Assessing Contributions of Synthetic Musk Compounds from Wastewater Treatment Plants to Atmospheric and Aquatic Environments.

The high environmental concentrations, persistence, and toxicity of synthetic musk compounds (SMCs) necessitate a better grasp of their fate in wastewater treatment plants (WWTPs). To investigate the importance of WWTPs as pathways of SMCs to the environment, air and wastewater samples were collected at four WWTPs in Ontario, Canada. Polycyclic musks (PCMs) were present at higher concentrations than nitro musks (NMs) and macrocyclic musks (MCMs). Three PCMs [galaxolide (HHCB), tonalide (AHTN), and iso-E super (OTNE)] were the most abundant compounds (0.30-680 ng/m3 in air, 0.40-15 µg/L in influent, and 0.007-6.0 µg/L in effluent). Analyses of multiyear data suggest that risk management measures put in place have been effective in reducing the release of many SMCs into the environment. The highest removal efficiency, up to almost 100% of some SMCs, was observed for the plant with the longest solid retention time. A fugacity-based model was established to simulate the transport and fate of SMCs in the WWTP, and good agreement was obtained between the measured and modeled values. These findings indicate that the levels of certain SMCs discharged into the atmospheric and aquatic environments were substantial, potentially resulting in exposure to both humans and wildlife.

Chronic Embryo-Larval Exposure of Fathead Minnows to the Pharmaceutical Drug Metformin: Survival, Growth, and Microbiome Responses.

Metformin is a glucose-lowering drug commonly found in municipal wastewater effluents (MWWEs). The present study investigated the chronic effects of metformin in early-life stages of the fathead minnow (Pimephales promelas). Endpoints assessed were growth, survival, and deformities. The larval gut microbiome was also examined using 16 S ribosomal RNA gene amplicon sequencing to determine microbial community composition and alpha and beta diversity. Eggs and larvae were exposed to metformin measured concentrations (mean [standard deviation]) of 0.020 (0.017) µg/L (for controls) and 3.44 (0.23), 33.6 (1.6), and 269 (11) µg/L in a daily static-renewal setup, with 20 embryos per beaker. The low and middle metformin exposure concentrations represent river and MWWE concentrations of metformin. To detect small changes in growth, we used 18 replicate beakers for controls and 9 replicates for each metformin treatment. Over the 21-d exposure (5 d as embryos and 16 d posthatch [dph]), metformin did not affect survival or growth of larval fish. Hatch success, time to hatch, deformities in hatched fry, and survival were similar across all treatments. Growth (wet wt, length, and condition factor) assessed at 9 and 16 dph was also unaffected by metformin. Assessment of the microbiome showed that the larvae microbiome was dominant in Proteobacteria and Firmicutes, with small increases in Proteobacteria and decreases in Firmicutes with increasing exposure to metformin. No treatment effects were found for microbiome diversity measures. Control fish euthanized with the anesthetic tricaine methane sulfonate had decreased alpha diversity compared to those sampled by spinal severance. This experiment demonstrates that metformin at environmentally relevant concentrations (3.44 and 33.6 µg/L) and at 10 times MWWE concentrations (269 µg/L) does not adversely affect larval growth or gut microbiome in this ubiquitous freshwater fish species. Environ Toxicol Chem 2022;41:635-647. © 2021 Her Majesty the Queen in Right of Canada. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Fate of anthropogenic cyclic volatile methylsiloxanes in a wastewater treatment plant.

The fate of cyclic volatile methylsiloxanes (cVMS) - octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) - was evaluated in a typical secondary activated sludge wastewater treatment plant (WWTP). Water samples (influent, primary effluent, and final effluent) and sludge (primary sludge and waste activated sludge) samples were collected at overnight low, morning high, afternoon low, and evening high flows. Concentrations of cVMS in influents fluctuated with the influent flows, ranging from 0.166 to 1.13 µg L(-1), 3.47-19.3 µg L(-1), and 0.446-3.87 µg L(-1) for D4, D5, and D6, respectively. Mass balance analysis of cVMS showed the average mass of D4, D5, and D6 entering and exiting the plant in influent and effluent, respectively, were 109 g d(-1), 2050 g d(-1), 280 g d(-1), and 1.41 g d(-1), 27.0 g d(-1), 1.90 g d(-1). The total removal efficiency of cVMS was >96%. To elucidate their detailed removal mechanisms, Mackay's fugacity-based treatment plant model was used to simulate the fate of cVMS through the WWTP. Due to the unusual combination of high hydrophobicity and volatility of cVMS, volatilization in the aeration tank and adsorption to sludge were the two main pathways of cVMS removal from water in this WWTP based on the experimental and modeled results. The morning and evening high influent mass flows contributed almost equally at approximately 40% of the total daily cVMS mass, with D5 accounting for the majority of this daily loading.

Qualitative analysis of halogenated organic contaminants in American eel by gas chromatography/time-of-flight mass spectrometry.

Target compound analysis with scanning mass spectrometers such as quadrupole or magnetic sector instruments is used extensively in environmental chemistry because of the selectivity, sensitivity, and robustness. Yet, target compound analysis selectively ignores the majority of compounds present in a sample, especially in complex matrices like fish. In this study, time-of-flight mass spectrometry was used to screen for and identify halogenated compounds in American eels (Anguilla rostrata). Individual and then pooled eel samples were analysed using electron ionization and electron capture negative ionization (ECNI) modes. Eels were differentiated by principal component analysis of chemical profiles and were grouped corresponding to their capture location, all with a single instrument injection per sample. Bromine containing compounds were further investigated by taking advantage of the selectivity of ECNI by utilizing the Br(-) ion m/z 79 and 81. A total of 51 brominated compounds were detected and their identities were attempted by authentic standards, library searching, and/or chemical formula prediction based on accurate mass measurements. Several PBDEs were identified in the samples, and the majority of the non-PBDEs identified were bromophenols, bromoanisoles, and bromobenzenes. These classes of compounds are synthesized for use in flame retardant production either as intermediates or as final products. However, their occurrence in eels was most likely the result of metabolism or break-down products of high production volume flame retardants like polybrominated diphenyl ethers and bromophenoxy compounds.

Mountain cold-trapping increases transfer of persistent organic pollutants from atmosphere to cows' milk.

Concentrations of long-lived organic contaminants in snow, soil, lake water, and vegetation have been observed to increase with altitude along mountain slopes. Such enrichment, called "mountain cold-trapping", is attributed to a transition from the atmospheric gas phase to particles, rain droplets, snowflakes, and Earth's surface at the lower temperatures prevailing at higher elevations. Milk sampled repeatedly from cows that had grazed at three different altitudes in Switzerland during one summer was analyzed for a range of persistent organic pollutants. Mountain cold-trapping significantly increased air-to-milk transfer factors of most analytes. As a result, the milk of cows grazing at higher altitudes was more contaminated with substances that have regionally uniform air concentrations (hexachlorobenzene, α-hexachlorocyclohexane, endosulfan sulfate). For substances that have sources, and therefore higher air concentrations, at lower altitudes (polychlorinated biphenyls, γ-hexachlorocyclohexane), alpine milk has lower concentrations, but not as low as would be expected without mountain cold-trapping. Differences in the elevational gradients in soil concentrations and air-to-milk transfer factors highlight that cold-trapping of POPs in pastures is mostly due to increased gas-phase deposition as a result of lower temperatures causing higher uptake capacity of plant foliage, whereas cold-trapping in soils more strongly depends on wet and dry particle deposition. Climatic influences on air-to-milk transfer of POPs needs to be accounted for when using contamination of milk lipids to infer contamination of the atmosphere.

Spatial trends of dioxin-like compounds in Atlantic anguillid eels.

Several temperate freshwater eel stocks have experienced unsustainable declines, yet to be explained. The decline of lake trout (Salvelinus namaycush) in Lake Ontario has been linked to aryl-hydrocarbon receptor agonists such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and polychlorinated naphthalenes (PCNs), and the question remains whether eels are affected similarly by these compounds. Concentrations of PCDD/Fs, dl-PCBs, and PCNs were determined in eels collected at seven locations in eastern Canada including L. Ontario, one location in New York, USA, and one location in Flanders, Belgium. Concentrations varied greatly among origins, indicating dissimilar historic loadings to local areas. The risk to eel reproduction was evaluated with 2,3,7,8-TCDD toxic equivalents, and increased by 10-fold from the least to most contaminated site. The risk to eel recruitment from dioxin-like compounds in American eel using available guidelines is low. The development of a more comprehensive model for eel recruitment risk assessment due to dioxin-like compounds, using eel-specific guidelines, is recommended. Toxic equivalents were 5-fold higher when based on mammalian toxic equivalency factors compared to fish values. About half of the eels captured in L. Ontario exceeded the Canadian guideline for fish consumption (20pg TEQ g(-1) ww), but there were no other exceedances in Canada. The current risk to eel consumers in Canada is low overall, except for highly urbanized and industrialized areas.

Dechlorane plus monoadducts in a Lake Ontario (Canada) food web and biotransformation by lake trout (Salvelinus namaycush) liver microsomes.

Compounds related to the high-production-volume flame retardant Dechlorane Plus (DP) were measured in a Lake Ontario food web located downstream of a DP manufacturing plant. These compounds, 1,3- and 1,5-DP-monoadducts (DPMA), are positional isomers and are thought to arise from the incomplete reaction of DP or impurities in the DP starting material during its manufacture. The 1,3-DPMA isomer was measured (0.12-199 ng g(-1) lipid wt) in all trophic levels, whereas 1,5-DPMA was measured only sporadically in the food web and was not detectable in the apex predator, lake trout (Salvelinus namaycush). Concentrations of DPMA isomers when detected in Lake Ontario biota were greater than that of total DP for all trophic levels. The prevalence of 1,3-DPMA in the food web, and especially in lake trout, may be due to obstruction of the existing carbon double bond to enzyme attack, rendering it less readily metabolized. To examine this hypothesis, biotransformation kinetic experiments using in vitro lake trout liver microsomal exposures were performed. Zero-order depletion rate constants for 1,3- and 1,5-DPMA were 92.2 and 134.6 pmole h(-1) , respectively, with corresponding half-lives of 2.03 ± 0.14 h (1,3-DPMA) and 1.39 ± 0.09 h (1,5-DPMA). Furthermore, the 1,5-isomer was depleted to a greater extent than 1,3-DPMA. Specific biotransformation products were not identified. These data support the hypothesis that 1,5-DPMA is more readily metabolized than 1,3-DPMA by lake trout. The present study also shows that the concentrations of these isomers, which the authors speculate might be unintended impurities or byproducts in some technical DP formulations, exceed that of the intended product in biota.

Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site.

A screening level human health risk assessment based on the worst-case scenario was conducted on the occupational and residential exposures to dechlorane plus (DP) in the manufacturing facility region and an electronic-waste (e-waste) recycling site in China, which are two of the most polluted areas of DP in the world. Total estimated exposure doses (EEDs) via dietary intake, dermal contact, and inhalation was approximately 0.01 mg kg(-1) d(-1) for people living in the manufacturing facility region. In comparison, total EEDs (approximate 0.03 µg kg(-1), d(-1)) were 300-fold lower in people living near an e-waste recycling site in China. Chronic oral, dermal, and inhalation reference doses (RfDs) were estimated to be 5.0, 2.0, and 0.01 mg kg(-1)d (-1), respectively. The oral RfD was markedly greater than Mirex (2×10(-4) mg kg(-1) d(-1)) and decabromodiphenyl ether (BDE-209; 7×10(-3) mg kg(-1) d(-1)), which have been or might be replaced by DP as a flame retardant with less toxicity. Monte Carlo simulation was used to generate the probability densities and functions for the hazard index which was calculated from the EEDs and RfDs to assess the human health risk. The hazard index was three orders of magnitude lower than 1, suggesting that occupational and residential exposures were relatively safe in the manufacturing facility region and e-waste recycling site.

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil, influent, effluent, receiving water, and sediment of wastewater treatment plants in Canada.

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography - mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282-6.69µgL(-1), 7.75-135µgL(-1), and 1.53-26.9µgL(-1), respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009-0.045µgL(-1), <0.027-1.56µgL(-1), and <0.022-0.093µgL(-1), respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009-0.023µgL(-1), <0.027-1.48µgL(-1), and <0.022-0.151µgL(-1) for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003-0.049µgg(-1)dw, 0.011-5.84µgg(-1)dw, and 0.004-0.371µgg(-1)dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008-0.017µgg(-1)dw, <0.007-0.221µgg(-1)dw, and <0.009-0.711µgg(-1)dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.

Analytical performance of a triple quadrupole mass spectrometer compared to a high resolution mass spectrometer for the analysis of polybrominated diphenyl ethers in fish.

Polybrominated diphenyl ethers (PBDEs) are a class of flame retardants used globally in many consumer products and industrial applications. Traditionally, gas chromatography-high resolution mass spectrometry (GC-HR-MS) is the method of choice for analysis of PBDEs in environmental samples because it offers high sensitivity and selectivity, resulting in less interferences. However, the specificity offered by gas chromatography-triple quadrupole tandem mass spectrometry (GC-QQQ-MS/MS), operated in selected reaction monitoring mode, provides a more affordable alternative to GC-HR-MS for the analysis of PBDEs in complex environmental samples. In this study, an analytical method was developed for the analysis of 41 PBDE congeners in fish using GC-QQQ-MS/MS. Results from the analysis of three fish species [lake trout (Salvelinus namaycush), yellow perch (Perca flavescens), and round goby (Neogobius melanostomus)] using GC-QQQ-MS/MS were compared with those obtained by GC-HR-MS. These species were selected because they represent varying levels of lipid-rich matrix and contaminant loads. Instrumental limits of detection for the GC-QQQ-MS/MS ranged from 0.04 pg to 41 pg, whereas those for the GC-HR-MS ranged from 5 pg to 85 pg. The PBDE values obtained from these two methods were highly correlated, R(2) values >0.7, for all three fish species, supporting the suitability of GC-QQQ-MS/MS for analysis of PBDEs in fish with varying fat content.

Emerging and historical brominated flame retardants in peregrine falcon (Falco peregrinus) eggs from Canada and Spain.

Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003-2007), are made between Canada (N=12) and Spain (N=13). Overall, concentrations of sum (Σ) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Σhexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2'4,4',5,5'-hexabromobiphenyl (BB-153)>hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO)>1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)>decabromodiphenylethane (DBDPE)>octabromotrimethylphenyllindane (OBIND)>hexabromobenzene (HBB)>bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of ∑HBCD (14,617 ng/glw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, ΣHBCD, and ΣPBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N=1). The in ovo PBDE congener profile was dominated by BDE-153>BDE-99>BDE-47>BDE-183>BDE-100>BDE-209, with the isomeric HBCD pattern being α-HBCD>γ-HBCD (ß-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (-) α-HBCD, suggesting selective enantiomeric enrichment or that the (+) α-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds.

Dechlorane plus and possible degradation products in white stork eggs from Spain.

The occurrence of the emerging chlorinated flame retardant Dechlorane Plus (DP) and three of its possible degradation products was investigated in white stork eggs from two colonies in Spain. The average DP concentrations were 401 pg/g wet weight (w.w.) for the urban/industrial colony and 105 pg/g w.w. for the rural colony. One possible degradation product, anti-[DP-1Cl], was found in approximately 10% of the samples. No significant stereoisomer enrichments were detected in any colony based on the average anti-DP fractional abundances found which agrees with previous studies in herring gulls. The relationship between DP and PBDE contents in both colonies was explored leading to different scenarios, i.e. no correlation was found in the urban colony but they were statistically correlated in the rural colony. To the best of our knowledge, this is the first study to report DP in a species from a terrestrial food web, and also to report a DP degradation product in biota.

Predominance of BDE-209 and other higher brominated diphenyl ethers in eggs of white stork (Ciconia ciconia) colonies from Spain.

Polybrominated diphenyl ethers (PBDEs) are ubiquitous pollutants for which there is still a lack of knowledge about the environmental behavior and fate of the higher brominated congeners (octa- to deca-BDEs). In this study, the PBDE content and congener profiles in failed eggs from two colonies of white stork (Ciconia ciconia) in Spain were studied. The average total PBDE concentration was 1.64ng/g (wet weight, w.w.) for the rural colony and 9.08ng/g (w.w.) for the urban colony. Higher brominated BDEs dominated the congener profiles of both colonies. Of particular interest was the determination of BDE-209 as the dominant congener accounting for 44.1% and 38.6% of the total PBDE content in the rural and urban colonies, respectively. BDE-202, considered an indicator of BDE 209 debromination, was detected in 83% and all of the samples from rural and urban colonies, respectively. The observed congener profile in which BDE-207>BDE-208>BDE-206 does not correspond to any known technical PBDE mixture and is evidence for possible BDE-209 degradation.

Dechlorane plus and related compounds in peregrine falcon (Falco peregrinus) eggs from Canada and Spain.

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

Polybrominated diphenyl ethers and their hydroxylated analogs in plasma of bottlenose dolphins (Tursiops truncatus) from the United States east coast.

Polybrominated diphenyl ethers (PBDEs) and hydroxylated PBDEs (OH-PBDEs) were determined in plasma of free-ranging bottlenose dolphins (Tursiops truncatus) from Charleston (CHS), South Carolina, and the Indian River Lagoon (IRL), Florida, U.S.A. Significantly lower sums (sigma) of PBDE concentrations (sum of 12 congeners) were found in animals from the IRL (arithmetic mean, 5.45 +/- 4.63 ng/g wet wt) compared with those from CHS (30 +/- 40 ng/g wet wt). Brominated diphenyl ether (BDE)-47 was the predominant PBDE in dolphins from the IRL (50% of the sigma PBDEs) and CHS (58%). The sigma PBDE concentrations in plasma of dolphins were negatively correlated with age at both locations. Fifteen and sixteen individual OH-PBDE congeners could be quantified in plasma of dolphins from IRL and CHS, respectively. Similar to sigma PBDE, mean sigma OH-PBDE concentrations were significantly higher in plasma of dolphins at CHS (1150 +/- 708 pg/g wet wt) compared with those at IRL (624 +/- 393 pg/g wet wt). The predominant congener at both locations was 6-OH-PBDE-47 (IRL, 384 +/- 319 pg/g wet wt; CHS, 541 +/- 344 pg/g wet wt), representing 61.5% of total sigma OH-PBDE at IRL and 47.0% at CHS. Concentrations of sigma OH-PBDEs were weakly negatively correlated with age in dolphins from both locations (p < 0.05; IRL, r2 = 0.048; CHS, r2 = 0.021). In addition to the OH-PBDE congeners identified with technical standards, eight and four unidentified OH-PBDEs were detected and quantified, respectively, in animals from CHS (sum of unidentified OH-PBDEs = 1.35 +/- 0.90 pg/g wet wt) and IRL (0.73 +/- 0.40 pg/g wet wt). Results of the present study suggest that, unlike OH-PCBs, OH-PBDEs in bottlenose dolphins are minor products in plasma relative to sigma PBDEs and a significant proportion may be a consequence of the dietary uptake of naturally produced methoxylated- and OH-PBDEs.

Occurrence of triclosan in plasma of wild Atlantic bottlenose dolphins (Tursiops truncatus) and in their environment.

The presence of triclosan, a widely-used antibacterial chemical, is currently unknown in higher trophic-level species such as marine mammals. Blood plasma collected from wild bottlenose dolphins (Tursiops truncatus) in Charleston, SC (CHS) (n = 13) and Indian River Lagoon, FL (IRL) (n = 13) in 2005 was analyzed for triclosan. Plasma concentrations in CHS dolphins ranged from 0.12 to 0.27 ng/g wet weight (mean 0.18 ng/g), with 31% of the sampled individuals having detectable triclosan. The mean IRL dolphin plasma concentrations were 0.072 ng/g wet weight (range 0.025-0.11 ng/g); 23% of the samples having detectable triclosan. In the CHS area, triclosan effluent values from two WWTP were both 190 ng/L and primary influents were 2800 ng/L and 3400 ng/L. Triclosan values in CHS estuarine surface water samples averaged 7.5 ng/L (n = 18) ranging from 4.9 to 14 ng/L. This is the first study to report bioaccumulation of anthropogenic triclosan in a marine mammal highlighting the need for further monitoring and assessment.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in the abiotic environment: surface water and precipitation from Ontario, Canada.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been identified as metabolites of PBDEs, and also as compounds of natural origin in the marine environment; however, there has only been very limited study of their presence in the abiotic environment. In the present study, OH-PBDEs were determined in samples of surface water and precipitation (rain and snow) collected from sites in Ontario, Canada. OH-PBDEs were detected in all the samples analyzed, although half of the observed peaks did not correspond to any of the 18 authentic standards available. Fluxes of sigmaOH-PBDEs ranged from 3.5 to 190 pg/m2 in snow and from 15 to 170 pg/m2/day in rain, and those were higher at three of the southern Ontario locations relative to a single northern remote site. Concentrations of sigmaOH-PBDEs ranged from 2.2 to 70 pg/L in water and from < 1 to 420 pg/g in particulate organic carbon (POC), and higher values were found near sewage treatment plant (STP) outfalls in Lake Ontario. Partition coefficients (log K(oc)) for OH-PBDEs ranged from 4.0 to 5.1. The results in this study suggest that OH-PBDEs are ubiquitous in the abiotic environment and most likely are produced through reaction of PBDEs with atmospheric OH radicals. As well, they may be present in surface waters near STPs due to oxidation of PBDEs and inflows from metabolism by humans and animals.

Polymeric brominated flame retardants: are they a relevant source of emerging brominated aromatic compounds in the environment?

A purge and trap method was used to study the release of brominated organic compounds from polymeric brominated flame retardants (BFRs), a relatively unknown class of flame retardant materials. Among the volatile brominated organics released, pentabromotoluene (PBTo), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were of particular interest because of their high potential to persist in the environment The impact of a thermal stress on the release of these compounds was assessed by applying different constant temperatures for one hour to a polymeric BFR sample. Release rates ranged between 22 +/- 2.1 ng g(-1) h(-1) for PBEB to 2480 +/- 500 ng g(-1) h(-1) for PBTo at room temperature. These rates of release reached 65 +/- 11 ng g(-1) h(-1) for PBEB and 42400 +/- 4700 ng g(-1) h(-1) for PBTo at 100 degrees C. This suggests that the compounding of thermoplastic polyesters done at high temperatures, up to 290 degrees C, could lead to the release of significant amounts of volatile brominated compounds in the environment when crude polymeric BFRs are used as flame retardants. To assess if this unsuspected source of volatile brominated compounds to the environment was relevant to support air concentrations in the Great Lakes area, air samples collected at Egbert (ON, Canada) were analyzed and PBTo, PBEB, and HBB were detected at low levels in some air samples (<0.01 to 0.09 pg/m3). As a second step, a Level III fugacity model was run using release rates of PBTo, PBEB, and HBB determined in this study. Results of the model indicated that prevailing PBEB and HBB air concentrations were not supported by their release from polymeric BFRs but by the use of these compounds as additive BFRs. However, these model predictions suffered from a lack of information on the actual use of polymeric BFRs. Hence, further work is needed to assess the release of potentially persistent brominated aromatic compounds from polymeric BFRs.

Detection of hydroxylated polychlorinated biphenyls (OH-PCBs) in the abiotic environment: surface water and precipitation from Ontario, Canada.

Hydroxylated PCBs (OH-PCBs) are well-known metabolites of PCBs in organisms, but there has been no direct study of their presence in the abiotic environment. In this study, OH-PCBs were determined in samples of rain, snow, and surface waters from sites in Ontario, Canada. OH-PCBs were quantified by gas chromatography with high-resolution mass spectrometry (GC-HRMS)in order to provide complete characterization of all OH-PCB homolog groups. OH-PCBs and PCBs were detected in all the samples analyzed, although half of the sigmaOH-PCBs could not be identified even with 71 individual congener standards. Total concentrations of OH-PCBs (sigmaOH-PCBs) in water ranged from 0.87 to 130 pg/L and from 230 to 990 pg/g in particulate organic matter. Total fluxes of those compounds in snow and rain were from < 1 to 100 pg/m2 and from < 1 to 44 pg/ m2/day, respectively. Higher sigmaOH-PCB fluxes in rain were found in southern Ontario than in a remote north-central Ontario site possibly reflecting greater sources of precursor PCBs near urban areas. Relatively higher sigmaOH-PCB concentrations were found in surface waters from sites near sewage treatment plant (STP) outfalls in the cities of Toronto (130 pg/L) and Hamilton (35 pg/L) than in offshore samples from Lake Ontario (1.6 pg/L). The results indicate that STPs are one of the sources of OH-PCBs for lake waters in this region. Similar homolog and congener profiles in rain and offshore surface water samples suggest that atmospheric deposition is the predominant source at offshore sites. This is the first report to detect the OH-PCBs in the abiotic environment.

Polychlorinated biphenyls and hydroxylated polychlorinated biphenyls in plasma of bottlenose dolphins (Tursiops truncatus) from the Western Atlantic and the Gulf of Mexico.

Polychlorinated biphenyls (PCBs) and hydroxylated metabolic products (OH-PCBs) were measured in plasma collected from live-captured and released bottlenose dolphins (Tursiops truncatus) from five different locations in the Western Atlantic and the Gulf of Mexico in 2003 and 2004. In 2004, the sum (sigma) of concentration of PCBs in plasma of dolphins sampled off Charleston, SC [geometric mean: 223 ng/g of wet weight (w.w.)] was significantly higher (p<0.05) than concentrations detected in animals from the Indian River Lagoon, FL (sigmaPCBs: 122 ng/g w.w.) and the Sarasota Bay, FL (sigmaPCBs: 111 ng/g w.w.). The PCB homolog profiles were similar among locations. Concentrations of OH-PCBs were significantly higher (p<0.05) in plasma of dolphins from Charleston, SC (sigmaOH-PCBs for 2003: 126 ng/g w.w.; 2004: 138 ng/g w.w.) than animals from Florida (sigmaOH-PCBs ranged from 6 to 47 ng/g w.w.) and Bermuda (8.3 ng/g w.w.); however, concentrations in the Charleston samples did not differ from animals captured in Delaware Bay, NJ (57 ng/g w.w.). The sigmaOH-PCBs constituted 2-68% of the total PCB concentrations in plasma. Dichloro- to nonachloro-OH-PCBs were quantified using high-resolution gas chromatography mass spectrometry, but only around 20% of OH-PCBs could be identified by comparison to authentic standards. Results from this study show that OH-PCB are important environmental contaminants in dolphins and suggest that PCBs, decades after their ban, may still constitute a threat to wildlife.