High Levels of Organophosphate Flame Retardants in the Great Lakes Atmosphere
14 Jan 2014-Environmental Science and Technology Letters (American Chemical Society)-Vol. 1, Iss: 1, pp 8-14
TL;DR: Levels of 12 organophosphate flame retardants (OPs) were measured in particle phase samples collected at five sites in the North American Great Lakes basin from March 2012 to December 2012 as discussed by the authors.
Abstract: Levels of 12 organophosphate flame retardants (OPs) were measured in particle phase samples collected at five sites in the North American Great Lakes basin from March 2012 to December 2012 (inclusive). The target compounds were three chlorinated OPs [tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP)], three alkyl phosphates [tri-n-butyl phosphate (TnBP), tris(butoxyethyl) phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP)], and six aryl phosphates [triphenyl phosphate (TPP), tri-o-tolyl phosphate (TOTP), tri-p-tolyl phosphate (TPTP), tris(3,5-dimethylphenyl) phosphate (TDMPP), tris(2-isopropylphenyl) phosphate (TIPPP), and tris(4-butylphenyl) phosphate (TBPP)]. Total OP (ΣOP) atmospheric concentrations ranged from 120 ± 18 to 2100 ± 400 pg/m3 at the five sites, with the higher ΣOP levels detected at Cleveland and Chicago. ΣOP concentrations at these urban sites were dominated by the chlorinated OPs (TCEP, TCPP, and TDCP...
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TL;DR: The present study shows that the release of OPs from a wide variety of commercial products and wastewater discharge might be considered as primary emission sources and that high potential of long-range atmospheric transport and persistence of OP would be responsible for their presence in various matrices on a global scale.
822 citations
TL;DR: In this article, the occurrence and spatial distribution of 11 OPE congeners and one synthetic intermediate triphenylphosphine oxide (TPPO) in 40 major rivers entering into the Bohai Sea were investigated.
296 citations
TL;DR: Children had higher urinary levels of BDCIPP, DPHP, ip-DPHP, and TBBA as compared to their mothers, suggesting higher exposure to flame retardant levels as a result of increased hand-mouth behavior and elevated dust exposure.
Abstract: As a result of the polybrominated diphenyl ether (PBDE) ban in the mid-2000s, the chemical flame retardant market has moved toward alterative compounds including chlorinated alkyl and nonchlorinated aryl organophosphate flame retardants (OPFRs) as well as aromatic brominated compounds such as Firemaster 550 (FM550). Recent studies have shown that the OPFRs and Firemaster 550 components are frequently detected in polyurethane foams and in indoor dust. Some OPFRs are considered carcinogenic and/or neurodevelopmental toxicants, and children's exposure to these compounds is a concern. OPFRs are readily metabolized and excreted in the urine as their dialkyl and diaryl compounds which function as biomarkers for OPFR exposure. Limited research has shown that adults are broadly exposed to OPFRs, but nothing is known about children's exposure. Similarly, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), a FM550 component, is metabolized to tetrabromobenzoic acid (TBBA). The current study measured levels of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), bis(1-chloro-2-propyl) phosphate (BCIPP), diphenyl phosphate (DPHP), 2 alkylated DPHPs, and TBBA in urine collected in 2013 from 21 US mother-toddler pairs. BDCIPP, DPHP, and ip-DPHP were detected in 100%, 98%, and 96% of all individuals, whereas BCIPP and tert-butyl-DPHP (tb-DPHP) were only detected in 8% and 13%. Further, TBBA was detected in 27% of adults but 70% of children. Overall, children had higher urinary levels of BDCIPP, DPHP, ip-DPHP, and TBBA as compared to their mothers, suggesting higher exposure. For example, on average, BDCIPP levels in children were 4.9 times those of mothers. BDCIPP and DPHP levels in mother's urine were also significantly correlated with levels in children's urine, suggesting similar exposure routes, likely in the home environment. Various potential predictors of OPFR exposure were assessed using a questionnaire. In children some predictors of hand-mouth exposure were associated with elevated BDCIPP and DPHP levels (e.g., less frequent hand washing for BDCIPP). Overall, these trends are consistent with higher flame retardant levels in children as a result of increased hand-mouth behavior and elevated dust exposure.
268 citations
TL;DR: Levels of 13 organophosphate esters (OPEs) and 45 brominated and chlorinated flame retardants (BFRs) were measured in particle phase atmospheric samples collected at Longyearbyen on Svalbard in the European Arctic from September 2012 to May 2013, and ΣOPE concentrations were 1-2 orders of magnitude higher than the ΣBFR concentrations.
Abstract: Levels of 13 organophosphate esters (OPEs) and 45 brominated and chlorinated flame retardants (BFRs) were measured in particle phase atmospheric samples collected at Longyearbyen on Svalbard in the European Arctic from September 2012 to May 2013. Total OPE (ΣOPEs) concentrations ranged from 33 to 1450 pg/m3, with the mean ΣOPE concentration of 430 ± 57 pg/m3. The nonchlorinated tri-n-butyl phosphate (TnBP) and 2-ethylhexyl-diphenyl phosphate (EHDPP) were the most abundant OPE congeners measured, and the sum of all nonchlorinated OPE concentrations comprised ∼75% of the ΣOPE concentrations. The most abundant chlorinated OPE was tris(1-chloro-2-propyl) phosphate (TCPP). Total BFR concentrations (ΣBFRs) were in the range of 3–77 pg/m3, with a mean concentration of 15 ± 3 pg/m3. 2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl)tetrabromophthalate (TBPH) were among the relatively abundant BFRs measured in these samples and comprised ∼46% and 17% of ΣBFR concentrations, respectively. Total PBD...
240 citations
TL;DR: 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.
Abstract: 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.
204 citations
References
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TL;DR: In this paper, the use of PFRs as potential substitutes for brominated flame retardants (BFRs) has been discussed and a number of potential alternatives for BFRs have been proposed.
1,953 citations
TL;DR: This paper analyzed foam samples from 26 different pieces of furniture purchased in the United States primarily between 2003 and 2009, including couches, chairs, mattress pads, pillows, and in one case, foam from a sound-proofing system of a laboratory-grade dust sieve.
Abstract: Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the increased use of alternate flame retardant chemicals to meet flammability standards. However, it has been difficult to determine which chemical formulations are currently being used in high volumes to meet flammability standards since the use of flame retardant formulations in consumer products is not transparent (i.e., not provided to customers). To investigate chemicals being used as replacements for PentaBDE in polyurethane foam, we analyzed foam samples from 26 different pieces of furniture purchased in the United States primarily between 2003 and 2009. Samples included foam from couches, chairs, mattress pads, pillows, and, in one case, foam from a sound-proofing system of a laboratory-grade dust sieve, and were analyzed using gas chromatography mass spectrometry. Fifteen of the foam samples contained the flame retardant tris(1,3-dichloro-2-propyl) phosphate (TDCPP; 1−5% by weight), four samples contained tris(1-ch...
627 citations
TL;DR: OP flame retardants may be associated with altered hormone levels and decreased semen quality in men, and a suggestive inverse association between TDCPP and free androgen index became less evident in adjusted models.
Abstract: BackgroundOrganophosphate (OP) compounds, such as tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP), are commonly used as additive flame retardants and plasticizers in a w...
591 citations
TL;DR: Quintana et al. as discussed by the authors discussed the major processes affecting the fate of OPEs in the environment, such as sorption, volatilization and biodegradation.
Abstract: Organophosphate esters (OPEs), in particular triesters, are high-production-volume chemicals used as flame retardants and plasticizers to protect or to enhance the properties of plastics, textiles, furniture and many other materials. The widespread usage, which may even increase due to the ban of brominated diphenylethers as flame retardants, and the diffusion from host materials result in continuous release of OPEs and their distribution through water, especially wastewater, and air, particularly associated with airborne particulate matter. This work highlights the occurrence of OPEs in wastewater, surface water and groundwater as well as indoor and outdoor air and particulate material. We discuss the major processes affecting the fate of OPEs in the environment, such as sorption, volatilization and biodegradation. Of the OPEs studied thus far, chlorinated tri(2-chloroethyl) phosphate (TCEP) and tri(chloropropyl) phosphate (TCPP) appear to be most recalcitrant and ubiquitous in water and air. We identified knowledge gaps concerning the fate of diesters and monoesters in the aqueous environment, the biodegradation of OPEs under less favorable conditions (sorbed to particles or under anoxic or anaerobic conditions) as well as the behavior of OPEs in the atmosphere and their potential for long-range transport. A second part, addressing analytical methods will published in the next issue [J.B. Quintana, R. Rodil, T. Reemtsma, M. Garci´a-Lopez, I. Rodri´guez, Trends Anal. Chem. (to be published in 27 (10) (2008))].
540 citations
TL;DR: Human exposure to OPs through eating fish or to breastfeeding babies seems to be of minor importance in relation to other potential sources, such as indoor dust inhalation and ingestion.
Abstract: The levels and relative proportions of 11 organophosphorus flame retardants and plasticizers (OPs), some of which are reportedly toxic to aquatic organisms, were investigated in human breast milk and samples of fish and mussels from Swedish lakes and coastal areas in order to assess spatial differences in environmental exposure and spatial and temporal differences in human exposure Some of the biota samples were collected at locations with known potential sources of OPs, but most were collected in background locations Tris-2-chloroisopropyl phosphate (TCPP) and triphenyl phosphate (TPP) dominated in the biota with levels ranging from 170 to 770 ng g−1 for TCPP in perch and between 21 and 180 ng g−1 for TPP In milk samples, TCPP (median 45 ng g−1) and tributyl phosphate (median 12 ng g−1) were the most frequently occurring OPs Among samples of fish from background locations, the concentrations and profiles of most OPs were quite similar, indicating that their sources were diffuse However, in fish from sample locations near known sources, there were marked differences in OP concentrations and profiles Fish from a stream receiving surface water from Arlanda airport displayed high levels of OPs (10 200 ng g−1) that are commonly used in aircraft hydraulic fluids Fish collected at points 1 or 2 km downstream of sewage treatment plants showed significantly higher levels of tris(2-butoxyethyl) phosphate (TBEP), one of the most typically abundant OP in effluents from such plants In the milk samples obtained from women in different towns no distinct differences were detected in OP concentrations or profiles However, the levels of TBEP tended to be higher in milk collected 10 years ago than in milk collected more recently However, human exposure to OPs through eating fish or to breastfeeding babies seems to be of minor importance in relation to other potential sources, such as indoor dust inhalation and ingestion
488 citations