. 

# POLYBROMINATED
DIPHENYL ETHERS:

RECOMMENDATIONS TO

REDUCE EXPOSURE IN

CALIFORNIA

A Report of the Cal/EPA PBDE Workgroup

February 2006

California Environmental Protection Agency Sacramento, California O Br

Br Br Br BrPBDEs: Recommendations to i February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### CAL/EPA PBDE WORKGROUP

Office of Environmental Health Hazard Assessment (lead)

Martha S. Sandy, Ph.D., M.P.H., Chief (Workgroup Chair) Cancer Toxicology and Epidemiology Section Reproductive and Cancer Hazard
Assessment Branch

Lauren Zeise, Ph.D., Chief Reproductive and Cancer Hazard
Assessment Branch

Mari Golub, Ph.D. Staff Toxicologist Reproductive Toxicology and Epidemiology Section Reproductive and Cancer Hazard
Assessment Branch

Air Resources Board

James Aguila Manager Substance Evaluation Section Air Quality Measures Branch Stationary Source Division

State Water Resources Control
Board

Gerald Bowes, Ph.D., Chief Toxicology and Peer Review Section Division of Water Quality

Integrated Waste Management Board

Bobbie Garcia Senior Integrated Waste Management Specialist Permitting and Enforcement Division Department of Toxic Substances

Control

Myrto Petreas, Ph.D., M.P.H., Chief Environmental Chemistry Branch Hazardous Materials Laboratory

Jeffrey Wong, Ph.D. Deputy Director Science, Pollution Prevention, and Technology

Cal/EPA

Steve Hui Special Assistant for Scientific
Evaluations Office of the Secretary

Department of Health Services

Michael Lipsett, M.D., Chief Exposure Assessment Section Environmental Health Investigations Branch

Diana Lee, M.P.H., R.D. Research Scientist Exposure Assessment Section Environmental Health Investigations Branch

Julia Quint, Ph.D., Chief, Hazard Evaluation System and Information Service Section Occupational Health BranchPBDEs: Recommendations to ii February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### TABLE OF CONTENTS

Executive Summary............................................................................ 1

Introduction......................................................................................... 5

Background ........................................................................................ 7

PBDEs: Chemical Identitie s, Production and Use ...................... 7 PentaBDEs and OctaBDEs: Concentrations and Toxicity........... 8 DecaBDE: Concentrations, Toxicity and Breakdown Products .. 9

Nature and Extent of the PBDE Problem ................................. 13

Cal/EPA Entities and DHS Past and Ongoing Activities................... 17

Air Resources Board ................................................................ 17 Department of Toxic Substances Control ................................. 18 Integrated Waste Management Board ...................................... 18

Office of Environmental Health Hazard Assessment................. 20

State Water Resources Control Board ..................................... 21 Department of Health Services.................................................. 21

Workgroup Recommendations ........................................................ 21

Outreach and Education ........................................................... 23

Pollution Prevention Initiatives .................................................. 26 Measurement and Monitoring ................................................... 27 Regulatory Initiatives ................................................................ 30 Summary of Recommended Cal/EPA Actions .......................... 32

References ....................................................................................... 36

Appendix I. Summary of ARB PBDE Monitoring Data...................... 40

Appendix II. The NTP Cancer Bioassay for DecaBDE and Workgroup Cancer Potency Derivation ........................................ 42

Appendix III. Publications and Presentations by DTSC, OEHHA, and ARB: PBDE Environmental Levels, Exposures and Risks .... 44PBDEs: Recommendations to 1 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Executive Summary

The manufacture, distribution and pr ocessing of products containing pentabrominated diphenyl et her (pentaBDE) and octabrominated diphenyl ether (octaBDE) flame retardants will be prohibi ted in California as of June 1, 2006 (California Health and Safety Code Sections 108920 et seq. ); only products manufactured after June 1, 2006, are subject to the prohibition. This prohibition was prompted by findings that exposur es to polybrominated diphenyl ethers (PBDEs) are widespread, and may pos e health risks. However, the manufacture, distribution and processing of products containing the most commonly used PBDE mixture, decabromi nated diphenyl ether (decaBDE), has not been prohibited. PentaBDEs and octa BDEs are ubiquitous and Californians will continue to be exposed to them a fter June 1, 2006. On May 27, 2005 the California Environmental Protection Ag ency (Cal/EPA) Secretary directed the formation of a workgroup of representat ives from Cal/EPA Boards, Departments and Office (BDO) to consider the nature and extent of the PBDE problem and to

recommend actions Cal/EPA could take to mitigate exposures to reduce risks of potential PBDE health effects. The Cali fornia Department of Health Services (DHS) also contributed expertise and prov ided representatives to the Cal/EPA PBDE Workgroup. This report was pr epared in response to the Cal/EPA Secretary’s directive.

The principal focus of this report is to address continuing exposures of Californians to PBDEs after June 1, 2006. The report provides information on PBDEs and briefly summarizes past and ongoing Cal/EPA BDO and DHS

activities related to PBDEs. Based on th is preliminary eval uation, the Cal/EPA PBDE Workgroup proposes specific steps to be taken by Cal/EPA BDOs and DHS to reduce PBDE exposures.

PBDEs have been widely used as flame re tardants in home and office building materials, motor vehicles , electronics, furnishings, textiles, high-temperature plastics and polyurethane foams. The general public is exposed to PBDEs through the use of consumer products in homes, offices, cars and schools. Exposures to PBDEs in some occupationa l settings, e.g., in computer recycling facilities, can be much higher than thos e of the general public. As consumer products are used and after they are di scarded, PBDEs are released into the environment where they can bioaccumulate in wildlife and food animals. PBDEs have been measured in house and office dust, indoor air, plant and animal-based foods, terrestrial and marine animals, and in human breast milk, blood and fat.

The levels of PBDEs measured in humans in the US and Canada are typically at least 10 times higher than those in Europe, and appear to be doubling every few years. Cal/EPA scientists have reported the highest tissue concentrations of

PBDEs measured in the world in California wildlife (shorebird eggs and fish), and rapid accumulation of PBDEs in the tissues of San Francisco Bay harbor seals.PBDEs: Recommendations to 2 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup PBDEs have structural similarities to polybrominated and polychlorinated biphenyls (PBBs and PCBs), and to ce rtain other persistent polyhalogenated organic pollutants. In the limited toxicity testing to date, PBDEs have produced some of the toxic effects and physiolog ic changes typical of many persistent polyhalogenated organic pollutants, in particular the PBBs and PCBs. These effects include developmental and nervous system toxicity, as well as mimicry of estrogen and interference with the activity of thyroid hormone. These effects are observed in experiments with octaBD E and pentaBDE. DecaBDE has been shown in one study in mice to cause similar toxic effects on the developing nervous system as pentaBDE. Although PBBs and PCBs are both carcinogenic, neither pentaBDEs nor octaBDEs hav e been tested for carcinogenicity.

DecaBDE is not affected by the recent legislation and its use and release into the

environment will continue unabated. Direct exposure to decaBDE appears to pose lower human health risks than those of the other PBDEs, due to its lower toxicity, absorption, and generally lowe r environmental concentrations. Still, decaBDE is the predominant PBDE measured in house and office dust, and the risk from such exposures r equires further evaluation. Also, levels of decaBDE found in sewage sludge suggest that decaB DE from the indoor environment is released through municipal sewage systems into the environment.

Use of decaBDE may result in human exposure to lower brominated PBDEs of greater toxicological concern, such as the pentaBDEs and octaBDEs. Recent

studies indicate that decaBDE breaks dow n by the actions of sunlight, heat, and

bacteria to these and other PBDEs that contain fewer bromine atoms. Such compounds are also formed through metabolism in certain animals consumed by humans (i.e., fish and chicken). These lower brominated PBDE congeners can undergo further debromination. In addi tion, during combustion of plastics containing decaBDE and other PBDEs (e .g., incineration), brominated dioxins and related compounds may form.

After June 1, 2006, exposures in Califo rnia to pentaBDEs and octaBDEs that result from new products should decrease. Nevert heless, exposures due to building materials, furnishings, and c onsumer products produced before June 1, 2006, containing pentaBDE and octaBDE fl ame retardants will continue for years

to come. These releases will result in ongoing exposure to and increased bioaccumulation of the prohibited PBD Es by humans and wildlife. The workgroup has made numerous recommendat ions to reduce the continuing exposures to PBDEs, including pentaB DEs, octaBDEs, and decaBDEs. The main recommendations are given in the table below.PBDEs: Recommendations to 3 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Main Recommendations to Reduce PBDE Exposures 1

Outreach and Education

 Educate key governmental offici als and the public about the PBDE prohibition and hazards to encourage compliance with the prohibition and exposure reduction behavior. This would include development of

educational materials such as fact sheets.

Pollution Prevention

 Encourage the purchase of PBDE-free products.

Measurement and Monitoring 2

 Conduct human biomonitoring to evaluate the effectiveness of the pentaBDE and octaBDE prohibition and other PBDE reduction efforts.

 Conduct environmental monitoring to identify sources, pathways and trends in PBDE levels, and to characte rize the environmental fate of

decaBDE.

Regulatory Initiatives

 Develop health guidance levels (e.g ., reference exposure levels) for PBDEs to aid in establishing ac ceptable environmental levels.

 Assess the need for further regulati on, such as the development of hazardous waste criteria and managem ent and disposal requirements and practices for PBDE contaminated waste, an Airborne Toxic Control Measure, the addition of PBDEs to t he Air Toxics “Hot Spots” list, and the

need to limit the use of decaBDE.

1 Subject to available funding.

2 DTSC will provide guidance to other Cal/EPA BDOs for the sampling and chemical analyses of PBDEs in environmental matrices.

Recommendations include near-term actions intended to reduce PBDE exposures through outreach and education, and voluntary pollution prevention. Longer-term recommendations include further environmental monitoring of PBDE

levels to increase the scientific base for decision-making, and consideration of specific regulatory actions. All of the Workgroup’s recommendations for Cal/EPA action are summarized on page 32. For each recommended action thePBDEs: Recommendations to 4 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup estimated timeframe for im plementation and the responsible BDOs are indicated. In recommending these specific steps for Cal/EPA to reduce PBDE exposures and health risks, the Workgroup explicitly di d not address the availability of state resources for their implementation. The majority of these recommendations cannot be acted upon without the prov ision of additional resources. This requirement for additional resources needs to be addressed as Cal/EPA evaluates and chooses recommendations to implement.PBDEs: Recommendations to 5 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Introduction

With the passage of Assembly Bill 302 (2003 Legislative Session, chaptered as California Health and Safety Code (H &SC) Sections 108920-108923, California

became the first state in the nation to prohibit the use in commerce of products containing pentabrominated diphenyl ethers (pentaBDE s) and octabrominated diphenyl ethers (octaBDEs). PentaBDEs and octaBDEs are two of the three common commercial mixtures of polybro minated diphenyl ether (PBDE) flame

retardants. PentaBDEs and octaBDEs were originally scheduled for phase-out in California in 2008. In 2004, the Legislat ure accelerated the timeframe for the PBDE phase-out by prohibiting the use of pentaBDEs and octaBDEs as of June 1, 2006. No product may be manufactu red, processed or distributed in

commerce in California after that date if it contains mo re than 0.1% of pentaBDE or octaBDE; only products manufactured after June 1, 2006, ar e subject to the prohibition. However, us e of the third major PBDE mixture, decabrominated diphenyl ether (decaBDE), has not been restri cted by this or any other legislation

in California.

This legislation was prompted by the findings that exposures to PBDEs are widespread, and that levels of thes e compounds have been doubling in human tissues and breast milk every few years. Some of the highest levels of PBDEs

measured worldwide have been in Californ ia human and wildlife populations. Figure 1 shows the high and increasing le vels measured by DTSC in Harbor Seals in the San Francisco Bay.

Figure 1. PBDEs in San Fr ancisco Bay Harbor Seals*

10 100 1000 10000

1988 1990 1992 1994 1996 1998 2000Concentration, ng/g fat

* Source: She et al. 2003

Exposures to PBDEs in the womb or early in life have affected the developing nervous system, and caused thyroid horm one disruption and male and femalePBDEs: Recommendations to 6 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup reproductive toxicity in animal toxico logy studies (McDonald, 2005). PBDEs have not been adequately studied for their potential to cause cancer, but some evidence suggests they may have carcinogenic potential. Human tissue and

blood levels of PBDEs measured in t he U.S. and Canada during the past few years have typically been at least 10 time s higher than those in Europe, where both the European Union (EU) and Scandina vian countries have prohibited the use of pentaBDEs and octaBDEs. Therefore, there is reason for concern about their potential health risks in humans.

Although products containing pentaBDEs a nd octaBDEs produced after June 1, 2006, will be prohibited from commerce a fter that date, exposure to them will continue due to their presence in hundr eds of consumer products in homes, workplaces and motor vehicles. Furt her, the continued use of decaBDE may pose health risks either directly or through breakdown products. The Cal/EPA Secretary directed the formation of a workgroup of Cal/EPA Boards, Departments and Office (BDO) representativ es to consider the nature and extent of the PBDE problem and to recommend actions Cal/EPA could take to mitigate the exposure to PBDEs. The California De partment of Health Services (DHS) contributed expertise and provided representatives to the Cal/EPA PBDE Workgroup as well.

This report of the Cal/EPA Workgr oup provides information on PBDEs and

makes recommendations to characterize the extent to which Californians are exposed to PBDEs and to reduce those expo sures. Specifically the Workgroup:

 Summarizes what is known about dec aBDE toxicity and environmental and human tissue concentrations, as well as its potential to breakdown to more hazardous chemicals;

 Summarizes environmental measurement s in California of pentaBDEs and octaBDEs;

 Characterizes the problem posed by legacy pentaBDEs and octaBDEs and continued use of decaBDE;

 Outlines ongoing activities of Cal/EPA BDOs and DHS; and

 Recommends further actions Cal/EPA can take to limit PBDE exposures

in California.

This report presents neither a compr ehensive literature review nor a risk

assessment for PBDEs. Rather it summa rizes information from the scientific literature to provide a context fo r the recommendations that follow.

In developing these recommendations, the Workgroup did not address the availability of state resources for impl ementation. The majority of these recommendations cannot be acted upon by individual Cal/EPA BDOs without the provision of additional resources for this purpose. This is a serious constraint

that must be addressed as Cal/EPA evaluates, prioritizes and chooses recommendations for implementation.PBDEs: Recommendations to 7 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Background

PBDEs: Chemical Identities, Production and Use

PBDEs are diphenylethers with bromines at tached, as illustrated in Figure 2 below. The number and the placement of the bromine atoms determine the type of PBDE. Figure 2 shows a non-subs tituted diphenyl ether and then as an example, one congener wit h five bromine atoms attached, 2,2',4,4',6- pentabromodiphenylether. T here are 209 individual ch emical congeners within

the chemical class of PBDEs.

Figure 2. Diphenyl ether structure

O Br

Br Br Br Br

2,2',4,4',6-Pentabromodiphenylethe r (PBDE-100) O

Diphenyl ether

The chemical properties depend on the number of bromines, other substituents, and their ring positions. PBDEs have been wi dely used as flame retardants: The

bromine atoms in the PBDEs quench flames by scavenging electrons. Historically, three commercial mixtur es of the PBDEs ha ve been manufactured and used – the penta, octa, and decaBDE formulations. Among the several different PBDE congeners found in t he pentaBDE formulation, the average number of bromines is five. Similarly, the average number of bromines is eight among the congeners present in the octa BDE formulation. DecaBDE (i.e., “PBDE 209”) is a diphenylether that is fu lly substituted with bromines, although

the commercial decaBDE formulation also contains other congeners.

PBDEs have been widely used in consum er products, including electronic equipment, fabrics, and polyurethane foam . When used as flame retardants, PBDEs are not chemically reacted with or bound to the product (e.g., polyurethane foam, plastics). Thus, they can and are readily released from these products.

Approximately 67,500 metric tons of PBDEs are manufactured annually worldwide, with North America accounti ng for much of the world’s PBDE use. DecaBDE is the most widely used PBDE formulation globally, with annual demand of 24,500 metric tons in t he American market. The pentaBDE

formulation has been used almost exclusivel y in North America, at a rate ofPBDEs: Recommendations to 8 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup approximately 7,100 metric tons per year. Use of the octaBD E formulation has been considerably less than t hat of the pentaBDE formul ation. In the U.S., manufacture of the pentaBDE and oc ta BDE formulations stopped in 2005.

The pentaBDE formulation contains the four congeners t hought to be most bioaccumulative (PBDE 47, 99, 100, 153). These four congeners have become ubiquitous in the environment worldwid e, and are found in wildlife and human

tissue.

PentaBDEs and OctaBDEs: Concentrations and Toxicity

Environmental Levels and Human Exposure to

Pe ntaBDEs and OctaBDEs

PBDEs have become ubiquitous in air, s ediments, wildlife and human tissues. Levels of pentaBDEs are consistently observed in breast milk, serum and adipose tissue throughout the world. T he highest levels have been measured in

the U.S. and Canada. Estimates of the half-lives in humans for these congeners range from 3.5 to 7.2 years. This in part explains the steady increase in human tissues over time of these PBDE congeners.

In 2004, the Air Resources Board (ARB ) conducted ambient air monitoring for PBDEs, including a tetraBDE (PBDE 47) and a pentaBDE (PBDE 99) congener, at six urban sites within California ( Los Angeles, Oakland, Richmond, Riverside, San Jose, and Wilmington). Appendix I summarizes the findings of ARB’s air monitoring effort. Concentrations of the tetraBDE r anged from 7-170 pg/m 3

. Concentrations of the pent aBDE ranged from 3-332 pg/m 3 . For comparison,

outdoor concentrations of various PBDE congeners have been found to range from 5-300 pg/m 3 in other parts of the world.

In 2004, the ARB contracted with the Univer sity of California at Davis (UCD) to conduct indoor air monitoring for PBDEs inside a computer training room containing 13 personal com puters manufactured befor e 2000 (See Appendix I). Indoor air concentrations of PBDEs, mo stly PBDE 47, ranged from 4-1,600 pg/m 3
in this room. For comparison, other researchers have measured indoor air concentrations of PBDEs up to 1,800 pg/m 3 (Hites, 2004). Analysis of dust from the room’s carpet indicat ed that PBDEs were present in the dust at 10 ppm, and that decaBDE was the predominant congener.PBDEs: Recommendations to 9 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Toxicity of PentaBDEs and OctaBDEs

Because of the structural similarity between PCBs and PBDEs, toxicological studies of PBDEs have focused on endpoints known to be induced by PCBs. For one pentaBDE congener, dioxin-like effe cts of metabolic enzyme induction and specific effects on the liver, thymus and immune systems were found to occur only at relatively high doses in rats (Fow les et al., 1994). In contrast, effects on thyroid are seen at fairly low doses (e.g., 0.8 mg/kg) (Zhou et al., 2001; Fowles et al., 1994). Estrogenic activity is also been observed for pentaBDEs and hexaBDEs (Meerts et al., 2001), and test icular and ovarian effects have been reported at a low dose (0 .06 mg/kg) for a pentaBDE (Kuriyama et al., 2005; Talsness et al., 2005). The tissue concentra tion in rodents associated with this low dose was relatively close to that observed in some humans. Effects on the developing nervous system of mice hav e been observed after exposure to several PBDEs (Viberg et al., 2003a and b; Viberg et al., 2002; Eriksson et al., 2002). HexaBDE and pentaBDE had gr eater potency than tetraBDE and

decaBDE.

Estimated ratios of tissue concentrati ons producing effects in rodents compared to those in highly exposed people in the U.S. tend to be small for the penta isomer PBDE 99 (McDonald, 2004, 2005). In other words, the levels of PBDEs detected in the tissues of people most exposed overlap with those seen in experimental animals in which toxic effe cts have been observed. This is in part due to its considerably longer half-life in humans compared to rodents (3-7 years versus 24-42 days). Several other PBDEs have relatively long half-lives in

humans.

Carcinogenicity testing of additional PBDE congeners (PBD E-47, PDBE 153) and of the pentaBDE technical mixture is pr esently in the planning phase at the National Toxicology Progr am (under the auspices of the National Cancer Institute). Based on the st ructural similarities of PBDEs to certain other polyhalogenated organic compounds, so me pentaBDEs and ot her PBDEs are expected to possess carcinogenic activity.

DecaBDE: Concentrations, Toxicity and Breakdown Products

Use of decaBDE, the most widely used PBDE, is not addre ssed by California

H&SC Sections 108920 et seq . Prohibition of certain uses of decaBDE has been proposed within the EU, but thus far t he EU has not limited its use. These

decisions reflect a lower concern for the toxicity of decaBDE, although toxicity testing of this congener has been limited and uncertainties remain. DecaBDE

does break down in the environment to more toxic chemicals; however, the identities, rates of format ion, and toxicities of decaBDE breakdown products have not yet been adequately characterized. What is known about the possiblePBDEs: Recommendations to 10 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup exposures in California and health risks of decaBDE is summarized below, along

with information on its breakdown in to more hazardous lower brominated

congeners.

Environmental Levels of DecaBDE

In 2004, the ARB conducted ambient air m onitoring of decaPBDE at the same six urban sites for the two congeners menti oned previously (s ee Appendix I).

Concentrations of the decaBDE congener ranged from 7-72 pg/m 3 , with an average monitored conc entration of 23 pg/m 3 . Thus exposure to the general population from breat hing outdoor air may be low (e.g., <10 -5 μ g/kg-day).

Working with UCD, the ARB also found decaBDE as the major component in air samples in the vicinity of two facilitie s: an indoor electronics recycling facility without air pollution control equipm ent, and an outdoor automobile shredding facility (see Appendix I). Inside the electronics recycling facility, air concentrations of PBDEs, mostly decaBDE, ranged from 5 – 830,000 pg/m 3 (the highest concentration is associated with a dose of roughly 0.1 μ g/kg-day for workers in the facility). Outdoor concentrations ranged from 1 – 11,000 pg/m 3

. For comparison, other researc hers have measured up to 200,000 pg/m 3 inside a Canadian electronics recycling facility. At the automobile shredding facility,

fence-line air concentrations of PBDEs , mainly decaBDE, ranged from 0.2 – 1,900 pg/m 3 (upper bound dose < 0.001 μ g/kg-day). The scient ific literature does not contain any similar studies on autos hredder operations for comparison.

Additional contract studies with UCD were conducted in 2004 by the ARB, measuring PBDE concentrations in the air and carpet dust of a computer training room containing 13 personal com puters manufactured before 2000 (See Appendix I). While PBDE 47 was the predominant PBDE in indoor air samples, decaBDE was predominant in carpet dus t. The carpet dust contained 10 ppm total PBDEs, which is consistent with findings of other researchers (EWG, 2004)

. A new piece of the same type of car pet was analyzed and found to contain 0.1 ppm of decaBDE. ARB is currently conducting chamber studies to more accurately characterize the release of PBDEs from personal computers.

PBDEs are present in house dust and clothes dryer lint, with the most abundant congener found being decaBDE. Young childr en, and in particula r, toddlers, are among those most likely to receive the highest exposure to the house dust through floor activities and hand-to-mouth behaviors. If one makes high end assumptions for dust consumption by toddlers and assumes a dust concentration of 10 ppm decaBDE, an estimated dose for toddlers of 0.2 μ g/kg-day for decaBDE from dust is obtained, which is comparable to occupational exposures at the electronics recycling facility not ed above. Further assessment of the potential for decaBDE exposure via house dust is needed, particularly for young

children.PBDEs: Recommendations to 11 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup DecaBDE has also been found in foods, incl uding fish and soy milk, at relatively

low levels. DecaBDE has been measur ed in wildlife throughout the world, including birds and bears from polar r egions, Swedish peregrine falcon eggs, freshwater fish, Belgian foxes, and ra ts at an urban dump site. These data demonstrate the potential for decaBDE to distribute throughout the food web.

DecaBDE has been measured in non-occupat ionally exposed individuals’ blood and breast milk. Given the relatively short half-life in humans (15 days) estimated for decaBDE (Thuresson et al ., 2006), these observations suggest that exposure to decaBDE occurs on a regul ar basis in the general population.

DecaBDE has also been measured in the blood of electronics dismantling workers. Still the highest decaBDE leve l measured in 23 breast milk samples in Texas was 8.24 ng/g lipid; decaBDE was not detected in 16 of the samples (Schecter et al., 2003). At the highest va lue measured, the Workgroup estimates that a young infant would consume an amount of 0.07 μg/kg-d decaBDE through nursing.

Toxicity studies of DecaBDE

DecaBDE has been assessed in animal stud ies investigating potential impacts on the developing nervous system and birth defects and other fetal harm. In one study, decaBDE given to mice caused i rreversible changes in brain function which worsened with age. The effect was observed in mice given the compound on the third day after birth, but not on the 10 th or 19 th day after birth. The dose of 20,100 μg/kg-day caused the effect but not a dose of 2,200 μg/kg. DecaBDE was less potent in causing this effe ct than tetraBDE, hexaBDE or penta BDE (Viberg et al., 2003b; Viberg et al., 2002).

Exposure of pregnant rats to 1,000,000 μg/ kg body weight of decaBDE caused delayed hardening of bones in their offspr ing (Norris et al., 1975). Other studies of developmental (Hardy, 2002), subchr onic and chronic toxicity (National Toxicology Program, 1986) essentially reported no non-cancer effects of decaBDE when tested at relatively high doses (up to 1,000,000 μg/kg body weight).

Thus, for non-cancer toxicity studies conducted to date, the dose causing an effect in the most sensitive study (V iberg et al., 2003b) wa s 20,100 μg/kg-day and no effects were seen at 2,200 μg/kg-day.

Based on the structural similarity of PBDEs with polybrominated biphenyls (PBBs) and other structure-activity cons iderations, decaBDE would be expected to be one of the least active congeners wi th regard to carcinogenicity. Further, decaBDE is not readily absorbed by the body , in contrast to the lower brominatedPBDEs: Recommendations to 12 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup PBDE congeners, which are readily absorbe d and also have a longer half-life in the body.

DecaBDE has been tested for carcinogenic ity by the National Toxicology Program (NTP, 1986) and Dow Chemical (N orris et al., 1975). In the Dow Chemical studies in rats no significant tumor findings were observed. In thesubsequent NTP studies conducted at higher doses, decaBDE induced nonmalignant liver tumors in rats of both sexes, and NTP concluded this provided “some evidence” of carcinogenicity in t hese animals. NTP (1986) concluded that there was “equivocal evidence” of carci nogenicity in male mice based on findings of thyroid and liver tumors t hat were marginally significant statistically. In female mice, there was little evidence of carcinogen icity. The NTP study is discussed in greater detail in Appendix II.

In reviewing the carcinogenicity evidenc e for decaBDE, the International Agency

for Research on Cancer concluded that there is “limited evidence” for the carcinogenicity of decaBDE in animals (I ARC, 1990), essentially due to the 1986 NTP findings.

To facilitate screening analyses, the Workgroup calculated an upper bound cancer potency for decaBDE from the NTP study (i.e., 0.00108 (mg/kg-day) -1 ; see Appendix II).

Screening Level Risk Considerati ons for Direct DecaBDE Exposures

While the exposure and toxicity data are limited for decaBDE, it is still instructive to compare doses causing effects in t he sensitive animal experiments to human

dose levels from environmental and o ccupational exposures. For non-cancer effects, the decaBDE dose observed to c ause no effect in the most sensitive experiment to date - that on the deve loping nervous system (2,200 μg/kg) - can be compared to doses associated with human exposures. The experimental dose causing no effect is roughly 30,000 ti mes the dose calculated for a day of breast feeding by human neonates (0.07 μg/ kg-d, see above); the value is 10,000 times that associated with toddler consumption of dust contaminated at 10 ppm on a given day. Further charac terization of the predicted doses to nursing human neonates and dust intake relative to the doses at which toxicity

was observed in animals would be included in a more detailed assessment.

Assuming chronic exposures to levels obs erved in ambient air, inside recycling facilities, or outside near recycling facilitie s results in cancer risk estimates below

10 -6 , and large margins of exposure when compared with doses causing effects in animal studies. This suggests that, given the current state of scientific knowledge, directly breathing decaBDE is not likely to be a significant health concern for workers or the general public. Levels received via food or mother’s milk also appear to be relatively low. However, a more reliable assessmentPBDEs: Recommendations to 13 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup comparing tissue concentrations in l aboratory animals and humans is needed. Also, other exposure scenarios, such as exposures of the general population and young children to house dust, require a more in-depth evaluation.

Breakdown of DecaBDE

The studies of ARB and others establis h that consumer products containing

decaBDE result in release and dissem ination of the ch emical through the environment. Further, a number of studies indicate t hat decaBDE loses bromine atoms in the environment by the action of ultraviolet light, heat, and bacteria, forming more persistent and toxic lo wer brominated compounds, such as nonaBDEs, which are further debrominated (Soderstrom et al. 2004; Gerecke et al. 2005). Research presented at the Di oxin 2005 Meeting in Toronto indicates that decaBDE in sewage sludge may be broken down under anaerobic conditions by bacteria to octaBDEs and nonaBDEs. The researchers hypothesize that these debrom ination reactions also occur in sewage treatment

facilities and in anaerobic soils and sediments. Other studies have demonstrated the ability of anaerobic bac teria to debrominate decaBDE to nonaBDEs and octaBDEs, and octaBDEs to lower brominated congeners.

Research also indicates that decaBDE is metabolized in fish, including rainbow trout, and in chickens, to lower brominated congeners (e.g., nonaBDEs, octaBDEs, and heptaBDEs). Another potent ial environmental health concern, apart from debromination of decaBDE, is the formation of brominated dioxins and dibenzofurans from decaBDE during combus tion (e.g., disposal via incineration of plastics).

Nature and Extent of the PBDE Problem

Continuing Exposures

PBDEs are ubiquitous subst ances present in homes, o ffices, and other buildings, and in transportation vehicles, including cars, trucks, planes and mass transit vehicles. The general populat ion comes into contact wi th materials containing PBDEs in nearly every indoor microenv ironment through the use of PBDEs in building materials, carpets, textiles, electronics, flooring, mattresses, foam furniture, and high temper ature plastics. As a c onsequence of the pervasiveness of PBDEs in the indoor environment, people are directly exposed to these bioaccumulative chemicals for that porti on of time spent indoors, which has been estimated by the ARB to range from 85% - 90% of each day. Thus, these direct human exposures make PBDEs strikingl y different from other recognized persistent bioaccumulative chemicals, for which diet represent s the primary route of exposure. PBDEs are measured in ind oor air, and in house and office dust. PBDEs have been detected in some foods, and in ambient air, especially near ewaste recycling and autoshredder facilities.PBDEs: Recommendations to 14 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Figure 3. Increasing PBDE Huma n Serum Levels in the U.S.*

0 20 40 60 80 100

1982 1987 1992 1997 2002

Collection yearng/g lipid Each point represents ~200 people Each point represents ~10 people

0 20 40 60 80 100

1982 1987 1992 1997 2002

Collection yearng/g lipid Each point represents ~200 people Each point represents ~10 people

*Source: Sjodin et al., 2003

Recent scientific reports have shown t hat PBDEs are rapidly accumulating in human tissues (Figure 3). This was firs t observed in 1998 in Sweden, which has

a national breast milk moni toring program. Based on se veral small studies, the levels of PBDEs measured in humans in Canada and the US are typically 10 times or more greater than in Eur ope (Table 1; Figure 4), and appear to be doubling every few years.

Figure 4. Distribution of P BDE levels among U.S. women*

*Source: McDonald, 2005

Biomonitoring data indicate that individ uals have measurable levels of decaBDE

in their blood. Unlike most of th e PBDE congeners, t he fully brominatedPBDEs: Recommendations to 15 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup decaBDE does not bioaccumulate. Thus, the finding of decaBDE in blood samples obtained from the general populat ion indicates that people experience repeated continuous exposures to decaBDE . In addition, Cal/EPA scientists have found the highest tissue concentrations of PBDEs in the world in California wildlife (shorebird eggs and fish), and have reported rapid accumulation of

PBDEs in the tissues of San Franci sco Bay harbor seals (Figure 1 above).

Table 1. Mean Concentrations of P BDEs in Humans in the U.S. and Three European Countries

Country Mean PBDE body burden (ng/g lipid) References

United States 90.3 McDonald 2005

Sweden 6.03 Bavel et al. 2002

Spain 4.12 Meneses et al. 1999 Finland 2.30, 11.7 St randman et al. 1999, 2000

With the coming prohibition in Californi a of products manufactured on or after June 1, 2006 containing pentaBDEs and octa BDEs, exposures to these PBDEs

should decrease over time but will nonethel ess continue for many years through the continued use of existing building materials, furnishings, and consumer products. Recycling and disposal of materials containing pentaBDEs and

octaBDEs will also result in continuing exposures.

It should be noted that the June 1, 2006 prohibition, wh ile banning the introduction of new sources of pentaBDEs and octaBDEs into the state, will not alter exposures arising from materials and consumer products currently in use. In fact, exposures will continue for year s. Moreover, it is possible that new sources of pentaBDEs and octaBDES will continue to be introduced into

California after the effective data of t he ban because California H&SC Sections

108920 et seq. do not specify how the pentaBDE and octaBDE prohibition will be enforced. In such cases, the Attorney General’s Office usually assumes the responsibility of enforcement; however, at this time it is not clear whether the Attorney General’s Office has the resour ces to enforce the relevant statutory provisions. Nor is it clear whether the A ttorney General’s Office would require the technical assistance of any of the Cal/EPA BDOs in this regard. As noted above, tissue PBDE concentrations producing effe cts in rodents overlap with existing human tissue concentrations, indicating the potential for human health effects and an urgent need to reduce human exposure.

DecaBDE is not affected by any legisl ation and its use and release into the

environment will continue unabated. Pr eliminary analyses suggest that

breakdown of decaBDE to more toxic fo rms is a more important concern than direct exposure to decaBDE, although this requires further study. WhilePBDEs: Recommendations to 16 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup exposures to decaBDE are continuous in the indoor air in homes and offices, the airborne concentrations are qui te low. Exposure to dust in these settings may result in higher doses to, for example, young children, as described above.

Further characterization of dust as a sour ce of exposure requires a more detailed

assessment. Levels of decaBDE found in sewage sludge suggest that decaBDE

from the indoor environment and perhaps laundering finds its way into municipal sewage systems and is further dispersed in the environment. This is an example whereby decaBDE enters the outdoor environment, and moves into the food chain and into aquatic and terrestrial wild life, along with the debrominated forms it gives rise to. A growing body of data indicates that decaBDE undergoes

debromination to lower brominated form s through sunlight, heat, bacteria, and through metabolism as it progresses thr ough the food web. Several of these

lower brominated forms are bioaccumulative.

Co-Exposures to PCBs and similar classes of chemicals

PBDEs have structural similarity to PBBs, PCBs, and certain other persistent polyhalogenated organic pollutants. In the limited toxicity testing to date, PBDEs have produced some of the toxic effe cts and physiologic changes seen with many persistent polyhalogenated organic po llutants, in particular the PBBs and PCBs. These effects include developmental and nervous system toxicity, as well as mimicry of estrogen and interference with the activity of thyroid hormone.

These observed similarities in the toxi cological profiles suggests that PBDEs, PBBs, PCBs, and certain other persist ent polyhalogenated organic pollutants may induce toxic effects via common mechanisms of action. The general population is exposed on a daily basis not only to PBDEs, but also to these other chemicals, primarily via thei r presence in the diet. Given this, there are concerns that co-exposures to PBDEs and ce rtain of these other persistent polyhalogenated organic pollutants may be addi tive, and that total levels of exposure to these compounds may be close to the point where frank developmental toxicity may occur in mo re highly exposed individuals (McDonald, 2005). To date, only one study has investi gated the effect of co-exposures in animals. In this study a greater than addi tive effect of PBDE 99 and PCB 52 was observed for effects on the developing nervous system (Eriksson et al., 2003).

Waste Disposal/Recycling Issues

Assembly Bill 2587 (2004 Legislative Se ssion, chaptered as California H&SC Sections 108920-108923) does not restrict the disposal of waste containing

PBDEs

. Other countries that have restri cted the use of PBDEs have not addressed waste disposal. To date, the Workgroup has not identified any measures or procedures that have been implemented for PBDE waste disposal by other countries. California should cont inue to monitor future activities of others with regard to PBDE waste disposal.PBDEs: Recommendations to 17 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Nonetheless, there is a need to identif y the waste stream s containing PBDEs,

and determine which contribute to releas e of PBDEs into the environment. Measurement and monitoring studies are needed to investigate this. While Assembly Bill 2587 prohibits the processi ng of products manufactured on or after June 1, 2006 that contain more than one-tenth of one perc ent pentaBDEs or octaBDEs, it does allow metallic recycl ables containing PBD Es (pentaBDEs and octaBDEs) to be processed for recycling or reuse, which includes automobiles, metal furniture, major appliances, and el ectronic products. Studies to date suggest that e-waste recycling facilitie s are significant sources of PBDEs

released into the ambient air. Autoshr edder facilities have also been shown to

release PBDEs into the ambient air. California should characterize these exposure pathways more fully.

Another need is to investigate the fate and transport of PBD Es via municipal waste water systems and the use of sewage sludge, especially regarding releases into the aquatic environment.

In addition to autoshredder and e-waste, PBDEs released from the processing and disposal of a variety of products should also have their exposure pathways

characterized. PentaBDEs are found in mattresses, foam packaging, cushioned furniture, and carpet padding; octaBDEs acrylonitrile butadiene styrene (ABS) plastic, housings for fax machines, computers and other electronic equipment, telephone handsets, small electronics par ts, and electric cable; decaBDE is found in housings for TVs, and other el ectronics, textile backings (curtains, upholstery covering), electrical boxes, wiring, and high impact polystyrene (HIPS) plastic.

In summary, exposures of the general pub lic to PBDEs occur through the use of consumer products and furnishings in homes, offices, cars and schools. As these consumer products are used and after they are discarded, PBDEs are released into the environment where they can bioaccumulate in wildlife and food

animals.



### Cal/EPA Entities and DHS Past and Ongoing Activities

Air Resources Board

As described in Appendix I and elsewhere in this report, ARB has conducted air monitoring to aid the characterizati on of PBDE pathways of exposure and the extent of exposure to total PBDE and the different PBDE congeners. ARB has reviewed its regulatory author ity and found that PBDEs fa ll within the class of polycyclic organic matter, which has been designated as a Toxic Air Contaminant

under H&SC sections 39660 et seq

.PBDEs: Recommendations to 18 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Department of Toxic Substances Control

DTSC’s Hazardous Materials Laborat ory has pioneered measurements of

PBDEs in human tissue and wildlife in the U.S. DTSC first reported the exponential increase of PBDEs in harbor s eals from the San Fr ancisco Bay that occurred between 1988 and 1998 (She et al . 2002). Moreover, DTSC reported

that levels of PBDEs in California human adipose and serum samples obtained in the late 1990s were 30 times higher than human tissue levels reported during the same time period from Europe and Japan (P etreas et al. 2003). The absence of PBDEs in California serum dating from the 1960s reflects the recent introduction

of PBDEs into commerce and the environm ent (Petreas et al. 2003). Because

PBDE concentrations did not correlate with PCB concentrations, that study also suggested that other exposur e pathways, such as indoo r air may be significant. Additionally, DTSC reported that levels of PBDEs measured in California marine fish and seabird eggs are among the highes t in the world (Holden et al. 2004; She et al. 2004; Brown et al. 2006). Curr ently, DTSC is completing a study of breast milk, the first such study specifical ly designed to identify PBDE sources of exposure. In addition, in an effort to identify major waste streams of concern, DTSC is measuring PBDEs in e-waste and autoshredder waste (Petreas et al. 2005) as well as consumer products, us ing both chemical methodologies and an XRF screening tool (Petreas et al. 2006) . DTSC has been hosting a Technical Working Group where scientists fr om government, industry, and nongovernmental organizations present and di scuss the latest information on PBDEs

and other brominated flame retardants. DTSC publications on PBDEs are included in Appendix III.

DTSC plans to:

 Complete ongoing PBDE research

 Seek/obtain funds for further research

 Develop integrated research plan with DTSC regulatory programs

 Define waste stream management alternatives

 Define/assess current PBDE disposal/destruction options

 Explore changes in regulations to define PBDEs as hazardous waste

 Develop an integrated approach to bi omonitoring with Cal/EPA and DHS

Integrated Waste Management Board

The CIWMB has authority to regulat e nonhazardous solid waste handling, transfer, composting, transformation, and disposal. The CIWMB does not

characterize waste and does not restrict the handling and di sposal of waste containing PBDEs. DTSC determines if a waste is hazardous and what management standards are required. T he SWRCB/RWQCB determines if any

constituents of concern contained in a waste would affect water quality and if specific management standards are required. At this time, no restrictions havePBDEs: Recommendations to 19 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup been identified by DTSC and the SWRCB /RWQCB for wastes containing

PBDEs.

Because PBDEs are ubiquitous subst ances that have been used for more than 30 years as flame retardants in home and office building materials, motor vehicles, electronics, furnishings, te xtiles, high temperature plastics and polyurethane foams, they are common in the waste st ream. The presence of

PBDEs in waste materials cannot be read ily discerned by solid waste facility operators. Should the di sposal of wastes containing PBDEs eventually be restricted, some method for identificat ion would need to be devised to let the solid waste facility operator k now if the waste contains PBDE. This is especially important in light of the fa ct that diverting waste fr om landfills through reuse and recycling is a major requirement of the Integrated Waste Manage ment Act (Act), and the operator needs to be able to discern when a waste has restricted handling.

Nonhazardous solid waste landfills are prohibited from accepting hazardous wastes with few exceptions. One exc eption is treated wood waste, which can be disposed in a composite-lined portion of a solid waste landfill. Another exception is asbestos containing waste, which c an be disposed in a designated disposal area at a landfill. Asbestos containing waste is cradle-to-grave manifested;

treated wood waste is not manifested or labeled, which has the potential to be a problem for operators who c annot readily discern if t he waste is treated or nontreated wood waste. Neither asbestos containing waste nor treated wood waste can be processed prior to disposal. To conserve landfill space, most landfill operators divert wood materials from disposal and typically ground and screen the wood before marketing it for r euse as a landscape product, compost feedstock, biomass fuel, etc. Because operators may hav e difficulty in discerning

whether a waste is treated wood waste or not, treated wood waste could end up being processed even though this activity is prohibited.

Used oil and electronic waste cons isting of CRTs and monitors have been classified by DTSC as hazardous wastes and cannot be disposed in nonhazardous solid waste landfills, but they can all be recycled. The handling and management of thes e wastes, including recycling, fall under the authority of

DTSC.

In the area of pollution prevention, t he CIWMB encourages t he procurement of products that do not contain PBDEs. Ex amples of this include the following:

o The CIWMB, working with the Departm ent of General Services (DGS) on Strategically Sourced St atewide Contracts, added specification language as provided below:

 Office Equipment: copiers and associated services; awarded July 2005; estimated value of contract $36 million – Specification language:PBDEs: Recommendations to 20 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Requirement that digital copier shall contain no polybrominated biphenyls (PBB) or diphenyl ethers (PBDE).

 Computer Hardware: desktop com puters and workstations, notebook computers, printers, monitors, and peripherals; awarded June 2005; estimated value of contract $116 million – Specification language: points awarded for meeting environment al requirement that electronics

manufacturers should demonstrate t hat they are co mplying globally with European Union’s Directiv e – Restriction of Hazardous Substances – which includes the phase out of certain PBDEs by 2006.

o The CIWMB adopted the Electronic Pr oduct Environmental Assessment Tool (EPEAT) rating system as environm ental purchasing criteria in June 2005, which can be used by State agencie s to identify electronic devices with reduced environmental impacts. The CIWMB has requested that the DGS issue a Broadcast Bulletin on the use of EPEAT by State agencies once EPEAT certified products are available.

EPEAT is an environmental procurem ent tool that is designed to help institutional purchasers in the public and private sectors evaluate, compare and select desktop computers, la ptops and monitors based on their

environmental attributes. EPEAT wa s initiated through a cooperative agreement between the Zero Waste A lliance and US EPA Region 10. To qualify for EPEAT, a product must c onform to 22 mandat ory criteria, including compliance with provisions of the European Directive for the

Restriction on use of certain Hazardous Substances in electronic products (RoHS Directive) that require s less than 1000 ppm PBDE within homogeneous materials.

o The CIWMB is working with DGS on implementing the recently developed environmentally preferable purchasing (EPP) standards fo r carpet, called

“the California Gold EPP Ca rpet Criteria.” The s pecifications include a requirement that the ca rpet contain no PBDE.

Office of Environmental Health Hazard Assessment

OEHHA has followed the emerging scientif ic information on the toxicity of PBDEs, and OEHHA staff have published se veral reviews and analyses of the available toxicity data in sci entific journals. Evaluation of the available toxicity data on the PBDEs, including decaBDE, is ongoing, and an assessment of the health risks from exposures to PBDEs is underway.PBDEs: Recommendations to 21 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup State Water Resources Control Board

The SWRCB has reviewed its authority and that of the Regional Boards to regulate PBDEs. Bioaccumulative c hemicals that are harmful to aquatic organisms at detected levels can be regul ated by the Regions. Chemicals in

waters at levels harmful to humans can also be regulated. Further, PBDEs are listed in DHS’ draft groundwater rechar ge regulations with a number of other emerging chemicals because they are endoc rine disruptors, found in wastewater treatment plant effluents (i.e ., the source of recharge water), and are ubiquitous. The identification of acceptable sampli ng and analytical protocols for PBDEs would facilitate SWRCB efforts, as well as values for maximal allowable concentrations in drinking water and ground and surface waters.

Department of Health Services

Activities of DHS have included the following:

 Developing over the past two year s a proposal to establish a human biomonitoring program in California, with a str ong emphasis on PBDEs.

 Along with DTSC staff, preparing and presenting a briefing on PBDEs to the Secretary of Cal/EPA and senior management of t he Cal/EPA BDOs.

 Assisting Kaiser’s Women’s Health Research Institute in developing Developmental Toxicants and Healthy Childbearing , a physician’s guide

that includes information on health effects, exposure sources, and exposure prevention recommendations for PBDEs, and other toxicants. The purpose of the guide is to increase physicians’ awareness of developmental toxicants and to assist them in taking relevant histories, and in addressing their patients’ concerns.

 Participated in the Technical Working Group on PBDEs convened by DTSC’s Hazardous Materials Laboratory.

 Conducted a qualitative assessment of workplace exposures to lead,

PBDEs and other toxicants at a computer recycling facility.



### Workgroup Recommendations

The Workgroup identified a number of recommendations that should lead to reductions in exposures to PBDEs as well as facilitate compliance with California

H&SC Sections 108920 et seq . For each of the reco mmendations identified, estimated timeframes for implementati on are provided. In instances where completion of one recommendation is nec essary before other recommendations can be implemented, this is noted.

In developing these recommendations, the Workgroup explicitly did not address issues related to the availability of suff icient state resources for implementation.PBDEs: Recommendations to 22 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup The Workgroup notes that the majority of these recommendations cannot be acted upon without the provision of additi onal resources. This is a serious

constraint that must be considered and addressed as Cal/EPA evaluates which of these recommendations to implement. It should be noted that some of these recommendations would also require the involvement of DHS as well as the

BDOs of Cal/EPA. The main recommendat ions are given in the table below.

More detailed recommendations follow.

Table 2. Main Recommendations to Reduce PBDE Exposures 1

Outreach and Education

 Educate key governmental offici als and the public about the PBDE prohibition and hazards to encourage co mpliance with the prohibition and exposure reduction behavior. This would include development of

educational materials such as fact sheets.

Pollution Prevention

 Encourage the purchase of PBDE-free products.

Measurement and Monitoring 2

 Conduct human biomonitoring to ev aluate the effectiveness of the pentaBDE and octaBDE prohibition and other PBDE reduction efforts.

 Conduct environmental monitoring to identify sources, pathways and trends in PBDE levels, and to characte rize the environmental fate of

decaBDE.

Regulatory Initiatives

 Develop health guidance levels (e.g ., reference exposure levels) for PBDEs to aid in establishing ac ceptable environmental levels.

 Assess the need for further regulati on, such as the development of hazardous waste criteria and managem ent and disposal requirements and practices for PBDE contaminated waste, an Airborne Toxic Control Measure, the addition of PBDEs to t he Air Toxics “Hot Spots” list, and the

need to limit the use of decaBDE.

1 Subject to available funding.

2 DTSC will provide guidance to other Cal/EPA BDOs for the sampling and chemical analyses of PBDEs in environmental matrices.PBDEs: Recommendations to 23 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Outreach and Education

1. Educate key governmental offi cials and the public about the PBDE prohibition and hazards and work with them to encourage compliance with the prohibition and exposure reduction behavior.

This would involve working with and educating state and local government, industry, public intere st groups, and the general public about the PBDE prohibition and environment al concerns about PBDEs. Targeted state officials would incl ude the State Fire Marshal and the Attorney General’s Office, as well as staff in General Services and other agencies responsible for developing and implementing policies related to purchasing and recycling. Local o fficials could include county health officers, environmental health offi cers and purchasing officials.

Timeframe: These activities would begin immediately, and would continue as long as there are significant amount s of PBDEs in commerce or in the

state’s waste streams. Departments involved: DTSC, ARB, OEHHA, SWRCB, IWMB, DHS.

a. Develop practical information on the prohibition of the use in commerce of products contai ning pentaBDEs and octaBDEs.

Timeframe: Fact sheets and similar documents would be completed and distributed/available to target audiences within six months. This would include development and distribut ion of educational materials for businesses, government entities, and the public regarding product purchasing, use and disposal. Writt en information would be reviewed and updated as needed. Departments involved: DTSC, ARB, OEHHA, SWRCB, IWMB, DHS.

b. Identify at-risk workers and develop a health hazard advisory/alert for workers and employers. Conduct outreach and education for workers and employers.

Identify and target dissem ination of a worker Health Hazard Advisory or Alert on PBDEs to PBDE-expos ed workers, including computer recyclers, janitors, foam fabricators, computer technicians, and to their unions and community-based organiza tions, employers, and health care providers. Develop a Health Hazard Advisory or Alert on PBDEs for workers and employers that provi des practical information on health effects, exposure sources, safe s ubstitutes, industrial hygiene controls, the prohibition of the use in comm erce of products containing pentaBDEs and octaBDEs, and additional information resources.

Publicize the Health Hazard Adviso ry or Alert by issuing a press

release.PBDEs: Recommendations to 24 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Obtain California customer lists from manufacturers, importer, and

distributors of PBDE-containi ng products and increase targeted

dissemination of the Alert.

Timeframe: Initiate educational outreac h to identified groups within one year, and continue educational outreach as needed. Department involved: DHS

c. Identify especially at-risk communi ties and other groups in the general population. Develop health hazar d advisories for dissemination to these groups.

High risk groups in the general public are identified through collaboration with community and other public interest groups, and targeted for dissemination of health advisories. Develop a health advisory on PBDEs that provides practical information on health effects, exposure sources, and safe substitutes, the PBDE prohibition,

and additional information resources.

Timeframe: Work completed within two years. Departments involved: OEHHA, DHS

2. Develop building operation and maint enance “best practices” guidelines for PBDEs for residential and business use. Incorporate these into guidelines for the public, schools, busi nesses, state and local agencies. Ensure that guideline information is reflected in pertinent State indoor air quality programs.

Timeframe: One year timeframe after fact sheets completed under “Outreach and Education,” 1.a, and update as needed. Departments involved: DTSC, ARB, OEHHA, IWMB, Cal/EPA, DHS

a. Develop a set of guidelines designed to reduce PBDE exposures

indoors.

Based on information developed by DTSC, it appears that indoor exposure to dust adds appreciably to PBDE body burdens. ARB could develop a set of guidelines designed to reduce PBDE exposures indoors. Conceptually, the guideli nes could contain recommendations, including more effective cleaning methods and vacuuming techniques and equipment to reduce exposure to PBDEs that adhere to dust. These “best practices” guidelines could be used as a model for the public, government agencies, businesses, and schools.PBDEs: Recommendations to 25 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Timeframe: Will be completed within 18 months. Departments involved: ARB, OEHHA, DHS

b. Work with the Collaborative for High Performance Schools (CHPS) to incorporate the new PBDEs “best practices” information developed under 2.a above into the Best Practices Manual for green buildings for

schools.

CHPS, which is comprised of severa l state agencies, public utilities and other organizations, has developed a very comprehensive Best Practices Manual for schools on green buildings. There are multiple

volumes to the Manual that include sections on design, purchasing, operations, maintenance and cleaning. The ARB could work with the

Collaborative to have the new inform ation on PBDEs incorporated into these guidelines. While the ne xt update is scheduled for 2008, ARB could work to get this information included in the ongoing revisions to the design and construction manual to raise awareness. In addition,

the ARB could also include the in formation in the Relocatable Classrooms volume when developed, and in training, e-bulletins, and

other resources that CH PS publishes. (available at www.chps.net , see “publications”).

Timeframe: Ongoing, but revisions to Best Practices Manual completed within one year. Departments involved: ARB, OEHHA, IWMB

c. Work with the Sustainability Manager and the Real Estate Services Division of the Department of General Services (DGS) to incorporate the new PBDEs “best practices” information developed under 2.a above into DGS Management Manuals as a requirement for buildings

to achieve the Silver le vel of certification.

DGS is developing guidelines and policies, called Management Manuals, to facilitate the implementat ion of Executive Order S-20-04, which calls for buildings to achieve the Silver level of certification, according to the U.S. Green Buil ding Council’s green building rating system, “Leadership in Energy and Environmental Design (LEED).”

The IWMB could work with DGS’s Sustainability M anager and the Real Estate Services Division to have information on PBDEs incorporated

into this effort.

Timeframe: Complete within one year after fact sheets are completed

under “1.a” above. Departments involved: OEHHA, IWMB, Cal/EPAPBDEs: Recommendations to 26 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Pollution Prevention Initiatives

1. Encourage institutions , state and local agencies (e.g., in cities and counties) to buy PBDE-free products by posting fact sheets on DTSC’s and DGS’s Environmentally Preferable Purchasing (EPP) Web sites that provide examples of PBDE-free pr oducts and manufacturers, including information on where such pr oducts can be purchased.

DTSC and IWMB could work with DG S to have the fact sheets posted on the state’s EPP Web site, which will help assure that state and local procurement officials know about PBDEs.

The information used in the fact s heets would be derived from products completed under “Outreach and E ducation,” 1.a, above.

Timeframe: Complete within one year after fact sheets completed under “Outreach and Education,” 1. a, and update lists as needed. Departments involved: DTSC, ARB, IWMB

2. Evaluate the use of incentives for “PBDE-free” products and product labeling by manufacturers.

Timeframe: Complete within one year. Departments involved: DTSC

3. Offer “Environmental Leadership” awards for phase-out of PBDEs.

Timeframe: Offer first set of awards within one year. Departments involved: DTSC, Cal/EPA

4. Compile a list of safer alternativ es that have been identified by other entities (e.g., Consumer Affairs, U.S. EPA Region IX, IWMB Household Hazardous Waste (HHW) safer alter natives brochure and website).

The list of alternatives could be promoted through the activities identified

for recommendations under “Outreach and Education” and “Pollution

Prevention Initiatives.”

Timeframe: Complete within one year, and update as needed. Departments involved: DTSC, ARB, OEHHA

5. Work with Department of General Services (DGS) and Prison Industry Authority (PIA) to encourage the purc hase of PBDE-free products by all state agencies.PBDEs: Recommendations to 27 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup DTSC and IWMB could work with DG S to have information on PBDE-free products included on DGS’s Environment ally Preferable Purchasing (EPP) Web site, which is part of the “Green CA” Web site, and in product catalogs used by purchasing agents. DTSC and IWMB could also work with PIA to encourage the latter organization to purchase PBDE-free products, since state agencies are r equired to purchase furniture and other office supplies made by the PIA.

Timeframe: Continue ongoing effort after fact sheets completed under

“Outreach and Educ ation,” 1.a. Departments involved: DTSC, IWMB

Measurement and Monitoring

1. Initiate and implement an environm ental measurement program to assess the effectiveness of PBDE pollution prevention measures, remediation activities, and regulations.

a. Convene an Inter-Agency PBDE Exposure Workgroup to facilitate implementation and coordination of the environmental measurement and monitoring conducted by Cal/EPA. This group would assist in the identification of sources and pathw ays of exposures, identify data gaps, and provide guidance and input to other exposure assessment

activities of Cal/EPA BDOs and DHS.

Timeframe: Initiate within three months, and continue as long as PBDE concentrations pose an environmental health threat. Departments involved: DTSC, ARB, OEHHA, SWRCB, IWMB, DHS

b. Develop guidance on acceptabl e sampling methods and testing protocols for identifying PBDEs in environmental matrices.

In the short term, DTSC will provide guidance on acceptable sampling methods and testing protocols for i dentifying PBDEs in environmental matrices of concern to the SWRCB. The SWRCB has requested this guidance in order to implem ent the Cal/EPA PBDE Workgroup recommendations on monitoring and m easurement in environmental

matrices.

Identification by ARB and DTSC of acceptable sampling and analytical protocols for PBDEs in matrices of in terest to Cal/EPA BDOs (e.g., air, ambient water, sludge, sediment, tr eatment plant influent, effluent). ARB and DTSC will help to ensur e that the PBDE measurement and monitoring data are collected and analyzed appropriately. This guidance on PBDE sampling and analytic al protocols will assist BDOsPBDEs: Recommendations to 28 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup in evaluating the reliability and co mparability of current and future California PBDE measurement and monitoring data.

The Environmental Laboratory Accr editation Program (ELAP) within DHS can use this guidance to develop a procedure to certify laboratories as competent in PBD E analyses. SWRCB and regional water boards require such certif ication of laboratories for PBDE analyses before they institute mo nitoring requirements for PBDEs. However, there currently are no cert ification programs in the U.S. for PBDEs. Therefore, the workgroup may have to develop certification criteria in conjunction with the State and Regional Water Boards, and

ELAP.

Timeframe: Complete within six months to one year. Departments involved: DTSC, ARB, SWRCB

c. Identify sources and pathways of PBDE exposure , including the importance of decaBDE.

The Inter-Agency PBDE Exposure Workgroup would assess existing

information on the extent of envir onmental PBDE contamination in California, identify data needs, prioritize data collection, and recommend additional sampling in a pilot project, to be implemented by Cal/EPA BDOs and DHS. The pilot project would address data gaps

with measurements and monitori ng of PBDEs, and would include investigation into the role decaB DE plays as a source of lower brominated PBDEs present in envir onmental matrices. This would be used by the Inter-Agency PBDE Exposure Workgroup to characterize sources and pathways of exposure. W orkplace exposures to PBDEs in targeted industries/workplaces coul d be investigated using the DHS’s right-of-entry mandate (H&SC 105175).

Timeframe: Complete within one to three years. Departments involved: DTSC, ARB, OEHHA, SWRCB, DHS

d. Characterize temporal and spat ial in-situ PBDE levels, including

decaBDE.

A monitoring program would be implem ented to track in-situ levels of PBDEs, including decaBDE and its br eakdown products, to assess the effectiveness of PBDE exposure miti gation measures. For example, the ARB could seek funding to c onduct additional outdoor and indoor air monitoring to better characterize temporal and spatial trends in PBDE concentrations throughout the state and in different indoor settings. This monitoring could in clude collecting additional PBDE data

from ARB’s network of air toxi cs monitoring sites, additional near-PBDEs: Recommendations to 29 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup source monitoring adjacent to probable sources of PBDEs, and additional indoor air monitoring in public buildings, schools, and homes. DTSC could seek funding to systematically characterize trends in waste streams (e.g., autoshredder , ewaste). DTSC could seek funding to expand its studies of PBD Es in human milk, adipose tissue,

serum and wildlife.

Timeframe: Complete within one to three years. Departments involved: DTSC, ARB, OEHHA, SWRCB

e. Archive environmental and biological samples to evaluate temporal trends, hotspots, and new chemicals.

Timeframe: Initiate within one year, and continue thereafter. Departments involved: DTSC, ARB, SWRCB

f. Examine potential environmental and public health risks of alternatives and substitutes, based on biological and environmental monitoring

data.

In examining alternatives and subs titutes for PBDE flame retardants, consider information on toxicity , persistence, bioaccumulation, and potential for environmental release. Alternative flame retardants may already be in use. Consider the utility of conducting pilot biomonitoring and environmental monitoring studies to evaluate the presence and persistence of these alter natives in the environment.

Timeframe: Initiate within one year, and continue thereafter. Departments involved: DTSC, ARB, OEHHA

2. Provide for a systematic, representa tive human biomonitoring of PBDEs in California, which would provide fo r systematic collection and chemical analysis of human biological samples to assess exposure trends and the effectiveness of the exposure reductions. This may also eventually aid in evaluating whether such exposures ar e associated with specific chronic diseases and, where appropriate, to inform public policy intended to prevent such diseases.

The value of biomonitoring has been dem onstrated in other parts of the world, as well as in the United St ates. For example, biomonitoring programs in Europe found decreasing leve ls of dioxins, probably reflecting implementation of pollution preventi on measures and emission controls.

Timeframe: Initiate within one to three years, and continue and expand

thereafter. Departments involved: DTSC, OEHHA, DHSPBDEs: Recommendations to 30 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 3. Encourage the University of Calif ornia Toxic Substances Research and Teaching Program (UC TSR&TP) to emphasize research on the fate and transport of PBDEs, especially decaBDE.

The UC TSR&TP is a University of Ca lifornia Multicampus Research Unit supporting research on toxic substances in the environment and teaching graduate students through funding of grants, fellowships, and lead

campus programs.

Timeframe: Initiate within one year, and continue as needed. Departments involved: DTSC

Regulatory Initiatives

1. Develop health values (e.g., chr onic Reference Exposure Levels (cRELs))

for PBDEs.

Completion of this recommendation is necessary before implementation of

recommendations 2 and 3 can occur.

Timeframe: Will be completed by summer 2007. Departments involved: OEHHA

2. Determine if there is a need to est ablish (1) hazardous waste criteria, and(2) management and disposal requirements and practices for PBDEcontaminated waste.

Timeframe: Complete within three years. Departments involved: DTSC

3. Conduct a Needs Assessment to determine the appr opriateness of developing an Airborne Toxic Control Measure (ATCM) for PBDEs, which, as polycyclic organic matter (POM), are already identified as Toxic Air Contaminants (TACs).

Under H&SC Sections 39666 et seq ., ARB could evaluate sources of

PBDE emissions that could be contro lled through development of ATCMs. In this case, ARB would prioritize sources, based on exposure and health risk characterization, and develop appropriate ATCMs to reduce exposure to PBDEs. However, before ATCMs could be developed, health values

are needed to characterize health ri sk and allow ARB to determine the

need for controls. OEHHA woul d develop health values.

Timeframe: Complete within three to four years. Departments involved: ARBPBDEs: Recommendations to 31 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 4. Consider adding PBDEs to the Air To xics “Hot Spots” list of chemicals.

The Air Toxics “Hot Spots” regulation (H&SC Sections 44300 et seq .) applies to stationary sources and r equires self-reporting. ARB could conduct a rulemaking to add PBDEs to the Hot Spots list of chemicals. Upon implementation, this may requi re facilities to report use and/or

emissions of PBDEs.

Timeframe: Proposed rulemaking in 2006. Departments involved: ARB

5. Examine evidence of toxicity and env ironmental fate of PBDEs, especially deca-BDE; evaluate the need for r egulation or legislation.

DHS could consider recommending an occupational health standard for the deca congener to Cal/OSHA, if warranted.

Timeframe: Complete within one to three years. Departments involved: DTSC, ARB, OEHHA, DHS

6. Survey aquatic toxicity dat a and determine research needs for considerations of development of water quality standards.

A critical prerequisite for implement ation of this recommendation is for Cal/EPA to identify acceptable samp ling and analytical protocols for PBDEs in matrices of interest (e .g., ambient water, sludge, sediment, treatment plant influent, effluent). I dentification of crit ical pathways and waste streams contributing to PBDE cont amination is also a prerequisite. Adequate funding and staff resource s and Agency support would also be necessary before embarking on devel opment of a regulatory program.

Set up a contract with the Southern California Coastal Water Research Project (SCCWRP) to survey existing aquatic toxicity literature for PBDEs, identify data useful for developin g standards, and recommend projects aimed at filling data gaps.

Timeframe: Complete within one to three years. Departments involved: DTSC, SWRCBPBDEs: Recommendations to 32 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Summary of Recommended Cal/EPA Actions

Departments 

### Actions

DTSC ARB OEHHA SWRCB IWMB DHS



### Outreach and Education

1. Educate key governmental officials and the public about the PBDE prohibition and hazards and work with them to encourage compliance with the prohibition and exposure reduction behavior. ( continuing timeframe ) X X X X Lead X

a. Develop practical information on the prohibition ( 6 month timeframe, update as needed ) X X X X Lead X

b. Identify at-risk work ers, develop a health hazard advisory/alert, and conduct

outreach and education for workers and employers ( 1 yr timeframe, with continuing

outreach ) Lead

c. Identify especially at-risk groups in the general population. De velop health hazard

advisories for dissemination to these

groups. ( 2 yr timeframe ) Lead X

2. Develop building op eration and maintenance “best practices " guidelines for PBDEs. (1 yr timeframe after fact sheets completed under “Outreach and Education,” 1.a, and update as needed.) X Lead X X X

a. Develop guidelines to reduce PBDE exposures indoors, incorporating this guidance into “Best Management Practices” guidelines for operating and maintaining buildings. (Will be completed within 18 months.) Lead X X

b. Work with the Collaborative for High

Performance Schools to have the information on PBDEs incorporated into the Best Practices Manual (BPM) for green buildings for schools (Ongoing, but revisi ons to BPM within one year.) Lead X XPBDEs: Recommendations to 33 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Summary of Recommended Ca l/EPA Actions (continued)

Departments 

### Actions
DTSC ARB OEHHA SWRCB IWMB DHS



### Outreach and Education (continued )

2c. Work with DGS to incorporate new best practices information on PBDEs into DGS Building Manuals as a requirement to

receive Silver level certification. ( Completed after one year of completion of fact sheets – per 1.a above) (Agency level involvement needed) X Lead



### Pollution Prevention Initiatives

1. Encourage institut ions, state and local agencies (e.g., in cities and counties) to buy PBDE-free products by posting fact sheets on

DTSC and DGS Envir onmentally Preferable Purchasing Web sites ( 1 yr timeframe after fact sheets completed under “Outreach and Education,” 1.a, and update lists as needed ) CoLead X CoLead

2. Evaluate the use of incentives for “PBDEfree” products and product labeling by

manufacturers ( 1 yr timeframe ) Lead

3. Offer “Environmental Leadership” awards for phase-out of PBDEs (Lead: Cal/EPA) (1 yr timeframe) X

4. Compile list of safer alternatives that have been identified by other entities ( 1 yr timeframe, update as needed ) X X Lead

5. Work with Department of General Services and Prison Industry Aut hority to encourage purchase of PBDE-free pr oducts by all state agencies (Continue ongoing effort after fact sheets completed under “Outreach and Education,” 1.a, and update lists as needed.) CoLead CoLeadPBDEs: Recommendations to 34 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Summary of Recommended Ca l/EPA Actions (continued)

Departments 

### Actions
DTSC ARB OEHHA SWRCB IWMB DHS



### Measurement and Monitoring

1. Initiate and implement an environmental measurement program to assess effectiveness of PBDE pollution prevention measures, remediation activities, and regulations. ( continuing timeframe ) Lead X X X X

a. Convene an Inter-Agency Exposure Workgroup to facilitate Cal/EPA environmental monitoring and

measurement (initiate within 3 months) X X Lead X X X

b. Develop guidance on acceptable sampling methods and testing protocols for identifying PBDEs in environmental

matrices. (six to 12 month timeframe) Lead X X

c. Identify source s and pathways of exposure, including the importance of

decaBDE (1-3 yr timeframe) Lead X X X X

d. Characterize temporal and spatial in-situ PBDE levels, including decaBDE (1-3 yr timeframe) Lead X X X

e. Archive environmental & biological samples to evaluate temporal trends, hotspots & new chemicals (1 yr timeframe to initiate) Lead X X

f. Examine potential environmental and public health risks of alternatives and substitutes, based on biological and environmental monitoring data (1 yr timeframe to initiate, continuing as needed) X X Lead

2. Provide for a systematic, representative human biomonitoring progr am of PBDEs in

California. (1-3 yr timeframe) X Lead X

3. Encourage the Universi ty of California Toxic Substances Research and Teaching Program (UC TSR&TP) to emphasize research on PBDE fate and transport, especially

decaBDE. (initiate within 1 yr) LeadPBDEs: Recommendations to 35 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Departments 

### Actions
DTSC ARB OEHHA SWRCB IWMB DHS



### Regulatory Initiatives

1. Develop health values (e.g., cRELs) for

PBDEs (Summer 2007) Lead

2. Determine if there is a need to establish (1) hazardous waste criteria, and (2) management and disposal requirements and practices for PBDE-co ntaminated waste (3 yr timeframe) Lead

3. Conduct a Needs Assessment to determine the appropriateness of developing an ATCM for PBDEs, which, as PO Ms, are identified as

Toxic Air Contaminants (3-4 yr timeframe) Lead

4. Consider adding PBDEs to the Air Toxics "Hot Spots" list of chemicals (2006) Lead

5. Examine evidence of toxicity and environmental fate of PBDEs, especially deca-BDE; evaluate the need for regulation or legislation (1-3 yr timeframe) X CoLead CoLead X

6. Survey aquatic toxicity data and determine

research needs for consideration of development of water quality st andards (1-3 yr timeframe) X LeadPBDEs: Recommendations to 36 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### References

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Eriksson P, Viberg H, Jakobsson E, Or n U, Fredriksson A (2002). A brominated flame retardant, 2,2',4,4',5-pentabromodi phenyl ether: uptake, retention, and

induction of neurobehavioral alterations in mice during a critical phase of neonatal brain development. Toxicol Sci 67 :98-103.

Eriksson P, Fischer C, Fredriksson A (2003). Co-exposure to a PBDE 99 and an

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Fowles JR, Fairbrother A, Baecher-Steppan L, Kerkvliet NI (1994). Immunologic

and endocrine effects of the flame-reta rdant pentabromodiphenyl ether (DE-71)

in C57BL/6J mice. Toxicology 86 :49-61.

Hites RA (2004). Polybrominated di phenyl ethers in the environment and in people: A meta-analysis of concentrations. Environ Sci Technol 38 :945-956.

Gerecke AC, Hartmann PC, Heeb NV, Kohler H-PE, Giger W, Schmid P, Zennegg M, Kohler M (2005). Anaerobi c degradation of decabromodiphenyl

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Hardy ML (2002). The toxicology of the three commercial polybrominated diphenyl oxide (ether) flame retardants. Chemosphere 46 :757-77.

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Kuriyama SN, Talsness CE, Grote K, Chahoud I (2005). Developmental exposure to low dose PBDE 99: effect s on male fertility and neurobehavior in rat offspring. Environ Health Perspect 113 :149-54.

Lindberg P, Sellstrom U, Haggberg L, de Wit CA. (2004). Higher Brominated Diphenyl Ethers and Hexabr omocyclododecane found in Eggs of Peregrine Falcons (Falco peregrinus) Breeding in Sweden. Environ Sci Technol 38 :93-96.PBDEs: Recommendations to 37 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Mazdai A, Dodder NG, Abernathy MP , Hites RA, Bigsby RM (2003). Polybrominated diphenyl ethers in ma ternal and fetal blood samples. Enviorn Health Perspect 111 :1249-1252.

McDonald TA (2005). Polybr ominated diphenylether leve ls among United States residents: daily intake and risk of harm to the developing brain and reproductive

organs. Integr Environ Assess Manag 1 (4):343-354.

Meerts IA, Letcher RJ, Hoving S, Mars h G, Bergman A, Lemmen JG, van der Burg B, Brouwer A (2001). In vitro estrogenicity of polybrominated diphenyl ethers, hydroxylated PDBEs, and polyb rominated bisphenol A compounds. Environ Health Perspect 109 :399-407.

Meneses M, Wingfors H, Schuhmacher M, Domingo JL, Lindstrom G, Van Bavel B (1999). Polybrominat ed diphenyl ethers detect ed in human adipose tissue from Spain. Chemosphere 39 :2271-2278.

National Toxicology Program (NTP, 1986). Toxicology and Carcinogenesis studies of decabromodiphenyl oxide (CAS no. 1163-19-5) in F344/N rats and B6C3F1 mice (feed studies) . Technical Report Series No. 309.

Norris JM, Kociba RJ, Schwetz BA, Rose JQ, Humiston CG, Jewett GL, Gehring PJ, Mailhes JB (1975). Toxicology of octabromobiphenyl and decabromodiphenyl

oxide. Environ Health Perspect 11 :153-61.

Northwest Environment Watch (NWEW, 2004) . Flame retardants in the bodies of

Pacific Northwest Residents. Sea ttle (WA) USA. Available at www.northwestwatch.org/toxics/PBDEs_in_NW.pdf.

Petreas M, She J, Brown FR, Winkler J, Windham G, Rogers E, Zhao G, Bhatia R, Charles MJ (2003). High body burdens of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in California women. Environ Health Perspect 111 :1175-1179.

Schecter A, Papke O, Tung K-C, Staska l D, Birnbaum L (2004). Polybrominated diphenyl ethers Contamination of United States Food. Environ Sci Technol

38 :5306-5311.

Schecter A, Pavuk M, Papke O, Ry an JJ, Birnbaum L, Rosen R (2003). Polybrominated diphenyl ethers (PBDEs) in U.S. mothers’ milk. Environ Health Perspect 111 :1723-1729.

Sharp R, Lunder S (2003). Mother’s milk: Record levels of toxic fire retardants

in American mothers’ breast milk. Washington DC: Environmental Working Group. Available at: www.ewg.org/reports_cont ent/mothersmilk/pdf/Mot hersMilk_final.pdf.PBDEs: Recommendations to 38 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup She J, Holden A, Sharp M, Tanner M, Williams-Derry C, Hooper K (2004). Unusual pattern of polybrominated diphenyl ethers (PBDEs) in U.S. breast milk. Organohalogen Compounds 66 :3945-3950.

She J, Petreas M, Winkler J, Visita P, McKinney M, Kopec D (2002). PBDEs in the San Francisco Bay Ar ea: Measurements in har bor seal blubber and human breast adipose tissue. Chemiosphere 46 :697-707.

Sjodin A, Jones RS, Lapeza C, Focant J- F, Wang R, Turner WE, Needham LL, Patterson DG (2003). Retrospective time trend study of brominated flame retardants and polychlorinated biphenyls in human serum from various regions of the United States, 1982-2002. Organohalogen Compounds 61 :1-4.

Soderstrom G, Sellstrom U, De Wit CA, Tysklind M (2004). Photolytic

debromination of decabromodi phenyl ether (BDE 209). Environ Sci Technol

38 :127-132.

Stapleton HM, Alaee M, Letcher RJ, Bake r JE (2004). Debr omination of the Flame Retardant Decabromodiphenyl ether by Juvenile Carp (Cyprinus carpio) following Dietary Exposure. Environ Sci Technol 38 :112-119.

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Strandman T, Koistinen J, Vartiainen T (2000). Polybrominated diphenyl ethers (PBDEs) in placenta and human milk. Organohalogen Compounds 47 :61-64.

Strandman T, Koistinen J, Kiviranta H, V uorinen PJ, Tuomisto J, Tuomisto J, Vartiainen T (1999). Levels of some polybrominated dipheyl ethers (PBDEs) in fish and human adipose tissue in Finland. Organohalogen Compounds 40 :355-

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Talsness CE, Shakibaei M, Kuriya ma SN, Grande SW, Sterner-Kock A, Schnitker P, de Souza C, Grote K, Chahoud I (2005). Ultrastructural changes observed in rat ovaries following in utero and lactational exposure to low doses of a polybrominated flame retardant. Toxicol Lett 157 :189-202.

Thuresson K, Höglund P, Hagmar L, Sj ödin A, Bergman Å, Jakobsson K (2006). Apparent half-lives of hepta- to decabr ominated diphenyl ethers in human serum as determined in occupationally exposed workers. Environ Health Perspect

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Handbook . EPA/600/P-95/002Fa; National Center for Environmental Assessment: Washington, DC, Augus t 197; Volume 1, Chapter 4.PBDEs: Recommendations to 39 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Viberg H, Fredriksson A, Eriksson P (2002). Neonatal exposure to the brominated flame retardant 2,2',4,4', 5-pentabromodiphenyl ether causes altered susceptibility in the cholinergic tr ansmitter system in the adult mouse. Toxicol Sci

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Viberg H, Fredriksson A, Jakobss on E, Orn U, Er iksson P (2003b). Neurobehavioual derangements in adult mice receiving decabr ominated diphenyl ether (PBDE 209) during a defined per iod of neonatal brain development.
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Zhou T, Ross DG, DeVito MJ, Crofton KM (2001). Effects of s hort-term in vivo exposure to polybrominated diphenyl ethers on thyroid hormones and hepatic enzyme activities in weanling rats. Toxicol Sci 61 :76-82.PBDEs: Recommendations to 40 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Appendix I:

Summary of ARB PBDE Monitoring Data

During 2004, ARB measured PBDEs in ambi ent air, near two recycling facilities (“near-source”), and indoors. The result s of these monitoring efforts are

summarized below.

Ambient

ARB operates a network of air toxics monitoring sites in urban areas within California. During 2004, ARB conducted monitoring for PBDEs at six of these sites (Los Angeles, Oakland, Richmond, Riverside, Sa n Jose, and Wilmington). At each site, integrated monthly sa mples for three PBDE congeners were collected. The samplers operated for fi ve days followed by two days with the sampler shut off, for four weeks. The samples were analyzed by a contract laboratory. Below is a summary of t he 2004 data from the six monitoring sites.

Congener Range Average (pg/m 3 ) (pg/m 3 )

PBDE 47 (tetra) 7-170 53 PBDE 99 (penta) 3-332 52 PBDE 209 (deca) 7-72 23

For comparison, outdoor concentrati ons of various PBDE congeners have been found to range from 5 – 300 pg/m 3 in different parts of the world.

Near-source

Due to the growing concer ns about PBDEs, ARB contra cted with a group at the University of California, Davis to conduct near-source a nd indoor air monitoring. Near-source air monitoring was conduct ed at two facilities: an electronics recycling facility and an automobile shredding facility.

Several electronics recycling facilities we re evaluated as possible locations for near-source air monitoring. At least one facility had installed air pollution control equipment. An electronics recycling fa cility without air pollution control equipment was selected for monitoring. Re cycling activity consisted of shredding old electronics for metal recovery and co mpacting of old plastic cases. Air samples of eight-hours in duration were collected on three days during operating hours. Indoor air samples were colle cted near the shreddi ng and compactingPBDEs: Recommendations to 41 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup equipment. Near-source air samples were collected upwind and downwind of the facility at a distance of 15-20 meters. Indoor concentrations ranged from 15 – 830,000 pg/m 3 , mostly decaBDE. Outdoor concentrations ranged from 1 – 11,000 pg/m 3 , also mostly decaBDE. For co mparison, other researchers have measured up to 200,000 pg/m 3 inside a Canadian electronics recycling facility.

Near-source monitoring was also conducted upwind and downwind of an automobile shredding facility. This ent ire operation is outdoors. Shredded metal and shredded plastics and foam (referred to as auto shredder fluff) is piled onsite following shredding, prior to remova l from the facility for uses as recycled materials. Air samples of 24-hours in duration were collected on three days at the facility’s fenceline (t he facility operated 24 hours per day). Samples were

collected at a distances of 150 – 300 me ters from the shredder and piles of

shredded materials. Fenceline air c oncentrations ranged from 0.2 – 1,900 pg/m 3

, mostly decaBDE. The scientific literatur e does not contain any similar studies on autoshredder operations for comparison.

Indoor

Finally, indoor air samples were collected inside a computer training room that contained 13 older model perso nal computers (i.e., m anufactured before 2000). Air samples of 24 hours in duration we re collected on six days with the computers on and two days with the comput ers off. Concent rations ranged from 4 – 1,600 pg/m 3 , mostly tetraBDEs. For com parison, other researchers have measured indoor air concentrations of PBDEs up to 1,800 pg/m 3

.

The carpet within the computer traini ng room was vacuumed for analysis of carpet dust. The carpet dust contained 10 ppm total PBDEs (mostly in the form of decaBDE), which is consistent with findings of other researchers regarding dust samples. A new piece of the sa me type of carpet was analyzed and found to contain 0.1 ppm of decaBDE.PBDEs: Recommendations to 42 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Appendix II:

The NTP Cancer Bioassay for DecaBDE and Workgroup Cancer Potency Derivation

The National Toxicolo gy Program (NTP, 1986) tested decaBDE for carcinogenicity in rats and mice of bot h sexes by administering the compound in the diet for two years. Ab sorption from the gastrointesti nal tract in these studies was minimal (i.e., <1 to 2%). Male rats received aver age daily doses of 1,120 or 2,240 mg/kg body weight, fema le rats received average daily doses of 1,200 or 2,550 mg/kg body weight. The average daily doses for male mice were 3,200 or 6,650 mg/kg body weight, and for female mice were 3,760 or 7,780 mg/kg body weight. In rats, dose-dependent incr eases in liver neoplastic nodules (hepatocellular adenomas) were observed in males [1/50, 7/50 (p=0.003), and 15/49 (p<0.001), test for trend p <0.001] and females [1/50, 3/49, and 9/50 (p = 0.008), trend test p=0.002]. Based on thes e findings, NTP (1986) concluded that there was “some evidence” of carcinogenicity in male and female rats. In male mice, a statistically significant dose-dependent increase in hepatocellular adenomas and carcinomas (combined) wa s observed [8/50, 22/50 (p=0.002), 18/50 (p=0.02), trend test p=0.02, for cont rol, low- and high-dose, respectively]. The incidence of hepatocellular tumors was not increased above historical controls, however. Increases in thyroid gland follicular cell adenomas or carcinomas (combined) were observed in male [0/50, 4/50, and 3/50; trend test p=0.08] and female mice [0/50, 3/50, 3/50, trend test p = 0.06] , but did not reach statistical significance at the p = 0.05 le vel. Based on these findings, NTP (1986) concluded that there was “equivocal evidence” of carcinogenicity in male

mice and “no evidence” in female mice.

The dose response data from the NTP studies in male and female rats can be used to derive upper bound estimates of human cancer poten cy. For regulatory purposes, the lifetime probabilit y of dying with a tumor (p) induced by an average daily dose (d) is often assumed to be:
p(d) = 1 - exp[-(q 0 + q 1 d + q 2 d 2 +

... + q j d j )] with constraints,

q i ≥ 0 for all i.

The q i are parameters of the model, which are tak en to be constants and are estimated from the data. The parameter q 0 represents the background lifetime

incidence of the tumo r. The parameter q 1 , or some upper bound, is often called the cancer potency, since for small doses it is the ratio of excess lifetime cancer risk to the average daily dose received. Here cancer potency will be defined as

q 1 *, the upper 95% confidence bound on q 1 , estimated by maximum likelihood techniques. When dose is expressed in units of mg/kg-day, the parameters q 1 and q 1 * are given in units of (mg/kg-day) -1

.PBDEs: Recommendations to 43 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup In the NTP studies which form the bas is for the estimation of the cancer potency, the decaBDE was administered in feed, and NTP estimated the doses in units of mg/kg-day. These dose esti mates are used in the potency derivation

here.

Once a potency value is estimated in ani mals, human potency is estimated. In the absence of detailed pharmacokinetic or other data indicating otherwise, a dose in units of milligram per unit surfac e area is often assumed to produce the same degree of effect in different species. Under this assumption, scaling to the estimated human potency (q human ) can be achieved by multiplying the animal potency (q animal ) by the ratio of human to animal body weights (bw h /bw
a ) raised to the one-third power when ani mal potency is expressed in units (mg/kg-day) -1 :

q human = q animal • (bw h / bw
a ) 1/3

From the male rat bioassa y data, an upper bound estimate of cancer potency is 0.000200 (mg/kg-day) -1 . Assuming a bodyweight of 450 grams for test animals (see NTP, 1986, p. 33), and 70 kg for human s, the interspecies scaling factor is 5.39. The resulting upper bound estimate for human cancer potency is 0.00108 (mg/kg-day) -1 . For the female rat, the upper bound potency estimate is 9.55 ×

10 -5 , corresponding to an upper bound human cancer potency estimate of 5.9 ×

10 -4 (mg/kg-day)-1 (assuming a body weight of 300 grams for female rats [NTP, 1986, p. 34] and an interspecies factor of 6.16).PBDEs: Recommendations to 44 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup 

### Appendix III:

Publications and Presentations by DTSC, OEHHA, and ARB: PBDE Environmental Levels, Exposures and Risks

Air Resources Board (ARB). "Report to the California Legi slature- Indoor Air Pollution in California", July 2005 http://www.arb.ca.gov/resear ch/indoor/ab1173/finalreport.htm

Brown FR, Winkler J, Visita P, Dhaliwal J, Petreas M. Levels of PBDEs, PCDDs, PCDFs, and Coplanar PCBs in Edible Fish from Ca lifornia Coas tal Waters. Chemosphere , In Press, 2006

Brown FR, O Kalantzi, Winkler J, Dhaliw al J, Petreas M. Combined PBDE/PCB analysis using GSMS wi th ECNCI detection. Organohalogen Compounds

, 67:129-131, 2005

Charles MJ, Groskova D, Cahill TM. "Near-Source Ambient Air Monitoring of Polybrominated Diphenyl Ethers", UC Davis Departm ent of Environmental Toxicology, Report prepared for the California Air Resources Board, Project Number 01-407, 2005

Geyer HJ, Schramm KW, Darnerud PO, Aune M, Feicht EA, Fried K, Henkelman B, Lenoir D, Schmid P, McDonald TA. Terminal elimination half-lives (T 1/2H ) of the brominated flame reta rdants TBBPA, HBCD, and lower

brominated PBDEs in humans. Organohalogen Compounds, 66:3867- 3871, 2004

Holden A., She J., Tanner M ., Lunder S., Sharp M., and Hooper K. PBDEs in the San Francisco Bay Area: Measurement in Fish. Organohalogen Compounds , 61, 255 – 258, 2003

Hooper K, McDonald TA. The PBDEs: An emerging environmental challenge and another reason for breast-milk monitoring programs. Environ Health Perspect, 108:387-392, 2000

Hooper K, She J. Lesson s from the polybrominated diphenyl ethers (PBDEs): Precautionary principle, primary prev ention, and the va lue of communitybased body burden monitori ng using breast milk. Environ Health Perspect

, 111:109-114, 2003

Hooper K, Holden A, She J. Deca-BDE: Ol d myths, new realities. Proceedings of the Third International Workshop on the Brominated Flame Retardants

, Toronto, CA June 6-9, 2004PBDEs: Recommendations to 45 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Hooper K, McDonald TA. The PBDEs: An emerging environmental challenge

and another reason for breast-mi lk monitoring programs. Environ Health Perspect, 108:387-392, 2000

Kalantzi O, FR Brown, C Er dman, M Caleffi, R Goth-Gol dstein, M Petreas. PBDEs in human breast adipose tissue from Brazil. Organohalogen Compounds

, 67: 479-481, 2005

McDonald TA. Polybrominated Diphenyle ther levels among United States Residents: Daily Intake and Risk of Harm to the De veloping Brain and Reproductive Organs. Integrated Environmental Assessment and Management , 1(4):343-354, 2005

McDonald TA. A perspective on t he potential health risks of PBDEs. Chemosphere, 46:745-755, 2002

McDonald TA. Distribution of PBDE leve ls among U.S. women: Estimates of daily intake and risk of developmental effects. Proceedings of the Third International Workshop on Bromi nated Flame Retardants. (BFR2004) ; 2004 June 6 - June 9; Toront o (ON) Canada pp. 443-446, 2004

Petreas M, C Li, P Visita, K Thakore, H Romine, J Garcha. Polybrominated diphenyl ethers (PBDEs) in building materials and consumer products: Screening tools for exposure assessment. Accepted for presentation at the Healthy Buildings Conf erence, Lisbon, 2006

Petreas M, C Li, P Visita, S Gill, M Gill, J Garcha. Autoshred der and e-waste as sources of PBDE expos ures in California. Organohalogen Compounds , 67: 1012:1015, 2005

Petreas M, J She, FR Brown, J Winkler, G Windham, E Rogers, G Zhao, R Bhatia, MJ Charles. High body burdens of 2,2’,4,4’-brom inated diphenyl ether in

California women. Environ Health Perspect, 111:1175-79, 2003

Petreas M, J She, P Visita , J Winkler, M McKinney, FR Brown, J Dhaliwal, G Denison, M Mok. Trends in persistent contaminants in California biota. Proceedings of the 221st Annual ACS Conference , San Diego, CA, 2001

Petreas M, J Garcha, B Si mmons. E-waste: Consum er electronics exceed hazardous waste criteria. Proceedings of the 229 th Amer Chem Soc National Meeting , San Diego, CA, 2005

Petreas M, D Smith, S Hurl ey, S Jeffrey, D Gi lliss, P Reynolds. Distribution of persistent, lipid-soluble chemicals in br east and abdominal adipose tissues:PBDEs: Recommendations to 46 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup Lessons learned from a breast cancer study. Cancer Epi Biomark &

Prevention , 13:416-424, 2004

Petreas MX. Temporal and Spatial Tren ds in Persistent Organic Pollutants. Envir
Sci & Pollut Research , (Special Issue 3):103-104, 2002

Petreas M, E Rogers, G Zhao, G Windham, R Bh atia, MJ Charles. Organohalogen Body Burden s in California Women. Organohalogen Compounds, 55:259-262. 2002

Petreas M, J She, FR Brown, J Winkler, P Visita, C Li, D C hand, J Dhaliwal, E Rogers, G Zhao, MJ Charles. High PBDE Concentrations in California Human and Wildlife Popula tions. Proceedings of the 22nd International Dioxin Conference, Barcelona, Spain, 2002

Rogers E, M Petreas, JS Park , G Zhao, MJ Charles. Ev aluation of four capillary columns for the analysis of or ganochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (BDEs) in human serum fo r epidemiologic studies. J Chromatography B

, 813:269-285, 2004

She J, MX Petreas, J Winkler, P Visita , M McKinney, D Kopec. Polybrominated Diphenyl Ethers (PBDEs) In the San Fr ancisco Bay Area: Measurements in

Harbor Seal Blubber and Hu man Breast Adipose Tissue. Chemosphere

, 46:697-707, 2002

She J, Holden A, Tanner M, Adelsbach T, Schwarzbach S, Thompson CS, Mahaffy M, Petreas M, Si mmons BP, Hooper, K. High PBDE levels in Piscivorous seabird eggs from t he San Francisco Bay and Washington

state. Organohalogen Compounds , 61:33 -36, 2003

She J, A Holden, M Tanner, M Sharp, T Adelsbach and K Hooper. Highest PBDE Levels (max 63 ppm) Yet Fo und in Biota Measured in Seabird Eggs from San Francisco Bay. Organohalogen Compounds , 66:3889 – 3892, 2004

She J, A Holden, M Sharp, M Tanner, C Williams-Derry , and K Hooper. Unusual Pattern of Polybrominated Diphenyl Ethers (PBDEs) in US Breast Milk. Organohalogen Compounds , 66:3895– 3900, 2004

She J, A Holden, M Sharp, M Tanner, C Williams-De rry, and K Hooper. PBDEs are Higher than PCBs in Thirty Percent of Breast Milk Samples from the

Pacific Northwest. Organohalogen Compounds , 67:647-650, 2005

She J, A Holden, M Tanner, M Sharp, T Adelsbach and K Hooper. Time Trends of PBDEs in Shorebird Eggs from San Fran cisco Bay. Organohalogen Compounds , 67:607-609, 2005PBDEs: Recommendations to 47 February 2006 Reduce Exposure in California Cal/EPA PBDE Workgroup She J, A Holden, M Sharp, M Tanner, C Williams-Derry, and K Hooper. PBDE Congener Pattern is an Indicator of Human PBDE Exposure in North

America. Organohalogen Compounds , 67:525-528, 2005