Mark J. La Guardia

Potential role of fire retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment

Five tetra- to hexabrominated diphenyl ether (BDE) congeners (BDE-47, -99, -100, -153 and -154) are the most frequently reported in wildlife and humans. The commercial penta-BDE product, used predominantly to flame-retard polyurethane foam, consists primarily of these same congeners. In 1999, North American demand accounted for 98% of the total global penta-market of 8500 metric tons. Frogs, housed with flame retardant-treated polyurethane foam as a dry substrate, accumulated 10,100 microg/kg (wet weight) of the above BDEs. Crickets kept therein as food contained 14,400 microg/kg. The crickets are believed to have browsed directly on the foam and, in turn, were consumed by the frogs. BDE congener composition in all three matrices matched that of the penta-commercial product. Similar congeners were also observed in soil and stream sediments collected near a polyurethane foam manufacturing plant. Summed concentrations of BDE-47, -99 and -100, the dominant congeners observed in these samples, ranged from < 1 to 132 microg/kg (dry weight basis). Sunfish fillets obtained from a nearby, off-site pond contained a total of 624 microg/kg (lipid basis). Sewage treatment plant (STP) sludge exhibited these same congeners at 1370 microg/kg (dry weight). BDE-209, the fully brominated congener predominant in the commercial deca-BDE product, was also present at 1470 microg/kg. While no known polyurethane foam manufacturers discharged to this plant, the distribution pattern of the low brominated congeners in the sludge matched that of the penta-product. After four weeks of exposure to ambient outdoor conditions, the surface of flame-retarded polyurethane foam became brittle and began to disintegrate. Subsequent dispersal of these penta-containing foam fragments may be one mechanism by which these BDEs reach the environment.

Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife

Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the use of alternative flame retardants in consumer products to comply with flammability standards. In contrast to PBDEs, information on the occurrence and fate of these alternative compounds in the environment is limited, particularly in the United States. In this study, a survey of flame retardants in San Francisco Bay was conducted to evaluate whether PBDE replacement chemicals and other current use flame retardants were accumulating in the Bay food web. In addition to PBDEs, brominated and chlorinated flame retardants (hexabromocyclododecane (HBCD) and Dechlorane Plus (DP)) were detected in Bay sediments and wildlife. Median concentrations of PBDEs, HBCD, and DP, respectively, were 4.3, 0.3, and 0.2 ng g⁻¹ dry weight (dw) in sediments; 1670, <6.0, and 0.5 ng g⁻¹ lipid weight (lw) in white croaker (Genyonemus lineatus); 1860, 6.5, and 1.3 ng g⁻¹ lw in shiner surfperch (Cymatogaster aggregata); 5500, 37.4, and 0.9 ng g⁻¹ lw in eggs of double-crested cormorant (Phalacrocorax auritus); 770, 7.1, and 0.9 ng g⁻¹ lw in harbor seal (Phoca vitulina) adults; and 330, 3.5, and <0.1 ng g⁻¹ lw in harbor seal (P. vitulina) pups. Two additional flame retardants, pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6 tribromophenoxy)ethane (BTBPE) were detected in sediments but with less frequency and at lower concentrations (median concentrations of 0.01 and 0.02 ng g⁻¹ dw, respectively) compared to the other flame retardants. PBEB was also detected in each of the adult harbor seals and in 83% of the pups (median concentrations 0.2 and 0.07 ng g⁻¹ lw, respectively). The flame retardants hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl) tetrabromophthalate (TBPH), and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), were not detected in sediments and BTBPE, HBB and TBB were not detected in wildlife samples. Elevated concentrations of some flame retardants were likely associated with urbanization and Bay hydrodynamics. Compared to other locations, concentrations of PBDEs in Bay wildlife were comparable or higher, while concentrations of the alternatives were generally lower. This study is the first to determine concentrations of PBDE replacement products and other flame retardants in San Francisco Bay, providing some of the first data on the food web occurrence of these flame retardants in a North American urbanized estuary.

Flame Retardant Transfers from U.S. Households (Dust and Laundry Wastewater) to the Aquatic Environment

Levels of flame retardants in house dust and a transport pathway from homes to the outdoor environment were investigated in communities near the Columbia River in Washington state (WA). Residential house dust and laundry wastewater were collected from 20 homes in Vancouver and Longview, WA and analyzed for a suite of flame retardants to test the hypothesis that dust collecting on clothing and transferring to laundry water is a source of flame retardants to wastewater treatment plants (WWTPs) and subsequently to waterways. Influent and effluent from two WWTPs servicing these communities were also analyzed for flame retardants. A total of 21 compounds were detected in house dust, including polybrominated diphenyl ethers (PBDEs), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB or EH-TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), 1,2-bis(2,4,6,-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD or HBCDD), tetrabromobisphenol A (TBBPA), and three chlorinated organophosphate flame retardants (ClOPFRs), tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(2-chloroethyl)phosphate (TCEP). Levels ranged from 3.6 to 82,700 ng g(-1) (dry weight). Of the 21 compounds detected in dust, 18 were also detected in laundry wastewater. Levels ranged from 47.1 to 561,000 ng L(-1). ClOPFRs were present at the highest concentrations in both dust and laundry wastewater, making up 72% of total flame retardant mass in dust and 92% in laundry wastewater. Comparison of flame retardant levels in WWTP influents to estimates based on laundry wastewater levels indicated that laundry wastewater may be the primary source to these WWTPs. Mass loadings to the Columbia River from each treatment plant were by far the highest for the ClOPFRs and ranged up to 114 kg/yr for TCPP.

Species-specific accumulation of polybrominated diphenyl ether flame retardants in birds of prey from the Chesapeake Bay region, USA

Compared to organochlorines, little is known about polybrominated diphenyl ether (PBDE) contamination of birds of prey breeding in the Chesapeake Bay, the largest estuary in the U.S. This study examined and compared PBDE contamination in eggs of osprey, double-crested cormorant, brown pelican and peregrine falcon from this area. Several legacy persistent organic pollutants such as PCBs and DDE were also investigated. The level of urbanization of the landscape appeared to influence the level of PBDE exposure. PBDE congener distribution patterns varied between piscivorous and terrestrial-feeding birds. This suggests individual congeners may be subject to differences in bioaccumulation, biomagnification or metabolism in the aquatic and terrestrial food webs. Biomagnification of PBDEs was studied in the Bay aquatic food chains for the first time. A biomagnification factor of 25.1 was estimated for SigmaPBDEs for the fish - osprey egg food chain. Hazard quotients, applied as a preliminary evaluation, indicated that PBDEs may pose a moderate hazard to ospreys and peregrine falcons through impairment of reproductive performance.

Occurrence of contaminants of emerging concern in mussels (Mytilus spp.) along the California coast and the influence of land use, storm water discharge, and treated wastewater effluent.

Contaminants of emerging concern were measured in mussels collected along the California coast in 2009-2010. The seven classes were alkylphenols, pharmaceuticals and personal care products, polybrominated diphenyl ethers (PBDE), other flame retardants, current use pesticides, perfluorinated compounds (PFC), and single walled carbon nanotubes. At least one contaminant was detected at 67 of the 68 stations (98%), and 67 of the 167 analytes had at least one detect (40%). Alkylphenol, PBDE, and PFC concentrations increased with urbanization and proximity to storm water discharge; pesticides had higher concentrations at agricultural stations. These results suggest that certain compounds; for example, alkylphenols, lomefloxacin and PBDE, are appropriate for inclusion in future coastal bivalve monitoring efforts based on maximum concentrations >50 ng/g dry weight and detection frequencies >50%. Other compounds, for example PFC and hexabromocyclododecane (HBCD), may also be suggested for inclusion due to their >25% detection frequency and potential for biomagnification.

Flame-Retardants and Other Organohalogens Detected in Sewage Sludge by Electron Capture Negative Ion Mass Spectrometry

Numerous halogenated organic compounds have been identified as pollutants of concern. Those with high persistence and hydrophobicity may concentrate in biota, sediments, and wastewater sludge. Nonetheless, the release to the environment of many remains largely unrecognized. Stabilized sewage sludge (biosolids) is increasingly being land-applied as a soil amendment. However, understanding the risks of land application has been hampered by the compositional complexity of biosolids. Compound specific analytical approaches may also underestimate environmental impact of land application by overlooking additional contaminants. However, utilizing an alternative analytical approach based on compound functional group (i.e., alkyl halides) enhanced the information content of the analysis. To illustrate, 49 organohalogens were observed by gas chromatography with electron capture negative ionization mass spectrometry in sewage sludge; 23 identified as flame-retardants: that is, PBDEs, hexabromocyclododecane, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), 2-ethylhexyl tetrabromophthalate, decabromodiphenyl ethane, 1,2-bis (2,4,6-tribromophenoxy) ethane and Dechlorane Plus. Concentrations ranged from 25 to 1,600,000 ng g(-1) total organic carbon. An additional 16 compounds were tentatively identified as triclosan, chlorinated-methoxy triclosan, chlorinated pesticides, hexachlorobiphenyl, TBB degradation products, brominated furans and nonabromochlorodiphenyl ethers. Such an analytical approach may enhance evaluations of the risks associated with biosolids land-application and assist in prioritizing specific chemicals for future environmental fate and toxicology studies.

Do temporal and geographical patterns of HBCD and PBDE flame retardants in U.S. fish reflect evolving industrial usage

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) are common flame retardants in polymers and textiles. Recognition of the persistent, bioaccumulative, and toxic properties of PBDEs has prompted reductions in their use. In contrast, HBCD has received less scrutiny. The U.S has historically been a dominant BFR consumer. However, the few publications on HBCD in wildlife here suggest modest levels compared to Asian and European studies. In contrast, the HBCD concentrations we detected in U.S. fish are among the highest reported in the world. The temporal trends observed suggest that HBCD use may have risen, and that of Penta-BDE declined, following the 2004 termination of its U.S. manufacture. For example, Hyco River carp collected in 1999-2002 exhibited a mean ∑HBCD (sum of α-, β- and γ-HBCD) concentration of only 13 ng/g (lipid weight basis), but was 4640 ng/g in fish collected in 2006-2007. In contrast, the mean ∑PBDE level in these same fish decreased from 40,700 ng/g in 1999-2002 to 9140 ng/g in 2006-2007. Concentrations of HBCD and PBDEs in several Hyco River fish species exceeded those from rivers less influenced by manufacturing outfalls. Results support the contention that textile-related production, relative to its BFR market share, may release disproportionately large amounts of HBCD to the environment.

Brominated Flame-Retardants in Sub-Saharan Africa: Burdens in Inland and Coastal Sediments in the eThekwini Metropolitan Municipality, South Africa

Brominated flame-retardant (BFR) additives are present in many polymeric consumer products at percent levels. High environmental concentrations have been observed near cities and polymer, textile, and electronics manufacturing centers. Most studies have focused on European, North American, and Asian locales. Releases are likely rising most dramatically in countries with weak environmental and human health regulation and enforcement, demand for electrical and electronic equipment (EEE) is escalating, and importation of waste EEE occurs. Several African countries meet these criteria, but little data are available on burdens or sources. To better understand the extent of BFR environmental dissemination in a southern African urban community, inland and coastal sediments were collected in the eThekwini metropolitan municipality, South Africa, and analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), 2-ethylhexyl 2,3,4,5-tretabromophalate (TBPH), 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), and decabromodiphenyl ethane (DBDPE). BFRs were detected in all samples (n = 45). Concentration data are presented on total organic carbon (TOC) normalized basis. ΣBFR ranged from 114 to 47 100 ng g(-1). Decabromodiphenyl ether was detected in 93% of samples (mean concentration 3208 ng g(-1)) followed by TBB at 91% (mean conc. 545 ng g(-1)). Durban Bay is strongly influenced by urban runoff and tidal hydrology, and sediments therein exhibited ΣPBDE concentrations ranging from 1850 to 25 400 ng g(-1) (median conc. 3240 ng g(-1)). These levels rival those in the heavily impacted Pearl River Delta, China. BFRs likely enter the South African environment during manufacture of BFR-containing products, during and following product use (i.e., after disposal and as a result of materials recycling activities), and from nonpoint sources such as atmospheric fallout and urban runoff. These results underline the need to investigate further the environmental burdens and risks associated with BFRs in developing countries.

Polybrominated diphenyl ethers in U.S. sewage sludges and biosolids: temporal and geographical trends and uptake by corn following land application.

Polybrominated diphenyl ethers (PBDEs) have been used extensively to flame-retard polymers and textiles. These persistent chemicals enter wastewater streams following manufacture, use, and disposal, concentrating in the settled solids during treatment. Land application of stabilized sewage sludge (known as biosolids) can contribute PBDEs to terrestrial systems. Monitoring sludge/biosolids contaminant burdens may be valuable in revealing trends in societal chemical usage and environmental release. In archived Chicago area sludges/biosolids from 1975 to 2008, penta-BDE concentrations increased and then plateaued after about 2000. Penta-BDE manufacture in the United States ended in December 2004. Deca-BDE concentrations in biosolids rose from 1995 to 2008, doubling on a 5-year interval. Evaluation of U.S. Environmental Protection Agency Targeted National Sewage Sludge Survey data from 2006 to 2007 revealed highest penta-BDE biosolids levels from western and lowest from northeastern wastewater treatment plants (2120 and 1530 μg/kg, respectively), consistent with patterns reported in some recent indoor dust and human blood studies. No significant regional trends were observed for deca-BDE concentrations. Congener patterns in contemporary Chicago biosolids support the contention that BDE-209 can be dehalogenated to less brominated congeners. Biosolids application on agricultural fields increased PBDE soil concentrations. However, corn grown thereon did not exhibit measurable PBDE uptake; perhaps due to low bioavailability of the biosolids-associated flame retardants.

Polybrominated Diphenyl Ether Accumulation in an Agricultural Soil Ecosystem Receiving Wastewater Sludge Amendments

Few studies have addressed bioaccumulation of organic pollutants associated with land-application of biosolids. We thus examined PBDE burdens within a soil ecosystem receiving long-term sludge amendments and a reference soil ecosystem receiving only manure inputs. No PBDEs were detected in reference site samples, but sludge-amended soils contained 17 600 ± 2330 μg/kg ∑3-7PBDE (total organic carbon (TOC) basis). ∑3-7PBDE burdens were highest in soil invertebrates with the greatest contact with sludge-amended soil (e.g., ∑3-7PBDE of 10 300 ± 2670 and 3000 ± 200 μg/kg lipid for earthworms and detritivorous woodlice, respectively). PBDEs were below quantitation limits in vegetation from the sludge-amended site. Surprisingly, we measured quantifiable PBDE burdens in only a single sample of predaceous ground spiders from the sludge-amended site. BDE-209 burdens in sludge-amended soil and earthworms were 7500 ± 2800 μg/kg TOC and 6500 ± 4100 μg/kg lipid, respectively. BDE 209 was detected in fewer taxa, but the burden in a detritivorous millipede composite was high (86 000 μg/kg lipid). PBDE congener patterns differed among species, with worms and ground beetles exhibiting Penta-BDE-like patterns. Penta-BDE biota-soil accumulation factors (BSAFs) ranged from 0.006 to 1.2, while BDE-209 BSAFs ranged from 0.07 to 10.5. δ(13)C and δ(15)N isotope signatures were poorly correlated with PBDE burdens, but sludge-amended samples were significantly δ(15)N enriched.