , 3.08 , 0.77 , 1.58 ,
6.50 , 0.69 , 1.08 , 0.40 , 0.33 , 0.77 , 0.40 ,

0.62 ,
1.59
. 1.78
. 1.28 , 0.07 , 0.44
. 2.25
. 1.14
. 4.9 7

5.2 4 2.9 1

12.8 0 17.6 0 3.4 8 12.6 0 9.7 9 1.0 0 14.1 0

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B- 4TABL E B-l
. RESPONS E FACTOR S WIT H 95 $ CONFIDENC E INTERVAL S ESTIMATE D A T 10,00 0 PPM V RESPONS E (cont'd. )

o o i t n CA

S No. »

77-75- 8 98-83- 9 110-91- 8 98-95- 3 79-24- 3 75-52- 5 25332-01- 4

109-66- 0

123-38- 6 79-09- 4 71-23- 8

115-07- 1 75-56- 9 110-86- 1 100-42- 5 79-34-S c

108-88- 3

71-55- 6 79-00- 5 79-01- 6 96-18- 4 Compoun d Nam e
Methylpentyno l Methy l styrene , A Morpholln e Nitrobenzen e Nltroethan e Nltromethan e Nltropropan e Nonane- N Octan e Pentan e Plcollne , 2 - Propan e Propionaldehyd e Propioni c aci d Propy l alcoho l Propy l benzene , N Propylen e Propylen e oxid e Pyridin e Styren e Tetrachloroethane , 1,1,1.2 - Tetrachloroethane , 1,1,2,2 - Te t rach1oroethylen e Toluen e Trichlorobenzene , 1,2,4 - TrIchloroethane , 1,1,1 - Trlchloroethane , 1,1,2 - Trlchloroethylen e Trlchloroprppane , 1,2,3 - Volatlllt y Clas s

L L L L L L H L L L L L L L L L L L L L L L G L L L L L L L L G L L L L L L L L L L L L L L H L L L L L L L L L OV A Respons e Facto r Confidenc e

1.1 7 13.9 0 0.9 2

1.4 0 3.5 2 1.0 5 1.5 4 1.0 3 0.5 2 0.4 3 0.5 5 1.1 4 1.3 0 0.9 3 0.5 1 0.7 7 0.8 3 0.4 7 4.2 2 4.8 3 7.8 9 2.9 7 0.3 9 1.2 1 0.8 0 1.2 5 0.9 5 0.9 6 B

I

0

I 0.71 ,

9.50 , 0.67 ,
1.20
. 3.03
. 0.80 , 0.94 , 0.89 , 0.42 , 0.38 , 0.46 , 1.00 , 1.03 , 0.77 , 0.45 , 0.44 , 0.74 , 0.40 , 3.45 , 1.24 , 5.01 , 1.71 , 0.36 , 0.50 , 0.72 , 1.05 , 0.83 , 0.64 , Interval s

2.4 8 21.5 0 1.4 0

1.6 5 4.1 5 1.4 8 2.9 8 1.2 1 0.6 6 0.5 0 0.7 2 1.3 2 1.7 0 1.1 6 0.5 8 2.6 6 0.9 5 0.5 5 5.2 7 >100.0 0 13.8 0 6.1 1 0.4 3 2.9 4 0.9 0 1.5 0 1.0 9 1.7 8 Respons e

3.4 2

2.5 9 0.0 1 3.4 5 7.6 0 2.0 2 11.1 0 2.1 1 0.6 3 1.1 8 0.6 0 1.7 1 5.0 8 1.7 4

1.7 4 1.1 5 1.1 6

6.9 1 25.4 0

2.6 8 0.4 7 2.4 0 3.6 9 3.9 3 1.9 9 TL

V Facto r

B I I

P

D

B I

B

B D I Confidenc e Interval s

1.83
.
0.64 , 0.00 , 1.56
. 1.91
. 1.17 , 3.13 , 1.68
. 0.57 , 1.08 , 0.59
. 1.11 , 0.73 , 1.06 ,
0.15 , 0.69 , 1.03 ,
3.14
. 8.06
.
0.79 , 0.32 , 1.81 , 2.77
. 2.68 , 1.27 , 8.5 4

10.5 0 82.8 0 13.0 0 >100.0 0 4.4 7 >100.0 0 2.7 5 0.7 0 1.2 9 0.6 9 3.0 6 >100.0 0 3.5 0

20.3 0 2.4 6 1.3 4

22.5 0 >100.0 0

>100.0 0 0.6 8 3.3 5 5.1 6 6.3 2 3.8 2TABL E B-l
. RESPONS E FACTOR S WIT H 95 % CONFIDENC E INTERVAL S ESTIMATE D A T 10,00 0 PPMV RESPONS E (cont'd. )

CA S No. * Compoun d Nam e Volatilit y Clas s OV A Response Fvecto rConfidenc e Interval s TL V Respons e Facto r Confidenc e Interval s

121-44- 8 Trlethylamln e 108-05- 4 Viny l acetat e 75-01- 4 Viny l chlorid e

Viny l propionat e 75-35- 4 Vlnyllden e chlorid e 106-42- 3 Xylene , P Xylene , M 95-47- 6 Xylene , O L L L L G L L L L LL LL L L 0.5 1

1.2 7 0.8 4 1.0 0 1.1 2 2.1 2 0.4 0 0.4 3 0.40 ,

0.95 , 0.61 , 0.57 , 0.87 , 1.71 , 0.36 , 0.28 , 0.7 0

1.8 2 1.3 8 1.7 4 1.5 2 2.6 8 0.4 6 0.8 5 1.4 8

5.9 1 1.0 6 1.2 1 2.4 1 7.8 7 5.8 7 1.4 0 0.96 .

1.26 , 0.59 , 0.46 , 1.82 , 3.49 , 0.91 . 0.61 . 2.7 6

>100.0 0 4.6 0 3.2 0 3.3 5 24.9 0 >100.0 0 9.3 3

I c n ^CA

S number s refe r t o th e Chemica l Abstract s Registr y number s o f specifi c chemicals.'Isomers , o r mixture s o f chemicals
. G = Gas ; L L - ligh t liquid ; H L = heav y liqui d I = Invers e estimatio n metho d D = possibl e outlier s i n dat a N = narro a rang e o f dat a X = n o dat a availabl e B = 10,00 0 ppm

v respons e unachievabl e P = suspec t point s eliminate d

2P.5 1

TABL E B-2 . TESTE D COMPOUND S WHIC H APPEA RT O J E UNABL E T O ACHIEV E A N INSTRUMEN T RESPONS E O F 10,00 0 PPM V A T AN YFEASIBL E CONCENTRATIO N

Instrumen t
CAS b

75-1-5 0 56-23- 5

- -

- -

- -

- - 122 1 98-01- 1 166 0 98-95- 3 108-95- 2

- - a OV

A Compound Name
Acetyl-1-propanol , 3 - Carbo ndisulfid e Carbo ntetrachlorid e Dichloro-1-propanol , 2, 3 Dichloro-2-propanol , 1, 3 Diisopropy l benzene , 1, 3 Dimethylstyrene , 2, 4 Freo n1 2 Furfura l Methyl-2,4-pentanediol, 2 Monoethanolamin e Nitrobenzen e Pheno l Phenyl-2-propanol , 2 - CAS b

98-86- 2

- - 74-86- 2 79-10- 7 100-52- 7 100-47- 0 98-88- 4 100-44- 7 56-23- 5 67-66- 3 4170-30- 0 98-82- 8 108-93- 0

- -

- -

- -

- - 64-18- 6 122 1 98-01- 1 115-11- 7

- - 98-83- 9 166 0 108-95- 2

- -

- - 100-42-0 5 286 0 

### TL

V Compound Nam

e
Acetophenon e Acetyl-1-propanol , 3 - Acetylen e Acryli c aci d Benzaldehyd e Benzonitril e Benzoy l chlorid e Benzy l chlorid e Buty l benzene , Tert Carbo ntetrachlorid e Chloroform Crotonaldehyd e Cumen e Cyclohexano l ^ Dichloro-1-propanol , 2, 3 Dichloro-2-propanol , 1, 3 Diisopropy l benzene , 2, 4 Dimethylstyrene , 2, 4 Formi c aci d Freo n1 2 Furfura l Isobutylen e Methyl-2,4-pentanedio l Methylstyrene , A Monoethanolamin e Pheno l Phenyl-2-propanol , 2 - Propylbenzene , N Styren e Tetrachloroethy1en e
OV A an d TL V ar e tw o portabl e hydrocarbo nanalyzer s tha t hav e bee nuse d i n previou s studie s o f fugitiv e emissions . Operatin g wit ha flame ionizatio n detecto r (FID) , OV

A measure s nonmethan e hydrocarbo nemissions ; TL V measure s tota l hydrocarbo nemissions . 3 CA S number s refe r t o th e Chemica l Abstract s Registr y number s o f specifi c chemicals , isomers , o r mixture s o f chemicals .

B- 7P.5 2



### APPENDI XC CALCULATIO N

O F MAS S EMISSIO N

RATE SP.5 3

APPENDI XC

Th e calculatio no f emissio nrate s i s illustrate dbelo w fo r VOC : E = E + E T V L wher e Ey

= tota l VO C emissio nrate , lb/hr , E . = condense dorgani c liqui dcomponen t of th e VO C emissio nrate , lb/hr , an

d E w = vapo r componen t of th e VO C emissio nrate , lb/hr .
Th e emissio nrat e of th e vapo r componen t i s calculate dfro m th e followin g equation :

F . . QPM A ( C s- C a > t v- K T wher e K=5. 6 x10 " , a facto r incorporatin g conversio nfactor s an d standar dtemperatur e an dpressure , Q = flow

rat e of ga s throug hth e sampl e train , actua l cubi c feet/minute , P = samplin g system

pressur e a t th e dr y

ga s meter , psia , M . = molecula r weigh t o f th e air/VO C mixture , C = concentratio nof VO C i nth e ga s sampl e fro m th e samplin g train , pp

m b y weight , C = concentratio nof VO C inth e ambien t air , pp m b y weight , an

d T = samplin g syste m

temperatur e a t th e dr y ga s meter , R .
Th e emissio nrat e of th e organi c condensat e component , E. , i s determine d fro m th e followin g equation :

c 0- 1 V fc L " t



### C-

1P.5 4



### wher e E ^ = organi c condensat e rate , lb/hr , V = volum e o f condensat e collected , ml , an d t = time ove r whic hth e sampl e wa s collected , min .
Thi s calculatio nassume s a naverag e densit y

o f 0.7 5 g/c c fo r th e organi c condensate . Thes e equation s ca nbe modifie da s necessar y t o provid e fo r water-miscibl e compound s an dt o expres s emission s interm s o f compound s othe r tha nhexane .

C- 2P.5 5



### APPENDI XD LEA KRATE/SCREENINGVALU E EQUATION STABL E D-1 . PREDICTIO N EQUATION S FO RNONMETHAN E LEA KRAT E FO R VALVES , FLANGES , AN D PUM P SEAL S I N SOCM I PROCESSE S

SOURC E TYP E INSTRUMEN T LEAS T - SQUARE S EQUATION 1 

### NUMBER O F DATA PAIR S CORRELATIO N

COEFFICIEN T (r ) STANDAR D

DEVIATION O F ESTIMAT E

Valves * Ga s Servic e OV A NML K= 1.6 8 (10~ 5 ) (MXOVA) 0-69 3 

### 9 9 0.6 6 0.71 6
Ligh t Liqui d Servic e OV A NML K= 3.7 4 (IO" 4 ) (MXOVA) 0 * 4 7 

### 12 9 0.4 7 0.90 2

o I i Flange s OV A NML K= 3.73 1 (IO* 5 ) (MXOVA) 0 " 8 2 

### 5 2 0.7 7 0.52 0

Pum p Seals ' OV A NML K= 1.33 5 (IO" 5 ) (MXOVA) 0,89 8 

### 5 2 0.8 1 0.65 0

NML K= Nonmethan e lea k rat e (lb/hr ) MXOV A = Maximu

m screenin g valu e (ppmv ) OV A instrumen t Source : Langley , G . J. , an d R . G . Wetherol d (Radia nCorporation ) 1981 . Evaluatio no f Maintenanc e fo r Fugitiv e VO C Emission s Control . EPA-600/52-81-080 . pp . 54-56 . 'Source : Wetherold , R.G. , L.P . Provost , an d CD . Smit h(Radia nCorporation) . Assessmen t o f Atmospheri c Emission s fro

m Petroleu

m Refining : Volume 3 . Appendi xB . (Prepare d fo r U.S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , Nort hCarolina . Publicatio nNo . EPA-600/2-80-075c . 'NML Ki s give ni

nunit s o f lb/hr . Th e unit s may hav e t o b e change d fo r reportin g purposes .P.5 7



### APPENDI XE SELECTIO N O F SAMPL E SIZ E FO

RFLANG E SCREENINGAPPENDI XE SELECTIO N

O F SAMPL E SIZ E FORSCREENIN GFLANGE S AN D OTHE RCONNECTOR S

Inestimatin g emission s fo r a give nproces s unit , al l equipmen t component s mus t b e surveye dfo r eac hclas s o f components . Fo r example , al l valve s i ngas/vapo r servic e mus t b e screene dt o establis hth e numbe r o f component s ineac ho f th e give nrange s o f screenin g values . Th e on e exceptio n t o thi s "tota l componen t screening " criterio ni s th e categor y o f flange s an

d othe r connectors . I ntypica l proces s units , flange s an dothe r connector s represen t th e larges t coun t o f individua l equipmen t components , makin g i t costl y t o scree nal l components . Th e purpos e o f thi s appendi xi s t o presen t a methodolog y

fo r determinin g how man y flange s o r othe r connector s mus t b e screene dt o constitut e a larg e enoug hsampl e siz e t o identif y th e actua l screenin g valu e distributio no f flange s an dothe r connector s inth e entir e proces s unit . Pleas e not e tha t th e samplin g i s t o b e a rando m samplin g throughou t th e proces s unit . Th e basi s fo r selectin g th e sampl e populatio nt o b e screene di s th e probabilit y

tha t a t leas t on e "leaking " flang e wil l b e i nth e screene d population . Th e "leaker " i s use da s a representatio no f th e complet e distributio no f screenin g value s fo r th e entir e clas s o f sources . Th e followin g binomia l distributio nwa s develope dt o approximat e th e numbe r o f flange s an

dothe r connector s tha t mus t b e screene dt o ensur e tha t th e entir e distributio no f screenin g value s fo r thes e component s i s represente dinth e sample :

n> N

* [ 1 - ( 1 -p) 1/D ] (E-1 ) wher e D ma y

b e take na s (fractio no f leakin g flanges ) * N an dp> 0.95 . Currentl y

availabl e dat a gathere dfo r flange s inVO C servic e inchemica l proces s unit s show

a nestimate d2.0 9 percen t flange s leaking . Th e EPA recommend s startin g wit hth e facto r 0.020 9 fo r th e fractio no f leakin g flanges , sinc e th e actua l lea k frequenc y fo r flange s ina chemica l proces s uni t probabl y

wil l no t b e know

nprio r t o th e selectio no f a sampl e siz e fo r screening . A

large r sampl e siz e wil l b e require dfo r unit s exhibitin g a lowe r fractio no f leakin g flange s an dothe r connectors . I f a lowe r lea k frequenc y



### E- 1

.P.59

_



### fo r a proces s uni t i s know no r canb e estimated , i t ma y be substitute dint o th e equatio nabov e inplac e o f 0.0209 . Afte r 'n ' flange s hav e bee nscreened , a nactua l lea k frequenc y

shoul db

e calculate da s follows :

Leakin g Frequenc y

= Numbe r o f leakin g flange s (£ 

### . 2 )


### Then , th e confidenc e leve l o f th e sampl e siz e ca nb e calculate dusin g th e followin g equation , base dupona hypergeometri c distribution :

p

### _. (N-D') l (N-n) ! Y 

### ~L

### N ! (N-D'-n) ! (E-3) wher e N = Tota l populatio no f flange s an dothe r connector s n= Sampl e siz e
D 

### , _Numbe r o f leakin g flange s an dconnector s * N 

### n I f 'p ' calculate dinthi s manne r i s les s tha n0.95 , the na les s tha n 9 5 percen t confidenc e exist s tha t th e screenin g valu e distributio nha s bee n properl y identified . Therefore , additiona l flanges/connector s mus t b e screene dt o achiev e a 9 5 percen t confidenc e level . Th e numbe r o f additiona l flange s require dt o satisf y th e requiremen t fo r a 9 5 percen t confidenc e leve l canb e calculate db

y solvin g Equatio n(E-1 ) again , usin g th e lea k frequenc y calculate dinEquatio n(E-2) , an dsubtractin g th e origina l sampl e size . Afte r thi s additiona l numbe r o f flanges/connector s hav e bee nscreened , th e revise d fractio no f leakin g component s an dth e confidenc e leve l o f th e ne w sampl e siz e (i.e. , th e origina l sampl e siz e plu s th e additiona l flanges/connector s screened ) shoul dbe recalculate dusin g Equatio n(E-3) . Th e Agenc y require s sufficien t screenin g t o achiev e a 9 5 percen t confidenc e level , unti l a maximu m o f 5 0 percen t o f th e tota l numbe r o f flange s an dothe r connector s inth e proces s uni t hav e bee nscreened . Th e EPA believe s tha t 5 0 percen t o f th e tota l flange/connecto r populatio ni s a reasonabl e uppe r limi t fo r a sampl e size . I f hal f o f th e tota l numbe r o f flange s an dothe r connector s ar e screened , n o furthe r flang e screenin g i s necessary , eve ni f a 9 5 percen t confidenc e leve l ha s no t bee nachieved .

E- 2P.6 0



### APPENDI XF

DETERMINATIO N

O F EMISSION

RATE S FOR DEFAUL T ZER O SCREENINGVALUE SP.6 1

APPENDI XF

DETERMINATIO N

O F EMISSIO N

RATE S FOR DEFAUL T ZER O SCREENIN GVALUE S

Indevelopin g emissio nestimate s usin g correlations , th e emission s associate dwit hzer o screenin g value s ar e estimate dusin g defaul t emissio n rates . Du e t o thei r logarithmi c form , th e correlation s estimat e zer o emission s fo r zer o screenin g values . Fiel dtesting , however , indicate s tha t ther e ar e finit e emission s associate dwit hequipmen t screenin g a t th e backgroun dconcentrations . T o accoun t fo r thes e emission s inth e protocol , EP A ha s establishe dsome defaul t zer o screenin g value s an dthei r associate d emissio nrate s base dondat a gathere ddurin g th e SOCM I Maintenanc e Study . Twelv e dat a pair s fo r valve s ingas/vapo r servic e wer e bagge dt o determin e mas s emission s durin g th e Maintenanc e Study . Th e mas s emissio n rate s fo r thes e twelv e source s wer e average dt o establis hth e emissio nrat e fo r gas/vapo r valve s screenin g a t 0 pp m abov e th e backgroun dlevel . Thi s averag e emissio nrat e i s 0.00003 3 kilogram s pe r hou r pe r source . Usin g th e S0CMI/0V A correlatio nfo r gas/vapo r valve s show ninAppendi xD an

dthi s emissio nrate , th e "defaul t zero " screenin g valu e wa s establishe d( 8 ppm) . Al l component s screenin g a t o r belo w thi s defaul t screenin g valu e ar e assume d t o hav e anemissio nrat e equa l t o th e defaul t zer o emissio nrate . No mas s emission s dat a fo r zer o screenin g value s wer e availabl e fo r equipmen t component s othe r tha nvalve s ingas/vapo r service . Th e defaul t zer o emissio nrate s fo r al l equipmen t type s andservice s wer e establishe dusin g th e correlation s show

ninAppendi xD an

dth e defaul t zer o screenin g valu e ( 8 ppm- ) calculate dfrom

th e gas/vapo r valve s baggin g data .
Equipmen t Type/Servic e Valves , ga s Valves , ligh t liqui d Flange s Pump s andal l othe r component s "Defaul t Zero " Screenin g Value , DD

m 

### 8 8 8
s 8 Zer o Screenin g Valu e Emissio n Rat e (kg/hr/source ) 0.00003 3 0.00045 1 0.00009 3 0.00003 9



### F- lP.6 2



### APPENDI XG

DEVELOPMEN T O F A

DEFAUL T EMISSION

RAT E FOREQUIPMEN T THA T DOE S NO T SCREE N ABOV E TH E BACKGROUN D CONCENTRATIO N

Tex t adapte dfro

m Guidanc e fo r Estimatin g Fugitiv e Emissions , publishe db y th e Chemica l Manufacturer s Association .APPENDI XG DEVELOPMEN T O F A

DEFAUL T EMISSIO N

RAT E FOREQUIPMEN T THA T DOE S NO T SCREE N

ABOV E TH E BACKGROUN D CONCENTRATION .

I f baggin g dat a fo r equipmen t component s tha t d o no t scree nabov e backgroun dd o no t exist , th e EPA defaul t emissio nrate s inAppendi xF shoul db e use dt o estimat e emission s fro m thes e sources . I f a proces s uni t intend s t o develo pit s ow ndefaul t zer o emissio nrates , i t mus t ba g sample s fro m eac hequipmen t typ e (e.g. , gas/vapo r valves , ligh t liqui dvalves ) fo r whic hi t plan s t o determin e defaul t zer o emissio nrates . I f baggin g dat a exist , th e firs t ste pindevelopin g a defaul t emissio nrat e i s t o adjus t fo r th e backgroun dconcentratio nb y subtractin g th e backgroun dba g fro m th e sourc e bag ; tha t is , calculat e
h • LR s, 1 - LR B, i wher e LR C . = lea k rat e fro m sourc e ba g i s , i LRp. = lea k rat e fro m backgroun dba g i
Next , tak e th e logarith m o f th e dat a an

dad da constan t (i f necessary ) t o avoi dtakin g th e logarith m o f a nonpositiv e X. . Th e followin g procedur e i s used :
Cas e 1 : I f al l o f th e dat a ar e positive , y . = log(Xi )
Cas e 2 : I f al l o f th e dat a ar e nonnegativ e wit ha t leas t on e zero ,

y / - log(X i +C ) wher e C = larges t powe r o f 1 0 les s tha nth e smalles t nonzer o valu e o f

X(e.g. , i f th e smalles t nonzer o valu e o f Xi s 8 x10 " , the nC = 1 x10"*) . Cas e 3 : I f some o f th e dat a ar e negative , th e smalles t valu e (Kl ) i s firs t subtracte dfro

m eac hobservatio ni nth e dat a se t (not e tha t K l i s a negativ e number) . Thi s result s i nal l nonnegatives , wit ha t leas t on e zer o value . The nK 2 i s adde dt o eac hobservatio ninth e set , wher e K 2 = larges t powe r o f 1 0 les s tha nth e smalles t nonzer o valu e o f th e update dnonnegativ e dat a set . Hence , th e logarithmi c expressio nuse di s
y . = log(X i + C ) wher e C = K2-K 1

G- lP.6 4

Th e average , standar d deviation , an d scal e bia s correctio nfacto r (SBCF )
ar e calculate d fo r th e Y . a s follows :

_n

ni- l 1

2 n- 2

- S ' =_]

_y

(y.-y) Z n- 1 ^ 1 i- l
SBC F = g [(lnlO) 2 (S 2 /2) ] wher e g(t ) = 1 + (n-1 ) t + (n-l) 3 t 2 + (n-l) 5 t 3 + .. . nn 2 2!(n+l ) n 3 3!(n+l)(n+3 ) (Approx . 10-1 5 term s require d t o obtai naccurac y o f + 10 " )

Th e estimat e o f emission s fo r component s screenin g below th e lowe r limi t o f detectio n(LLD ) fo r th e screenin g instrument , (EF,*) , i s then :

EFj * = ma x[(10 y SBCF)-C , 0 ]

wher e C = 0 fo r Cas e 1 , an d previousl y

state d fo r Cas e 2 an d Cas e 3 .

A statistica l tes t i s use d t o compar e th e calculate d EF, * wit hth e establishe d 'defaul t zero ' i nAppendi xF . Th e result s o f thi s tes t determin e whic hvalu e (EF, * o r 'defaul t zero' ) i s use d t o represen t emission s fo r component s screenin g below th e LLD . Th e tes t involve s tw o cases :



### G- 2P.6 5

•• > *-AA* ^



### Cas e A : I f EFj^'Defaul t zero' , the nus e EF, * i f



# 3W< y+t(.95 , n-l) V

S.y n E F U L 

### = 1 0 SBC F < 'Defaul t zero '
(Us e 'Defaul t zero ' i f EF U L 

### > 'Defaul t zero' )

Cas e B : I f EF, * > 'Defaul t zero' , the nus e EF, * i f



### y-t(.95 , n-l)Vs^ n EF L L= 1 0 SBC F > 'Defaul t zero ' (Us e 'Defaul t zero ' i f EF L L< 'Defaul t zero' )
A confidenc e interva l fo rEF , ca n b e calculate d as :



### y+tj(.975 , n-lj\fs?/n y-tj(.975 , n-ll^S 2 

### / ^ (1 0 SBCF , 1 0 SBCF )

Note : Thi s interva l shoul donl y involv e th e nonnegativ e region . I n th e cas e wher e th e abov e computatio ninclude s negativ e values , i t shoul d b e truncate dt o zero .

G- 3P.6 6

" - N -*>&•• 1 rt TECHNICA L REPOR T DAT A (Please read

Instructions on the reverse before completing)

.. REPOR T NO
. 3
. RECIPIENT' S ACCESSIO N NO
.
4
. TITL E AN D SUBTITL E Protocol s fo r Generatin g Unit-Specifi c Emissio n Estimate s fo r Equipmen t Leak s o f VO C and HA P 5
. REPOR T OAT E Octobe r198

8 6
. PERFORMIN G ORGANIZATIO N COD E

7
. AUTHOR(S ) 8
. PERFORMIN G ORGANIZATIO N REPOR T NO
.

9
. PERFORMIN G ORGANIZATIO N NAM E AN D ADDRES S 10
. PROGRA M ELEMEN T NO
.

11
. CONTRACT/GRAN T NO
. 68-02-437 8

12
. SPONSORIN G AGENC Y NAM E AN D ADDRES S Offic e o f Ai r an

d Radiatio n Offic e o f Ai r Qualit y Plannin g and Standard s U.S . Environmenta l Protectio nAgenc y Researc hTriangl e Park , Nort hCarolin a 2771 1 13
. TYP E O F REPOR T AN D PERIO D COVERE D Fina l 14
. SPONSORIN G AGENC Y COD E

15
. SUPPLEMENTAR Y NOTE S

16
. ABSTRAC T EPA ha s develope da Protoco l fo r Generatin g Unit-Specifi c Emissio nEstimate s fi r Equipmen t Leak s o f VO C an d VHAP . Th e protoco l provide s severa l method s fo r estimatin g emission s fro

m equipmen t leaks . Thes e method s rang e fro m th e applicatio no f averag e emissio nfactor s fo r th e equipmen t componen t inventor y t o th e us e o f baggin g dat a fo r generatin g unit-specifi c lea k rate/screenin g valu e correlations . In addition , th e protoco l provide s technicall y soun dmethod s o f sourc e screenin g and mas s emission s samplin g (bagging) . Th e documen t wil l hel pfacitilie s generat e accurat e plant-specifi c equipmen t lea k emissions .

17
. a . KE Y WORD S AN D DOCUMEN T ANALYSI S DESCRIPTOR S b.lOENTIFIERS/OPE N ENDE D TERM S C
. COSAT I Field/Grou p

18
. DISTRIBUTIO N STATEMEN T Unlimite d distributio n 19
. SECURIT Y CLAS S (This Report) Unclassifie d 2 1
. NO
. O F PAGE S 11 0 20
. SECURIT Y CLAS S (Thispage) Unclassifie d 22
. PRIC E

EP A For m 2220- 1 (Rev
. 4-77 ) PREVIOU S EDITIO N I S OBSOLET E3. 0 SOURC E SCREENING

Thi s sectio npresent s protocol s an dmethodologie s fo r conductin g screenin g o f equipmen t component s wit ha portabl e organi c analyzer . Th e overal l surve y

procedur e i s presente dt o giv e th e perspectiv e o f a unit^wid e screenin g plan . Inaddition , screenin g protocol s ar e give nfo r th e differen t equipmen t types . Th e selectio no f a nappropriat e portabl e monitorin g instrumen t i s discusse dan da sectio nondat a handlin g i s als o included . 3. 1 SCREENIN GSURVE YPROCEDURE S Fo r developmen t o f a unit-specifi c emissio nestimate , th e concentratio n o f organi c material s a t seals , shafts , an dothe r potentia l lea k point s mus t be measured . Inpreparin g t o scree nal l equipmen t ina unit , al l equipmen t t o be include di nth e emissio nestimat e uni t need s t o be identified . A listin g o f equipmen t type s tha t ar e potentia l source s o f fugitiv e emission s i s give nin Tabl e 3-1 . Th e firs t ste pinth e screenin g surve y i s t o defin e precisel y th e proces s uni t boundaries . Thi s i s usuall y quit e straightforward , bu t occasionall y multipl e unit s ma y

be buil t onth e same pa dan dshar e some commo nfacilities . A proces s uni t ca nbe define da s th e smalles t se t o f proces s equipmen t whic h
ca noperat e independentl y an dinclude s al l operation s necessar y t o achiev e it s proces s objective . Th e exac t basi s fo r th e uni t definitio nshoul dbe documented . A

plo t pla no f th e uni t shoul db e obtaine dan dmarke dwit hth e appropriat e boundaries . Th e nex t ste pi s t o obtaina simplifie dflow diagra m o f th e proces s an

d not e th e proces s streams . Th e actua l screenin g an ddat a collectio nca nbe don e mos t systematicall y b y followin g eac hstream . Fo r instance , a logica l startin g poin t woul db e wher e on e o f th e fee dline s enter s th e proces s boundary . Th e screenin g tea m woul dfollow

tha t line , screenin g al l sources , unti l th e lin e terminate s a t th e flange s o f a reacto r o r separatio nstep . Screenin g woul dthe ncontinu e onth e outle t sid e o f th e reacto r o r separatio n equipment . Mino r loop s lik e a bypas s aroun da contro l valve , pump , o r hea t exchange r shoul db e screene donth e initia l pass . Large r loop s o f proces s equipment , suc ha s paralle l passe s an dprocessin g alternatives , ar e mor e



### 3- 1

•MiiiiaJ^HI ^ ! "" "P.6 8



### TABL E 3-1 . FUGITIV E EMISSIO N SOURCE S
Equipmen t Type s Pum pseal s Compresso r seal s Valve s Pressur e relie f device s Samplin g connection s Flanges , screwe dconnections , etc .

Open-ende dline s Drains , vents , door s Agitato r seal s
Servic e Gas/vapo r Ligh t liqui d Heav y liqui d

3- 2P.6 9

effectivel y

treate da s separat e streams . I f th e emissio nestimat e i s bein g generate di nsuppor t o f contro l strategie s fo r individua l chemica l compounds , thi s approac hoffer s th e advantag e o f screenin g group s o f equipmen t component s wit hroughl y

th e same compositio no f material s inth e line . Eac hsourc e shoul db e uniquel y identifie dt o indicat e tha t i t ha s bee n screened . Fo r example , source s ca nb e tagged . Tag s ca nconsis t o f an y for m o f weatherproo f an

dreadil y

visibl e identification . Alternatively , a proces s uni t ca nb e considere dappropriatel y tagge di f th e uni t ha s a syste m o f identifyin g marking s wit ha nassociate ddiagra m

allowin g eas y

locatio no f marke dsources . Onc e al l th e equipmen t alon g th e majo r stream s ha s bee n screened , th e uni t shoul db e divide dint o a gri dt o searc hfo r fitting s misse d
onth e initia l survey . Th e uni t surve y i s complete dwhe nal l source s inth e uni t hav e bee neithe r screene do r identifie da s a nonhydrocarbo nfitting . Leakles s equipmen t an dequipmen t no t i

nVO C (o r VHAP ) servic e shoul dno t be include di nth e screenin g survey . Equipmen t documente da s inaccessibl e shoul d b e include dinth e survey ; suc hequipmen t mus t b e screene dannuall y unde r regulation s fo r fugitiv e emissions . Consisten t wit hequipmen t leak s standard s fo r hazardou s ai r pollutants , unsafe-to-monito r equipmen t d o no t nee dt o b e include dinth e survey . Documentatio nmus t b e provided , however , t o substantiat e th e unsaf e natur e o f
suc hequipment . 3. 2 MONITORIN GINSTRUMEN T A numbe r o f portabl e VO C detectio ndevice s ar e capabl e o f measurin g leak s fro m proces s units . Thes e device s operat e ona variet y o f principles , th e thre e mos t commo nbein g ionization , infrare dabsorption , an dcombustion . Any analyze r ca nb e use dprovide di t meet s th e specification s an dperformanc e criteri a se t fort hinEPA Referenc e Metho d21 . Referenc e Metho d2 1 i s include di nthi s documen t a s Appendi xA . Any analytica l instrument s ar e permitte dprovide dthe y ar e show

nt o measur e th e organi c compound s o f interes t an

dth e result s ar e relate dt o EPA' s dat a bas e generate dusin g a flame ionizatio ndetector , calibrate dt o methane . Analytica l instrument s reference dt o compound s othe r tha nmethan e mus t develo prespons e factor s t o relat e screenin g value s t o concentration . Thi s wil l allo w us e o f man y instrument s tha t canno t b e calibrate dwit hmethane .



### 3- 3P.7 0



### 3.2. 1 Operatin g Principle s an dLimitation s o f Portabl e VO C Detectio nDevice s Ionizatio ndetector s operat e b y ionizin g th e sampl e an dthe nmeasurin g th e charg e (numbe r o f ions ) produced . Two method s o f ionizatio ncurrentl y use dar e flame ionizatio nan dphotoionization . A standar dflame ionizatio ndetecto r (FID ) usuall y measure s th e tota l carbo nconten t o f th e organi c vapo r sampled . Althoug hcarbo nmonoxid e an d carbo ndioxid e d o no t produc e interferences , FI D analyzer s d o reac t t o wate r vapor , althoug ha t a lo w sensitivity . Furthermore , i f wate r condense s inth e sampl e tube , errati c reading s ma y result . A

filte r i s use dt o remov e particulat e matte r fro m th e sample . Whe nequippe dwit hoptions , certai n portabl e FI D instrument s ar e capabl e o f measurin g tota l gaseou s nonmethan e organic s o r individua l organi c components . Certai norgani c compound s containin g nitrogen , oxygen , o r haloge natom s whe nsample dwit hanFI D giv e a reduce dresponse ; an

dsome organic s ma y

no t giv e an

y respons e a t all . Fo r thi s reason , i t i s necessar y t o develo prespons e factor s fo r eac hcompoun d tha t i s t o b e measured . Respons e factor s ar e discusse dinSectio n3.2.2.1 . Photoionizatio ndetector s us e ultraviole t ligh t (instea do f a flame ) t o ioniz e organi c vapors . A s wit hFID's , th e detecto r respons e varie s wit hth e functiona l grou pinth e organi c compounds . Photoionizatio ndetector s hav e bee nuse dt o detec t leak s i nproces s unit s use dinth e syntheti c organi c chemica l manufacturin g industry , especiall y fo r certai ncompound s suc ha s formaldehyd e tha t wil l no t giv e a respons e o na nFI D o r combustibl e detector . Nondispersiv e infrare d(NDIR ) instrument s operat e onth e principl e o f ligh t absorptio ncharacteristic s o f certai ngases . NDI Rinstrument s ar e usuall y subjec t t o interferenc e becaus e othe r gase s suc ha s wate r vapo r an d carbo ndioxid e ma y

als o absor bligh t a t th e same wavelengt ha s a compoundo f interest . Thes e detector s ar e generall y use donl y

fo r th e detectio nan

d measuremen t o f singl e components . Fo r th e detectio nan dmeasuremen t o f singl e components , th e wavelengt ha t whic ha certai ncompoundabsorb s infrare d radiatio ni s predetermine dan dth e devic e i s prese t fo r tha t specifi c wavelengt hb

y usin g optica l filters . Fo r example , i f se t t o a wavelengt ho f 3. 4 micrometers , infrare ddevice s ca ndetec t an dmeasur e petroleu

m fractions , includin g gasolin e an

dnaphtha .

3- 4P.7 1

Combustio nanalyzer s ar e designe d eithe r t o measur e th e therma l conductivit y

o f a ga s o r t o measur e th e hea t produce d b y combustin g th e gas . Th e mos t commo nmetho duse d inportabl e VO C detectio ndevice s i s measurin g th e hea t o f combustion . Thes e device s ar e referre d t o a s ho t wir e detector s o r catalyti c oxidizers . Combustio nanalyzers , lik e mos t othe r detectors , ar e nonspecifi c fo r ga s mixtures . I naddition , combustio nanalyzer s exhibi t reduce drespons e (i nsome cases , no response ) t o gase s tha t ar e no t readil y combusted, suc ha s formaldehyd e an d carbo ntetrachloride . 3.2. 2 Performanc e Criteri a an d Evaluatio nfo r Portabl e VO C Detector s A s previousl y

stated , an

y portabl e VO C detecto r ma y b e use d a s a screenin g devic e directl y provide d i t meet s th e performanc e criteri a specifie d inReferenc e Metho d2 1 (se e Appendi xA) . Althoug hthi s approac hha s bee n show nt o b e applicabl e t o many organics , i t canno t b e universall y applied . Facilitie s ma y

nee dt o develo p a

nappropriat e metho d fo r testin g inorgani c an d
some organi c compounds . A discussio no f th e performanc e criteri a an d detecto r evaluatio nprocedur e i s presente d below an d summarize d inTabl e 3-2 . Inadditio nt o th e performanc e criteria , Referenc e Metho d2 1 als o require s tha t th e analyze r mee t th e followin g specifications :

o Th e VO C detecto r shal l respon d t o thos e organi c compound s bein g processe d(determine d b y th e respons e factor) .
o Th e analyze r shal l be capabl e o f measurin g th e lea k definitio n specifie dinth e regulatio n(i.e. , 10,00 0 ppm v o r "n o detectabl e limit") .
o Th e scal e o f th e analyze r shal l b e readabl e t o + 5 percen t o f th e specifie dlea k definitio nconcentration .
o Th e analyze r shal l b e equippe d wit ha pum ps o tha t a continuou s sampl e i s provide d a t a nomina l flow rat e o f betwee n0. 5 and 3. 0 liter s pe r minute .
o Th e analyze r shal l b e intrinsicall y saf e fo r operatio ninexplosiv e atmospheres . Also , criteri a fo r th e calibratio ngase s t o b e use d ar e specified . Two o r mor e calibratio ngase s ar e require d fo r analyze r performanc e evaluation . On e i s a zer o ga s whic hi s ai r wit hles s tha n1 0 ppm v VOC . Th e othe r calibratio ngases , o r referenc e gases , us e referenc e compound s inai r mixtures . Th e concentratio no f th e referenc e ga s shoul d represen t th e rang e
3- 5

IMHH I 

### asmP.7 2



### TABL E 3-2 . PERFORMANC E CRITERI A FO RPORTABL E VO C DETECTORS '

Criteri a Requiremen t Time Interva l
Instrumen t respons e facto r

Instrumen t respons e time

Calibratio nprecisio n Mus t b e <1 0 unles s correctio ncurv e i s used . Mus t b e <3 0 second s

Mus t b e <10 % o f calibratio nga s valu e On e time , befor e detecto r i s pu t inservice .
On e time , befor e detecto r i s pu t inservice . I f modificatio nt o sampl e pumpin g o r flow

configura tio ni s made , a new

tes t i s required . Befor e detecto r i s pu t in servic e an

da t 3-mont h interval s o r nex t use , whicheve r i s later .
Source : Referenc e Metho d21 .

3- 6

### o f response s measured . Fo r th e purpos e o f developin g unit-specifi c emissio n

estimates , a referenc e ga s fo r th e appropriat e rang e shoul db e used . 3.2.2. 1 Respons e Factor . Th e sensitivit y o f a nanalyze r varies , dependin g onth e compositio no f th e sampl e an dconcentratio ndetected . Th e respons e facto r (RF ) help s t o quantif y th e sensitivit y

fo r eac hcompound . Th e respons e facto r i s define dby :

D

### . c^ri-nv

Actua l concentratio no f compound Kespons e r-acio

r = observe dconcentratio nfro m detecto r I t i s importan t t o not e tha t th e respons e facto r ma y b e use da s a guid e t o selectin g a

nappropriat e monitorin g device . Fo r example , fro m th e dat a presente di nAppendi xB , i t ca nb e readil y see ntha t inscreenin g equipmen t in a proces s uni t containin g cumene , a nFI D canb e use d(R

F = 1.87 ) directly , wit hn o correctio nfo r respons e factor ; whil e th e catalyti c oxidationdetecto r canno t (R F ha s no value) . Similarly , fro m th e same data , neithe r o f thes e device s woul db e capabl e o f detectin g leak s fro m a sourc e containin g carbo n tetrachlorid e i f respons e facto r adjustment s ar e no t used . Usin g respons e factor s a s a genera l guid e t o analyze r applicabilit y i s especiall y

importan t whe ndealin g wit hchemica l mixtures , sinc e many proces s stream s inindustria l plant s ar e compose do f mixture s o f chemicals . On e EPA stud y conclude dtha t analyze r respons e factor s fo r a chemica l mixtur e fal l 5 betwee nth e response s expecte dfo r th e pur e components . Therefore , i f desired , aninterpolate do r weighte daverag e ca nb e use dt o predic t th e respons e fo r mixture s base donknow nresponse s fo r individua l chemicals . I f sufficien t informatio nonpur e component s i s no t availabl e o r i f desired , th e respons e facto r o f a mixtur e fo r a specifi c instrumen t ma y b e determine d experimentall y

inth e laboratory . Suc hresult s shoul db e wel l documented . Fo r furthe r informatio nse e EPA-600/2-81-110 , Respons e o f Portabl e VO C Analyzer s t o Chemica l Mixtures , an dEPA-600/2-8-051 , Respons e Factor s o f VO C A 

### Analyzer s a t a Mete r Readin g o f 10,00 0 ppm v fo r Selecte dOrgani c Compounds . Respons e factor s als o ma y b e use dt o correc t screenin g valu e measurement s gathere dt o estimat e emission s whe nusin g a nemissio nfacto r approac h(e.g. , leak/no-lea k approac ho r three-strat a approach) . I f usin g lea k rate/screenin g valu e correlations , however , a standar dcurv e coverin g th e entir e rang e o f
3- 7P.74.
.



### screenin g value s measure dmus t b e used . A respons e facto r must b e determine d fo r eac hcompoun dtha t i s t o b e measured , eithe r b y testin g o r fro

m referenc e 4 5 6 sources . ' ' A

nanalyzer' s respons e facto r fo r individua l compound s t o b e measure dmus t b e les s tha n1 0 a t o r nea r th e concentration s definin g emissio n factor s (e.g. , 1,00 0 an d10,00 0 ppmv ) t o b e acceptable . Th e respons e facto r test s ar e require dbefor e placin g th e analyze r i nservice , bu t d o no t hav e t o b e repeate da t subsequen t intervals . Respons e factor s ca nbe determine db y th e followin g method . First , th e analyze r i s calibrate dusin g th e referenc e gas . Then , fo r eac horgani c specie s tha t i s t o b e measured , a know nstandar dinai r i s obtaine do r prepared . Thi s mixtur e i s the ninjecte dint o th e analyze r an dth e observe d mete r readin g i s recorded . Th e analyze r i s the nzeroe db y injectin g zer o ai r unti l a stabl e readin g i s obtained . Th e procedur e i s repeate db y alternatin g betwee nth e mixtur e an dzer o ai r unti l a tota l o f thre e measurement s i s obtained . A

respons e facto r i s calculate dfo r eac hrepetitio nan dthe n average dove r th e thre e measurements . Alternately , i f respons e factor s hav e bee npublishe dfo r th e compound s o f interes t fo r th e combinatio no f detecto r an dcalibratio nga s desired , th e respons e facto r determinatio ni s no t required , an dexistin g result s ma y be referenced . Result s o f a study developin g respons e factor s o f FI D (Foxbor o OVA-10 8 an

d0VA-128 ) an

dcatalyti c oxidatio n(J . W . Bacharac hTL V Sniffer ) 4 analyzer s ar e presente di nTabl e B- l o f Appendi xB . Thes e respons e factor s ca nb e use dwhe ndeterminin g i f a screenin g concentratio ni s abov e o r below 10,00 0 ppmv . Th e value s ar e fo r pur e organi c chemical s only . Tabl e B- 2 o f Appendi xB present s teste dcompound s tha t appea r unabl e t o achiev e a n instrumen t respons e o f 10,00 0 ppm v a t an y feasibl e concentratio nunles s A 

### respons e factor s ar e used . Thes e singl e respons e factor s ar e adequat e fo r respons e facto r adjustment s whe nusin g on e o f th e emissio nfacto r approache s fo r estimatin g emissions . Whe napplyin g correlations , however , anaccurat e correctio nfo r th e non-linea r respons e o f a ninstrumen t i s needed . Respons e factor s mus t b e evaluate da t severa l concentration s t o establis ha correctio n curv e fo r us e intranslatin g instrumen t readings . 3.2.2. 2 Respons e Time . Th e respons e time o f a nanalyze r i s define da s th e time interva l fro

m a ste pchang e i nVO C concentratio na t th e inpu t o f a

3- 8samplin g system , t o th e time a t whic h9 0 percen t o f th e correspondin g fina l

valu e i s reache da s displaye do nth e analyze r readou t meter . Th e respons e time mus t b e equa l t o o r les s tha n3 0 seconds . Th e respons e time mus t be determine dfo r th e analyze r configuratio ntha t wil l be use ddurin g testing , an dth e respons e time tes t i s require dbefor e placin g a nanalyze r inservice . I f a modificatio nt o th e sampl e pumpin g system o r flow

configuratio ni s mad e tha t woul dchang e th e respons e time , a ne w tes t i s require dbefor e furthe r use . 3.2.2. 3 Calibratio nPrecision . Calibratio nprecisio ni s th e degre e o f agreemen t betwee nmeasurement s o f th e same know nvalue . T o ensur e tha t th e reading s obtaine dar e repeatable , a calibratio nprecisio ntes t mus t b e complete dbefor e placin g th e analyze r inservice , an da t three-mont h intervals , o r a t th e nex t use , whicheve r i s later . Th e calibratio nprecisio n mus t b e equa l t o o r les s tha n1 0 percen t o f th e calibratio nga s value . T o perform

th e calibratio nprecisio ntest , a tota l o f thre e measurement s i s require dfo r eac hnonzer o concentration . Measurement s ar e mad e b y firs t introducin g zer o ga s an dadjustin g th e analyze r t o zero . Th e specifie d calibratio nga s (reference ) i s the nintroduce dan dth e mete r readin g i s recorded . Th e averag e algebrai c differenc e betwee nth e mete r reading s an dth e know nvalu e o f th e calibratio nga s i s the ncomputed . Thi s averag e differenc e i s the ndivide db

y th e know

ncalibratio nvalu e an dmultiplie db

y 10 0 t o expres s th e resultin g calibratio nprecisio na s percent . 3.2.2. 4 Safety . Portabl e instrument s t o detec t VO C emission s fro m equipmen t lea k source s ar e require dt o b e use dinhazardou s location s suc ha s petroleum

refinerie s an

dbul k gasolin e terminals . Th e Nationa l Electrica l Cod e require s tha t instrument s t o b e use dinhazardou s location s be certifie d t o b e explosion-proof , intrinsicall y safe , o r purged . Hazardou s location s ar e divide dint o thre e classes : Clas s I , Clas s II , an dClas s III . Eac hclas s i s divide dint o two division s (Divisio n1 o r 2 ) accordin g t o th e probabilit y tha t a hazardou s atmospher e wil l b e present ; an d als o int o seve ngroup s dependin g o nth e typ e o f hazardou s materia l exposure . Group s A throug hD ar e flammabl e gase s o r vapors , an dGroup s E , F , an

dGappl y t o combustibl e o r conductiv e gases . Clas s I , Divisio n1 , Group s A , B , C , an d D location s ar e thos e i nwhic hhazardou s concentration s o f flammabl e gase s o r



### 3- 9P.7 6



### vapor s ma y

exis t unde r norma l operatin g conditions . Clas s I , Divisio n2 , Group s A , B , C , an

dD location s ar e thos e inwhic hhazardou s concentration s o f flammable s ma y

exis t onl y

unde r unlikel y

condition s o f operation . A s o f 1982 , fiv e manufacturer s produce dportabl e VO C detectio n instrument s tha t ar e certifie dt o b e intrinsicall y safe . Tabl e 3- 3 list s thes e manufacturers , approve dinstrumen t mode l numbers , instrumen t certificatio ncategories , an dperformanc e specifications . Additionally , newe r instrument s ma y

b e availabl e tha t mee t th e performanc e requirement s fo r generatin g emissio nestimates . 3.2. 3 Monitorin g Device s Fo r Difficul t Situation s I nsome cases , a monitorin g devic e ma y no t b e availabl e tha t meet s al l o f th e performanc e specification s o f Metho d21 . Fo r example , ther e ar e severa l case s (e.g. , phosgene ) wher e th e respons e facto r a t 10,00 0 ppm v i s greate r tha nte n(10) . Th e instrumen t ma y mee t al l othe r requirements , bu t fail s a s a Metho d2 1 instrumen t becaus e i t canno t mee t th e respons e facto r requirement . Th e instrumen t ca nstil l b e use dt o estimat e emission s fro m equipmen t leaks , provide dth e instrumen t i s show nt o b e sufficientl y

reliabl e i nprovidin g dat a tha t ca nb e relate dt o EPA' s dat a collecte dusin g a nOV A calibrate dt o methane . Severa l step s mus t b e take ninitiall y t o documen t th e viabilit y o f a devic e tha t fail s t o mee t th e Metho d2 1 requirements . First , a laborator y program mus t b e undertake nt o demonstrat e th e respons e o f th e monitorin g instrumen t t o th e compound s bein g measured . Thi s respons e must b e documented . Th e secon dste pinvolve s relatin g th e instrumen t respons e (i.e. , screenin g value ) t o actua l concentrations , o r i nothe r words , developin g a ninstrumen t respons e curve . Th e screenin g valu e respons e curv e mus t b e develope dfo r th e entir e screenin g valu e rang e an ddocumente ds o tha t screenin g value s take ni n th e fiel dca nb e adjuste dt o actua l concentrations . Third , th e testin g program shoul db e sufficientl y wel l documente dt o demonstrat e how th e instrumen t wil l b e use di nscreenin g equipment . (Fo r example , i f th e respons e time o f th e candidat e instrumen t exceed s th e Metho d2 1 performanc e specification , th e tes t pla nshoul dreflec t adde dscreenin g time a t eac h potentia l lea k poin t t o b e screened . Onc e thi s laborator y demonstratio nha s bee ncomplete dan

dth e screenin g valu e correctio ncurv e ha s bee nestablished , th e screenin g ca nbegin . 3-1 0TABL E 3-3 . PORTABL E VO C DETECTIO N INSTRUMEN T PERFORMANC E SPECIFICATION S

Manufa c tur e r Mode l No . Pollutant(s ) Detecte d Principl e o f Operatio n Rang e

(ppm ) Certificatio n

Bacharac hInstrumen t Co . , Sant a Clara , Californi a Combustibl e gase s Catalyti c Combustio n 0-100 Z LE L Intrinsicall y safe . Clas s I , Divisio n 1 , Group s C an d D

TL V Sniffe r Combustibl e gase s Catalyti c 0-1,00 0 an d Intrinsicall y safe . Clas s I , Combustio n 0-10,00 0 Divisio n 1 , Group s C an d D i an d Clas s I , Divisio n 2 , Group s A an d B
Foxboro , S . Norwalk , Connecticu t 0VA-12 8 Tota l hydrocarbon s FID/G C 0-1,00 0 Intrinsicall y safe . Clas s I , Divisio n 1 , Group s A , B , C an d D
OVA-10 8 Tota l hydrocarbon s FID/G C 0-10,00 0 Intrinsicall y safe . Clas s I , Divisio n 1 , Group s A , B , C and D

C J I HN USystems , Inc .

Newto n Uppe r Falls , Massachusett s

Min e Safet y

Appliance s Co . Pittsburgh , Pennsylvani a

Surve y an d Analysis , Inc. , Northboro , Massachusett s PI-10 1

4 0

O n Mar k Mode l 5 Chlorinate d hydrocarbons ,

aroma t ics , aldehydes , ketones , any

substanc e whic hU

V ligh t ionize s
Combustibl e gase s

Combustibl e gase s an d vapor s Photo ionizatio n

Catalyti c Combustio n

Therma l Conductivit y 0-20 ,

0-200 . 0-2,00 0

0-10 Xan d 0-100 X LE L

0- 5 an d 0-100 X LE L Intrinsicall y safe . Clas s I , Divisio n 2 , Group s A , B , C an d D

Intrinsicall y

safe , Clas s I , Divisio n 1 , Grou p D ; an d Clas s I , Divisio n 2 , Group s A , B , an d C
Intrinsicall y

safe . Clas s I , Divisio n 1 , Group s A , B , C an d DE-TBL.



### 3. 3 SCREENINGPROCEDURE S 3.3. 1 Calibratio nProcedure s Pretes t procedure s t o b e followe dinclud e calibratio no f th e monitorin g instrument . Th e VO C analyze r shoul db e assemble dan dstarte du

paccordin g t o th e manufacturer' s instructions . Afte r th e appropriat e warm-u pperio dan dzer o interna l calibratio nprocedure , th e calibratio nga s i s introduce dint o th e sampl e probe . Th e instrumen t mete r readou t i s the nadjuste dt o correspon dt o th e calibratio nga s value . I f th e mete r readou t canno t b e adjuste dt o th e prope r value , a malfunctio no f th e instrumen t i s indicate dan dcorrectiv e measure s shoul dbe take nbefor e use . 3.3. 2 Procedur e fo r Screenin g Equipmen t Th e mechanic s o f th e screenin g operatio noutline dinReferenc e Metho d2 1 ar e summarize di

nth e followin g discussion . Th e prob e inle t i s place da t th e surfac e o f th e lea k interfac e wher e leakag e coul doccur . (The lea k interfac e i s th e boundar y

betwee nth e proces s flui dan dth e atmosphere. ) Car e mus t b e take nt o ensur e tha t th e prob e i s hel dperpendicular , no t tangential , t o th e lea k interface . Otherwise , inaccurat e reading s wil l result . Th e prob e mus t the nb e move dalon g th e interfac e peripher y whil e observin g th e instrumen t readout . I f anincrease dmete r readin g i s observed , slowl y mov e th e prob e alon g th e interfac e wher e leakag e i s indicate dunti l th e maximu m mete r readin g i s obtained . Th e prob e inle t shoul db e lef t a t thi s maximu m readin g locatio n fo r approximatel y

two time s th e instrumen t respons e time . Th e maximu m readin g i s recorde da s th e screenin g value . Th e instrumen t measuremen t ma y excee dth e scal e o f th e instrument . Fo r example , th e readin g ma y excee d10,00 0 ppm

v whe nusin g a

nOV A analyzer . Fo r th e purpose s o f generatin g a nemissio nestimate , thes e highe r reading s als o mus t b e recorded . A

dilutio nprob e shoul db e employe dt o allow measuremen t o f concentration s greate r tha nth e instrument' s norma l range . Th e OV A ca nb e equippe dwit ha dilutio nprob e tha t permit s measuremen t o f concentration s u p t o 100,00 0 ppmv . I t i s importan t t o not e tha t extendin g th e measuremen t rang e als o necessitate s th e calibratio no f th e instrumen t t o th e highe r concentrations . Car e shoul db e take nt o avoi dfoulin g o f th e prob e wit hgrease , dust , o r eve nliquids . A

shor t piec e o f Teflo ntubin g ca nb e use da s a prob e ti p

3-1 2P.7 9

extende r an

dsnippe dof f a s th e ti pfouls . I narea s wit ha noticeabl e particulat e loading , thi s tubin g ca nb e packe d wit huntreate d fiberglas s t o ac t a s a filter . (Not e tha t th e instrumen t mus t als o be calibrate d wit hthi s filte r inplace) . I f a surfac e t o b e screene d i s obviousl y dirty , hol dth e prob e ti pjus t ove r th e surfac e t o avoi d scoopin g u p contaminants . Some foulin g i s unavoidable , s o i t i s recommende d tha t th e prob e ti p sintere dstee l filte r b e cleane da t leas t dail y an d th e side-pac k filte r o na weekl y basis . Normally , thes e filter s ca nb e cleane d b y jus t rappin g them

lightl y

ona tabl e top , bu t i f th e deposit s ar e we t an dcake d on , washin g wit ha naqueou s solutio no f soa pan

dalcoho l i s recommended . Thi s ca nals o b e use d t o was h th e prob e an

dtransfe r lin e periodically . Car e shoul d b e take nt o blow th e equipmen t dr y

befor e reuse . Thi s genera l procedur e ca nbe use d t o scree nequipmen t suc ha s valves , flanges , pump s an

dcompressors , pressur e relie f devices , an dothe r potentia l
source s o f VO C leakag e suc ha s proces s drain s an d open-ende d line s o r valves . Fo r valves , th e mos t commo nsourc e o f leak s i s a t th e sea l betwee nth e ste m an dhousing . T o scree nthi s source , th e prob e i s place d wher e th e ste m exit s th e packin g gland . Th e prob e i s move daround th e ste m circumference . Th e maximu

m readin g i s recorde d a s th e screenin g value . Also , th e prob e i s place da t th e packin g glan d take-u p flang e sea t an d th e prob e i s move dalon g th e periphery . Inaddition , valv e housing s o f multipar t assemblie s shoul db e screene da t th e surfac e o f al l point s wher e leak s coul d occur . Figure s 3- 1 throug h3- 5 illustrat e screenin g point s fo r severa l differen t type s o f valves . Fo r flanges , th e prob e i s place d a t th e oute r edg e o f th e flange-gaske t interfac e andth e circumferenc e o f th e flang e i s sampled . Fo r screwe d flanges , th e threade dconnectio ninterfac e mus t als o be screened . Othe r type s o f nonpermanen t joints , suc ha s threade d connections , ar e sample dwit ha simila r traverse . Pump s an dcompressor s ar e screene d wit ha circumferentia l travers e a t th e oute r surfac e o f th e pum p o r compresso r shaf t an d sea l interfac e wher e th e shaf t exit s th e housing . I f th e sourc e i s a rotatin g shaft , th e prob e inle t i s positione dwithi n1 c m o f th e shaft-sea l interface . I f th e housin g configuratio nprevent s a complet e travers e o f th e shaf t periphery , al l accessibl e portion s mus t b e sampled . Al l othe r joint s o nth e pum p o r

3-1 3

j H BP.8 0

Scree n Her e PtekiB f au t Scree n Her e

Figur e 3-lb
. Non-risin g ste m type
.

Figur e 3-la
. Risin g ste m type
.



### Figure3-1

. Gate valves

. 3-1 4P.8 1

Ptekis f a m Scree n Her e

Bod y

Uu



### Figur e 3-2a
. Manua l Glob e Valv e Scree n Her e

Packin g

L P Du k


### Figur e 3-2b
. Glob e typ e contro l valv e

Figur e 3-2
. Glob e valves
.

3-1 5P.8 2

Screen Her e

Figur e 3-3
. Lubricate d plu g valve
.



### 3-1 6Scree n Her e

Figur e 3-4a
. Bal l valve
.

Scree n Her e

Oii k Figur e 3-4b . Butterfl y valve .

Figur e 3-4 .
3-1 7P.8 4

Oiaehrag m Scree n Her e

Figur e 3-5a . Wei r typ e diaphragm valv e

Scree n Her e

Figur e 3-5 . Figur e 3-5b . Chec k valves ,

3-1 8compresso r housin g wher e leakag e coul doccu r shoul dals o b e sampled.

Figur e 3- 6 illustrate s screenin g point s fo r two type s o f centrifuga l pumps . Agitato r seal s shoul db e screene di na simila r manner . Th e configuratio no f mos t pressur e relie f device s prevent s samplin g at th e sealin g seat . Becaus e o f thei r desig nan dfunction , pressur e relie f device s mus t b e approache dwit hextrem e caution . Thes e device s shoul dno t b e approache ddurin g period s o f proces s upsets , o r othe r time s whe nth e devic e i s likel y t o activate . Similarly , car e mus t b e use di nscreenin g pressur e relie f device s t o avoi dinterferin g wit hth e workin g part s o f th e devic e (e.g. , th e sea l disk , th e spring , etc. ) Fo r thos e device s equippe dwit ha nenclose d extension , o r horn , th e prob e inle t i s place da t approximatel y th e cente r o f th e exhaus t are a t o th e atmosphere . Again , onl y th e prob e shoul dbe place di n th e horn ; personne l conductin g th e screenin g shoul dno t plac e hands , arms , o r an y part s o f th e bod

y int o th e horn . Figur e 3- 7 illustrate s th e screenin g point s fo r a spring-loade drelie f valve . Fugitiv e leak s fro

m mos t othe r source s suc ha s proces s drains , open-ende d line s o r valves , an

dsea l system

degassin g vent s an

daccumulato r vents , ar e emitte dthroug ha regularl y shape dopening . I f tha t openin g i s ver y smal l (a s i nsamplin g line s o f les s tha non e inc hdiameter) , a singl e readin g inth e cente r i s sufficient . Fo r large r opening s (lik e a si xinc hdrai nmouth) , i t i s necessar y

t o travers e th e perimete r o f th e opening . Th e concentratio nat th e cente r mus t als o b e read . Fo r eve nlarge r source s (lik e a wash-u pdrai n grate) , a gri do f reading s shoul db e take nonabou t si xinc hcenters . Fo r acces s doo r seals , th e prob e inle t i s place da t th e surfac e o f th e doo r sea l fo r th e periphera l traverse . Fo r al l o f thes e type s o f equipment , i t i s th e maximu m valu e tha t i s recorde da s th e screenin g concentration . 3. 4 DAT A

HANDLIN G T o handl e th e screenin g dat a uniformly , i t i s recommende dtha t dat a be recorde do nprepare ddat a sheets . Th e dat a collecte dshoul dinclud e th e following : 1 . Date . 2 . Hydrocarbo ndetecto r type . 3 . Sourc e identification . (I f permanen t ID' S ar e no t inplace , assig n ID' s consecutivel y

a s eac hsourc e i s screened . Th e firs t sourc e screene di s assigne dID1 , th e secondsourc e screened , ID2 , an ds o on. ) 3-1 9

SXMMP.8 6

Mevia f ibsh



### Figur e 3-6a . Vertica l centrifuga l pump .

Figure 3-6b . Horizonta l centrifuga l pum p Figur e 3-6 . 3-2 0P.8 7

Screen Her e

Figur e 3-7 . Sprin g loade drelie f valve .

3-2 1P.88

_

4 . Screenin g valu e recorde di nppmv . 5 . Sourc e typ e (i.e. , typ e o f valve , pump , compressor , flange , etc. ) 6 . Service . Fo r example , gas , ligh t liquid , an d heav y liquid . Liquid s ar e classifie dbase d onthei r mos t volatil e componen t presen t a t 2 0 weigh t percen t o r more . I f th e component s hav e a tota l vapo r pressur e equa l t o o r greate r tha n0.0 4 ps i a t 2 0 C , th e materia l (containin g greate r tha no r equa l t o 2 0 percen t VOC ) i s classifie d a s a ligh t liquid ; i f not , i t i s classifie d a s a heavy liquid . Classificatio ni s base d upo nth e actua l proces s conditions , no t ambien t conditions . 7 . Comments . I f an y explanatio ni s required , i t shoul d b e note dina "comments " section . A nexampl e dat a shee t i s give ninTabl e 3-4 . Insome cases , i t ma y b e necessar y

o r desirabl e t o adjus t th e screenin g value s fo r respons e factor . I nthes e cases , th e dat a shee t shoul d b e designe d t o accommodat e extr a column s fo r respons e facto r an d correcte d screenin g values . 3. 5 CALIBRATIO N

PROCEDURE S FORQUALIT YASSURANC E Calibratio nprocedure s mus t b e use d fo r qualit y contro l t o ensur e th e collecte ddat a ar e o f hig hqualit y an d ca nb e compare d t o th e dat a already gathere db

y EPA . Eac hscreenin g instrumen t shoul d be checke dfo r calibratio nbefor e eac h
us e an dreading s fro

m thes e check s recorded . A s a nexample , instrument s shoul db e calibrate deac hmornin g befor e us e an d befor e us e inth e afternoon . Th e calibratio nshoul dals o b e checke d periodicall y (suc ha s durin g break s in th e dail y

testin g schedule ) t o ensur e tha t calibratio nha s no t drifted . Th e instrument s shoul db e calibrate d i f th e readin g i s of f b y mor e tha n+5 % onth e hig hstandard , o r +2 0 o nth e low standard . I f mor e tha non e instrumen t i s bein g use da t on e proces s unit , th e calibratio nreading s fo r al l instrument s mus t be recorded .

3-2 2TABL E 3-4 . EXAMPL E DAT A SHEE T

o o i r o Nv O | Hydrocarbo n Detector | Sourc e | Screenin g Valu e | Proces s | | Primar y |

Dat e | Type | I D j (ppmv ) J Uni t j Servic e j Materia l j Comment s

1 I I I I 1 1P.9 0

SECTIO N 4. 0 MAS S EMISSION S SAMPLING

Th e proces s o f measurin g organi c concentration s a t potentia l lea k point s o f equipmen t whe ncombine dwit hth e EPA' s leakin g an dnon-leakin g emissio n factor s give s a goo destimat e o f th e lea k rat e fro m a proces s unit . Mor e rigorou s procedure s ma y be use dt o determin e th e mas s emissio nrat e mor e accurately . Measurin g mas s emissio nrate s require s sourc e enclosur e combine d wit hsamplin g o f th e ga s inth e enclosure . Th e dilutio no r vacuu m metho di s th e preferre dtechniqu e fo r samplin g th e emission s fro m source s tha t ca nbe enclosed . A

nalternat e samplin g techniqu e i s th e blow-throug hmetho dwhic hi s usuall y use dfo r source s wit hver y larg e lea k rate s (i nexces s o f th e vacuu m pum pcapacity) . A

nimportan t ste pineithe r o f these methods , however , i s sourc e enclosure , a procedur e calle dbagging . 4. 1 VACUU

M METHO D Inth e past , th e metho dpreferre dfo r samplin g leak s fro m baggabl e source s ha s bee nth e dilutio no r vacuu m method . Th e samplin g trai nuse di n thi s metho di s show

ninFigur e 4-1 . Th e trai nca nbe mounte do na portabl e cart , whic hca nb e easil y move d
aroundth e proces s uni t fro m sourc e t o source . Th e majo r equipmen t item s i n th e samplin g trai nar e th e vacuu m pum puse dt o dra w

ai r throug hth e system , an dth e dr y

ga s mete r use dt o measur e th e flo w rat e o f ga s throug hth e train . I npreviou s studie s tha t EPA conducted , a 4. 8 CFM Teflon-rin g pisto ntyp e vacuu m pum pequippe dwit ha 3/4-horsepowe r air-drive nmoto r wa s used . Low pressur e ai r (-10 0 psig ) i s availabl e a t o r nea r mos t proces s units . A n exampl e o f a suitabl e dr y ga s mete r i s a Rockwel l Mode l 175 5 Tes t Ga s Mete r 1 2 wit ha Numbe r 8 3 Tes t Index . Othe r equipmen t tha t EPA use dinth e trai n include s White y

valves , coppe r an

dstainles s stee l tubing , Teflo ntubing , 10 0
c c glas s airtigh t syringe , thermometers , mercur y an dwate r manometers , a col d trap , an da nair-drive ndiaphragm samplin g pump . Th e lea k sourc e i s show na s a valve i nFigur e 4-1 . However , th e same samplin g trai nca nbe use dfo r al l equipmen t t o b e sample dusin g th e vacuu m technique . A s describe di nSectio n4.3 , th e siz e an dshape o f th e enclosur e (tent ) aroundth e potentia l lea k poin t i s adjuste dt o fi t th e particula r shap e

4- 1

E2BBMagneheli c

i r o Thi s lin e shoul d be as shor

t a s possibl e

Ten t
J " l| J L | A Col d Tra p L_| L r

§J (Ic e toth) Leakin g Valv e Tra p

Vacuu m Pum p DryGa s Mete r
Sampl e Ba g Smal l Diaphrag m Pum p Tw

o Wa y Valv e
Figur e 4-1
. Samplin g trai n fo r baggabl e source s o f hydrocarbo n emission s usin g a diaphragm
.an doperatin g conditio no f th e equipment . Whe nth e ful l samplin g trai ni s connected , th e vacuu

m pum pi s abl e t o maintai na maximu m flow rat e o f approximatel y

2. 5 cubi c fee t pe r minut e (0.00 1 cubi c meter s pe r second) . Th e ten t i s connecte db y mean s o f a bulkhea dfittin g an dTeflo ntubin g t o th e samplin g train . A separat e lin e i s connecte dfro m th e ten t t o a magnaheli c t o allow

continuou s monitorin g o f th e pressur e insid e o f th e tent . I f a significan t vacuu m exist s insid e th e ten t whe nai r i s bein g pulle d through , a hol e i s mad e inth e opposit e sid e o f th e ten t fro m th e outle t t o th e samplin g train . Thi s allow s ai r t o ente r th e ten t mor e easil y an dthu s reduce s th e vacuu

m inth e enclosure . I npractice , i t ha s bee nfoundtha t onl y a yery sligh t vacuu

m (0. 1 inche s H-0 ) i s presen t inth e ten t durin g mos t o f th e sampling , eve ni nth e absenc e o f a hol e throug hth e ten t wall . Sufficien t ai r enter s aroun dth e seal s t o preven t th e developmen t o f a significan t vacuu m inth e tent . Sampl e bag s ar e use dt o collec t ga s sample s an dtranspor t the

m t o th e laborator y

fo r analysis . A s wit hth e ten t material , sampl e bag s mus t b e constructe do f materia l tha t i s impermeabl e t o hydrocarbon s s o tha t th e proces s component s ar e containe dwithi nth e sampl e bag . Myla r plastic , Teflon , an

dTedla r ar e material s wel l suite dt o thi s function . A typica l sampl e ba g i s show

ni nFigur e 4-2 . A col dtra pi s place di nth e system t o condens e wate r an dheav y organics , thu s preventin g condensatio nindownstrea m line s an

dequipment . Th e col dtra p ca nbe simpl y

a 50 0 m

l flas k i na

nic e bat hplace da s clos e a s possibl e t o th e tent . Whil e no t alway s necessary , thi s ic e bat hcol dtra pi s ver y effectiv e i npreventin g condensatio ni nth e remainde r o f th e samplin g trai nan dinth e ga s sampl e bag . An y

organi c condensat e tha t collect s i nth e col dtra pmus t b e measure dfo r late r us e i ncalculatin g tota l lea k rates . Onsome stream s th e us e o f a col dtra pi s critical . Th e flow rat e throug hth e system ca nb e varie db

y throttlin g th e flow wit ha contro l valv e immediatel y upstream

o f th e vacuu

m pump . A s th e flow rat e i s decreased , th e concentratio no f hydrocarbo nincrease s i nth e ga s flowin g throug hth e samplin g system . Thi s allow s considerabl e flexibilit y in avoidin g operation s wit ha nexplosiv e mixtur e o f hydrocarbo ni nth e air . I f
a nexplosiv e mixtur e i s present , th e blow-throug hmetho dshoul db e used .



### 4- 3P.9 3

Figur e 4-2 . Myla r plasti c sampl e bag ,



### 4- 4I nsummary , th e vacuu

m samplin g procedur e consist s o f th e followin g steps :
• Obtai nan

drecor da screenin g valu e wit hth e portabl e hydrocarbo n detector , • Enclos e th e sourc e i na tigh t shroud , • Connec t th e ten t t o th e samplin g train ,
• Immers e th e col dtra pina nic e bath ,
• Not e th e initia l readin g o f th e dr y ga s meter ,
• Star t th e vacuu

m pum pan da stopwatc hsimultaneously ,
• Recor dth e temperatur e an dpressur e a t th e dr y ga s meter , • Observ e th e VO C concentratio na t th e vacuu m pum pexhaus t wit hth e hydrocarbo ndetector , • Recor dth e temperature , pressure , dr y ga s mete r reading , outle t VO C concentratio nan

delapse dtime eyery

2 t o 5 minutes , • Fil l a ga s sampl e ba g fro m th e discharg e o f th e Teflon-line d diaphragm

pum pwhe nth e outle t VO C concentratio nstabilize s (i.e. , th e system

i s a t equilibrium) , § Fil l anothe r ba g wit hambien t ai r nea r th e ten t are a t o detec t * th e backgroun dVO C concentration , • Tak e a fina l se t o f reading s an dsto pth e vacuu

m pump ,
• Remove , seal , an dtranspor t th e col dtra pi s t o th e laborator y alon g wit hth e two ba g sample s an dth e dat a sheet , • Remov e th e tent , • Rescree nth e sourc e wit hth e portabl e hydrocarbo ndetecto r an d record . Al l o f th e abov e dat a an dan y pertinen t comment s shoul dbe recorde dina permanen t laborator y

notebook . * Thi s ba g sampl e ma y

b e omitte di nfavo r o f th e hydrocarbo ndetecto r readin g i f th e backgroun dVO C concentratio ni s les s tha n5 percen t o f th e lowe r limi t o f th e screenin g rang e (i.e. , <5 0 pp m fo r th e 1,00 0 t o 10,00 0 pp m class) . Whe nbaggin g a "zero " screenin g valu e component , i t i s extremel y importan t t o tak e a backgroun dbag . Dat a obtaine dwithou t a backgroun dba g wil l bia s emissio nfactor s o nth e highsid e unles s thi s correctio ni s made .



### 4- 5P.9 5

4. 2 BLOW-THROUG H METHOD 3 Blow-throug hrefer s t o blowin g nitroge nthroug ha flexibl e ten t t o creat e a constan t VO C concentratio ninsid e th e tent . Nitroge ni s metere dint o th e ten t throug h1 o r 2 polyviny l chlorid e tubes . Th e temperatur e an doxyge n concentration s ar e measure dinsid e th e ten t wit ha platinum-RTD.thermocoupl e anda noxygen/combustibl e ga s monitor . Th e flow o f nitroge ni s monitore di na ga s rotamete r calibrate dt o nitrogen . Th e nitroge npasse s thoug hactivate d charcoa l anddrierit e t o remov e an y organic s and ; moisture . Th e pressur e i n th e ten t neve r exceed s 1 psig . Figur e 4- 3 illustrate s th e equipmen t require d fo r th e blow-throug hmethod . A t leas t two OV

A (Foxbor o 10 8 Organi c Vapor 1 Analyze r ) measurement s ar e mad e insid e th e tent , eac hmeasuremen t a t two o r mor e differin g nitroge nflo w rate s t o increas e accuracy . [Th e OV A mus t b e attache dt o a dilutio nprob e an d calibrate dt o nitrogen-dilute dgase s t o allow it s us e i

nth e nitroge n atmospher e i nth e tent. ] Th e OV A reading s ar e converte dt o emissio nrate s o f VO C vi a respons e factor s fo r th e OVA ; th e calculatio ni s show ninTabl e 4-1 . Alternatively , ga s sample s fro m th e ten t ca nb e collecte dwit ha portabl e samplin g pum

pan dtransporte dt o a la bfo r chemica l speciatio nan d concentratio nmeasurement . Th e calculatio ni nTabl e 4- 1 i s als o applicabl e fo r concentration s measure dinthi s manne r (excep t tha t th e respons e facto r i s se t equa l t o 1) . Th e oxyge nconcentratio ni s als o measure dt o determin e th e tota l ga s flow rat e throug hth e tent . However , oxyge nconcentratio ni s als o use dt o rat e th e qualit y o f th e tent , an

dexcep t fo r a few

extremel y

difficul t situations , VO C concentration s ar e no t measure dunti l th e oxyge nconcentratio ni nth e ten t i s reduce dbelo w

5% . Ai r ca nreplac e nitroge na s a dilutio nga s i f th e hydrocarbo n concentratio ni s no t expecte dt o b e hig henoug ht o caus e a nexplosiv e atmospher e insid e th e tent . However , calculation s base donai r ten t dat a mus t
assum e a nomina l ten t leakag e rate , i.e. , extr a flow throug hth e ten t du e t o ai r enterin g th e ten t tha t i s no t metere dthroug hth e tubing . Safet y ha s bee na ke y

facto r i nth e developmen t o f thi s procedure . Ove r 40 0 valve s hav e bee ntente dwit hthi s techniqu e withou t incident . Nitroge ni s

a Tex t adapte dfro

m Chemica l Manufacturer s Association , Guidanc e fo r Estimating Fugitiv e Emissions , July , 1987 . 4- 6I Pressur e Plan t Regulato r Nitroge n •>— • (o r Air )

Activate d

Charcoa l 1/4 " Insulate d Teflo n Tubin g
Valv e Ste m

Tap e o r Adjustabl e Meta l Ban d

Sampl e Por t fo r Collectin g Oat a o n

—Temperatur e

—Hydrocarbo n Concentratio n

—Oxyge n Concentratio n

Tap e o r Compresse d Foi l

Figur e 4-3 . Equipmen t require d fo r th e blow-throug hsampling technique .

### TABL E 4-1 . CALCULATIO N PROCEDURE S FO

RTENTE D LEA

KRAT E

Ten t rat e
_

4.83 6 xIO" 5 

### (QHMWHOVAHRF ) (lb/hr ) " T + 46 0 wher e Q = flow

rat e int o ten t incubi c meters/hou r N , flo w rat e i nliters/minut e m 

### 3 m 

### . -ll4 

### . / % 

### = 2 I- Q Q C m -minute- . , ,ten t oxvoe nconcentratio ni n% > L 

### ' liter-hour- 1 

### i - l 2 1 

### )
MW * = molecula r weigh t o f ga s i npounds/pound-mol e T = temperatur e i nten t i n° F OV A = instrumen t readin g minu s backgroun dreading , i nvpp m RF* * = respons e facto r fo r leakin g ga s relativ e t o calibratio nga s

_ 5 4.83 6 x1 0 = a conversio nfacto r takin g int o accoun t th e ga s constan t an d assumin g a pressur e i

nth e ten t o f 1 atmospher e

* 

### Fo r mixtures : ga s molecula r weigh t = (mol e fraction-ga s 1)(molecula r weight-gasl ) + (mol e fraction-ga s 2)(molecula r weight-ga s 2 ) + .. .
* * 

### Fo r mixtures : ga s respons e facto r = (mol e fraction-ga s 1)(response factor-ga s 1 ) + (mol e fraction-ga s 2)(respons e factor-ga s 2 ) + .. . wher e respons e facto r i s calculate da t th e OV A concentration . Fo r liqui d mixtures , a detaile danalysi s base donvapor-liqui dequilibriu m mus t be don e t o us e OV

A concentrations .

4- 8use da s a dilutio nga s instea do f ai r t o preven t a nexplosiv e atmospher e withi nth e tent . Al l o f th e instrument s use dar e battery-operate dan d approve dfo r Clas s I , Divisio nI use . I nsummary , th e blow-throug hmetho d consist s o f th e followin g steps :
o Intervie w

th e uni t operato r t o determin e th e compositio no f th e materia l i nth e designate dequipmen t componen t (i nweigh t o r volum e % ) , an dth e operatin g condition s o f th e component .
o Scree nth e componen t b y placin g a Tygo nnozzl e o nth e endo f th e Foxboro/Centur y

OV A (Organi c Vapo r Analyzer) , holdin g th e en do f th e nozzl e withi n1 centimete r o f th e lea k interface , an drecordin g th e highes t concentratio nsee nonth e OV A readout .
o Cu t a ten t fro

m appropriat e materia l (se e sectio n4. 3 - Sourc e Enclosure ) tha t wil l easil y fi t ove r th e equipmen t component .
o Connec t tubin g fro m th e neares t lo

w pressur e nitroge nstatio nt o a rotamete r stand , whic hinclude s a regulator , dessicant , activate d charcoal , an

da rotamete r inseries .
o Ru ntubin g fro

m th e rotamete r outle t t o a "Y " tha t split s th e nitroge nflow

int o two piece s o f tubing . Inser t th e tube s int o opening s locate doneithe r sid e o f th e tent .
o Tur no

nnitroge na t th e utilitie s statio nan dregulat e i t a t th e rotamete r t o approximatel y 4 0 liters/minute .
o Afte r th e nitroge ni s flowing , wra paluminu m foi l aroundthose part s o f th e equipmen t componen t wher e ai r coul dente r th e tent-enclose d volume .
o Us e duc t tape , wire , and/o r rop e t o secur e th e ten t t o th e component .
o Pu t a thir dhol e i nth e ten t roughl y equidistan t fro

m th e tw o nitrogen-fe dholes .
o Measur e th e oxyge nconcentratio ninth e ten t b y insertin g th e lea d fro m a n0 » mete r int o th e thir dhole . Adjus t th e ten t (ad d additiona l tape , foil , rope , etc. ) unti l th e 0 2 concentratio ni s les s tha n5% .
o Measur e th e temperatur e inth e ten t wit ha platinum-RT D thermocouple .
o Calibrat e th e OV A t o methan e o r hexan e a t a know nconcentratio nin nitroge nusin g th e OV A dilutio nprobe . Remembe r t o correc t fo r th e dilutio nbefor e insertin g th e OV A concentratio nreadin g int o th e calculatio ni nTabl e 4-1 . 4- 9o Chec k th e VO C concentratio na t severa l point s inth e ten t wit hth e OV A t o insur e tha t th e ten t content s ar e a t steady state .
o Measur e th e hydrocarbo nVO C concentratio ni nth e ten t wit hth e OV A a t thre e differen t nitroge nflo w rates . Typicall y

th e flow

rate s wil l b e 40 , 3 0 an

d 2 0 liters/minut e i f ther e i s n o OV A respons e a t th e highe r rate s (i.e. , th e mas s lea k rat e fro m th e componen t i s ver y low) . Afte r eac hadjustmen t o f th e nitroge nflow , chec k th e 0 ? concentratio nt o ensur e i t stay s below 5% . Alternatively , collec t sample s inTedla r o r aluminize d sampl e bag s b y drawin g sampl e ou t o f th e ba g wit ha portabl e samplin g pump .
o Remov e th e ten t an d an y plug s fro

m th e componen t an

d collec t an

y condensat e onth e insid e o f th e ten t i na plasti c graduate d cylinder . Recor d th e amoun t collecte d an d th e elapse d tim e th e ten t wa s onth e component .
o I f ther e i s liqui d drippin g fro m th e component , collec t th e drip s fo r a time dperio dwhic hproduce s enoug hcollecte d materia l fo r accurat e volume measurement . Recor d th e amoun t inth e report , bu t d o no t ad

di t t o th e vapo r lea k rate . 4. 3 SOURC E ENCLOSUR E T o measur e th e lea k rat e fro m an y give nfittin g accurately , i t i s necessar y

t o isolat e tha t fittin g fro m th e ambien t air . Thi s i s accomplishe d b y anenclosur e (o r tent ) forme d aroun d th e lea k source . Appropriat e ten t materia l mus t b e selected , s o tha t th e substance s foundi nth e proces s flui d
ar e containe dwithi nth e tent . Fo r example , becaus e polyethylen e i s permeabl e t o hydrocarbons , i t i s a ninappropriat e ten t material . By comparison , Myla r plasti c (polyethylen e terephthalate ) i s wel l suite d t o thi s functio na s i t doe s no t absor bsignifican t amount s o f hydrocarbons , i t i s ver y tough , an

di t ha s a highmeltin g poin t (250°C) . Othe r suitabl e material s ar e Tedla r (PV F film ) an dTeflo n(fluorocarbo nresin) . Fo r convenience , Myla r wil l b e use d a s a nexampl e o f ten t materia l i nth e followin g discussions . Th e thicknes s o f th e ten t materia l ca nrang e fro m 1. 5 t o 1 5 mi l dependin g onth e typ e o f equipmen t bein g bagged . A typica l ten t i s show ni nFigur e 4-4 . Th e enclosure s shoul db e kep t a s smal l a s practical . Thi s ha s severa l beneficia l effects :
o th e time require d t o reac hequilibriu m i s kep t t o a minimum , o th e tim e require dt o construc t th e enclosur e i s minimized , o a mor e effectiv e sea l result s fro m th e reduce d sea l area , an d



### •1 0,fpr»H_Mi-.i,- « •-•-•>•jr^i'---**-'

- P. 1

Surgica l tubin g pressur e ta p

Outlet t o pum p

Figur e 4-4
. Ten t constructio n aroun d th e sea l are a o f a vertica l pump.

4-1 1_EL2.
.

o condensatio no f heav y hydrocarbon s insid e th e enclosur e i s minimize d
o r prevente ddu e t o reduce dresidenc e time an ddecrease d surfac e are a availabl e fo r hea t transfer . Ten t constructio nfo r individua l source s i s discusse d inth e section s 4.3. 1 throug h4.3.5 . 4.3. 1 Valve s Th e mos t importan t propert y o f th e valv e tha t affect s th e typ e o f enclosur e (tent ) selecte dfo r us e i s th e meta l ski ntemperatur e o f th e are a enclose db

y th e ten t an

daround whic hth e sea l i s made . A t ski ntemperature s o f 400° F o r less , th e valv e ste m and/o r ste

m suppor t
ca nb e wrappe dwit h1.5-2. 0 mi l Myla r an d seale d a t eac hen

d an d a t th e sea

m wit hduc t tape . A

leak-tigh t sea l i s no t require d whe nth e vacuu m metho d o f lea k measuremen t i s used . Actually , i t i s bette r t o allo w fo r some area s o f incomplet e sealin g t o provid e acces s fo r ai r bein g draw nthroug hth e ten t b y th e vacuu

m pum pin.th e samplin g train . Two bulkhea dfitting s ar e the nattache d t o th e Myla r tent . On e i s fo r th e wate r manomete r o r differentia l pressur e gaug e connection , an d th e othe r i s fo r th e lin e t o th e samplin g train . If , afte r startin g th e sampling , a vacuu m greate r tha n0. 1 inche s o f wate r i s foundt o exis t inth e tent , a hol e ca nb e adde donth e sid e o f th e ten t opposit e th e outle t t o th e samplin g train . Thi s provide s a nadditiona l entranc e fo r th e dilutio nair , an d reduce s th e vacuu

m inth e ten t whil e sampling . Th e Myla r ten t mus t b e constructe d t o enclos e th e valv e ste m sea l an

d th e packin g glan d seal . Whe nski ntemperature s ar e inexces s o f 400°F , othe r method s o f tentin g th e valve s ca nb e used . Inon e method , adjuste d meta l band s o r wire s ar e wrappe daroun dal l ho t point s tha t ar e i ncontac t wit hth e Myla r ten t material . Seal s ar e the nmad e agains t th e insulatio nusin g duc t tap e o r adjustabl e meta l band s o f stainles s steel . A t extremel y

hig htemperatures , meta l foi l ca nb e wrappe d aroun d th e valv e lea k area . Ina previou s study , seal s wer e mad e usin g adjustabl e meta l bands . A t point s wher e th e shap e o f th e equipmen t prevente d a satisfactor y sea l wit hmeta l bands , th e foi l wa s crimpe d t o mak e a seal . I t wa s necessary , insome o f thes e instances , t o us e a relativel y hig hcapacit y

vacuu m pum pt o insur e a constan t inflow o f ai r throug hal l sea l areas .

4-1 2Mixed-phas e valv e leak s ar e enclose dwit hth e same typ e o f ten t describe d

above . Th e rat e o f leakag e o f liqui di s measure db y collectin g i t ove r a measure dlengt ho f time . A low poin t i s forme di nth e ten t t o collec t th e liqui ds o it s volum e ca nb e measure dan dconverte dt o a mas s rate . Th e tota l
mas s lea k rat e ca nthe nb e estimate db y addin g th e liqui dmas s lea k rat e t o th e ga s mas s lea k rate . 4.3. 2 Pump s an

dAgitator s A s wit hvalves , th e propert y o f mos t concer nwhe npreparin g t o sampl e a pum po r agitato r i s th e meta l ski ntemperatur e a t area s o r point s tha t ar e i n contac t wit hth e ten t material . A t ski ntemperature s belo w 400°F , Myla r plasti c an dduc t tap e ar e satisfactor y

material s fo r constructin g a ten t aroun da pum po r agitato r seal . Th e vas t majorit y

o f centrifuga l pump s inVO C servic e hav e a housin g o r suppor t tha t connect s th e pum pdriv e (o r bearin g housing ) t o th e pum pitself . Th e two support s normall y enclos e abou t hal f o f th e are a betwee nth e pum pan d driv e motor , leavin g ope narea s onth e sides . I t i s usuall y a relativel y simpl e matte r t o cu t panel s t o fi t thes e remainin g ope nareas . I na previou s study , th e panel s wer e cu t fro m 1 4 mi l Mylar . Bulkhea dfitting s fo r th e outlet s t o th e wate r manomete r an dsamplin g trai nar e place dthroug hon e Myla r pane l an dsealed . A

nopenin g (hole , bulkhea dfitting ) i s mad e inth e opposin g panel , i f necessary , t o allow easie r flow

o f dilutio nai r int o th e enclosur e aroun dth e seal . Inman y horizonta l pumps , ther e i s a lin e fro m th e bottom

o f th e lowe r meta l suppor t t o a drain . Thi s lin e serve s a s a drai nfo r coolant , sealant , and/o r proces s liqui dleakin g fro m th e pum pseal . Thi s lin e (an dal l othe r line s fro

m th e enclosure ) shoul db e seale dof f t o avoi ddrawin g ai r an d hydrocarbo nvapor s fro m th e drai nbac k u

pt o th e seale denclosures . I f ther e i s n o liqui dflowin g throug hthi s drai nline , i t ca nb e plugge doff . I f liqui di s goin g t o th e drain , a shor t lengt ho f hos e o r tubin g ca nb e attache d t o th e en

do f th e drai nlin e an dloope dupwar dt o for m a neffectiv e liqui d seal . I nth e case s wher e support s ar e absen t o r quit e narrow , a cylindrica l enclosur e aroun dth e sea l ca nb e mad e s o tha t i t extend s fro m th e pum

phousin g t o th e moto r o r bearin g support . Thi s enclosur e ca nb e mad e o f 1 4 mi l Mylar , sinc e thi s thicknes s provide s considerabl e strengt han drigidity . 4-1 3

O BP. 4

Reciprocatin g pump s presen t a somewha t mor e difficul t tentin g problem . I f support s ar e present , th e same typ e o f two-pane l Myla r ten t ca nb e constructe da s tha t fo r centrifuga l pumps . I nmany instances , however , sufficientl y

larg e support s ar e no t provided , o r th e distanc e betwee npum p an d drive r i s relativel y

long . Inthes e cases , a cylindrica l enclosur e simila r t o tha t use dfo r centrifuga l pump s ca nb e constructed . I f i t i s impractica l t o exten dth e enclosur e al l th e wa y fro m th e pum

p sea l t o th e pum

p driver , a sea l
ca nb e mad e aroun dth e reciprocatin g shaft . Thi s ca nusuall y b e bes t mad e b

y usin g heav

y aluminu

m foi l an

dcrimpin g i t t o fi t closel y aroun d th e shaft . Th e foi l i s attache dt o th e Myla r plasti c o f th e enclosur e an dseale d wit h duc t tape . I f th e temperatur e i s to o higho r th e potentia l point s o f contac t ar e to o numerou s t o insulate , a nenclosur e mad e o f aluminu m foi l ca nb e constructed . Thi s enclosur e i s seale daround th e pum p an d bearin g housin g usin g silicon e fabri c insulatin g tape , adjustabl e meta l bands , o r wire . I ncase s wher e liqui d an dvapor s ar e leakin g fro m a pump , th e enclosure s describe dabov e fo r valve s ca nb e used . Th e outle t fro m th e ten t t o th e samplin g trai ni s place da t th e to po f th e enclosur e an da s fa r awa y

fro m sprayin g leak s a s practical . Thus , entrainmen t o f th e liqui d int o th e samplin g trai n(an

dcol dtrap ) i s avoided . Th e rat e o f leakag e o f liqui d i s measure db

y collectin g i t ove r a measure d lengt ho f time . A low poin t i s forme dinth e ten t t o collec t th e liqui d s o it s volum e ca nb e measure d an d converte dt o a mas s rate . Th e tota l mas s lea k rat e ca nthe nb e estimate d b y addin g th e liqui dmas s lea k rat e t o th e ga s mas s lea k rate . 4.3. 3 Compressor s Ingeneral , th e same type s o f tent s tha t ar e suitabl e fo r pump s ca nb e directl y applie dt o compressors . Th e constructio nan d applicatio no f thes e enclosure s hav e bee ndescribe di nth e precedin g discussion s o f pum p samplin g an dwil l no t b e repeate dinthi s section . Compressor s generall y handl e ligh t gases , an d inmany

cases , th e seal s ar e enclosed . Th e sea l enclosure s ar e vente d t o th e atmospher e a t a high-poin t ven t o r ma y b e vente d t o th e blowdown/flar e system . I f th e seal s ar e vente d t o a high-poin t vent , thi s ven t Hn e ca nb e sampled . A

Myla r ba g ca nb e constructe d an d seale d aroun d th e outle t o f th e

4-1 4P. 5

ven t an dconnecte dt o th e samplin g train . Th e lea k rat e fro m th e vente d compresso r seal s i s the nmeasure d usin g th e norma l flow-throug hmethod . I f th e high-poin t vent s ar e inaccessible , th e ven t line s fro m th e compresso r sea l enclosure s ca nbe disconnecte da t som e convenien t poin t betwee nth e compresso r an d th e norma l ven t exit . Samplin g i s the ndon e a t thi s intermediat e point . Whe nenclose dcompresso r seal s ar e vente db y mean s o f induce ddraf t blower s o r fans , th e outle t fro m th e blower/fanca nb e sampled . Ina previou s study , a pito t tub e wa s use d t o determin e th e ai r flow rate . A

sampl e o f th e outle t ai r wa s take nan d returne d t o th e laborator y fo r methan e an

d nonmethan e hydrocarbo nanalysis . Ambien t ai r sample s wer e take naroun d th e compresso r sea l enclosur e are a a t th e sam e time an

d wer e analyze d fo r hydrocarbo ncontent . Th e compresso r sea l lea k rat e wa s determine d fro m th e knowledg e o f ai r flow rate , it s hydrocarbo ncontent , an dth e hydrocarbo n conten t o f th e ambien t air . 4.3. 4 Flange s Inmos t cases , th e physica l configuration s o f flange s len d themselve s wel l t o th e determinatio no f lea k rates . Fo r smal l t o moderatel y larg e leak s fro m flange s wit hmeta l ski ntemperature s u p t o abou t 400°F , a narro w sectio n o f Myla r fil m

ca nb e use d t o spanth e ope ndistanc e betwee nth e tw o flang e face s o f th e leakin g source . Th e Myla r i s attache dan dseale d t o eac hflang e wit hduc t tape . Connection s (bulkhea d fittings ) fo r th e wate r manomete r an d samplin g trai nar e attache d t o th e Mylar . Whe ntestin g flange s wit hski ntemperature s abov e 400°F , th e outsid e perimete r o f bot hside s o f th e flang e connectionar e wrappe d wit hasbesto s insulatin g tape . Then , a narrow stri p o f aluminu

m foi l ca nb e use d t o spa n th e openin g betwee nth e flang e faces . Thi s narro w stri p o f materia l ca nb e seale dagains t th e asbesto s tap e usin g adjustabl e band s o f stainles s steel . 4.3. 5 Relie f Valve s Relie f device s i ngas/vapo r servic e generall y reliev e t o th e atmospher e throug ha larg e diamete r pip e whic hi s normall y locate d a t a hig hpoin t onth e proces s uni t tha t i t serves . Th e "horns " ca nb e easil y bagge d b

y placin g a Myla r plasti c ba g ove r th e openin g an d sealin g i t t o th e hor nwit hduc t tape . Becaus e man y

o f thes e device s ar e hig habov e grade , accessibilit y t o th e

4-1 5



### •I HP. 6



### samplin g trai nma y

b e limite do r prevented . I t i s sometime s possibl e t o ru na long piec e o f tubin g fro m th e outle t connectio nonth e ba g t o th e samplin g trai nlocate da t grad e leve l o r ona stabl e platform . Anda s discusse d previousl y

i nth e sectio nonscreening , th e purpos e o f pressur e relie f device s make s them

inherentl y

dangerou s t o sample , especiall y ove r a lon g perio do f time . I f thes e equipmen t ar e t o b e sample dfo r mas s emissions , specia l car e an dprecaution s shoul db e take nt o ensur e th e safet y o f th e personne l conductin g th e fiel dsampling . 4. 4 ACCURAC YCHECK S A naccuracy

chec k i s normall y

performe dinth e laborator y b y samplin g a

n artificiall y

induce dlea k rat e o f a know ngas . Thi s effectivel y point s ou t an y bia s inth e tes t method s an ddefine s th e varianc e componen t du e t o sampling . I f th e resul t i s outsid e th e 8 0 percen t t o 12 0 percen t recovery range , th e problem

shoul db e investigate dan dcorrecte dbefor e samplin g continues . Th e problem s an dassociate dsolution s shoul db e note dinth e tes t report . 4. 5 ANALYTICA L TECHNIQUE S Th e technique s use dinth e laborator y analysi s o f th e bagge dsample s wil l depen donth e typ e o f processe s sampled . Th e followin g section s describ e th e analytica l instrumentation , calibration , analytica l technique s fo r condensate , an dqualit y

control . Thes e ar e guideline s fo r th e fiel dsamplin g tea m an dar e no t mean t t o b e a detaile dprotoco l fo r th e laborator y personnel . Laborator y personne l shoul db e wel l verse di nth e analysi s o f hydrocarbo nmixture s an d shoul ddesig nthei r specifi c analyse s t o th e sample s bein g examined . 4.5. 1 Analytica l Instrumentatio n Th e selectio no f analytica l instrumentatio ni s critica l t o identificatio n o f individua l organic s inth e sample . Th e instrumen t o f choic e depend s o nth e typ e o f sampl e bein g processed . Organi c component s o f th e stream s o f som e proces s unit s ma y

produc e widel y

differin g response s wit ha nFID . Fo r thi s reason , mor e comprehensiv e analyse s b y ga s chromatography

mus t b e performe dt o identif y individua l components . FI D ga s chromatograph s o r electro ncaptur e ga s chromatograph s ar e commonl y use dt o identif y

individua l component s o f a sample . Othe r consideration s beside s instrumen t choic e ar e th e typ e o f colum n used , an dwhethe r o r no t temperatur e programmin g i s necessar y t o separat e ou t
4-1 6P. 7



### individua l component s o f th e proces s strea m wit hsufficien t resolution . A n exampl e o f a ga s chromatograp htha t ha s bee nuse di n previou s studie s i s th e Hewlet t Packar d573- A

Dua l FI D Ga s Chromatograph. 1 2 

### Fo r some proces s stream s suc ha s ethylen e an dcumene , tota l hydrocarbo n analyse s ar e satisfactory . Th e respons e o f th e FI D t o thes e compound s i s similar ; therefor e an instrumen t suc ha s th e Byro nTota l Hydrocarbo nAnalyze r (THC ) ca nb e calibrate dwit ha singl e representativ e hydrocarbon . This instrumen t ha s a

n FI D an dresolve s sample s wit hmethan e an dnonmethan e components . Th e emissio nstream s ca nthe nb e analyze dfo r th e tota l hydrocarbo nconten t wit hreasonabl e accuracy . 4.5. 2 Calibratio n Prope r calibratio no f bot hth e laborator y an dfiel dinstrument s fo r th e wid e rang e o f organic specie s i s different . Eac hinstrumen t mus t b e calibrate dwit hth e appropriat e specie s eac hda y i t i s used . Calibratio no f th e portabl e hydrocarbo ndetecto r shoul db e don e wit h standard s o f hexan e in air . A hexan e standar do f approximatel y 2,00 0 ppm

v i s availabl e i n a bottl e supplie dan dcertifie dt o + 2 percen t b y th e manufacturer . Highe r concentration s tha nthi s ma y leadt o problem s involvin g condensatio na t ambien t temperatures . Lowe r concentration s mus t b e generate d b y dilution . Th e tota l hydrocarbo nanalyze r ca nb e calibrate dwit hth e sam e hexan e standard . Th e standar di s relate dt o a n NB S propan e standar db y measurin g th e concentratio no f th e NB S standar dusin g th e tota l hydrocarbo nanalyze r afte r th e analyze r ha s bee ncalibrate dwit hth e hexan e standard . Th e ga s chromatograp hi s calibrate dwit heithe r ga s standard s generate d fro m calibrate dpermeatio ntube s containin g individua l VO C component s o r bottle dstandard s o f commo ngases . 4.5. 3 Analytica l Technioue s fo r Condensat e Any condensat e collecte db y th e ic e bat hi n th e samplin g trai nshoul dbe brough t t o th e laborator y seale di n th e col dtra pflask . This materia l i s transferre dt o a graduate dcylinde r t o measur e th e volum e collected . I f ther e i s enoug hvolum e t o mak e i t feasible , th e organi c laye r shoul db e separate d fro m th e aqueou s laye r (i f present ) an dweighe dt o determin e it s density . Bot hth e aqueou s an

dorganic phase s shoul dbe analyze db y ga s chromatography i f water-miscibl e organic compounds ar e present . 4-1 7

iiBH^HHlHI|^^^^^HH___________________________________-^^^^^^^^^^^^^BBB^^iHi^^^K____UP. 8

4.5. 4 Oualit v

Contro l fo r Analytica l Technioue s Blindstandard s shoul db e prepare dan d submitte d fo r analysis . Th e blind standard s ar e prepare db y dilutin g o r mixin g primar y standard s ina prescribe d fashio ns o tha t th e resultin g concentration s ar e known . Th e calculate d concentration s an

d th e analytica l result s shoul db e logge d int o a laborator y notebook . I f th e result s ar e no t withi n2 5 percen t o f th e certifie d level , furthe r analyse s mus t b e performe d t o determin e th e reason . Suc ha procedur e no t onl y define s th e analytica l varianc e componen t an d analytica l accuracy , bu t i t serve s t o poin t ou t equipmen t malfunction s and/o r operato r erro r befor e many dat a ar e affected .

4-1 81
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.

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2 .

3 .

4 .

5 .
6 .

7 .

8 .

9 .

10 . P. 9

SECTION 5. 0 REFERENCE S

Cod e o f Federa l Regulations , Titl e 40 , Par t 60 , Appendi xA . Referenc e Metho d21 , "Determinatio no f Volatil e Organi c Compoun d Leaks. " Harris , G.E . an

dG.J . Langley . (Radia nCorporation. ) Detaile d Screenin g Pla nfo r Fugitiv e Emission s fro m SOCM I Proces s Units . (Prepare d fo r U . S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N. C Decembe r 1979 . Joseph , G.T . an

dM . Peterson . (Northro p Services , Inc. ) APT I Cours e S1.41 7 Controllin g VO C Emission s fro m Leakin g Proces s Equipmen t Studen t \ Guidebook . (Prepare d fo r U.S . Environmenta l Protectio nAgency. ) Researc h Triangl e Park , N.C . Publicatio nNo . EPA-450/2-82-01 . 1982 . U . S . Environmenta l Protectio nAgency . Respons e Factor s o f VO C Analyzer s a t a Mete r Readin g o f 10,00 0 ppm v fo r Selecte d Organi c Compounds . Publicatio nNo . EPA-600/2-81-051 . 1981 . U . S . Environmenta l Protectio nAgency . Respons e o f Portabl e VO C Analyzer s t o Chemica l Mixtures . Publicatio nNo . EPA-600/2-81-110 . 1981 . Brown , G.E. , e t al . (Radia nCorporation. ) Respons e Factor s o f VO C Analyzer s Calibrate d wit hMethan e fo r Selecte dOrgani c Compounds . (Prepare dfo r U . S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/2-81-022 . Septembe r 1980 . Anastas , M.Y. , an

dH.J . Belknap . (PEDC o Environmental , Inc. ) Summar y o f Portabl e VO C Detectio nInstruments . (Prepare d fo r U . S . Environmenta l Protectio nAgency. ) Washington , D.C . Publicatio nNo . EPA-340/1-80-010 . Marc h1980 . Langley , G.J. , an

dL.P . Provost . (Radia nCorporation. ) Revisio no f Emissio nFactor s fo r Nonmethan e Hydrocarbon s fro m Valve s an

d Pum p Seal s inSOCM I Processes . (Prepare d fo r U . S . Environmenta l Protectio n Agency. ) Researc hTriangl e Park , N.C . Novembe r 1981 . Langley , G.J. , e t al . (Radia nCorporation. ) Analysi s o f SOCM I VO C Fugitiv e Emission s Data . (Prepare d fo r U . S . Environmenta l Protectio n Agency) . Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/2-81-111 . Jun e 1981 . Radia nCorporation . Assessmen t o f Atmospheri c Emission s fro m Petroleu

m Refining : Volum e 4 . Appendi xC , D , E . (Prepare dfo r U.S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA 600/2-80-075d . Jul y

1980 .

5- 1

S HP,]0

.

11 . Wetherhold , R.G. , L.P . Provost , an d CD . Smit h(Radia nCorporation. ) Assessmen t o f Atmospheri c Emission s fro m Petroleu

m Refining : Volume 3 . Appendi xB . (Prepare d fo r U.S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/2-80-075c . Apri l 1980 . 12 . Radia nCorporation . Tes t Planfo r Contro l o f Fugitiv e Emission s fro m th e Syntheti c Organi c Chemica l Manufacturin g Industry . (Prepare d fo r U . S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Octobe r 1979 . 13 . U.S . Environmenta l Protectio nAgency . Fugitiv e Emissio nSource s o f Organi c Compound s - Additiona l Informatio no nEmissions , Emissio n Reductions , an

d Costs . Researc hTriangl e Park , N.C . Publicatio nNo . EPA-450/3-82-010 . Apri l 1982 . 14 . Langley , G.J . an d R.G . Wetherhold . (Radia nCorporation. ) Evaluatio no f Maintenanc e fo r Fugitiv e VO C Emission s Control . (Prepare d fo r U.S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/52-81-080 . Ma y 1981 . 15 . Blacksmith , J.R. , e t al . (Radia nCorporation. ) Problem-Oriente d Report : Frequenc y

o f Lea k Occurrenc e fo r Fitting s i nSyntheti c Organi c Chemica l Plan t Proces s Units . (Prepare d fo r U.S . Environmenta l Protectio n Agency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/2-81-003 . Septembe r 1980 . 16 . Stelling , J.H.E . (Radia nCorporation. ) Emissio nFactor s fo r Equipmen t Leak s o f VO C an

d HAP . (Prepare d fo r U.S . Environmenta l Protectio n Agency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-450/3-86-002 . Januar y 1986 . 17 . Wetherhold , R.G. , an d L.P . Provost . Emissio nFactor s an d Frequenc y

o f Lea k Occurrenc e fo r Fitting s inRefiner y Proces s Units . (Prepare d fo r U.S . Environmenta l Protectio nAgency. ) Researc hTriangl e Park , N.C . Publicatio nNo . EPA-600/2-79-044 . 1979 . 18 . Draper , N . an

d H . Smith . Applie d Regressio nAnalysis . JohnWile y an d Sons , 1966 . 19 . Draper , N.R . an

d H . Smith . Applie d Regressio nAnalysis . Secon d Edition , JohnWile y

an d Sons , New

York , 1981 . 20 . Finney , D.J . "O

nDistributio no f a Variat e Whos e Logarith m i s Normall y Distributed" , Journa l o f th e Rova l Statistica l Society . Serie s B , 7 (1941) , 155-161 . 21 . Rickmers , A.D . an d H.N . Todd , Statistics . A nIntroduction . McGraw-Hil l Boo k Co. , Ne w

York , 1967 .



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