REPORT ON ETPYLENE DIBROMIDE TO THE.SCIENTIFIC REVIEW PANEL

Prepared by the S ta f f s of the Air Resources Board and

the Department of Health Services

April 1985

( T h i s report has been reviewed by the s t a f f s of the California Air Resources Board and the California Department of Health Services and approved for pub1 f cation. Approval does not signify t h a t the contents necessarily r e f l ec t the views and policies of the Air Resources Board o r the Department of Health Services, nor does mention of trade names o r commercial products consti tute endorsement o r recomendation fo r use. )

REPORT ON ETHYLENE DIBROMIDE TO THE S C I E N T I F I C REVIEW PANEL

CONTENTS

OVERVIEW AND RECOMMENDATION

PART A WITH APPENDICES C - H

PART B WITH APPENDICES

PART C - PUBLIC INPUT REQUESTS, COMMENTS, AND RESPONSES

REPORT ON ETHYLENE DIBROMIDE TO THE SCIENTIFIC REVIEW PANEL

OVERVIEW

I. INTRODUCTION

Under t h e p rov is ions o f D i v i s i o n 26, Chapter 3.5 o f the Health and Safety

Code, t h e A i r Resources Board (ARB o r t h e Board) i s responsible f o r the

i d e n t i f i c a t i o n and c o n t r o l o f t o x i c a i r contaminants, except i n t h e i r

p e s t i c i d a l use. The Department o f Food and Ag r i cu l t u re i s responsible f o r t he

regu la t ion o f t o x i c a i r contaminants i n t h e i r p e s t i c i d a l use (Health and

Safety Code Sections 39650(g) and 39655; Food and Agr icu l tu re Code Sect ion

1 / 14021 e t seq.). Heal th and Safety Code Section 39650- e t seq., and Food

and Agr icu l tu re Code Sect ion 14021 e t seq., enacted i n Septenber 1983,

(Assenbly B i l l 1807; Stats. 1983, ch. 1047) sets f o r t h a procedure f o r t he

i d e n t i f i c a t i o n and con t ro l o f t o x i c a i r contaminants (TAC) i n Cal i forn ia .

We are proposing, i n accordance w i t h these provis ions, t h a t ethylene

d i b r m i d e (EDB) be i d e n t i f i e d as a t o x i c a i r contaminant. This overview

reviews b r i e f l y our repor t on t he uses of, and t h e extent of emissions of and

pub l i c exposure t o EDB i n C a l i f o r n i a (Part A o f t h i s repor t ) , and the

Department of Health Services' (DHSI evaluat ion of t h e heal th e f f e c t s of EDB

(Part B of t h i s repor t ) . The f i n d i n g s i n these repor ts c m p r i s e t he r a t i o n a l e

f o r the se lec t ion o f EDB as a candidate substance f o r l i s t i n g as a t ox i c a i r

contaminant. Heal th and Safety Code Sect ion 39655 def ines a " tax ic a i r

contaminant" as an a i r p o l l u t a n t which nay cause' o r

11 A l l s ta tu to ry references are t o t h e Health and Safety Code unless - otherwise indicated.

b

b

cont r ibu te t o an increase i n m o r t a l i t y o r an increase i n serious i l l ness , or

which may pose a present or po ten t i a l hazard t o human health."

Health and Safety Code Section 39650 sets f o r t h t h e Leg is la tu re 's

f i nd ings w i t h respect t o substantes which may be t o x i c ai'r contaminants. The

Leg is la tu re has declared:

"That pub l i c health, safety, and welfare may be endangered

by the emission i n t o t h e ambient a i r o f substances which

are de tem i ned t o be carcinogenic, t e r a t ogenic , mutagenic,

o r otherwise t o x i c o r i l l j u r i o u s t o humans. I1

The f ind ings a lso inc lude d i r e c t i v e s w i th respect t o the cons iderat i on of

s c i e n t i f l c evidence and the basis f o r regulatory action. With respect t o the

con t ro l of t o x i c a i r contaminants, t he Legis la ture has declared:

"That i t i s t he pub l i c p o l i c y of t h i s s ta te t h a t emissions

of t o x i c a i r contaminants should be con t ro l l ed t o l e v e l s

which prevent h a m t o the pub l i c health."

The Legis la ture has f u r t h e r declared tha t , "whi le absolute and undisputed

s c i e n t i f i c evidence nay not be ava i lab le t o determine the exact nature and

extent o f r i s k f rm t o x i c a i r contaminants, i t i s necessary t o take ac t ion t o

p ro tec t pub1 i c health."

With respect t o t he evaluat ion of substances, t h e Legis la ture has

declared t h a t t he best ava i lab le s c i e n t i f i c evidence, gathered from both

pub l i c agencies and p r i v a t e sources, inc lud ing industry, should be used. The

Leg is la tu re has a lso determined t h a t t h i s informat ion should be reviewed by a

s c i e n t i f i c review panel and by members o f the publ ic.

Under the procedures establ ished i n t he Health and Safety Code t o

implement the Leg is la tu re 's f ind ings, t h e determination by t he Board as t o

whether a subsTance i s a t o x i c a i r contaminant includes several steps. First.,

we request t he DHS t o evaluate t he hea l t h e f f e c t s o f a substawe (Section

39660). The evaluat ion inc ludes a canprehensive review o f a l l ava i lab le

s c i e n t i f i c data. Second, upon rece lp t and i n cons iderat ion of t he DHS

evaluat ion and recormendation, we prepare and submit a hea l th e f fects r e p o e

t o t he S c i e n t i f i c Review Panel (SRP) f o r i t s review (Sect ion 39661). The

repor t i s prepared i n a form which nay serve as t he bas is f o r fu ture

regulatory ac t i on by t he Board. The repor t i s a lso made ava i lab le t o the

publ ic , which nay submit cannents on the repo r t t o t h e SRP. A f t e r rece iv ing

the w r i t t e n f i nd ings o f t he SRP, concerning t h e repor t , the Board issues a

pub1 i c hearing no t i ce and proposed regu la t ion which i mludes the proposed

determinat ion as t o whether t he substance i s a t o x i c a i r contaminant. The

Board's determination, a f t e r a pub l i c hearing and s ther prccedures t o conply

w i t h appl icab le prov is ions o f Government Code Section 11340 e t seq., t h a t a

substance i s a t o x i c a i r contaminant must be set f o r t h i n a regu la t ion

(Sect ion 39662). The Health and Safety Code a l s o includes procedures f o r t h e

development and adoption of con t ro l measures f o r substances i d e n t i f i e d by

regu la t ion as t w i c a i r contaminants (Sections 39665-39667).

11. EVALUATIOIJ OF ETHYLENE DIBROMIDE

Consistent w i t h t h e p rov is ions of Chapter 5, D i v i s i o n 26 o f t he Health

and Safety Code, t h e ARB and the DHS f i r s t p r i o r i t i z e d candidate substances

f o r evaluat ion and regu la t ion as " t o x i c a i r contaminantsn pursuant t o Section

39660(f). B r i e f l y , t he se lec t i on o f a substance f o r t he Board's eva luat ion

and cons iderat ion as a t o x i c a i r contaminant i s t o be based on the r i s k t o t h e

pub l i c f r a n exposure t o t he substance, amount o r po ten t i a l anount o f emissions

f ra use o f t h e substance, manner o f usage i n Cal i fornia, atmospheric

persistence, and ambient concentrations. A f te r consul t ing w i t h DHS, we

selected EDB f o r the Board's considerat i on f o r 1 i sting. as a TAC. We selected

EDB because i t i s a known animal carcinogen, i t i s ub iqu i tous ly emitted fra

evaporation and burning of leaded gasoline, i t i s pers is tent i n the

atmosphere, and i t s presence i n t he atmosphere has been documented. Pert inent

data f o r C a l i f o r n i a are summarized below. The emissions estimates show

pes t i c ide appl icat ions represented 96 percent o f statewide emissions i n 1983.

Since near ly a l l pes t i c i da l uses of EDB are now prohibi ted, t he marketing and

use of leaded gasoline w i l l be t he primary EDB emission sources i n Ca l i fo rn ia .

South Coast 1983 Emissions Statewide A i r Basin

Stat ionary sources Pesticides* 362 t ons/year 4 tons/year Gasoline evaporation 0.5 0.2

Vehicular 15 I, 7 'I

Atmospheric Hal f - L i f e (OH. attack, pol'luted atmosphere)

Anbi ent Concentration Average (annual f

Range (24 hour)

50 days

Unknown .OD74 pa r t per b i l l i o n

Unknown <.005-.18 p a r t per b i l l i o n

Pursuant t o Health and Safety Code Sect ion 39660, we requested t h a t t he

DHS conduct a heal th e f f e c t s eva luat ion o f EDB. The DHS evaluat ion was

conducted i n accordance w i t h t he prov is ions o f t h a t section, which requires

* Under Chapter 3.5. D i v i s i on 26, o f t he Health and Safety Code, TACs which are pest ic ides are t o be regulated i n t h e i r pes t i c i da l use by the Department of Food and Agr icu l ture.

t h a t the DHS consider a l l avai lable s c i e n t i f i c data, including, but not

l i m i t e d to, re levant data provided by the ARB, the Department o f Industr ia l

Relations, in ternat ional and federal health agencies, pr iva te industry,

academic researchers, and publ i c health and environmental organizations. To

f a c i l i t a t e the i den t i f i ca t i on o f a l l avai lable data p r i o r t o formally

requesting the DHS evaluation, we sent a l e t t e r t o owners o f potent ial sources

of EDB emissions i n Cal i fo rn ia and other interested members o f the publ ic

requesting t h a t they submit any information they considered pert inent t o the

DHS evaluation. We also received a reference search on EDB health e f fec ts

using the MEDLARS I1 and DIALOG Information Services and included a

bibliography from tha t search i n our request f o r information. The data

compiled i n the search were provided t o the DHS. Also, the DHS report and our

draf t repor t were released t o the publ ic upon completion on December 14, 1984;

providing addit ional time during our preparation o f the repor t t o the SRP f o r

the publ i c ' s preparation o f coments. These reports were also provided t o the

SRP on t h a t date.

Section 39660 speci f ies t ha t the DHS evaluation sha l l assess the

a v a i l a b i l i t y and qua l i t y o f data on health effects, including potency, mode o f

action, and other relevant b io log ica l factors o f the substance. Section 39660

also requires t h a t the DHS evaluation contain an estimate o f the levels o f

exposure which may cause or contr ibute t o adverse health effects, and, i n the

case where there i s no threshold o f s i gn i f i can t adverse health effects, the

range o f r i s k resu l t i ng from current o r ant ic ipated exposure.

F ive major issues discussed i n the DHS health e f fec ts evaluation o f ED6

are.: 1 ) Are health e f fec ts other than cancer expected t o occur a t current

ambient levels? 2) I s EDB an animal carcinogen? 3) Should EDB be considered

* it

a p o t e n t i a l human carcinogen? 4) Does EDB have a threshold below which cancer

does n o t occur? and 5) What i s the range o f added l i f e t i m e cancer r i s k f o r

populat ions cont inuously exposed t o C a l i f o r n i a ' s urban a i r EDB

concentrat ions? Based on i t s review o f a l l ava i l ab le s c i e n t i f i c data, the DHS

evaluat ion concludes that : 1 ) hea l th e f f e c t s o ther than cancer are n o t

- expected t o occur a t cu r ren t ambient l eve l s ; 2) t he DHS s t a f f agrees w i t h the

In te rna t iona l Agency f o r Research on Cancer (IARC) t h a t EDB i s an animal

carcinogen; 3 ) s ince EDB i s a potent animal carcinogen, i t should be

considered a p o t e n t i a l human carcinogen; 4 ) EDB should be t rea ted as a

carcinogen without. a threshold; and 5 ) the added 1 i f e t i m e cancer r i s k from

ambient a i r EDB exposure ranges from 1.02 t o 5.53 cases per m i l l i o n per 10

PPt.

The DHS r e p o r t f i n d s t h a t the adverse heal th e f f e c t s i n d i c a t i v e o f

systemic t o x i c i t y o f EDB, and reproduct ive e f fec ts , occur a t l e v e l s o f

exposure t o EDB which are thousands o f t imes h igher than ambient l e v e l s l i k e l y

t o be found i n C a l i f o r n i a ' s urban a i r . Thus, the DHS concludes t h a t hea l th

e f f e c t s other than cancer are n o t expected t o occur a t cur ren t ambient leve ls .

According t o the DHS repor t , s tud ies on the mutagenic po ten t i a l o f EDB

were reviewed by the Occupational Safety and Health Admin is t ra t ion (OSHA).

EDB was shown t o have genotoxic a c t i v i t y i n a r t i f i c i a l environments outs ide o f

l i v i n g organisms ( i n v i t r o ) , and w i t h i n l i v i n g organisms ( i n v ivo). It can

induce gene mutat ion i n bacter ia, fungi, p lants, insects, and mammalian c e l l s.

According t o the DHS repor t , animal cancer bioassays show EDB i s a po ten t

carcinogen i n both sexes i n more than one animal species. When administered

t o animals, EDB caused malignancies both a t the s i t e o f f i r s t contact (skin,

forestomach, and nasal cavity) , as well a s remote s i t e s (circulatory system,

lung, and pi tu i tary , among others). Thus, the DHS agrees w i t h IARC1s

conclusion t ha t EDB is a proven animal carcinogen.

The DHS evaluation indf ca tes t ha t the one pub1 ished epidemiological study

of 161 workers fa i led t o show a s t a t i s t i c a l l y signif icant increase i n cancer

ra tes from exposure to EDB. However, the DHS agrees w i t h the authors of the

study tha t i t can neither rule out nor establish EDB as a human carcinogen

because of the small s ize of the population studied. Since the scant human

data for carcinogenicity are inconclusive, and the animal data establish EDB

as a potent animal.carcinogen, the DHS s t a f f recommends t ha t EDB be considered

a potential human carcinogen.

To determine that a substance has a carcinogenic threshold, the DHS

requires strong positive evidence t ha t the substance acts only through

mechanisms which ought t o have a threshold. No positive evidence ex i s t s t o

suggest tha t the carcinogenicity of EDB has a threshold. The DHS report

s t a t e s tha t EDB should be treated as a carcinogen without a threshold i n

humans.

The DHS estimated the carcinogenic potency of EDB a t 20 ppm and 10 ppt by

applying the Weibull-Mu1 t is tage model, t h e mu1 t i s tage model, and the Probit

model to data from animal bioassays. Table A shows the 95 percent upper

confidence 1 imit (UCL) and the maximum likelihood risk estimates (MLE) fo r

each model' based on nasal malignancies i n male ra t s , and circulatory system

malignancies (hemangiosarcomas) i n female mice. The risk estimates using

these models a r e not grossly incompatible w i t h the results from the one small

epidemiological study.

Table A

Risk Assessment Estimates fo r EDB i n Air

20 PPm 10 P P t Occupational Community

Species/Tumor Model UCL*/MLEf* Exposure Exposure (PEL)**

Male Rats Weibull- 95% UCL 985/1000 5.53/million Nasal Ma1 ignancies Mu1 ti stage MLE 91 6/1000 2.85/mill ion

Mu1 ti stage 95% UCL 708/1000 3.15/million ML E 627/1000 2.53hil l ion

. P r o b i t 95% UCL 721 /lo00 d/ /mi l l ion

MLE 638/1000 million

Female Mice Weibull- 95% UCL 732/1000 3.23/mill ion Hemangiosarcomas Mu1 ti stage ' MLE 549/1000 2.03/million

~ u l ti stage 95% UCL 406/1000 1.34/million. MLE 328/1000 1.02/million

Probi t 95% UCL 438/1000 d//mi 11 ion

MLE 357/1000 0://mi 1 1 ion

* UCL - Upper confidence l imi t f* MLE - Maximum 1 i kel i hood estimate *** PEL - Permissible Exposure Limit

Predictions fo r the Probit model ranged from 0-10-31 - The DHS recommends the MLE from the multistage model for hemangiosarcomas

in female mice fo r calculating the lower bound of risk. The DHS recommends

the 95" percent UCL estimate from the Weibull -Mu1 t is tage model for nasal

malignancies i n male r a t s for calculating the upper bound of risk. The DHS

s t a f f suggests t ha t we consider tha t risk estimates between these bounds

consti tute the most reasonable estimates of risk from ambient EDB exposure.

While l ess conservative risk estimates can also be defended a s reasonable, the

DHS s t a f f does no t feel t h a t any can be c l ea r l y preferred, and the more 1 ,

conservative o f equally reasonable elements should const i tute the basis for

regulation. Using these bounds f o r the range o f r isk, then, the added

l i f e t i m e cancer r i s k from exposure t o EDB i n urban a i r ranges from 1.02 t o

5.53 cases per m i l l i o n per 10 ppt.

Using the range o f r i s k suggested by the DHS, we estimated the added

l i f e t i m e cancer r i s k t o a population exposed continuously f o r 70 years t o EDB

a t the annual average concentration o f 7.4 ppt estimated f o r the South Coast

A i r Basin. The added l i f e t i m e cancer r i s k i s i n the range o f 1 t o 4 cases per

m i l l ion persons exposed. To place t h i s i n context, the comparable baseline

1 i fetime r i s k o f a1 1 cancers combined (SEER program, 1981 , Surveil lance

Epidemiology and End Results Incidence and 1-lortal i ty Levels, 1973-77, N C I

Monograph #57), can be estimated a t 23.7 percent o r 237,000 cases per m i l l i on .

persons exposed.

I I I. ENVIRONMENTAL IMPACTS . . . ..

The i den t i f i ca t i on o f EDB as a t ox i c a i r contaminant i s not expected t o

r e s u l t i n any adverse environmental impacts. However, i f the Board determines

t h a t EDB i s a tox ic a i r contaminant, the Board and a i r po l lu t ion control

d i s t r i c t s w i l l be required t o evaluate the need for, and appropriate degree

of, airborne tox ic control measures. Thereafter, based on t h i s control

measure evaluation, the Board and the d i s t r i c t s may be required t o adopt

airborne tox ic control measures. Hence, the i den t i f i ca t i on o f EDB as a tox ic

a i r contaminant may ul t imately r e s u l t i n environmental benefits.

Environmental impacts i d e n t i f i e d w i t h respect t o speci f ic control measures,

w i l l be included i n the consideration o f such control measures pursuant t o

Sections 39665 and 39666.

IV. RECObIMENDATION

Since the evidence s t rong ly suggests t h a t E D 0 i s a known animal .

carcinogen and po ten t i a l human carcinogen, and since the evidence does n o t

warrant t he assumption t h a t carc inogen ic i t y i s conf ined t o the dose above any

thresh01 d, we consider a v a i l able evidence s u f f i c i e n t t o recommend 1 i s t i n g E D 0

as a t o x i c a i r contaminant having no threshold leve l .

REPORT ON ETHYLENE DIBROMIDE TO THE SCIENTIFIC REVIEW PANEL

PART A - A REVIEW OF ETHYLENE OIBROMIDE USES, EMISSIONS AND PUBLIC EXPOSURE

A p r i l 1985

(This r e p o r t has been reviewed by t he s t a f f s o f the C a l i f o r n i a A i r Resources Board and the C a l i f o r n i a Department o f Heal th Services and approved f o r pub1 icat ion. Approval does no t s i g n i f y t h a t t he contents necessari ly r e f l e c t the views and p o l i c l e s o f the A i r Resources Board o r the Department o f Health Services, nor does mention o f t rade names o r commercial products cons t i t u te endorsement o r recommendation f o r use.)

SUMMARY

Par t A o f the ethylene dibromide (EDB) repo r t t o the S c i e n t i f i c Review

Panel includes informat ion on 1 ) EDB sources and emissions i n Ca l i fo rn ia ; 2 )

atmospheric persistence o f EDB; 3 ) EDB concentrations i n ambient a i r ; and 4) .

other routes o f exposure t o EDB. I n 1983, about 360 tons o f EDB were emit ted

from pes t i c ide appl icat ions , represent ing 96 percent o f t o t a l emissions.

Since near ly a l l pes t i c i da l uses o f EDB are now prohib i ted, the marketing and

use o f leaded gasoline w i l l be the primary sources o f EDB emissions i n

Ca l i fo rn ia . EDB i s pers is ten t i n the atmosphere, having an estimated h a l f

l i f e o f about 50 days. Recent ambient monitor ing i n the South Coast A i r Basin

i d e n t i f i e d a d a i l y range between 4.005 and .18 ppb w i t h an annual average o f

.0074 ppb. P r i o r t o the recent EPA ban on pes t i c i da l use o f EDB, about 32

percent o f t o t a l EDB exposure i n C a l i f o r n i a was from a i r and about 57 percent

was from foods. We estimate t h a t 75 percent o f current EDB exposure i s from

a i r . We have no recent ambient a i r data f o r other areas o f C a l i f o r n i a and

therefore are unable t o estimate such exposures. Such data would be obtained

dur ing the r i s k management phase as p a r t o f the development o f con t ro l

measures.

REPORT ON ETHYLENE DIBROMIDE TO THE SCIENTIFIC REVIEW PANEL

Part A - A Review of Ethylene Dibromide (EDB) Uses, Emissions, and Public Exposure

TABLE OF CONTENTS

LIST OF TABLES AND FIGURES

I. EDB USAGE AND EMISSIONS

A. PRODUCTION AND USAGE

8. CURRENT AND PROJECTED STATIONARY AND EiOBILE SOURCE EMISSIONS

11. PERSISTENCE IN THE ATMOSPHERE

A. PHYSICAL AND CHEMICAL PROPERTIES

B. FORMATION AND FATE IN THE ATMOSPHERE

I 1 I. AMBIENT CONCENTRATIOIIS IN THE COMMUNITY

A. AMBIENT AIR DATA

. B. OTHER ROUTES OF EXPOSURE T O EDB

APPENDIX C* - HEALTH EFFECTS REQUEST TO DHS AND LETTER OF RESPONSE APPENDIX D - SAMPLING AND ANALYSIS METHODS FOR EDB APPENDIX E - AMBIENT MONITORING DATA AND ANALYSIS APPENDIX F - SUPPORTING INFORMATION ON EDB EMISSION ESTIVATES APPENDIX G - ESTIMATE OF EDB EMISSIONS REQUIRED FOR OBSERVED AMBIENT

CONCENTRATIONS

APPENDIX H - ASSEMBLY BILL 1807

* Former Appendices A and B are included in Part C - Public Input Requests, Comments, and Responses.

LIST OF TABLES ANU FIGURES

TABLES

1-1 Estimated Ethylene Di bromide (EDB) Emissions i n C a l i f o r n i a

11-1 Physical Propert ies o f EDB

111-1 Summary o f 24-Hour Monitoring Data i n the South Coast A i r Basin

111-2 Summary o f ED6 Exposure i n C a l i f o r n i a

FIGURE

I 1 1-1 Sumary o f EDB Exposure i n C a l i f o r n i a

I. I.IANNER OF USAGE AND AI4OUKT OR POTENTIAL AMOUNT OF EMISSIONS

A., PRODUCTION AND USAGE

Ethylene d i bromi de (EDB) i s commercially produced by reac t ing bromine

w i t h ethylene gas." There are no known natura l sources o f EDB.

I n 1982, about 85,000 tons o f EDB were produced i n the Uni ted

states.=' This amount r e f l e c t s a decrease o f 31 percent from 1977,

p r i m a r i l y due t o the decrease i n leaded gasoline production. 'EDB i s used as a

l ead scavenging agent i n leaded gasoline, as a solvent f o r resins, gums, and

waxes, i n the manufacture o f dyes, pharmaceuticals and other organic

compounds, and as a pest ic ide. EDB i s n o t ava i lab le as a consumer

EDB i s n o t produced i n Ca l i f o rn ia ; i t i s imported from other states. The

only known uses o f EDB i n C a l i f o r n i a are f o r pes t i c i da l purposes and as a lead

scavenger i n leaded gasoline. An ARB survey o f EDB manufacturers shows

pest ic ides conta in ing 448 tons o f EDB were shipped i n t o Ca l i f o rn ia i n 1983.

I n 1983, 362 tons o f EDB were repor ted t o the Department o f Food and

Agr icu l tu re (DFA) as used f o r fumigation. The f a t e o f the remaining 86 tons

o f EDB i s n o t known.

I n 1983, about 2,100 tons o f EDB were used i n leaded gasoline i n

~ a 1 i f o r n i a . y Appendix F shows the method used t o estimate the amount o f

EDB used i n leaded gasoline i n Ca l i fo rn ia .

P r i o r t o September 1983, the major a g r i c u l t u r a l and re la ted uses o f EDB

included fumigat ion o f s o i l , s tored g ra ins and f r u i t s , g ra in m i l l s and

termi t e - i n fested areas. I n September 1983, EPA announced the cancel 1 a t i on o f

near ly a l l major pes t i c i da l uses o f EDB. However, EDB fumigants i n the

possession o f users could be used u n t i l September 1984.y Consequently,

nearly a l l of the agr icul tural uses of EDB in California have ceased, a s of

October 1984.

The to t a l amouht of EDB used i n Cal i fornia decreased 22 percent from 1982

t o 1983 and 24 percent from 1983 t o 1984. 4 s9*12 / Further reductions in use

wi l l occur i n 1986 i f a proposal by LPA t o s ign i f ican t ly reduce the lead

content of gasoline is implemented. I f EPA implements i t s proposed lead

standard i n 1986, EDB use will decrease about 70 percent from 1984 t o 1986.

I f EPA does not implement t h i s standard i n 1986, EDB use will probably

decrease 49 percent from 1984 t o 1986 primarily due t o the .8 gram lead/gallon

California standard s t a r t i n g i n October 1984, and the decrease i n leaded

gasoline consumption. The ban of pes t ic ida l use s t a r t i ng in October 1984

accounts for 7 percent of t h i s decrease.

B. CURRENT AND PROJECTED STATIONARY AND MOBILE SOURCE EMISSIONS

Preliminary emission estimates f o r 1983 show pest ic ide appl icat ions

contributed about 95 percent of the estimable EDB emissions statewide and

about 35 percent in the South Coast Air Basin (SCAB). The other s ta t ionary

emission sources a r e gasol ine marketing and gasol ine blending f a c i l i t i e s .

These sources contributed l e s s than one percent of the estimable EDB emissions

statewide and about 4 percent i n the SCAB. Motor vehicles contributed about 4

percent of the estimable EDB emissions statewide and about 61 percent i n the

SCAB. However, the motor vehicle emission estimate i s uncertain; motor

vehicles may contribute a subs tan t ia l ly la rger portion t o the to ta l emission

inventory. The vehicle EDB emission t e s t data base used f o r the inventory i s

very l imited. Table 1-1 summarizes the estimates of EDB emissions statewide

and i n the SCAB. Appendix F documents the methods used t o estimate EDB

emissions .

Table 1-1 shows t h a t t he p ropor t iona l con t r i bu t i on o f s ta t ionary and

mobile sources t o t o t a l EDB emissions va r i es between the SCAB and other par ts

o f Ca l i fo rn ia . Because the 1983 ambient EDB moni t o r i n g data are f o r the SCAB

only, an est imate was made o f the EDB emissions requi red i n the SCAB t o

account f o r the observed ambient concentrations. Assuming t h a t ARB monitor ing

data are r e f l e c t i v e o f the whole SCAB, t h i s estimate p red ic ts EDB emissions i n .

the SCAB ranging from 41 t o 67 tons per yea r ( ca l cu la t i on included i n

Appendix 6 ) . Table 1-1 shows only 11 tons per year EDB emissions i n the

SCAB. Three poss ib le explanations f o r the discrepancy between estirfiated EDE

emissions and observed ambient EDB concentrat ions i n the SCAB are: 1 ) there

are other sources o f EDB emissions i n the SCAB; 2 ) the EDB emissions from

known sources i n the SCAB are underestimated; o r 3 ) uncer ta in t ies i n the

moni tor ing data.

Because the ambient EDB concentrations i n the SCAB ind i ca te EC6 emissions

l a r g e r than the estimated 11 tons per year, we looked f o r other possible

sources o f EDB emissions. Fumigated produce imported i n t o the SCAB were

evaluated as a possible source o f EDB emissions. The method f o r ca l cu la t i ng

EDB emissions from t h i s source ( inc luded i n Appendix F) shows imported

fumigated produce account f o r l ess than one ton per year o f EDB emissions i n

the SCAB. Thus, the estimated EDB emissions i n the SCAB do no t account f o r

the observed ambient EDB concentrations.

Excluding EDB pes t i c ide emissions, a l l o f the EDB emission estimates i n

Table 1-1 are based on l i m i t e d data. Addi t ional t e s t i n g o f EDB emissions from

s ta t ionary and mobile sources i s planned p r i o r t o considering cont ro l measures

f o r these sources.

Recent trends in ED0 uses i n California were evaluated to predict future

stationary and mobile source EDB emi ssions. EDB emissions from pesticide use

decreased almost 20 percent from 1982 to 1983.4'12' Gasol ine-related ED0

emissions will decrease with decreasing leaded gasoline production. A lead

content standard of 1.1 grams lead per gallon was i n effect in 1983 and i s the

basis for the baseline emission estimates. A 0.8 gram lead per gallon

standard went into effect October 1 , 1984 and a 0.1 gram lead per gallon

standard has been proposed by EPA t o go 1 nto effect i n 1986. ED0 emissions

from mobile sources will decrease with the phase-out of leaded gasoline.

Table 1-1

Estimated Ethylene Dibromide Emissions in California

Source Em1 ssi ons Inventory Source Type (tonsly r ) Year Reference

Statewi de SCAB - Pesticide Area 362* 4* 1983 4

Vehicular Exhaust Area 8 4 1983 6, 7 , 9

, . Vehicular Evaporative

Emissions Area 7 3 1983 7, 8

Gasoline Marketing** Area 0.32 0.15 1983 10, 11

Gasoline Production Area 0.19 - 0.09 1983 6, 11

Total 378 11

* Assumes emission of al l applied EDB. ** Includes bulk terminals, bulk plants, service station tanks and vehicle refueling operations.

REFERENCES

1. U.S. Environmental Protection Agency, 1980. Volat i le Organic Compound ( V O C ) Species Data Manual, 2nd Edition, EPA 450/4-80-015.

2. Johns, R., 1976. Air Pollution Assessment of Ethylene Dibromide, Mitre Corp. f o r U.S. Environmental Protect ion Agency, Washington, O.C., NTIS No. PB 256736

3. U.S. International Trade Comnission. 1978. 1982and1963. Synthetic

4. Cal i fornia Department of Food and Agriculture (CDFA), 1984. Pest ic ide Use Report, Annual 1983. pg. 106.

5. Wells, J. W . , 1984. EDB S ta tus of Uses, Calf fornia Department of Food and Agriculture, Sacramento, CA.

6. Roberts. R. M., 1980. An Inventory of Carcinogenic Substances Released i n t o the Ambient Air of Cal i fornia , Final Report Task I1 and IV, K V B , Inc. f o r Science Applications, Inc.. Los Angeles, CA.

7 . Sigsby, John E. et. a l . , 1982. "Automotive Emissions of Ethylehe Dibromide," SAE Technical Paper Ser ies , Society of Automotive Engineers Passenger Car Meeting, Troy, Michigan, June 7-10, 1982.

8. California Air Resources Board, 1983a. "BURD1983," computer report dated 9/2/83, Emissions Inventory Branch, Technical Support Division, Sacramento, CA.

9. Morgester, James, 1'364. "Report of Gasoline Production f o r Consumption i n Cal i fornfa ," April 17, 1984. California Air Resources Board, Compliance Division, Sacramento, CA.

10. Cal i fornia Air Resources Board, 1984. Data re t r ieved from Emissions Data System (EDS) f o r inventory years 1979 and 1981, Emissions Inventory Branch, Technical Support Division, Sacramento, CA.

11. S ta f f estimate. Discussion included i n Appendix F.

12. Cal i fornia Department of Food and Agriculture (CDFA), 1983. Pest ic ide Use Report, Annual 1982.

11. PERSISTENCE IN THE ATMOSPHERE

A. PHYSICAL AND CHEMICAL PROPERTIES

The chemical s t ruc tu re of ethylene di bromi de (1,2-dibromoethane) i s

BrH2C-CH2Br. I t i s soluble i n ethanol and acetone and i s sparingly

soluble i n water. Ethylene dibromide is a non-polar, s tab le compound. I t s

proper t ies a r e shown i n Table 11-1.

Table 11-1

Property Value Reference

Boiling point, 1 atm 2 6 9 ' ~ 1

Density, l iqu id 2.18 g/cm3 1

Heat capacity, 60°F .I73 cal /*C-gm 1

Heat of combustion ( H H V ) , 25°C

1.48 kcal /gm

Henry's Law Constant .56 atm. m3/mole 2

Heat of fusion 13.5 cal/gm 1

Heat of vaporization, 46.2 cal/gm 130°C

Index of refract ion 1.54 3

holecular weight 187.9

Octanol : water par t i t ion 00 7

Solubi l i ty i n water, 30°C 5..3 mg/cm3 1 .

Vapor pressure, -16'F t o 1nP (mmHg) 1 269'F = -7975 x l/T('K)

+I 7.56

B. FORMATION AND FATE IN THE ATMOSPHERE

EDB reacts slowly i n the atmosphere; i t is sl ightly l e s s reactive

photochemically than ethane. The most important photochemical reaction,

hydroxyl radical attack, occurs i n polluted a i r . EDB's hal f - l i fe under t h i s

4/ reaction i s 50 days o r longer- a t the hydroxyl radical concentration 1 x 3 5/ lo6 molecules/cm . This concentration was estimated by Calvert- as the

diurnal mean i n Los Angeles. The other known removal reactions, attack by

peroxides or ozone, ere a1 so very slow, having 100-aay half-1 ives . ' Thus,

EDB i s a persistent pollutant that can be transported long distances and i s

apt t o be present throughout an urban a i r shed.

The hydroxyl radical attack produces f ree bromine atoms or BrO radicals,

which are reactive and thus short-lived. The ultimate fa te of EDB and the

derivatives is not certain. The derivatives may become part of aerosols that

are removed by rainfal l or by dry deposition.

REFERENCES

1. Perry 's Chemical Engineers' Handbook, 5 th ed.

2. Chio, C. T. e t a l ; " ~ i a p o r a t i o n Studies from Water," Environment In ternat ional . - 3, 231 (1980).

3. CRC Handbook o f Chemistry and Physics.

4. Atkinson, Roger; SAPRC, Un ivers i t y o f Ca l i fo rn ia a t Riverside, phone conversation w i t h Richard Vincent o f ARB, January 1985.

5. Cal vert; J.G. ; "Hydrocarbon Involvement i n Photochemical Smog Formation i n Los Angeles Atmosphere," Environ. Sci. and Techn., - 10, 1976.

6. Verscheren, K, Handbook o f Environmental Data on Organic Chemicals 2nd. ed., Von Nostrand Reinbold Co. (1983).

7. Mara, Susan J., and Lee, Shonh S., J u l y 1978. Atmospheric Ethylene Dibromi de: A Source-Speci f i c Assessment. Prepared by S R I In te rna t iona l 'For the Of f ice o f Toxic Substances, U.S. Environmental Protect ion Agency.

111. AMBIENT CONCENTRATIONS IN THE COMMUNITY

A. AMBIENT AIRDATA

The California Air Resources Board Haagen-Smit Laboratory (HSL) has been

monitoring ambient EDB a t four s i t e s i n the South Coast Air Basin (SCAB) since

January 1983. These are in downtown Los Angeles (DOLA), Eominguez, El Monte,

and Riverside. All samples are collected over 24-hour periods, beginning a t

9 a.m., in Tedlar bags a t constant flow rates. Analysis of the samples i s by

gas chromatography. Details of the sampling and analytical procedures are i n

Appendix D. Samples are collected f ive days per week a t the El Monte s i t e and

about once every s ix days in DOLA, Dominguez, and Riverside.

Between January, 1983, and May, 1984, 511 samples were collected. Thirty

percent of the samples had concentrations above 5 p p t ( v ) , the minimum

reporting level. Table 111-1 summarizes the data. The mean concentrations

during 1983 ranged among the s i t e s from 5.0 t o 9.3 p p t w i t h the average for

a l l s i t e s a t 7.4 ppt.

The average ambient EDB levels for 1983 exceeded the averages for Januaky

to May, 1984, because of strong oeaks during the summer of 1983 a t three

stations. T h i s phenomenon i s inconsistent w i t h the estimated inventory for

known sources i n the SCAB in 1983, which was heavily weighted to automotive

emissions in the summer. Other pollutants that are predominantly from

vehicles ( C O and lead) are measured a t the i r lower ambient concentrations

during the summer in the SCAB and thei r higher concentrations in the winter

because of the poor dispersion in the lower atmosphere du r ing the winter.

Preliminary data for 1984 (not included i n this report) , also indicate

summertime peaks.

Table 111-1

Summary of 24-Hour Monitoring Data In the SCAB ( P P ~ )

Avg. Among DOLA El Monte Dominguez Riverside Si t e s

Jan.- Dec. 1983 9.0 9.3 5.0 6,4 7.4 Jan. - May 1 984!!/ 3.0 3.4 4.2 3.6 3.6 A11 data 7.2 7.4 4.7 5.5 6.2

Highest 24-hour 180.0 130.0 37.0 '51.0 -- datum

includes the value 2.5 for each sample with EDB below the reporting l i m i t of 5.0 ppt

!!I data f o r l a t e r months not y e t ava i lab le ; not representative of year-round means

A second unexpected aspect of the monitoring r e su l t s i s t h a t i f the

monitoring data a r e used as an ind ica tor of emissions, the emissions should be

three to f i v e times greater than estimated. If EDB, l i k e carbon monoxide and

lead, is emitted predominantly from vehicles i n the SCAB, i t s ra t io . of ambient

concentration to emission r a t e should equal those of the l a t t e r pollutants.

However, a s de ta i led i n Appendix G , the r a t i o i s four t o s i x times higher than

expected. This could r e s u l t from any combination of three causes: ( 1 )

automotive emissions are great ly underestimated, ( 2 ) an as-yet-unknown type of

EDB source emits large amounts around the basin, o r (3 ) small unknown sources

emit upwind and near the four monitors. The analysis i n Appendix G suggests

t h a t hypothesis (1 ) i s par t ly , but not so l e ly , the cause of the discrepancy.

Attempts t o cor re la te the EDB monitoring data among s t a t i o n s , o r w i t h

ambient concentrations of CO and lead, o r w i t h various meteorological data

were a l l unsuccessful (Appendix E ) . This leaves no means of extrapolating the

data from these four s i t e s t o general ambient l e v e l s throughout the South

Coast A i r Basin. Therefore, the mean annual concentrat ion f o r the four

monitor ing s i t e s (7.4 p p t ) i s assumed t o be the year-round exposure

concentrat ion i n the basin.

The HSL moni tor ing program provides the on ly anbient EDB data gathered

fo r more than a year i n Ca l i fo rn ia . A few short-term data taken dur ing 1976

t o 1982 are ava i l ab le from other sources. They a r e shown i n Appendix E. Mean

concentrations a t two remote s i t e s were 0.0 and 5 ppt. A t s i x urban s i tes ,

mean concentrat ions ranged from 10 t o 34 ppt. These measurements probably

r e f l e c t the higher concentrations o f EDB i n gas01 i n e a t t h a t time.

B. OTHER ROUTES OF EXPOSURE TO EDB

Before the EPA banned EDB pes t i c i de uses, the Department o f Health

Services (DHS) and the C a l i f o r n i a Department o f Food and Ag r i cu l t u re (CDFA)

sampled f o r EDB i n gra in products, c i t r u s f r u i t s and wel l water i n

1 / Cal i forn ia . The DHS- found an average EDB concentrat ion o f 37 ppb i n

twenty-f ive percent o f t he gra in products sampled. Seventy-f ive percent o f

2,3/ the gra in products sampled were no t contaminated w i th EDB. The CDFA-

found EDB concentrat ions ranging from 1.2 t o 113 ppb i n c i t r u s f r u i t s and f r o n

t race amounts t o .38 ppb i n wel l water.

To ca l cu la te the d a i l y exposure t o EDB from food, data on the average

d a i l y i n take o f g ra in and c i t r u s f r u i t s were obtained from two EPA

studies.%' These studies show an a d u l t weighing 70 ki lograms consumes 133

grams o f g ra in per day and 16.8 grams o f c i t r u s f r u i t per day. ARB s t a f f

estimates d a i l y a i r and water i n t a k e are 20 mJ and two l i t e r s respect ively.

The DHS and CDFA data on food and water exposure, and the ARB data on

ambient a i r exposure were used t o est imate t o t a l d a i l y EDB exposure i n

8

Cal i fo rn ia . This estimate does no t inc lude occupational exposure t o EDB and

assumes the indoor a i r EDB concentrat ion t o be equivalent t o the ambient .

l eve l . S t a f f i s not aware o f any indoor a i r qua1 i t y studies (excluding

occupational ) which tested f o r EDB contamination.

Table 111-2 and Figure 111.-1 summarize the d a i l y exposure t o EDB i n

Ca l i fo rn ia . Table 111-2 and Figure 111-1 show t h a t p r i o r t o EPA's ban on EDB

pes t i c ide uses, EDB exposure from a i r accounted f o r near ly one-third o f the

t o t a l EDB exposure i n Cal i forn ia . Tlie estimated exposure from a i r exceeds the

exposure from c i t r u s f r u i t , and i t was the c i t r u s f r u i t exposure l e v e l f which

l e d t o EPA's ban on EDB c i t r u s fumigation. With the phase-out o f EDB

pes t i c ide uses, a i r w i l l be the l a rges t source o f EDB exposure i n Ca l i fo rn ia .

Table 111-2

Sunmary o f EDB Exposure i n Ca l i fo rn ia*

ug/day Percent o f Total

f rainy 1.2 34

C i t r u s ~ r u i t / .8 23

w a t e r / .4 11

A i r4/ Total

* Before the EPA ban on EDB pes t i c i da l uses.

11 Assumes 25 percent o f the gra in consumed has an EDB concentration o f 37 - P P ~ .

;/ Assumes a l l of the c i t r u s f r u i t consumed has an EDB concentration o f 45 P P ~

31 Assumes a l l o f the water consumed has an EDB concentration o f .19 ppb. if/ Assumes a l l o f the a i r inhaled has an EDB concentration o f 7.4 ppt.

Workers i n gasoline blending f a c i l i t i e s are exposed t o addi t ional

.quant i t ies o f EDB where they work. According t o studies by the American

7/ Petroleum I n s t i t u t e ( ~ ~ 1 1 6 1 and Centaur Associates- , o i l r e f i n e r i e s have

indoor EDB concentrations ranging from 0.4 t o 40 ppb. A study by Rumsey and

~ a n i tag/ shows f a c i l i t i e s t h a t formulate and use fue l addi t ives have indoor

EDB concentrations ranging from 0.2 t o 54 ppb.

REFERENCES FOR CHAPTER I11

1. "EDB Sample Results Summary t o March 20, 1984," California Department of Health Services .

2. Cal i fornia Department of Food and Agriculture; "Studies and Evaluation by the CDFA on EDB Used i n Fumigation of F ru i t , " HS-956, Progress Reports 1 through 4, 1981.

3. Cal i fornia Department of Food and Agriculture; "A Survey of Well Water i n Selected Counties of Cal i fornia f o r Contamination by EDB i n 1983," HS-1123, September 12, 1983.

4. U.S. EPA, 1984. Ethylene Dibromide ( E D B ) - S c i e n t i f i c support and decision document f o r grain and grain mil l ing fumigation uses. Washington, D.C., Office of Pes t ic ide Programs, p. 118, Feb. 8, 1984.

5. U.S. EPA, 1984. Ethylene dibromide ( E D B ) - Technical support document f o r quarantine fumigation uses. Washington, D.C., Office of Pest ic ide Programs, p. 106, March 2, 1984.

6. American Petroleum I n s t i t u t e , 1982. Coments on OSHA advance notice of proposed rul emaking on occupational exposure t o ethylene dibromi de. Docket H-111 . Comment No. 5-54. June 1, 1982.

7. Centaur Associates, Inc., 1983. Analysis of four industry segments which would be a f fec ted by proposed EDB standard. Prepared for the Occupational Safety and Health Administration. ps. 60-69.

8. Rumsey, D. W . , and R. K. Tanita, 1978. An industrywide industr ia l hygiene study of ethylene dibromide. DHEW (NIOSH) Pub. No. 79-112. Prepared by Stanford Research I n s t i t u t e f o r t he U.S. Department of Health, Education and Welfare under Contract No. 210-76-0162. Cincinnati , NIOSH, p. 36.

APPENDIX C

HEALTH EFFECTS REQUEST TO DHS AND

LETTER OF RESPONSE

Te : p e t e i Rank, D i r e c t o r Depar tment o f X e a l t h S e r v i c e s 714 P S t r e e t Sac ramen to , C A , 959.14:

Dote : May 1 8 , 1984

Subiea: E v a l u a t i o n of E t h y l e n e Dibromide

I am w r i t i n g t o f o r n a l l y r e q u e s t t h a t t h e Department e v a i u a t e t a e h e a l t h e f f e c t s o f e t h y l e n e d ib romide a s a c a n d i d a t e t o x i c a i r c o n t a m i n a n t i n a c c o r d a n c e w i t h Assembly B i l l 1807 ( T a n n e r ) . Accord ing t o H e a l t h and S a f e t y Code S e c t i o n s 39660-62, your DeFartment h a s n i n e t y d a y s t o submi t a w r i t t e n e v a l u a t i o n and r ecomnenda t ions on t h e h e a l t h e f f e c t s o f e t h y l e n e d ibromide t o t h e A i r Resources Board.

A t t a c h e d f o r your s t c f f ' s c o n s i d e r a t i o n i n e v a l u a t i n g e t h y l e n e d i b r o m i d e a r e : A t t e c h n e n t I - a l i s t o f r e f e r e n c e s cn e t h y l e n e d i b r o m i d e h e a l t h e f f e c t s which were i d e n t i f i e d i n an AaB l e t t e r o f p u b l i c i n q u i r y and r e c e i v e d i n r e s p o n s e t o t h e i n q u i r y le t te? ; At t achmen t I1 - a s u g ~ e s t e d l i s t o f c o p i c s t h a t we b e l i e v e s h o u l d be i n c l u d e d i n ycu r e t h y l e n e d ib romide e v a l u a t i o n and recorrinendations; a n d At t achmen t I11 - a m b i e n t e t h y l e n e d ibromide c o n c e n t r a t i c n d a t a which s h o u l d b e used t o e s t i z e t e t h e r ange of r L s k t o C a l i f o r n i a residents a s r e q u i r e d i n B e a l t h and S a f e t y Code . S e c t i o n 39660 (c) .

My s t a f f i s a v a i l a b i e f o r c o n s u l t a t i o n i n conduc t ing t h i s h e s l t h e f f e c t s e v a l u a t i o n . We l o o k f o r w a r d t o c o n t i n u i n g t o wcrk c l o s e l y w i t h you and y o c r s t a f f i n c a r r y i n g o u t t h i s l e g i s l a t i v e

. mendate . I f you have any f u r t h e r q u e s t i o n s r e g a r d i n g t h i s m z t r e r , ? l e a s e c o n t a c t me a t 445-4383 o r have you: s c a f f c o n t a c t l e t e r D. V e n t u r i n i , Chie f o f *he S t a t i o n a r y Souzce D i v i s i o c , a t 445-0650.

A t t achmen t s

cc: G. Duffy A . K e l t e r w/a tcacnr .en ts R. Neut ra w / a t t a c h r e n t s P. V e n t u r i n i Assemblywoman Tanner C. B e r r y h i l l

M e m o r a n d u m

TO, 1 J a w s D. Boyd, Executive Officer A1 r Resources Board 1102 Q St ree t 8-4

AUL 2 7 %c Deportment of Health St,

From : Office of the Director 714 P St ree t , Room 1253

.5-1248

On May 18. 1984, you requested t he Departrent of Herlth Services (DHs) t o evaluate t h e health e f fec t s of ethylene dibromide as a candidate toxic a i r contaminant. According t o Health and Safety Code Sections 39660-62, 1 have 90 days t o submit a written evaluation and recommendztions t o you.

This mem const i tu tes a formal request for the 30-day extension described in Section 39660 (d ) . As you know, The Department delivered the document describing the health e f fec t s of benzene t o ycu abcui three weeks ago. Since t ha t time, s t a f f has been devoted t o several risk assessment reviews requested by various a i r pollution control d i s t r i c t s , items considered a high priori ty by your s t a f f .

The Uepartmnt will .be conducting c iv i l service examinations in several c l a s s i f i ca t i ons i n the next four t o eight weeks fo r the express purpose of h i r ing highly qual i f ied candidates t o f i l l the four professional positions dedicated t o the toxic a i r contaminant program. I anticipate t h a t h i r i n g will begin by l a t e Septenber or early October and will be complete shortly a f t e r the f i r s t of the year. Until t h a t time, i t Kill be very d i f f i cu l t t o maintain the

. . level of e f for t necessary for the completion of these docurrents according t o the t imetable you have set.

I f you have any questions, please contact ne a t the above nunber or Dr. Donald Lyman, Deputy Director (Acting), a t 5-1102. I

.- . 50 . Gordo:. h f f y

Secre;ery of Znviroruental k-ff eirs

1102 C: Szree t S a c r ~ e a t o , CA 95814

D a e : @CT I ? m4 .

Subitti : Request f o r Zxtensic of Toxic Air C c a t a i c m r Reports. on ZijB ea2 EDC

from : Office of t h e Direc tor 7 1 1 ? Street, Room 1253 5-12&E

As yoc 'mow f r o n previous disci lss ic3s, t he D e p c b e s t ' s Zi;.ide=iological . .. S y ~ d i i s Sect ion has exzperiencec c . - f f ic-~1ty iz ~ e e t i a g che decLLi2es f o r yoxz requested tox i c 2ir ~~~~~~~~~r r i s k essessmezcs b e c ~ u s ~ of proble Ln e c ~ i r i n g the r e q u i s i t e specie1izeE perscanel e26 the dezzxd f o r - I?'-" S L L - ~ , znalyses from o ther sources. Given t h i s , we esk thzc the dea2-

.c ILnes f o r r e c e i p t o; t h e .ED3 r?C 3 D C r e ? o r t s be e z t ~ a Z e 2 -;7zil Decez55r 15 , 5 - 5 B l i , 2nd Februzry 28, 1985, resgect ively . Q s c ~ f f Esscre ne t h a t zhe r s ~ o r t s c m be con?lete6 by' t h e s e 62to-s, although such requires =her ve r e d i r e c t our e f f o r r s from severe l ozher i L g 5 pzLoriry p=ojec;s.

. . f Ia edvtzce, thank you ;for Chis c o n s i d e r a = i o ~ .

cc: I:exneth V. fLzer , M.D, &-:ex Kelrer , M.D. .-

! , ~ e m o r a n d u m flu 2 9 ~ 3 4 .'

b Gordon Duffy Date I October 22 , 1984 -

Sec re t a ry of Env i romen ta l Af fa i r s and Chairman of A i r Resources Subie* Toxic A i r Cantznicrr Board . Reports on EDB a d EDC

1102 Q S t r e e t

- ' O f f i c e of t he Di rec tor 714 P S t r e e t , Room 1253 5-1248

I n follow-up t o my memo of October 17, 1984, p lease be,advised ttat I have in s t ruc t ed my s t a f f t o give top. p r i o r i t y t o t he EDB and E X t o x i c ' a i r contaminant rep0rt .s and t o proceed a s rap id ly as possible with then. I hope t o be a b l e t o de l ive r them t o you e a r l i e r t'czn December 15, ,1984 (EDS), a d Februerp 28, 1985, (EDC), elthough rEs w i l l depend on some th ings no t e n t i r e l y wi th in our control . 05 note , I have. spoken wi th Assemblywoman S a l l y .Tanner about t h i s .

I should a l s o t e l l you. khct ocr experience so . far wi th t he Toxic Mr. C o n z d n a n t Program ( i . e., ,+th t h e benzene r epo r t a d . our work r-ith t he EDB and EDC r e p o r t s t o d a t e ) i nd i ca t e s . t h a t the report ing periods- s p e c i f i e d i n AB 1807 s e e d t o be lengthened i n order t o produce the h igh q u a l i t y r epo r t s t h a t you need. ' This i s a func t ion of t he adti'- d i s c i ~ l i n a r y approach needed t o roduce t h e r e q u i s i t e r i s k assess=ents , as w e l l as t he z v a i l a b i l i t y of ,t !, e n e c e s s a r y ' s c i e n t i f i c l i t e r a t a r e and other f a c t o r s . Wnatever, we p l z n t o Lntroduce l e g i s l a t i o a r o extend these time lines i n t h e next Leg is la t ive sess ion.

c-'il;iz1 ~imed by Stanley Cqji;ansU

Peter Rank Director

' cc: Kenneth W. Kizer , M.D., M.P .H. Depucy Direct01 Prkventive , Health Services

Davil B . Swoep, Secre:ary iieal=h and Welf zro, Agency

M e m o r a n d u m

yo , James 0. Boyd Execut ive O f f i c e r A i r Resources Board 1102 Q S t r e e t 8-4

st+ ~ e h ~ t h f f f e c t s Ethylene Dtbromide (EDB)

from : O f f i c e o f the D i r e c t o r 714 P St reet , Room 1253 8-1248

Attached i s t he document prepared i n response t o your memo request ing the assistance o f the Department o f Hea l th Services i n eva luat ing the h e a l t h e f f e c t s o f ethylene d i bromi de (EDB) .

- .

Peter Rank f

DI r e c t o r

At tac hmcnt

cc: C. B e r r y h i l l G. Bu f fy A. K e l t e r R. Neutra Assemblywoman Tanner P. Ven tu r in i

APPENDIX D

SAMPLING AND ANALYSIS METHODS FOR ETHYLENE DIBROMIDE

APPENDIX D

SAMPLING AND ANALYSIS METHODS FOR ETHYLENE DIBROMIDE (EDB)

1. S i t e s

Toxic sampling by the ARB s t a f f i n t h e SCAB comenced i n January, 1983 (see

F igure 1 f o r r e l a t i v e loca t ions) . E l Monte, t h e f i r s t operat ional s i t e i s 15

k i lometers east o f t h e Downtown Los Angeles (DOLA) North Main S t r e e t a i r

moni tor ing s t a t i o n operated by the South Coast A i r Q u a l i t y Management D i s t r i c t

(SCAQMD). The DOLA s i t e , a lready i n use f o r c r i t e r i a p o l l u t a n t s sampling, was

the second s i t e se lected f o r t o x i c sampling. A t h i r d sampling s i t e was

establ ished a t the C a l i f o r n i a State Un ive rs i t y Dominguez H i l l s f a c i l i t y i n

Carson, some 25 k i lometers south o f DOLA. A f o u r t h sampling s i t e was located.

a t the SCAQl.iD ~ i v e r s i d e s t a t i o n i n Riverside, 125 k i lometers east o f DOLA.

Table 0-1 summarizes the a c t i v i t i e s around the f o u r moni tor ing s i tes . . . . . . ,..

2. P r i n c i p l e o f t h e Method

2.1 Ambient a i r i s sampled i n t o a po l yv iny l f l u o r i d e (Tedlar) sample bag

a t a constant r a t e f o r a 24-hour t ime i n t e r v a l by means o f an

automatic sanpl er.

2.2 A f t e r sampling, the' ambient a i r bag sample i s re turned t o the

labora to ry and t h e contents a r e analyzed by gas chromatography (GC),

us ing an e lec t ron capture de tec to r (ECD) .

3. Range and Detect ion L i m i t

3.1 The minimum measurable concentrat ion o f EDB has been determined t o

be 5 p a r t s per t r i l l i o n (pp t ) using prescr ibed instrument

condi t ions, 100 m l o f sample, and a cryogenic trap.

3.2 The range o f EDB measurement i s 5 p p t t o 100 ppb. The upper l f m i t

nay be expanded by d i l u t i n g the sample.

4. Conf i rmat ion q f Chemical I d e n t i t y

4.1 Any organic compound present i n the sample having a re ten t i on t ime

s i m i l a r t o t h a t o f ED0 under t he operat ing condi t ions described i n . t h i s method may i n t e r f e r e w i t h t he analysis. Chemical i d e n t i t y f o r

EDB i s confirmed us ing a GC-Hall Electroconduct iv i ty Detector. Ten

percent o r more o f the samples are reanalyzed using the same column

and GC t o check precis ion.

5. Ca l ib ra t ion , Prec is ion and Accuracy

5.1 The c a l i b r a t i o n procedure employs the p r i n c i p l e s s e t f o r t h i n .

Volume 1 o f the "Qua1 i t y Assurance Handbook f o r A i r P o l l u t i o n

Measurement SystemsU (U. S. Environmental Pro tec t ion Agency, 1976).

5.2 Standards are used i n the l i n e a r i t y check a t concentrations which

bracket the ant ic ipated range o f po l l u tan t concentrations. The

c a l i b r a t i o n data are f i t t e d t o a s t r a i g h t l i n e , y=a + bx, by the

method o f l e a s t squares. The c a l i b r a t i o n i s acceptable i f the

f - r a t i o i s less than the 95 percent re jec t i on l i m i t .

5.3 The 95 percent confidence i n t e r v a l s are obtained by mu l t i p l y i ng the

square r o o t o f variance by the appropriate value o f "t" from a "t"

table.

5.4 References:

Bennett, C.A. and Frankl in, N.L., " S t a t i s t i c a l Analysis i n Chemistry

and Chemical Industry," p. 222-232. John Wiley & Sons, Inc.,

New York (1954).

' Draper, N.R. and Smith, H., "Applied Regressing Analysis," p. 30,

John Wiley & Sons, Inc., ~ e w York (1966).

Prunel l , H., "Gas Chromatography," p. 301-302, John Wiley & Sorts,

Inc., New York (1962).

U. S. Envi ronmental Protect ion Agency, "Qua1 i t y Assurance Handbook

f o r A i r Po l l u t i on Measurement Systems, Volume I Pr inc ip les. "

Research Tr iangle Park, North Carol ina 2771 1 ( 1 976).

6. Advantages and Disadvantages o f t h e Sampling Method

6.1 The a i r sampling equipment i s e a s i l y s e t up and i n v o l v e s no

l i q u i d s . The ambient concen t ra t i on o f EDB i s s t a b l e f o r a t l e a s t 72

hours i n t h e Tedlar sampling bags. Sampling bags a r e k e p t away from

d i r e c t s u n l i g h t and are n o t exposed t o temperatures greater than 30

degrees C.

6.2 A rep resen ta t i ve i n t e g r a t e d sample i s r e a d i l y ob ta ined because t t ie

equipment samples a t a cons tan t r a t e over a 24-hour per iod.

6.3 The accuracy o f the a n a l y t i c a l data i s n o t dependent on t h e accuracy

o f t h e volume o f a i r c o l l e c t e d b y t h e sampling apparatus.

6.4 The minimum de tec t i on l i m i t o f t h e ana lys is nay be extended by

, f r e e z i n g o u t a l a r g e r volume o f t h e samp1.e.

6.5 The maximum measurable l i m i t o f t h e ana lys i s may a1 so be extended by

d i l u t i n g the sample.

6.6 The p o l y v i n y l f l u o r i d e ( T e d l a r ) f i l m sample bag i s suscep t i b le t o

l eaks and permeation through t h e bag.

6.7 The sample i s suscep t i b le t o contaminat ion from t h e bag and t h e

diaphragm pump.

7. Apparatus

7.1 The sampling system consis ts of a diaphragm pump, seven day timer,

flow indicator, pressure regulator, flow controller , flow by-pass

system and the sample bag (see Figure 2). The diaphragm pump (made

of s tee l and Teflon o r Viton construction) draws ambient a i r through

the sample system a t approximately 5 l i t e r s per minute. Thirty-five

m i l l i l i t e r s per minute of this a i r stream is sampled, the remaining

flow is by-passed and vented. The sample flows through a diaphragm

pump, a Solenoid valve, a pressure regulator ( s e t f o r 2-3 psig t o

prevent 'any accidental bu r s t i ng of over-fil led sample bags), a flow

control needle valve, a flowmeter, and in to the sample bag. A

seven-day timer regulates the sampling period.

7.2 Tedlar bags, 2 mil thickness, 50 l i t e r capacity, equipped w i t h

, stain1 ess s tee l quick disconnect f i t t ings .

7.3 Rigf d opaque containers f o r Tedlar bag samples a re used t o protect

contents from s u n l i g h t and accidental puncture.

7.4 A gas chromatograph equipped w i t h a cryogenic system and electron

capture detector.

7.5 A freeze-out system consisting of a s ta inless steel loop, a l iquid

nitrogen Dewar and a hot water Dewar.

7.6 A g l a s s column (6 f t x 1/4 inch) , packed with 0.2 percent Carbowax

1500 on 80/100 mesh Carbopack C.

7.7 An analog recorder and an in t eg ra to r t o quan t i t a t e peak areas.

7.8 A ground g l a s s syringe t o t r a n s f e r a i r samples from the Tedlar bag

t o t he GC sample i n l e t .

7.9 Assorted gas cyl inder regulator , flow meters, thermometers and a

barometer.

7.10 A 145 cubic f e e t (4160 l i t e r s ) g l a s s l ined tank t o prepare standard

ca l ib ra t ion mixture.

8. Reagents

8.1 A1 1 chemicals a r e t o reagent grade: 1,2-di bromoethane (ethylene

dibromide, EDB), methyl ch lor ide , methyl bromide, Freon-1 1.

Freon-1 2, dichloromethane (methylene chl o r ide) , t rans-

dlchloroethene, 1,2-dichloropropane, chloroform, 1 ,I ,I - t r ichloroethane (methyl chrloroform) , carbon te t rach lor ide ,

bromodichloromethane, t r ichloroethane (TCE), chlorodibromomethane,

bromoform, Freon-113, and te t rachloroethene (PERC) .

8.2 Helium, 99.995%

8.3 Zero n i t rogen

9. Procedure

9.1 Preparation o f the bags

- 9.1.1 Bags are constructed from 2 m i l Tedlar sheeting (27 inches

x 27 inches).

9.1.2 The seams are heat sealed t o form an envelope which

contains about 50 l i t e r s .

9.1.3 Swagelock, SS-QC4-D-400VT, s ta in less s tee l quick

disconnect f i t t i n g s are attached w i t h a s ta in less steel

adapter and buna O-ring, Cajon SS-4-TA-OR-ST.

9.1.4 A l l newly fabr icated bags are leak and contamination

tested. This involves three pressur izat ion and evacuation

cycles using zero a i r . A f te r a f i n a l pressur izat ion t o a

drum-head t ightness, the bags are stored f o r 24 hours to

t e s t f o r leakage. I f the bags do not remain taut , they

are repaired o r discarded. I f the bags renain taut , the

contents o f the bags are analyzed f o r EDB by GC. The

contents o f t h e bag must n o t exceed t h e EDB con ten t o f the

zero a i r by more than 1 ppt. I f t h i s c r i t e r i a i s met, the

bags a r e evacuated f o r f i e l d use. I f the bags exceed t h e

EDB 1 eve1 , t h e p r e s s u r i z a t i on/evacuat ion and ana lys i s

c y c l e i s repeated.

9.1.5 Due t o ex tens ive handl ing, most bags a r e n o t s u i t a b l e f o r

recyc l i ng . Bags s u i t a b l e f o r r e c y c l i n g a r e analyzed w i t h

a f lame i o n i z a t i o n de tec tor , evacuated, r e f i l l e d w i t h zero

a i r and evacuated f o r f i e l d use.

9.2 Prepara t ion o f sampling device f o r arrbient sampling

9.2.1 The sample bag i s a t tached t o t h e sampler v i a t h e

s t a i n l e s s s t e e l quick disconnect.

9.2.2 The sample pump i s t u rned on and t h e f l o w ad jus ted w i t h a

meter ing va l ve t o 35 ml/min as determined on t h e rotameter.

9.2.3 The t imer i s s e t t o s t a r t the sampler a t 7 t o 9 a.m. o f

the scheduled sampling day and s e t f o r a 24 hour du ra t i on .

9.2.4 Check t h e pressure r e g u l a t o r s e t t i n g .

9.2.5 A label i s attached t o the sample bag noting the bag

number, sampl ing day, sampling time, s t a r t i n g sample flow

and sampling 1 ocation.

9.2.6 After sampling i s completed, the sampler i s turned on

manually and the f i na l sample flow i s noted on the bag

labe l . The sampler i s turned off and the sample bag i s

removed via the s t a i n l e s s s tee l quick disconnect.

9.3 The sample bags a r e transported t o the laboratory i n a r i g i d opaque

container.

9.4 The bag samples received a t the laboratory a r e logged i n and

analysis i n i t i a t e d .

9.5 Analysis of samples . ( freeze-out method)

9.5.1 Immerse the freeze-out loop i n 1 iquid nitrogen and allow

the temperature t o s t a b i l i z e (approximately 5 minutes).

9.5.2 Flush the syringe w i t h about 100 ml of the sample,

discharge the sample in to a hood and withdraw exactly 100

ml from the sample.

9.5.3 Transfer the sample i n t o the precooled freeze-out 1 oop

through a Luerlock stopcock.

9.5.4 Back f i l l the syringe w i t h 100 m l o f helium and t rans fe r

i t i n t o the loop; then f l ush the loop w i th helium f o r 2

minutes. '

9.5.5 Stop the helium f l ush ing and remove the 1 i q u i d ni t rogen

Dewar from the freeze-out loop.

9.5.6 I so la te the cryogenic loop wi th an " i s o l a t i o n valve."

9.5.7 Replace the l i q u i d ni t rogen Dewar w i th a Dewar containing

ho t water a t about 80 degrees C.

.9.5.8 Allow the loop t o come t o equi l ibr ium w i t h the h o t water.

9.5.9 Introduce the sample i n t o the ca r r i e r gas stream wi th an

" i n j e c t i o n valve."

9.6 Measure the areas o f each o f the GC peaks with an e lec t ron ic

in tegrator .

9.7 GC condit ions:

9.7.1 Helium gas flow: 25 ml/min

9.7.2 Make up gas: 10% methane i n argon: 40 m l /min

9.7.3 .Heating bath temperature: 80 degrees C

9.7.4 Column temperature: 6 t o -160 degrees C a t 8 degrees C/m i n

9.7.5 Detector temperature: 300 degrees C

9.7.6 Column backflush: 23 min a f t e r i n j e c t i o n

13. Cal i b r a t i o n and Standards

10.1 Standard reference mater ia l f o r ethylene dibromide i s no t ava i lab le

from the National Bureau o f Standards. The standard ca l i b ra t i on

mixture used by the CARB i s prepared w i t h i n the laboratory .

The standard ca l i b ra t i on mixture i s prepared by d i l u t i n g pure gases

and vaporizing pure l i q u i d s i n t o a l a rge chamber o f zero a i r

according t o the fo l lowing procedure:

10.1.1 C l e a n t h e 1 4 5 c u b i c f o o t ( 4 1 6 0 l i t e r s ) g l a s s - l i n e d s t e e l

tank by evacuat ing ( t o 6-10 t o r r ) and then f l u s h i n g i t

w i t h zero a i r several times.

10.1.2 Pressur ize t h e tank t o 5 ps ia w i t h zero a i r a f t e r t h e

f i n a l evacuation.

10.1.3 F lush a 100 ml o f 18.7 t o r r o f methyl c h l o r i d e , 8.7 t o r r

o f methyl bromide, 0.4 t o r r o f Freon 11 and 0.4 t o r r o f

Freon 12 i n t o t h e tank.

10.1.4 I n j e c t 100 m i c r o l i t e r s o f the m ix tu re o f l i q u i d standards

i n t o the tank th rough a heated i n j e c t o r (150 deg. C) w i t h

a He c a r r i e r f l o w o f 100 rnl/min. The m i x t u r e o f l i q u i d

standards was prepared by m ix ing 3.0 m l o f methylene

ch lo r ide , 500 u l o f t r ans -d i ch l oroethene, 500 u l

1,2-dicl i loroethane, 1 m l o f 1,2-dichl oropropane and 100 u l

o f each o f t h e f o l l o w i n g : chloroform, 1,1,1-

t r i ch lo roe thane, carbon t e t r a c h l o r i d e , bromodichloro-

methane, t r i ch lo roe thene , chlorodibromomethane, bromoform,

dibromoethane, Freon 113 and te t rach loroethene i n 44 m l o f

methanol .

10.1.5 Humidify t h e tank by bubb l ing zero a i r through 40 ml o f

water (heated t o b o i l i n g ) i n t o t h e tank till a l l t h e water

I s vaporized.

10.1.6 Pressurize the tank t o 20 ps ia w i t h zero a i r .

10.1.7 Record the temperature and pressure.

10.1.8 S t a b i l i z e the mix ture f o r 24 hours ( t o be sure the

equ i l ib r ium between the wal l surface and the gas i s

establ ished).

- 10.1.9 Check the new standard mixture against t he previous

standard mixture and the EPA qua1 i t y assurance c y l i nders

t o va l ida te the concentrations before the new standards

mixture i s used f o r ca l ib ra t ion .

10.1.10 The standard c a l i b r a t i o n mixture thus prepared has the

fo l low ing concentrations:

water methanol methyl ch lo r i de methyl bromide d ich l oronethane chloroform trans-1.2-dichloroethene l ,2-dichloroethane ( EDC) 1 ,1 ,1-tr ichloroethane carbon te t rach lo r i de bromodi ch l oromethane I ,2-dichl oropropane t r ich loroethene (TCE) d i bromochl oromethane bromoform dibromoethane (EDB) Freon-1 13 Freon-1 1 Freon-1 2 Tetrachloroethene

0.96% 9.4 ppm 430 ppb 200 ppb 400 ppb

11 P P ~ 57 P P ~ 54 P P ~

8.6 ppb 8.9 ppb '0 P P ~ 88 P P ~ 9.6 ppb 10 P P ~ 9.8 ppb 10 P P ~ 7.2 ppb 9.3 ppb 9.3 ppb 8.4 ppb

10.2 Standards o f lower concen t ra t i ons a r e prepared by d i l u t i n g t h e above

m ix tu re w i t h zero n i t rogen .

10.3 C a l i b r a t i o n

10.3.1 Trans fer va r i ous volumes ( t h e volume used depends on t h e

concen t ra t i on o f t h e sample normal ly 10, 30, 70 and 100

m l ) o f t h e standard m ix tu re from t h e 4000 l i t e r tank i n t o

t h e GC and analyze according t o t h e procedure i n 9.5.

10.3.2 F i t t h e data t o a s t r a i g h t l i n e by t h e method o f l e a s t

squares. I f t h e c a l i b r a t i o n i s l e s s than t h e 95 percent

r e j e c t i o n l i m i t , i t i s accepted, o therw ise t h e c a l i b r a t i o n

i s repeated.

.10.3.3 A s i n g l e c a l i b r a t i o n check i s done by t r a n s f e r r i n g 10 m l

o f t h e s tandard m i x t u r e from t h e tank i n t o t h e GC and

ana lyz ing i t accord ing t o the procedure i n 9.5.

11. Qua1 i t y Assurance

11.1 Bag ma te r ia l t e s t s were performed t o determine s ~ i t a b i l i t y o f Tedlar

used t o c o n s t r u c t sample bags.

11.1.1 Bag contaminat ion t es t : A bag was f i l l e d w i t h zero

n i t rogen and the contents analyzed. The EDB concentrat ion

was below the de tec t i on l e v e l o f 1 ppt.

11 .I .2 Bag s t a b i l i t y t e s t : S i x bags were f i l l e d w i t h 10 ppb o f

EDB i n zero n i t r o g e n and the contents were analyzed a t

var ious i n te rva l s . The recovery o f EDB was b e t t e r than

80% i n 72 hours (Toxjc A i r Moni tor ing Technical Advisory

Committee, A p r i l 1985).

11.1.3 Bag record: A l o g o f each bag i s kep t t o ensure t h a t a t

no t ime has an ambient bag been used t o sample h igh

concentrat ions o f (>lo0 ppb) any compound. The l o g

contains date o f fabr ica t ion , leak test ing, sampling,

sampling s i te/date, bag i d e n t i f i c a t i o n and bag des t ruc t ion

date.

11.2 Each sampler i s t es ted f o r contamination before f i e l d use by pumping

zero a i r i n t o a sample bag. The contents o f the bag are analyzed

for EDB contamination. I f the EDB concentrat ion i s found t o be

below the de tec t ion l i m i t , t he sampler system i s then deemed ready

f o r f i e l d use. I f the system f a i l s t h i s tes t , it i s dissassembled,

decontaminated, re&ssembled and retested. This check i s repeated

every s i x months f o r each sampler system o r more f requent ly i f

anomol i e s occur.

11.3 Analysis

11.3.1 Zero n i t rogen i s run every day t o be sure the GC shows no

signal f o r t he blank, othenrise, the instrument i s cleaned

o u t and the blank re run u n t i l the GC passes the blank tes t .

11.3.2 A standard c a l i b r a t i o n i s run before any samples are.

analyzed. ?his i s t o ensure the c a l i b r a t i o n f a c t o r o f the

instrument has n o t changed. I f the c a l i b r a t i o n f a c t o r i s

. changed by more than 5 percent, t l i e GC i s checked f o r any

ma1 funct ion. I f there i s malfunction, i t i s repai red and

the GC reca l ibrated. I f there i s no malfunction, two more

c a l i b r a t i o n runs are performed dur ing the day. I f the

c a l i b r a t i o n runs are w i t h i n 10 percent o f each other, t he

analyses f o r t h a t day are ca lcu la ted based on the average

o f the new c a l i b r a t i o n factors. . I f the c a l i b r a t i o n runs

are n o t w i t h i n 10 percent, the GC has t o be examined f o r

any malfunctions. When the i n s t r u w n t i s repai red the

ca l i b r a t i o n i s rerun.

11.3.3 Ten percent o r more o f the samples are reanalyzed t o check

precis ion.

11.4 Q u a l i t y assurance audi t : The standard mixtures prepared i n the

laboratory are checked annually w i t h the EPA Q u a l i t y Assurance Audi t

Cylinders. These Q u a l i t y Assurance Cylinders are no t ava i lab le f o r

a1 1 the compounds, bu t those t h a t are ava i l able have agreed we1 1

w i t h our standards.

12. Calculat ions

12.1 The ED0 concentrations, i n p p t are ca lcu la ted by a data system using

the external standard method.

Concentration = Area x Ca l ib ra t ion Factor

Area = In tegrated ED0 Peak Area

12.2 The c a l i b r a t i o n f ac to r (CF) i s ca lcu la ted dur ing c a l i b r a t i o n by the

equation:

CF = Concentration/Peak Area

Rep1 i c a t e ca l i b ra t i ons are averaged and the ar i thmet ic mean i s

stored as the CF t o be used i n subsequent analyses.

3 12.3 Concentrations may be converted from ppt t o ng/m by means o f the

fo l low ing formula:

P = Pressure i n atmospheres

MW = Molecu lar we ight o f 1.2-dibromoethane (EDB)

8 2 = Gas constant i n (atm)/deg K mole

T = Absolute temperature (deg. K )

Otscript ion of ARDIHSLO 7oric Ccupound I b n i t o r i n g Sites

DOrntwn Lus Angeles Ominwe2 H i l l s E l hlonte ~ i v e r s i d e L.A. Dlpt. of Yater U Stat. Universi ty ARBlllragcn-Wit 7W1 Hlgnol l a m d P o u r ~ ~ l i n g u e z n i l l s Laboratory Areme -- Surrounding 1b)U N. ! b i n Street 1000 E. V ic tor ia S t . 95211 Te lsUr Ave. Riverside.

~ c t i v i t i e s Los Angeles. ~1 Carson. UI/ ~1 Ibntc.

Residential Yest: Tw-sUry North: Student worth: Low density North: Lw dennty *went units. G X n g . t r a i l e r rcSlOences m e family units. r l n r n r a r y schbol park South h Yest: convales~ent h a .

South: single f r u i l y Lo r denary swera l schools m single fanily Sovthvast i Uest:

un l t s R i x w r e or single . and r u l t i p l e fani ly

uoi ts. several

South 6 East: Low aensl ty n n g l e

T ra f f i c - Continuous gasolinc Light-duty F rcaay worth Hnvy t r a f f i c along and diesel powered res ident ia l of the mni to r . Ar l ington ana l f g h t and heavy t r a f f i c 0n T c l s t l r - Magnolia Avenues. duty v e h i ~ l e s along grsol lne m d Mainly l i g h t m d uorth t h i n S t m t diesel vehicles m d i w duty gaso-

r f t h passenger l i n e m d diesel- cars dcainant. powered vehicles Greatest v o l ~ s during c lmut ing hours.

s t r i p ccu lcrc ia l Business uark Office ma s t r i p area. comercial. c o t ~ . r r c l a l uses l i g h t industr ial . along Arl ington and of f ice use and rtagnolia Ares.

L i h t North: Carnation A t r i a l w s s i n g

olant. rubbcr . - . . - - -

products coopany. brass UINlfacwring and tholesaling. Easf: Milk processing. - winery, railway transportation. concrete coapny, c ~ ~ r c i a l t w k i n g and shipping. paint coupany SouM: Railway V l n l w r t a t i o n . trucking and shipping overations

3 rnoustr ial

north: O i l well - pwalng S o u e : - ~ i l re f in ing -tarage ac t i v i t i es . chwica l omnufacwring East: O i l wel l pmping - North and East: b P T r c i a ~ nursery QOP*

1/ m t l i t o r i n r Zna s U r / wtnaor of 2 1/2 s a y buildins. Annual preaminmt tdnd airection: southurst.

2.' wanitor i n a van soutneast of calpus. Annua: preooninant wind direction: r s i . w n i t o r i n a t r a i l e ? i n tne scuvlrest p r r t i ne lo:. Annual preaonindnl wind direction: wth. 5; m n i t l - i n a one-story bui laing on tnr SouMeaS: stce of tne Arlrnglon-Ibgnollr i n t c r r u t l o n . Annual preow1n.n: wtno airection: .err.

APPENDIX E

AMBIENT MONITORING DATA AND ANALYSIS

I. AMBIENT A I R CONCENTRATIONS

The ARB'S Haagen-Smit Laboratory (HSL) monitors the ambient concentration

o f ED8 a t four s i t e s i n the South coast A i r Basin (SCAB): El Monte,

Riverside, downtown Los Angeles (DOLA), and Dominguez H i 11 s. Twenty-four hour

samples a re co l lec ted and analyzed by t he methods presented i n Appendix D.

Each o f the four s i t e s has a d i f f e r e n t sampling schedule f o r EDB. Samples are

co l l ec ted a t El Monte f i v e days each week. A t the other s i tes , samples are

co l l ec ted approximately once each week, b u t on d i f f e r e n t days a t each s i te .

(i.e., there a re two samples co l l ec ted each day, one o f which i s a t El Monte.)

Seventy percent o f a l l data taken between January 1983 and May 1984 are

l e s s than HSL's minimum repor tab le value, 5.0 par ts per t r i l l i o n , volume

(ppt ) . For s t a t i s t i c s , such data a re assigned the value 2.5 ppt. Table E-1

shows the r e s u l t i n g average concentrat ions by s ta t i on f o r 1983, f o r the f i r s t

f i v e months o f 1984, and overa l l . It a lso shows the numbers o f samples above

and below the repor t ing l i m i t . Figures E-1 through E-4 dep ic t monthly

averages over the per iod ~ a n u a r y 1983 t o May 1984.

The 1983 averages f o r DOLA, El Monte, Riverside, and Dominguez H i l l s are,

respect ively, 9.0, 9.3, 6.4, and 5.0 ppt. The mean o f these four averages i s

7.4 ppt. A t a l l stat ions, the EDB concentrations were h ighest dur ing the

summer o f 1983, although the e f f e c t i s ra ther weak a t Riverside. Data from

the summer o f 1984 are n o t y e t ava i lab le .

Table E-2 shows the 15 highest 24-hour neasurements among a l l s i tes . It

a lso shows the same day measurements a t whichever second s t a t i o n was a lso

sampl i ng .

Table E-1

Summary o f Moni tor ing Resul ts i n the South Coast A i r Basin (SCAB)

DOLA El Monte Dominguez Rivers ide Total ~ e a n ~

January t o Decenber, 1983

Number o f data 45.0 p p t 40 117 39 32 228 75.0 - p p t 14 80 13 15 122

Mean (ppt ) - >5.0 p p t 27.5 19.3 12.4 14.7 18.0 1 dataa 9.0 9.3 5.0 6.4 7.4

January t o May, 1984c

Number o f data <5.0 p p t 20 76 14 18 128 ~ 5 . 0 p p t - 3 19 6 5 33

Mean (pp t ) 75.0 pp t 6.0 6.9. 8.0 7.6 a 1 dataa 3.0 3.4 4.2 3.6

A l l Samples

Nunber o f data 45.0 p p t 60 193 53 50 356 75.0 - p p t 17 99 19 20 155

Mean (pp t ) >5.0 p p t 23.7 17.9 11 .O 12.9 16.0 1 dataa 7.2 7.4 4.7 5.5 6.2

a data t h a t were reported l ess than 5.0 p p t a re assigned the value 2.5 p p t

average o f the four s i t e means

data f o r l a t e r months n o t y e t ava i lab le ; does n o t represent year-round means

Jan f r b m a r opr m a y Jun Ju l aue orp oot nov dro Jon f rb m a r opr m a y

1883 1884

Figure E-1. Monthly Average EDB concentrations a t El Monte.

PPT

Figure E-2. Monthly Average Ed0 concentrations a t Downtown LA.

PPT

Jon Prb m a r apr m a y Jun Ju l oug r a p oct nov doc Jan frb m a r apr m a y

Figure E-3. Monthly Average ED0 Concentrations at Dominguez Hills.

E- 5

Jan fab mar apr may Jun Jul oug map oot nov dao Jan fab m a apr may

1883 1884

Figure E-4. Monthly Average ED0 Concentrations at Riverside.

Table E-2

Fi f teen Highest EDB Concentrations and Same-Day Concentrations a t Other Sites.

Highest Concentration Same-Day C~ncent ra t ions 'Rank Date s i t e Ppt S i t e Ppt

7/26/83 R'side 8/ 9/83 E l M. 7/25/83 El M. 8/11 /83 El M. 6/20/83 E l M. 5/22/83 Dom. 8/ 4/83 El M.

El M. DOLA R'side DOLA Dom. (None ) El M. R'side E l M. (None ) DOLA R'side (None El M. DOLA

11. AEIALYSIS AND CONCLUSIONS

The data from E l Monte were examined f o r s t a t i s t i c a l c o r r e l a t i o n w i t h

those taken on the same days a t each o f the other stat ions. No s t a t i o n ' s data

y ie lded a co r re la t i on c o e f f i c i e n t (j) above 0.35 versus El Monte. This r e s u l t

suggests t h a t each s ta t i on i s predominantly a f fected by d i f f e r e n t sources

( r e l a t i v e t o El Monte), possibly rri t h d i f f e r e n t temporal var ia t ions. A1 so,

the r a t i o o f h ighest 24-hour measurement t o annual average i s unusually high - 20 and 14 - a t DOLA and El Monte, respectively. This ind ica tes t h a t these

s i t e s are a f fec ted by nearby l o c a l i z e d sources ra ther than by emissions t h a t

are s p a t i a l l y uni form over a l a r g e area.

Therefore, the data po in t to an emission pa t te rn dominated by i so la ted

sources w i th strengths varying i n time. I t i s a lso possible t h a t incons is tent

meteorology, espec ia l ly wind direct ion, could have caused o r cont r ibuted t o

the above s t a t i s i ca l patterns. However, t h i s i s u n l i k e l y because regressions

o f EDB measurements stat ion-by-stat ion against d a i l y resu l t an t wind d i rec t ions

and speeds y ie lded no correlat ions.

Tablle E-3 shows the other var iables we used i n 1 inear and mu1 t i p 1 e 1 inear

regressions against each s ta t ion 's EDB data. It ind ica tes the e f f e c t which

each independent var iab le was intended t o represent; None o f the regressions

y ie lded co r re la t i on coe f f i c i en t s greater than 0.4. This suggests t h a t the

dominant emisslon source(s) - a t l e a s t dur ing the periods o f h igh ambient

concentrations - was no t auto exhausts o r gasoline. However, because 69

percent o f the dependent var iable (EDB) data were a r b i t r a r i l y f i x e d a t a

constant value (1/2 the repor t ing l i m i t), the lack o f cor re la t ion cannot be

used t o make sound conclusions.

Table E-3

Independent Regression Variables

Variable Represented E f fec t

CO (ppm) Automotive exhaust emissions EDC (ppmIa Gas01 i n e composition Maximum d a i l y temp. Minimum d a i l y temp. Evaporation o f gas01 i n e Dai ly temp. change Resul t a n t winds Plume d i rec t ion and dispersion Temp. a t 850 mi l l i ba rb Inversion height . Mixing i n atmosphere

a 1,2-dichloroethane; present i n a f i x e d r a t i o t o EDB i n leaded gasoline

b temperature a t the a1 ti tude where atmospheric pressure i s 850 m i l l i b a r s

The lack of a correlating variable leaves no means to extrapolate the

measurements a t the monitoring sites t o the r e s t of the SCAB, other than t o

assume tha t the en t i re population i s exposed to the in ter-s i te mean, 7.4 ppt,

as the annual average.

I1 I. AOOITIOtiAL DATA

The only other data on ED8 concentrations i n California are short-term

data from 1976 t o 1982. They a re summarized i n Table E-4.

Table E-4

Miscellaneous Dafa on EDB Concentrations

Month/ Place Year Duration Number Mean ( p p t ) Ref.

Los Angeles 3/76 14-1 9 hrs 2 15.4 1 10s Angeles 4/79 24 hrs 8a 33.7 1,496 Los Angeles 11 /81 3 hrs 156 23.4 2

t o 4/82 ~l Monte 11 /81 -- 106 28.5 2

t o 5/82 Oak1 and 7/79 24 hrs 8b 16.5 1,3,4,6 Riverside 4 i i l 10 days 1 23.0 1 Riverside 7/80 24 hrs 1 Oc 23.2 1,3,5 Mill Valley 1 /77 26 days 1 10.0 1 Badger Pass 5/77 8 days 1 0.0 1 Point Arena 5/77 7 days 1 5.0 1

a plus one a t 14 hours b . plus one a t 10 hours c p l u s one a t 12 hours

REFERENCES FOR APPENDIX E

1. Brodzinsky, R. and Singh, H.B; V o l a t i l e Organic Chemicals i n the Atmosphere - An Assessment o f Ava i lab le Data, S R I In te rna t iona l , A p r i l 1983, LPA 600/3-83-027a.

2. A i r Resources Board, Haagen-Smit Laboratory Div is ion, "Prel iminary Inventory o f Ambient Concentrations o f Toxics", July, 1982.

3. Singh, H. B., e t al.; Measurements o f Hazardous Organic Chemicals i n the Ambient Atmosphere, SRI In te rna t iona l , EPA 600/3 - 83 - 002 , PB 156935, January, 1983.

4. Singh, H. 'B., e t a1 .; Atmospheric Measurements o f Selected Toxic Organic Chemicals, SRI In ternat ional , EPA 600/3 - 80 - 012 , PB 198989 , J U ~ Y , 1980. .

5. Singh, H. B., e t al.; " D i s t r i b u t i o n o f Selected Gaseous Organic Mutagens and Suspect Carcinogens i n Ambient A i r , " Environmental Science and Technology 8 - 16 (12), p. 872, 1982.

6. Singh, H. B.. e t al.; "~easurements o f Some P o t e n t i a l l y Hazardous Organic Chemicals i n Urban Environments," Atmospheric Environment, - 15, p. 601 -61 2, 1981 .

APPENDI'X F

SUPPORTING INFORMATION ON ETHYLENE DIBROMIOE

EMISSION ESTIMATES

APPENDIX F

supporting Informat ion on EDB Emission Estimates

CALCULATION OF EDB TO LEAD RATIO

Atomic r a t i o -- 1 atom Pb: 1 atom Br (Roberts, 1980, pg 3-82)

molecular weight -- 1 mole EDB: 2(CH2Br) = 2 (12.01 + 2 (1.01) + 79.91) =

187.88

1 mole Pb: 207.19

A mole o f EDB has 2 atoms Br, therefore 0.5 mole ED0 i s required per mole Pb.

0.5 mole EDB/mole Pb = 0.5 (187.88)/(207.19) = 0.453 1b EDB/lb Pb

CALCULATIOU OF EDB CONSUMPTION IN 1983

Total lead used i n 1983: 4,228,879 k g (Morgester, 1984)

(4,228,879 kg Pb)(2.205 lb/kg)(ton/2000 l b ) = 4662 tons Pb

(4662 tons Pb/yr)(0.453 l b EDB/lb Pb) = 2112 tons EDB/yr i n leaded fue l

CALCULATION OF MOTOR VEHICLE EXHAUST EMISSIONS

Survival r a t e o f EDB -- \ r t i n exhaust/wt i n fue l = 0.37% = 0.0037 (Sigsby,

e t . al., 1982, pg 12 -- This i s based on l i m i t e d t e s t data).

(2112 tons EDB/yr i n fue l l(0.0037 exh. EDB/fuel EDB) = 7.8 tons EDB/yr

statewide

Since the South Coast A i r Basin (SCAB) has 47 percent o f Ca l i f o r n i a ' s

population, assume i t accounts f o r 47 percent of the EDB consumed i n fue l

(2112 tons EDB/yr i n f u e l ) (.47) (0.0037 exhaust EDB/fuel EDB) = 3.7 tons

EDB/yr i n the SCAB.

I f the t e s t r esu l t s f o r the Mazda automobile are excluded from Sigsby's paper,

because the Mazda was reg is tered f o r unleaded fuel and many o f the t es t s

ind icated zero EDB emissions ( f rom telephone conversation w i t h Mr . Sigsby on

8/14/84], the survival r a t e o f EDB i s 0.45% which gives an estimated emissions

Of 9.5 tons EDB statewide and 4.5 tons EDB i n the SCAB.

CALCULATION OF MOTOR VEHICLE EVAPORATIVE EMISSIONS

evaporative EDB = 9 x 1 o ' ~ 1 b EDB/ l b HC

(Sigsby, e t al., 1982, pg 6 - NOTE: on ly data f o r TEL fue l were used and t h i s

i s a rough value based on l l m i t e d t e s t data. However, the weight f r a c t i o n o f

ED0 t o THC i s 1.03 x 1 0 ' ~ i n the vapor phase based on Raoul t l s law. So t h i s

number appears reasonable.)

Evap. emissions from non-catalyst on-road vehicles i n 1983 = 77,771 tons HC/yr

(CARB , 1983a )

(77,771 tons ~ C / y r ) ( 9 x 10m5 i b EDB/I~ HC) = 7 tons EDB/yr statewide

Applying the .47 population f ac to r f o r the SCAB:

(77,771 tons HC/yr)(.47)(9 x l b EDB/lb HC) = 3.3 tons EDB/yr i n the

SCAB

CALCULATION OF GASOLINE MARKETING EMISSIONS

I n an EPA report , the mass f r a c t i o n o f EDB i n saturated gasoline vapor f o r

0.015 Vol % EDB a t 70'F i s 5.2 x (EPA, 1984, pg 2-71. EDB i n -

C a l i f o r n i a gasoline i s estimated as 0.00604 Vol %, based on the weight r a t i o

1.000:0.294 o f te t rae thy l l ead t o EDB, respect ive ly and 1.1 g. Pb per ga l lon

o f leaded gasoline. An EDB emission fac to r f o r gasoline marketing based on

these data i s therefore:

(5.2 x 1 0 ' ~ lb.EDB/lb.THC)~0.00604/0.015) = 2.1 x lb.EDB/lb.THC

The TOG'emissions from gasoline marketing, inc lud ing emissions from po in t

sources are forecasted as 36,800 tons i n 1983. Assuming TOG emissions from

leaded gasoline are proport ional t o the amount of leaded gasoline produced a t

the re f i ne r i es , 41.2 percent o f the estimated TOG emissions are from leaded

gasoline (ca lcu la ted by the percentage o f leaded gasoline t o t o t a l gasoline

output from r e f i n e r i e s - CEC, 1984, pg 30,311.

For gasoline evaporation, a ton o f TOG i s equivalent t o a ton o f THC (CARB,

1983b, pg H-17). The EDB emissions from gasoline marketing are thus:

EDB Ems = (36,800 tons T ~ ~ / y r ) ( 0 . 4 1 2 ) (2.1 x 1 0 ' ~ i b . ~ ~ B / l ~ . T H C )

= 0.32 tons/yr., statewide

Applying the .47 population f ac to r f o r the SCAB:

EDB Ems i n the SCAB = (0.32 ton ly r . x .47)

= .15 t on /yr.

CALCULATION OF GASOLINE PRODUCTION EMISSIONS

The estimated THC release from gasoline mixing, t ransfer and storage operation

a t Douglas re f inery i n 1979 was 38 l b / h r (Roberts, 1980. pg 3-92).

Gas01 i ne production capacity a t Douglas re f i ne ry i n 1979 was 8,500 bbl/day

(Roberts, 1980, pg 3-84). Assuming product ion a t 70% capacity, 5,950 bbl /day

o f gasoline would have been produced a t the Douglas re f inery . An emission

fac to r fo,r gasoline production ca lcu la ted from these data i s thus:

Emission Factor = (38 lb.THC/hr) (2.1 x 1 0 ' ~ 1 b.EDB/l b.THC (24hr./day

(5950 bbl /day I-'

= 3.22 x 1 0 ' ~ lb . EDB/bbl gasoline

The t o t a l leaded gasoline production i n 1983 was 119,472,000 bbls (CEC, 1984,

pg 31 I . Using these data, ED8 emissions f o r gasoline production are estimated

t o be:

EDB Emissions = (119,472,000 bbl/yr)(3.22 x loe6 lb . EDB/bbl)

(ton/2,000 l b . 1

= 0.19 tonlyr.. statewide

Applying the .47 population f ac to r f o r the SCAB:

EDB Emissions i n the SCAB = 0.19 ton/year x .47

= 0.09 ton EDB/year

EDB Emissions i n the SCAB from Produce Fumigated Outside Ca l i f o rn ia -

It i s possible t h a t i n 1983, f r u i t s and gra ins fumigated outside o f Ca l i f o rn ia

released EDB i n the South Coast A i r Basin when cooked, processed o r simply l e t

stand exposed. Appropriate data are too few f o r an accurate estimate o f such

emissions. This appendix presents t he ca l cu la t i on o f an upper bound o f

p laus ib le emissions. Data from years other than 1983 must be used.

Emissions o f EDB could occur a t many steps i n the h i s t o r y o f an out-of-state

shipment o f produce a f t e r i t has crossed i n t o Ca l i fo rn ia . However, i f we

assume t h a t a l l EDB enter ing Ca l i f o rn ia i s released here ( t h a t is , ne i ther

eaten, borne i n exported products, nor borne i n returned cargo containers 1,

the t o t a l emissions equal the import r a t e o f fumigated produce times i t s mean

EDB concentration plus the t o t a l EDB i n the vo id volumes o f shipping

containers.

Upper Bound Concentrations

The Ca l i f o rn ia Department o f Food .and Agr icu l tu re (CDFA)

reported1 0'11 *' 2/ the resu l ts o f several s tud ies analyzing the EDB content

o f the pu lp o f fumigated c i t r u s f r u i t , mangoes, and papayas a r r i v i n g i n

Cal i forn ia . Table F-1 sumnarizes the data.

Table F-1

EDB i n Fumigated F r u i t from Outside Ca l i f o rn ia (CDFA, Ref. 10)

F r u i t - Orig in o f Sample ED0 i n Pulp, ppb

Papaya Shipping container 20

. Papaya Shi pping container 31

Oranges Wholesaler 11 3

~ i m e s Who1 esal e r 1.2

Grapefruit Who1 esal e r 82

Papaya

Mangoes

Whol esal e r

Whol esal e r

To be conservative (bias e r ro rs high), we used 100 ppb for fumigated

f r u i t pulp i n subsequent calculat ions.

CDFA a1 so present a few data, sumnarired i n Table F-2, f o r the

r a t i o o f EDB i n skins t o EDB i n pulp.

Table F-2

Ratio of Skin and Pulp Concentration o f EDB (CDFA. Ref, 10 , l l )

F r u i t - Papaya

Oranges 1 t o 24

Oranges 11 t o 22

To be conservative, we assumed tha t the papaya and mango pulp

concentrations i n Table F-1 apply t o the en t i r e f r u i t s and t h a t the c i t r u s

f r u i t s ' overal l concentration i s given by:

- C t ~ t a l - Cpulp x (90% o f weight as p;lp)

+ 20 Cpulp x (10% o f weight as sk in )

= 2.9 x C P U ~ P

= 290 ppb

The Department o f Health Services (DHS) analyzed 171 samples o f whole

13/ gra in from l a t e 1983 t o spring, 1984, and detected ED8 i n 17 o f them.-

They repo r t only t h a t the maximum was 650 ppb. I f t h a t f i g u r e i s used as a

h igh estimate o f the average, the ove ra l l average was 65 ppb. This agrees

w i t h monitoring by P i l l sbu ry o f gra ins a r r i v i n g i n Los ~ n ~ e 1 e s . X ' A few

shipments had ED0 concentrations exceeding 100 ppb, b u t most had

concentrations be1 ow 10 ppb.

DHS a lso analyzed 1,291 samples o f products derived from grains and

nuts. Three hundred twenty were pos i t i ve , w i t h 56 above DHS's "act ion l eve l "

o f 150 ppb. I f 150 ppb i s used as a h igh estimate o f the average o f the

p o s i t i v e samples, the overa l l mean i s 37 ppb.

10 121 F ina l l y , CDF- measured the ambient concentration o f ED0 i n closed

shipping containers and trucks a r r i v i n g w i t h fumigated produce. Tab1 e F-3

summarizes the data.

Table F-3

Ambient EDB i n A r r i v i n g Containers (CDFA, re fs . 10,121

Enclosure F ru l t Pmblent EDB, ppb

Sea van payapas 88 t o 261

A i r cargo container papwas 34 to 91 (co ld )

Truck papayas 364

Truck 1 emonr 25 t o 1,523 -

To be conservative, we used 1.000 ppb as the h igh estimate o f ambient

concentrations i n cargo containers.

Import Rates

Data f o r imports o f whole grains and f r u i t t o Los Angeles are shown i n

Table F-4.

Table F-4

Imports o f F r u i t and Grain t o Los Angeles

Item - Reference - Year - Tons

Total grains 15 1982 3.01 x 106**

C i t rus 16 1983 2.2 x 104

Mango 16 1983 4,250

Papaya* 16 1983 200

* " f r u i t s , other, Mexico" i n re f . 16

** t o t a l t o s ta te divided by 2

There are no data avai lab le f o r the amount o f g ra in products imported t o

Ca l i fo rn ia . To be conservative (est imate high), we assumed the import r a t e i s

6 one pound per day per person, o r about 1.8 x 10 tons per year i n the South

Coast A i r Basin.

We assume t h a t cargo containers enclose 67% empty space when loaded and

t h a t the produce density i s 60 pounds per cubic foot . The enclosed a i r volume

per ton o f produce i s thus:

ED0 Emi ssf ons

The high estimate o f EDB emissions i n the SCAB i n 1983 from produce

(assuming - a l l produce ar r i ved fumigated) i s :

Items Tons/yr x F rac t ion = Emissions

Whole grains: 3 x l o 6 65 x lo-' .20

Grain products: 1.8 x l o 6 37 x 10-9 .07

Mangoes. papayas:

Ci t rus:

The high estimate o f emissions from cargo a i r i s :

x 188 l b EDB x ton/2,000 l b 3-anwnr~

Therefore, the maximum p laus ib le emission r a t e o f ED0 from imported

fumigated produce i s minor compared t o the known inventory f o r the South Coast

Air Basin.

REFERENCES FOR APPENDIX F

1. Roberts, R. M., 1980. An Inventory o f Carcinogenic Substances Released i n t o the Ambient A i r o f Ca l i f o rn ia , F ina l Report Task I 1 and I V , KVB, Inc . f o r Science Applications, Inc., Los Angeles, CA.

2. Morgester, James, 1984. "Report o f Gas01 i ne Production f o r Consumption i n Cal i fornia," A p r i l 17, 1984. Ca l i f o rn ia A i r Resources Board, Compl iance D i v i sion, Sacramento.

3. Sigsby, John E., e t al., 1982. "Automotive Emissions o f Ethylene Dibromide," SAE Technical Paper Series, Society o f Automotive Engineers Passenger Car Meetlng, Troy, Michigan, June 7-10, 1982.

4. Ca l i f o rn ia A i r Resources Board, 1983a. "BURD1983," computer repo r t dated 9/2/83, Emissions Inventory Branch, Technical Support Div is ion, Sacramento. -

5. Technical Data Book - Petroleum Refining, 3 r d Edi t ion, Vol. 1, Chapter 5, published by API, 1976.

6. Verschueren, K., 1983. Chemical s 2nd Edit ion,

7. Ca l i f o rn ia A i r Resources Board, 1984. Data re t r i eved from Emissions Data System (EDS) f o r inventory years 1979 and 1981, Emissions Inventory Branch, Technical Support Div is ion, Sacramento, CA.

8. Ca l i f o rn ia Energy Comnission, Quar te r l y O i l Report, F i r s t Quar ter 1984, June 1984.

9. . Ca l i f o rn ia A i r Resources Board, 1983b. Supplement 4 t o Procedure and Basis f o r Estimating On-Road Motor Vehicle Emissions, Emissions Inventory Branch, Technical Support Div is ion, Sacramento, CA.

10. Ca l i f o rn ia Department o f Food and Agr icul ture; "Studies and Evaluat ion by the CDFA on EDB Used i n Fumigation o f Fru i t , " HS-956, Progress Reports 1 through 4, 1981.

11. Maddy, Kei th T.. e t al.; "Analyses f o r Residues o f EOB i n Selected F r u i t Which Had Been Fumigated P r i o r t o Entry i n t o Cal i fornia," CDFA, February 8, 1980.

12. Maddy, Kei th T., e t a1 .; "Ven t i l a t i on o f Truck T r a i l e r s Containing EDB Fumigated Comodi t ies," HS-957, CDFA, March 3, 1982.

13. "EDB Sample Results Sumnary t o 03/20/1984," Ca l i f o rn ia Department o f Health Services.

14. Conversation between R. Vincent (ARB) and Carl Smith (P i l l sbury , Minneapolis, 61 2-330-51 65) June, 1984.

15. Federal -State Market News Service; "Grain Shipped i n t o Ca l i fo rn ia from Out-of-State by Rai l and Truck - 1982.'

16. U. S. Department o f Agriculture, "Fresh F r u i t and Vegetable Arr iva ls i n Western C i t ies , " 1983.

17. U.S. Environmental Protection Agency; Evaluation o f Air Pol 1 ut ion Control Strategies f o r the Gasoline Marketing

F-12

APPENDIX G

ESTIMATE OF ED0 EMISSIONS REQUIRED FOR

OBSERVED AMBIENT CONCENTRATIONS

APPENDIX G

ESTIMATION OF EDB EMISSIONS REQUIRED TO ACCOUNT FOR OBSERVED AMBIENT CONCENTRATIONS

The means o f a l l anbient EDB monitor ing data taken dur ing 1983 a t DOLA,

Dominquez, El Monte, and Riverside a re 9.0 ppt, 5.0 ppt, 9.3 pp t and 6.4 ppt,

respectively.* The mean o f these four values i s 7.4 ppt, o r .057 ug/m5. We

assume t h a t t h i s f i gu re t y p i f i e s the annual mean concentration o f the e n t i r e

SCAB.

One can estimate the emission r a t e o f EDB needed t o account f o r the mean -

observed ambient concentration. Carbon monoxide, 1 ead, and EDB are a1 1

emitted by road vehiclesn, and a1 1 have neg l i g i b l e photo-react iv i t ies .

Therefore, i f EDB, 1 i k e CO and lead, i s predominantly from vehicles, the r a t i o

o f ambient concentration t o emission r a t e should be approximately equal among

a1 1 three compounds.

Table G-1 shows the 1983 mean concentrations o f CO and lead a t the four

s ta t ions nearest the EDB monitors.

Tab1 e G-1

1983 Mean Anbient Concentration (ug/m3) (Source: ARB Aerometric Data D iv is ion)

Pico Rivera Lynwood (El ~ o n t e ) k / DOLA (Dom. Hi1 1 s)b/ ~ i v e r s i d e l Average

a/ Magnolia S t ree t 61 Parentheses ind ica te the EDB monitors f o r which Pico Rivera and

Lynwood serve as the nearest CO monitor ing s i tes.

* These means were calculated using 2.5 p p t f o r data reported as l e s s than 5.0 ppt.

** I n the South Coast A i r Basin, 92 percent o f estimated CO emissions and 98 percent o f estimated lead emissions are vehicular (ARB Technical Support Div is ion) .

6 CO emissions i n 1983 i n the SCAB were 2.05 x 10 t 0 n s . 1 ~ The amount

o f lead used i n gasoline i n Ca l i f o rn ia i n 1983 was 4.031.000 kg (8,870,000

1 b I . y Roughly h a l f o f the lead was i n fue l burned i n the SCAB, and roughly

32% o f the lead introduced i n t o vehic les becomes avai lab le f o r ambient

sampling as vapor o r small aerosol . / Thus, the e f f ec t i ve lead emissions i n

the SCAB were 71 0 tons i n 1983.

Table 6-2 shows the r a t i o o f emissions t o mean annual ambient

concentration f o r CO and f o r lead and the respective estimates o f ED0

emissions.

Table 6-2

EOB Emission Estimates. SCAB, 1983

Emissions EDB ~ m i s s i o n s i / Surrogate Eoncentrati or& ( tonslyear)

a/ from l a s t column o f Table G-1 - bl based on the ambient concentration .057 ug/m3

These r e s u l t s are four t o s i x times the known emission inventory o f EDB

i n the SCAB. It thus appears t h a t e i t h e r vehicular emissions o f EOB have been

underestimated o r t ha t an as-yet-unknown type(s 1 of source a f f ec t s the

monitoring s i tes . Such a source type could e i t h e r be la rge b u t spread over

the basin o r minor bu t unfortunately near the monitoring s i tes.

The arnbient monitoring data i n 1983 show Strong peaks i n June through

August a t three o f the four s i tes. The mean concentrat ion among the s ta t ions

f o r the other n ine months i s 4.7 ppt. I f t h i s f igure i s hypothesized as a

"vehicular background" upon which short-term unknown sources added the June t o

August peaks, the above methodology y i e l d s 4.7/7.4 x (41 o r 67) = 26 o r 43

tons per year, o r two t o three times the known inventory. So, i t appears t h a t

i n add i t ion t o some seasonal source, a year-round correct ion t o the emission

inventory may be needed.

REFERENCES

1. Air Resources Board Technical support Division.

2. Air Resources Board Compliance D i v i s ~ o n .

3. Huntzicker. J. J., e t a l ; "Material Balance fo r Automobile-Emitted Lead i n Los Angeles Basin," Environmental Science and Technology 9 ( 5 ) . May 1975.

' -

APPENDIX H

ASSEMBLY BILL 1807

Assembly Bill Na. 1807

- . Passed the k c m b l y September 15, 1983

Chief Clerk ofthe Assemb&

Passed the Senato September 15,1983

Secretary of the Senate

This bill was received by the Governor this

dily of , 1953, at o'clock 2. .

Priv~te Secretary of the Governor

Taauelsqns jo X~!J!XOJ swajja . qqcaq. aq1 30 uo!lsnps Q! u! pmoq 33~3s aql aS!hpE '

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s1! uo posnq 'pmoq alels atla a ~ ! n b a ~ p[noA\ 11!q a q ~ . ,

'sealnos ap!agoad asoql w o ~ j xuo!ss!wa aanpal oq pauZ!sap sa~nsvaur I O J I U ~ adopc pus dolohap 03 pai!nbal aq pinom . 'sa!luno3 pqaaue ~ q ; U! SIJ!~S!P pun SlaUO!SS!UIWOJ rc~nl~na!sSe Xlunoa ql!m uo!lellnsuoa u! 'lolaaJ!p a q , ' -s:ucrr!urcj~~oa i!c a!xol sc pag!luap! sap!a!1sod ~ n j papaaa s2msaaw loi:uo~ jo asleap a~c!~do~ddu aya 'saa!~as!p pue 'p~coq alcls aql 'soa!ruaS qxlcaIIjo ~uawlsndaa oact~ aql q l ! ~ uo!lcl[nsuoa u! 'au!wlalap o: puc s~ucu!wvauoa . l!c a!xol asc sapp~lsad qqqm ao!rula~ap 03 paqnbar aq ~lvwr'- r*.nlnnt.*Flv pt*V pHs& Ja aapa?iltt

.pali:tf!a!:utt ?lo slaajja qllnaq auaApl: luca!j!uS~ ou qqq.c\ ;! '.(ac j! 'la.\"; aa~soclxa ~[oqsalq; 391 n?o;sc c22mss :rlnz;:ja~uou wolj s:uct~!c;'vlcoa l!v :!lo4 jq trrcqsr;ma ampa1 oa samscatu lo~luoa a!sol at:.~oq.~!,: i

:r!csr cl p ~ : ; n b ~ l aq plnom p~Loc~ alms aqj- ,;sp!?!;ssd., 1:;:- ,,'n.:!~a!.?!:r ~J;::cJ J I X O ~ ~(I.IO~.!I~! '1:!!:11:11!1!1110.1 . -.A

SF 31x02.. Suual aql s w a p p p o ~ 11 .ir,lcaq ucmny 03 moplemq aq Xrrw pun l!e lua!qurc aq; clu! pall!rtra slt 30 aq Xcur qJ!qM Sap!~!asadjo slaajja qllvay alunlma oa pal!nbax aq pinom 'plcoq alcls aql puc saa!,uaS qt[eaH 30 ~uauraladaa aacas aql q ~ n \ uc!~r~lnsuoa u! 'asnqlnap3y put poo,~ jo lolaana aq& ~ ~ u c n ~ u ~ c ~ r : ~ lye a!xoi r: s! aau1:lsqns e ~;~qloqn\ 'uo!l~?lnRsl Xq 'o:~!mralap 03 puv uo!~sc X~olcjn2as loj slscq aql se anlas p [ n o ~ qa!tfn~ l~odaa c axudald 01 'soj!,uas ql[caH jo ~uauialrrdaa awls aq: 30 uo!aect!a!~~ud aql ga!m pue q l ! ~ uo!lel[nsuoa u! 'p-uoq aarls aq; al!nbar . '

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. .. qalzaq aql uo suo!gspuawuroaas azcdald put? alenlona . hl

03 'picoq alcls aqa jo uo!~ed!a!l~ed at11 q~!.+\ puc rl;!n\ .: - 4 uo!~el[nsuo3 u! 'saawras qqeaH jo 1uaur;lcdaa n;caS a* .. . . 'pleoq alc;s aql jo asanbal uodn 'a~!nba~ plnom 11!q S ~ J , .; 'sap!a!~sad alc1n33lo~ X~!loqlns lelaaa8 scq a.1nqn3!~5y~ PUC pooj jo ;uaui~mdaa aqL .spIrptrclr X~![cnb ' . 1!1! ;ua!qua u!su!uur puc a.\a!qJn oa ape- s! uo!s!,rold a[qcuosual ley; olnssu qa!rjA\ suo!ll?[nSal pun s ? p ~ oarcfua purr ;dope ot psl!nbal ale sja!:ls!p arr~ur3Zr3cru X~!lsnb ~ ! e pun sp!~;s!p [os~uoa uo!gn[lod i!y .sas!.\laS yl[caH jo auawuedsa awls aq1 ;o SLI0!1~FIl~~~1IIIO~~l at[; uodn pascq aq oa po~!nba~ ole s33~3ja qlleaq 01 Su!lcla~ sp~cpuqs .a:rls aq1 r:! u!scq ~! r : yaca 10j sp~epuc~s k!lanb 1!~ ica;c(ure qciope o: ~al!nba.t s! plcoa saalnosaU 1!v alnaS oq3 'ME\ Su!>s!sa lapun ( 1 )

's]ueu!w\!~uo:, J!n 'a!xol. :uo!~nl[od my 'J?UUCJ, ' tog1 ~y

JS331(1 E7JSSfl03 3AILY1SI:Xil

.uo!Jnllod i!c o; Bu!l.j~a;l 'apoq Al~~t?q puw q i i i a ~ aysje gz no!s!A!a jo z ~ J C J c i (omcjd oc!:aa$ . qa!m Q U ! ~ U ~ W U I O ~ ) S.C la ldsqj ppc 04 prru '2703 I C J ~ J

-135p9y PUI! PM)J r)y$jo L nc!s!n!a;o ~ l a l d l ! ~ ~ 01 ( l c ~ b i uo!jaaS ~ I I A ~ Su~auac~uroa) 61 ap!glv ppv 01 lac uir

d...... ..... 4 ' Tine: bil! \vould n:aXc any pe~sol: w!lo violates any rule : or rog~lixtion, emission linlitalion, or pcrmit co:ldition

adopted io control n toxic .lir cantai1ri:lant liable for a civil panalt). not ercecc!ing s:O.COO pc; day.

(2) The bill would decinre lcgislutive intent that the stnta board, thc Stiitc Dcl>:~rtmcnt of Ilcoltlt Services, nnd thc Drpartment of Food a n d Agriculture perform fi~nctions required by thc biil in the 198344 fiscal year

within thcir esisling resources and budrctarv - " , authorizations. (3) Article XI11 B of the California Constitution and

Sections 2231 and 2231 of the Revenue and Taxation Code require the stsce to reinlburse local agencies and s~?hool districts for certain costs mnndatcd by the state. Other pro\isions rzquire the Dcpartment of Finance to review statutes disclaiming these costs and provide, in certain cases, for making c!aims to the State Board of Control for rcimbursemcnt.

However, this hill would provide that no appropriation is mode and no reimbursement is required by this act for a specified reason.

. The p&e of the State of CafliFnia do enact 8s fbffows:

? w SECTION 1. Chapter 3.5 (commencing ~ 4 t h Section

39530) is added to Part 2 of Division 26 of the Health and Safety Code, to read:

Article 1. Findings, Declarations and Intent

396.50. The Legislature finds and declares the following:

;a) ?'h:lt public hcaltl~, s:~Ccty, ant1 wclk~re may bc cndangcrcd by thc cc~Lsion inti, the ambient air of sub~tanccs which are dctormined to be carcinogenic, . teratogenic, mutagenic, or otherwise taxic or injurious to humans.

(b) That persons residing in California may be csposed to a multiplicity of toxic rir contaminants from

.numerous sourccs which ;a;.!. t c . :a>

: producc adversc effects, and ;!lot this pS.c;:ori;..n.x-. should be tai;~n into account w1:i.n a\*dl;a:ing t!ie ccikh effects oi in2ividual cornpaunds.

! (c) That it is the public policy of the rta:c that .. .. ' ' emissions of tonic air contamln~nts rhou!d bc controlled to levels which prevent harm to the pul;lic hcaltb.

a (d) That the identification and rcguli~tion of tosic air i 1 contaminants should uti!izc t!:c best available scicr.tiEc i , evidence gathercd from thc public, private indcstiy, thc '

.: . scientific community, and federal, state, and local '

agencies, and that the scientific research on \rhich 1 : decisions related to health effects are based should be : reviewed by a scientific review panel and members of the

public. (e) That, while absolute and undi$utcd scientific

evidence may not be available to de:srmine the exact nature and extent of risk from toxic air contaminunts, it is necessary to take action to protect public health.

(f) That the state board has adopted regulations . regarding the identification and control of tosic ;ir , ' contaminants, but that the statutory authority of the state

board, the relationship of its proposed program to the j activities of other agencies, and the ro!e of scientific and

oi~blic review of the regulations should be clarified by the Legislature.

.

(g) That the Department of Food and Apicl;ltl;re has jurisdiction over pesticides to protect the public from

' environmentally harmful pesticides by regulating the . . i . registration and uses of pasticider. . . i lh\ T h n t while there is a statewide Dropram to control \.., ----- ....-- . ~

'. I levels of air contaminants subject to>tare and national I ambient air quality standards, there is no specific ;

statutory frumcwork in this division for thc cval~ution I and control of substnnccs which may, be tonic ~ i r ? contaminants.

(i) That the purpose of this chap:er is to crcnte a program which specifically addresses the evaluaticn ar:d control of st~bstances which may be toxic dir t

contaminants and which complements existing authority to establish, achieve, and maintain ambient air quality j

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a!sot JO lo13uoa a1qua:iae~d lsaglaa aqj a,\a!r;ac 01 'sla!lls!p aqlol aaul!ls!ssc ~!J!Iu~!~s PUJ {uapqa31 ap t~oid 0 4 laplo tr! a[qal!sap puz Xlcssaaau s! sltrruyrualxoa Jlw afnol pqI!se a1 srr:l2o4rl O~I.WOJI?;P e fvtrj. (?I)

's~uutr~urcluca J!n ap03 SU pag~uap! ale vJ!qM s=p!J!lsad 311!t1~0auoa ~a!:ls!p JO Xar:aSe

AUC jc &!:O~ICE aqa St:g;t~!~ :C S:r!puzdsa se par.~lsuoa aq 01 s! za~dcqa ayl u! S:!j.;lou puc sluec:wcluoa 1 ajx~a O; pal?;i S! I s!ql leil~. (0 - .

.~p:y~r:$ .I -

] . ,,,. :.Ii tlla drs.-E:.l,. cr..t,.:.. ,-! . .---. ... , ..... . ,.. ..... cL. ;XI :>is i:^tia~r, :he stztc 7 board si~all irnmed~~telv tmns11:it to :hc. Anrmb!v

~ ~ ~, Committee on Rulesaiid i!:c Senate Committee on Rules, foi tr~qsmitta! to the nppropiiate standing, select, or joint - . . comni:tce of thc Legislature, a sta:c;:liint of reasons for extension of the deadline, along with copics of the departmcrit's statemcilt ofrcasons which prevcnt it from comp!etin,n its evaluation and recommendations in a timely manner.

(e) The state boazd or a district msy request, and any . person sh;~l: provide, ic:^orrrialio~: on ;lny sabstance which is or may be under c\,aluation and which is manufacturcd, distributed, emitted, or used by tho pcrson of whom the rcq:cst is mnde, in ordcr to carry out its rcsponsibilitics pursu.Int to this chapter. To the extent practica!, the statc board or a district may collect the iniorz~ation in aggregatc form or in any othcr manner. designed to protect tmde sccrcts.

Afiy person providing information pursuant to this subdivision may, at thc time of submission, identify a portion of the information submitted to the state board or a district as a.trnde secrct and shall support the claim of a tr.?de secret,upon the written request of thestate board

'I: or district board. Information supplied which is a trade secret, as specified in Section 6254.7 of the Government

L" Code, and which is so marked at the tinlc of submission, shall not be released to any member of the public. This section shall not be construed to prohibit the exchange of properly designated trade secrets between public agencics when those tradc secrets are relevant and ni-cossary to the exercise of their jurisdiction provided that the pubiic agencies exchanging those trade secrets shall prescivc the 1xo:ections afforded that information by this p~ragr;y)h.

Any information not identified as a trade secret shall be available to the public unless cxcmptcil from disclosure by othcr provisions of larv. The fact tlrat information is claimed to be a trade secret is public information. Upon receipt of a request for the re!c;lsc of information which has been claimed to be E tradc secrct, the state board or district shall immediately notify -the person who

subtni~lkd thc i n f ~ r ~ n a t i ~ ~ l , :I:?;! JI;!! 22:2r;::i:1? \r l:. ::.. : b--.-. - or not the information c!:imcd to bc a tr-cic sccrct 1s :3

. be released to the public. The s tzc b o d cr diAiict board, as the cJse may be, shall nukc its dc!e:r?.ir.a:icn wi:hin 60 days after rcceiving thc request for discl~surc. k hot not before 30 days followir.g the notification of thc. pcrson who submitted thc infornl;ttion. If the sti~tc board :

or district decides to make thc inrormtion public, it sha!l .provide the person who submitted thc informaticn 10. day$ notice prior to public tlisclosurc of the inlorri-.ation. .

(f) The Shtc Dcpartmc~lt of IIcalk Scrviccs ant1 :he i state board shall give priority to ihc cv;.itr;l:ion and regulation of substu~ccs b:lsctl on factors rclz:cd to the rislcof harm to publicheal:h, alsount orpotcntial ai;lour.t . of emissions, manner of usaga of the subs:ance ir. Ci~liiornia, persistence in the atn~osp!lcrc, and ambient conccnt:ations in thc commlmiiy.

39661, (a) Upon reccipt oi the evaluation and recom(ncndations prepnrcd pursuant to Scction 39660, thc state board, in consultation with and with' :he participation of the State Department of Health Services. : shall vreoare a renort in a form which may serve as the - basis for regulaiory action regarding - a particular substance vursuant to subdivisions (b) and (cl of Section - . . 39662.

The report shall include and be developed in consideration of the evaluation nnd rccommcndations of the State Department of Health Services.

(b) The rcport, together with the scientific dn:a on which the re ort is based, shall, with the exception of e trade secrets, e made available to the public and shall be formally reviewed ' by the scientific rcvicw pmel established pursuant to Section 39670. The panel shall rcvicw tho scicnlific procctlurc~ and methods uscd to support the data, the data itself, and the conclusions and asscsstncnts on which thc rcport is Lascd. Any pcrson may submit any information for considcration by the panel which may, at its discretion, receive oral testimony. The panel shall submit its written findings to the state board within 45 days after receiving the report. The panel may, however, petition the stnte board for an

w I*)

.,..-..i.Y.. uGauiurc, WIIIL'II 1113Y i l ~ r cxceca 15 -i. workicg days.

(c) If the scientific review pmel determines that the health effects report is seriously deficient, the report shall. br rcturned to the state board, acd thc statc board, in consultation with and with thc participation of the State Departmerit of Health Services, shall prepare revisions to

-the report \vhich shall be rea~bmitted, within 30 days follo\\.ing rcccipt of the panel's dctermination, to the

: scicntific rcvicw p:tccl ivhich shall rcvizw thz rcport in . co:lformancc with subdivision (b) prior to a formal - prol~osill by thc statc board pursi~ant to Scctior~ 39662.

29662. (a) Within 10 working days following rcceipt . '

of the findings of the scientific review panel pursuant to subdivision (c) of Seckion 33651: tho itate board shall prepare a heariilg ncticc :ulcl a proposcd regulation which shall Ii~cl~cla tlic proposed clctcrmi~~:~tion as to . .

whclher a mbstoncc is a toxic air contaminant. (b) After conducting a public hearing pursuant to

Chapter 3.5 (commencing with Section 11340) of Part 1 of Division 3 of Title 2 of the Government Code. the state . bosd shall list, by regulation, substances determined to be toxic air contaminants.

(c) If a substance is determined to be a toiic air -.

ccntsminmt, the regulation shall specify a threshold I m exposurc level, if any, bciow which no significant adverse

Eea!th effects are anticipated. (4) In e\,aluating the nature of the adverse health

effect and the range of risk to humansfrom exposure to , a substance, the state board shall utilizc scientific criteria - . which are protective of public. health, consistent with current scientific data. '

(c) Any person may petition the state board to review . . n dctermination madc pursuant to this scction. The

petition shdl specify the additional scientific evidence . .

regarding the health cffects of a substance which was not avnilable at the time the original determination was made and any other evidence which would justify a revisad dctcrmination.

. .

Article 4. Control of Toxic Air C~n:arr.in~:its fr"-- . . . . a 3966.5. (a) Following adoption of the detcrrr.in~lior,s

I pursuant to Section 39652, tha esccurive officer of ti:e . . state board shall, with the participation of the districts,

6 1 *\ and in consultation with affected sourccs and the ! interested public, prepare a repcrt on thc nccd md ! . . appropriate dcgrco of rcgclation for each substance

whicb thc state board has dctcrmincd to bc a toxic air conk~minant.

I (1)) Thc rcport shall ndclrcss all of thc followin:! issucs,

i to the cxtcnt data cun reasonably bc mndc nvi~ili~blc: - - ~ ~

(1) The rate and extent of present and nn:icipnted future emissions and estimated levels of humnn crpcsurc.

(2) The stability. pcrsistence, transformztion . . products, dispcrsioli potential, and othcr physical and

chcmicnl char~ctcristics of the substancc whcn prcscnt in ' the ambient air.

5 . (3) The categories, numbers, and relative contribution ! of present or anticipated sources of the substance,

including mobile, industrial, agricultural, and natural, sources.

. . . . (4) The availabiity and technological fensibility of airborne toxic control measures to reduce or eliminate

emissions, and the anticipated effect of airborne toxic control measures on levels of exposure.

(5) The approximate cost of each airborne toxic control measure and the magnitude of risks posed by the substances as reflected by the amount of emissions from the source or category of sources.

. (6) The availability, suitability, and relative efficacy of substitute compounds of a less hnzardous nature.

- 8 (7) The potential adverse health. safety. or . . . environmcntal impacts that may occur as a result of ' : , implementation of an airborne toxic control nearwe.

(c) The staff report, and rc!evant comments reccived . during consultation with thc districts, affected sources. nnd the public, shall be made available for public review

! and comment at l c s t 45 days prior to the public heitring

. . required by Section 39666. 39666. .(a) Following a noticed .public hearing. the

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b

I '-'..'' I .-.-... c; wrns?r~rtl *r---y.o? 27x9: :x::,:qz!c l:!c?: ii2.y~ pl;:~~ :-.,.:lq. ;

w.. . .s . . r . rr v.. ~ ~ r : r s a , uinu v s rratusrt JII~(II ~ 1 : c1u'mrIea ns n biost~tktician and onc of whom shall be a physician or ' 1

' scientist specidizing in occupztional medicine. 1 9

(3) Two membcrs shall be appointcd by the Speaker . . 1 of the Assembly, one of whom shall be qualified as a I . . toxicologist .and one of whom shall be qualified as a 4 ! ;

! biochemist. t

(4) blcmbcrs of the pancl shall bc appointed from a i pool of ~~ominccs submitted to each appointing body by I

1 the President of the University of California. The pool ; shall include. at a minimum, three nominees for each - .

i I

discipline reprssented on the panel. ;)nd shall include ' ' - 1 only individuals who hold, or have held, academic or ' ;

t .ec,uiva!ent a2pointments at universities and their affiiiates in Ca!ifornia.

(c) The panel may establish ad hoc committ'ecs. which . . '

1 . i

may include other scicntists, to assist it in performing its : I - -

functions. (d) Members of the panel, and my ad hoc committee f

cstab!ished by thc panel, shall submit annually a financial ! disclosure statement that includes a listing of income I

received within the preceding three years, 'including !

investments, grants, and consulting fees derived from individuals or businesses which might be affected by regulatory actions undertalcen by the state board or

j A districts pursuant to this chapter. The financial disclosure i

statcmcnts submitted pursuant to this subdivision are i i

pub!ic information. hjcmbers of the panel shall be subject to thc disqt~alificntion rcquircments of Scction 8110 of !

the Government Code. (e) Members of the panel shall recclve one hundred ! .

dollars ($100) per day for attending pmel meetings, and j !

shall be reimbursed for reasonable and necessary travel j

an& other expenses incurred in the performance of their . , j . duties. (0 Tke state. board and the State Department of ' '

Eeillth Services, and, in the case of pesticides, the . '

Dcpiirtment of Food and Agriculture shall provide ,

technical and clerical staff support to the panel. . .

. .

39674. ia) Any person who violates any rule or regulation, emission limitation. or pcrrait condition adopted pursuant to Article 4 (commencing with Section 39665) is liable for a civil emlty not to excccd ten thousand dollars ($10,000) or each day in which the violation occurs.

P (b) There is no liability under subdivision (a) if the

person accused of the violation alleges by affrrmati\,a defense and establishes that the violation is caused by an act which was not the result of intentional or negligent conduct. SEC. 2. Article 1.5 (commencing wi:h Scction 14&21)

is added to Chapter 3 of Division 7 of the Food and Agricultural Code, to read:

Article 1.5. Pesticidcr

14021. (a) As used in this article. "pesticide" meam any economlc poison as defined in Section 12753.

(b) For purposes of this article. "to~ic air contaminant" means an air pollutant which may cause or contribute to an increase in mortality or an increase in serious illness, or which may pose a present or potential hazard to human health. Pesticides which have been identified as hazardous air pollutants pursuilnt to Scction 7412 of Title 42 of tho United States Code s h d bc identified by thc dircctor ns toxic nir contaminants.

14022. (a) In consultation with the Statc Departrncnt of Health Services and the State Air Resources Board. the director shall evaluatc the health effects of pcsticidcs which may be or are emitted into the ambient air of California and which may be dctermined to bc a toxic air contaminant which poses a present or potential hazard to h u m health. Upon rc uest of the State .4ir Resources Board, the director s h include a pcsticidc for evaluation.

(b) In conducting this evaluation, the dircctor shill consider all available scientific data, including. but not limited to, relevant data provided by the State

w & V

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subdivision (e) af Section 14023 and pursuant to provisions of this code, the director, in consultation with the ngriculturzl commissioners and air pollution control districts and air quality management districts in the affected counties, shall develop and adopt control mcasured designed to rcducc emissions sufricicntly so that the source \\.ill not expose the public to the levels of exposure which may causs or contribute to significant ndversc henlth effects. Where no demonstrable safe level or threshold of significant ndvcrse health effects has been cstablished by the director, the control measures shall be dcsigcd to adequately prevent nn endangerment of public hralth through the application of best practicable control techniques.

(b) Bcst practicul~lc control techniques may include, but urc not lilnitcd to, tho following:

(1) Lnbcl ~~i~~c:;rI~ncnts. (0) Applicator training. (3) l~cslriclions olr usc pnttorris or locatio~lu. (4) Changes in application procedures. (3) ReciassiEcatioil as a restricted material. (6) Cancellation. 140-2.5. Acy person mny petition the department to

review a determination made pursuant to this article. The petition shall specify the additional scientific evidence regarding the health effects of a pesticide which was not availilble at thc time the original determination wns made and any other evidence which would justify u rcvised determinstion.

14026. Xothing in this article shall be conitrued to limit or expalid thc department's authority regarding pesticides which are not determined to be toxic nir contaminants.

SEC. 3. It is the intention of the Legislature, in the enactment of this act, that the Statc Air Resources Bonrd. the State Deoartment of Health Services. and the . . -

Department of Food and Agriculture shall p;rfo~m the fu~ictions rcquircd by this act within their respective existirig resources and budgetary authorizations during the 198384 fiscal yew, by appropriating sufficient funds

. ..- ---. ---- -I. ".', ~--n-"",-"I) r 4260-001-644, 4260-001-439, &57M)Ol-001, 83i@G31-111. , 8370-001-690,8570-101-001 m d 8570-101-111 of the Budget , .

. . Act of 1983 (Ch. 324, Stats. 1933). I . , SEC. 4. No appropriation is made and ao . reimbursement is required by this act purumnt to Section ' t

6

! 6 of Article XlII U of the CnliTor~~ia Constitution or Section W1 or !234 of the Revenue and Tmatiol~ Codc ,

i I

bccnusc the local agency or school district has thc , : authority to levy sorvicc charges, fccs, or erressmcnts i ! sufficlcnt to pny for tho program or lovd of survicc , I mandated by this act. I