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.

Comparative Effects of Embryonic Metformin Exposure on Wild and Laboratory-Spawned Fathead Minnow (Pimephales promelas) Populations.

Metformin is routinely detected in aquatic ecosystems because of its widespread use as a treatment for Type 2 diabetes. Laboratory studies have shown that exposure to environmentally relevant concentrations of metformin can alter metabolic pathways and impact the growth of early life stage (ELS) fish; however, it is unknown whether these effects occur in wild populations. Herein, we evaluate whether findings from laboratory studies are representative and describe the relative sensitivities of both populations. Duplicate exposures (0, 5, or 50 µg/L metformin) were conducted using wild- and lab-spawned fathead minnow (Pimephales promelas) embryos. Apart from the water source, exposure conditions remained constant. Wild embryos were exposed to previously dosed lake water to account for changes in bioavailability, while reconstituted freshwater was used for the laboratory study. Developmental metformin exposure differentially impacted the growth and morphology of both cohorts, with energy dyshomeostasis and visual effects indicated. The fitness of wild-spawned larvae was impacted to a greater extent relative to lab-spawned fish. Moreover, baseline data reveal important morphological differences between wild- and lab-spawned ELS fatheads that may diminish representativeness of lab studies. Findings also confirm the bioavailability of metformin in naturally occurring systems and suggest current exposure scenarios may be sufficient to negatively impact developing fish.

Spatiotemporal patterns and relationships among the diet, biochemistry, and exposure to flame retardants in an apex avian predator, the peregrine falcon.

Flame retardants (FR) are industrial chemicals and some are proven environmental contaminants that accumulate in predatory birds. Few studies have examined the influence of diet on FR profiles in nestling raptors and the possible physiological implications of such FR exposure. The objectives of this research were (1) to determine spatial patterns of ≤ 48 polybrominated diphenyl ether (PBDE) congeners and ≤ 26 non-PBDE FRs, including organophosphate esters (OPEs), in nestling peregrine falcons (Falco peregrinus) across the Canadian Great Lakes-St. Lawrence River Basin (GL-SLR; 2010) and in the eastern Canadian Arctic (2007); (2) to identify temporal changes in FR concentrations from the mid-2000s to 2010 in GL-SLR peregrine nestlings; (3) to investigate the role of diet using stable isotopes on exposure patterns of quantifiable FRs; and (4) to assess possible associations between circulating FRs and total (T) thyroxine (TT4) and triiodothyronine (TT3), tocopherol, retinol and oxidative status (isoprostanes). The summed concentrations of the top 5 PBDEs (Σ5) (BDE-47, -99, -100, -154, -153) were significantly higher in rural nestlings than urban nestlings in the GL-SLR, followed by the eastern Arctic nestlings. The PBDE congener profile of rural nestlings was dominated by BDE-99 (34‰), whereas BDE-209 (31‰) became dominant in the 2010 urban PBDE profile marking a shift since the mid-2000s. Low (ppb) concentrations of 25 novel non-PBDE FRs (e.g., 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE)) were measured in the nestlings in at least one region, with the first report in peregrines of 15 novel non-PBDE FRs (e.g., 2-ethyl-1-hyxyl 2,3,4,5-tetrabromobenzoate (EHTBB), pentabromo allyl ether (PBPAE), tetrabromoethylcyclohexane (α-, ß-DBE-DBCH)) as well as of tris (2-butoxyethyl) phosphate (TBOEP) (0-7.5ng/g ww) > tris(2-chloroisopropyl) phosphate (TCIPP) (0.1-5.5ng/g ww) > tris(2-chloroethyl) phosphate (TCEP) (0.02-2.0ng/g ww) > tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (0-1.0ng/g ww). Within the GL-SLR, the urban nestlings' diet had significantly more terrestrial sources (greater δ13C values) than the broader, more aquatic-based diet of rural peregrines. Dietary source (δ13C) was significantly associated with concentrations of Σ5PBDE, BDE-209, EHTBB, and 2,2-4,4',5,5'-hexabromobiphenyl (BB-153), with trophic level (δ15N) also positively associated with BDE-209 levels. Compared to urban nestlings, the rural nestlings had significantly lower circulating concentrations of thyroxine (TT4), triiodothyronine (TT3), a greater proportion of TT3 relative to TT4 (TT3:TT4), tocopherol and oxidative status (isoprostanes), but higher retinol levels; the most recalcitrant PBDE congener, BDE-153, in combination with low concentrations of some novel FRs, particularly octabromotrimethylphenyllindane (OBIND), may influence circulating thyroid hormones, especially TT4, and retinol levels of peregrine falcon nestlings. These associations of FR-endocrine-biochemical measures suggest possible exposure-related changes in these birds and further study is warranted.

Effects of metformin on wild fathead minnows (Pimephales promelas) using in-lake mesocosms in a boreal lake ecosystem.

Due to its widespread use for the treatment of Type-2 diabetes, metformin is routinely detected in surface waters globally. Laboratory studies have shown that environmentally relevant concentrations of metformin can adversely affect the health of adult fish, with effects observed more frequently in males. However, the potential risk to wild fish populations has yet to be fully elucidated and remains a topic of debate. To explore whether environmentally relevant metformin exposure poses a risk to wild fish populations, the present study exposed wild fathead minnows (Pimephales promelas) to 5 or 50 µg/L metformin via 2 m diameter in-lake mesocosms deployed in a natural boreal lake in Northern Ontario at the International Institute for Sustainable Development - Experimental Lakes Area (IISD-ELA). Environmental monitoring was performed at regular intervals for 8-weeks, with fish length, weight (body, liver and gonad), condition factor, gonadosomatic index, liver-somatic index, body composition (water and biomolecules) and hematocrit levels evaluated at test termination. Metabolic endpoints were also evaluated using liver, brain and muscle tissue, and gonads were evaluated histologically. Results indicate that current environmental exposure scenarios may be sufficient to adversely impact the health of wild fish populations. Adult male fish exposed to metformin had significantly reduced whole body weight and condition factor and several male fish from the high-dose metformin had oocytes in their testes. Metformin-exposed fish had altered moisture and lipid (decrease) content in their tissues. Further, brain (increase) and liver (decrease) glycogen were altered in fish exposed to high-dose metformin. To our knowledge, this study constitutes the first effort to understand metformin's effects on a wild small-bodied fish population under environmentally relevant field exposure conditions.

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.

In-situ molecular-level elucidation of organofluorine binding sites in a whole peat soil.

The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)F→(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)F→(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.

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.

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.

Analysis and occurrence of emerging chlorinated and brominated flame retardants in surficial sediment of the Dalian coastal area in China.

The concentrations and distributions of some typical chlorinated flame retardants (Dechlorane or Mirex, Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane Plus (DP)) and brominated FRs (polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)) were analyzed in surficial sediment collected from the Dalian coastal area in northeast China. Dec 603, Dec 604, and BTBPE were below their respective limits of detection (LOD) in all sediment samples, while Dechlorane, Dec 602, DP, Σ13BDE (tri- to hepta-BDEs), BDE 209, and PBEB were identified in the ranges <0.015-39.9 ng g(-1) dry weight (dw), <0.011-0.156 ng g(-1) dw, 0.69-7.00 ng g(-1) dw, 0.017-1.33 ng g(-1) dw, 3.94-103 ng g(-1) dw, and <0.073-1.9 ng g(-1) dw, respectively. Relationships between these chlorinated and brominated FRs were analyzed using Pearson's correlation and principal component analysis (PCA). DP, Dechlorane, Σ13BDE, and BDE 209 showed significantly positive correlation (p<0.05), and these relationships showed excellent agreement with PCA results. The spatial trends for Dechlorane, DP, BDE 209, and Σ13BDE showed that high concentrations were found in the industrial zone and lower concentrations in residential and garden zones. The results imply that these FRs are originating from a common source, and support the view that direct input from the effluent of sewage outlets is a major source of these compounds in Dalian sediment.

Fugacity approach to evaluate the sediment-water diffusion of polycyclic aromatic hydrocarbons.

Diffusion is an important process for sediment-water exchange and plays a vital role in controlling water quality. Fugacity fraction (ff) was used to estimate the sediment-water diffusion of polycyclic aromatic hydrocarbons (PAHs) between seawater and surficial sediment. A total of 33 surface sediment and sea water samples were collected concurrently from the northeast coastal area in China and 25 PAHs were analyzed including the alkylated and chlorated PAHs. Fugacity fraction was calculated based on the PAH concentrations in water and sediment, octanol-water partition coefficient of PAHs, organic matter content in sediment, and density of sediment. The calculated results showed that ff increased with decreasing molecular weight of PAHs. The low molecular weight PAHs (2-3 rings) transferred from sediment to water and the sediment acted as a secondary source to the water. The medium molecular weight PAHs (4-5 rings) were close to the sediment-water equilibrium and the transfer tendency shifted between sediment and water. The high molecular weight PAHs (5-6 rings) transferred from water into sediment and the sediment acted as a sink. Soot carbon and the difference of PAH concentrations between sediment and water were found to be important factors affecting the sediment-water diffusion. This study provided new insight into the process of sediment-water diffusion, which has a great influence on the quality of water, especially in severely-polluted sediment areas.

An Asia-specific source of dechlorane plus: concentration, isomer profiles, and other related compounds.

The distribution of dechloranes, a group of chlorinated flame retardants, were investigated in air, soil, and sediment around a newly discovered Dechlorane Plus (DP) production facility in China (Anpon). To date, the only known DP manufacturing plant is located in Niagara Falls, NY (OxyChem). Dechloranes including DP, Dechlorane (Mirex), and the recently discovered Dechlorane 602 (Dec 602) were detected in air, soil, and sediment, while Dechlorane 603 and Dechlorane 604 were below detection limit in all matrices. DP air concentrations near the facility ranged from 7737 to 26 734 pg m(-3), the greatest reported thus far. Soil concentrations in the same area for DP, Dechlorane, and Dec 602 were 1490+/-3580 ng g(-1), 81.6+/-96.5 ng g(-1), and 7.24+/-13.2 ng g(-1) dry weight, respectively. Interestingly, lower concentrations of DP (4.93+/-4.34 ng g(-1)), Dechlorane (30.2+/-19.9 ng g(-1)), and Dec 602 (2.14+/-2.23 ng g(-1)) were found in sediment from a nearby canal. Spatial trends of Dechlorane and Dec 602 in soil were similar to DP, implying that the DP manufacturing plant may also be a source of these other flame retardants. DP soil concentrations surrounding the facility decreased by an order of magnitude within 7.5 km. The syn-DP fractional abundance (fsyn) value (0.40) for the commercial DP product manufactured at Anpon was slightly higher than that (0.20-0.36) produced by OxyChem. The fsyn value in most air samples was largely similar to the Chinese commercial DP mixture, while most soil and sediment abundances were lower, suggesting a stereoselective depletion of syn-DP.

Direct analysis of volatile methylsiloxanes in gaseous matrixes using atmospheric pressure chemical ionization-tandem mass spectrometry.

Atmospheric pressure chemical ionization-tandem mass spectrometry (APCI-MS/MS) was applied for the first time to the direct analysis of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in gaseous matrixes without extraction or prior chromatographic separation. Mass spectrometric characteristics of both compounds under APCI conditions and their fragmentation behavior in MS/MS were investigated. Unlike the classical gas chromatography/mass spectrometry (GC/MS), which involves solvent extraction before gas chromatography, the proposed approach prevents contamination from GC system components and provides unambiguous structural assignments. The method performs well achieving good linearity (R(2) > 0.997), low limits of detection (4-6 microg/m(3)), good precision (RSD < 10%) and accuracy (>93%), and a wide dynamic range. Its applicability to real-world samples was evaluated through measurements of D4 and D5 concentrations in air and biogas samples. The high sensitivity, selectivity, and reliability of this method render our approach a good alternative to the commonly used GC/MS method.

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.

Global contamination of coplanar polybrominated/chlorinated biphenyls (Co-PXBs) in the market fishes from Japan.

Polybrominated chlorinated biphenyls (PXBs, X=Br, Cl) are a group of environmental contaminants that have not been studied previously. The introduction of the second halogen to the biphenyl backbone increases the number of possible congeners to more than 9000. Only a limited number of PXBs are commercially available. In order to determine the occurrence of these compounds in environmental matrices, an isotope dilution HRGC/HRMS method for determination of five co-planar polybrominated/chlorinated biphenyls (Co-PXBs) in biota was developed. The method detection limit for these compounds ranged between 0.05 and 0.5 pg/g for 4'-monobromo-3,3',4,5-tetrachlorobiphenyl and 3',4',5'-tribromo-3,4-dichlorobiphenyl, respectively. Concentrations of five co-planar polybrominated and chlorinated biphenyls in eighteen different fish fillets from Japanese markets ranged between 4 and 46 pg/g wet weight for mink whale and young yellow-tail fish. These values are substantially lower than those reported for Co-PCBs; however, it should be noted that due to the unavailability of standards, identification and quantification of all the isomers was not possible.

Dioxin-like contaminants are no longer a risk to the American eel (Anguilla rostrata) in Lake Ontario.

The embryotoxicity of extracts of American eels (Anguilla rostrata) was measured to determine whether maternally derived contaminants contribute to the declining recruitment of eels to Lake Ontario. Sexually maturing, large yellow and silver eels were sampled in 2007 and 2008 from 5 locations in eastern Canada, including Lake Ontario; positive controls included eels from the Hudson River, United States, and Canal Dessel-Schoten, Belgium (European eel, Anguilla anguilla). Japanese medaka eggs were injected immediately after fertilization with 1 or 10 nL of eel extract and, after 12 d, scored for signs of toxicity. Eel extracts did not cause dioxin-like embryotoxicity, reflecting the low concentrations of total dioxin equivalents measured chemically in these same extracts. Embryo mortality and reduced hatching success at high doses of eel extracts may reflect the bioaccumulation of legacy or emerging chemicals of concern. The results were consistent with long-term trends of declining concentrations of persistent organic pollutants (POPs) in tissues of eels and other fish species from Lake Ontario, trends of declining embryotoxicity of eel tissue extracts, and recent increases of recruitment of juvenile eels to Lake Ontario. If dioxin-like compounds contributed in the past to the decline of recruitment and abundance of American eels in Lake Ontario, these data suggest that recruitment should recover, following the same trends as the recovery of lake trout reproduction in Lake Ontario. Environ Toxicol Chem 2018;37:1061-1070. © 2017 SETAC.

Time-weighted average water sampling with a diffusion-based solid-phase microextraction device.

A new diffusion-based solid-phase microextraction (SPME) time-weighted average (TWA) field water sampling device was developed and investigated by field trial. The sampler is constructed with copper tube and caps and a commercial SPME fiber assembly. The device possesses all advantages of SPME; it is solvent-free, reusable, combines sampling, isolation and enrichment into one step, and the fiber can be directly injected into a gas chromatograph for analysis with a commercial SPME fiber holder, without further treatment. Field trials in Laurel Creek (Waterloo, Ont., Canada) and Hamilton Harbour (Hamilton, Ont., Canada) illustrated that the device is durable, easy to deploy, and the mass uptake of the device is independent of the face velocity. The device provides good precision [relative standard deviations (RSDs) are less than 20%] and the data obtained with this device are quite comparable to those obtained with the spot sampling method, which demonstrates that the newly developed SPME water sampling device is suitable for long-term monitoring of organic pollutants in water.

Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge.

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.

Determination of linear and cyclic volatile methylsiloxanes in blood of turtles, cormorants, and seals from Canada.

We measured the concentrations of linear and cyclic volatile methylsiloxanes (VMS) concentrations in the blood plasma of turtles, cormorants, and seals collected from Canadian freshwater and marine ecosystems. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed to quantify the levels of linear and cyclic VMS in the plasma samples. The cyclic VMS of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were present in the plasma of all three species. Linear VMS compounds were observed only in seal plasma from one contaminated site. There was no statistically significant difference among species and locations for D3, D4, and D6 concentrations. Average D5 concentrations ranged from 0.143 to 7.39ngg-1; these concentrations appeared to be associated with diffuse/urban sources. Snapping turtles, cormorants, and seals all exhibited elevated D5 concentrations in contaminated sites relative to the reference sites. Our data indicate that local urban sources of VMS contributed significantly to the observed D5 concentrations in free-ranging wildlife. The presence of cyclic VMS in the plasma of the three species from Canada demonstrates that these chemicals are ubiquitous in aquatic biological systems. This finding raises concerns regarding their persistence in freshwater and marine environments. To the best of our knowledge, this study reports the first measurements of VMS compounds in the plasma of reptiles, birds, and mammals.

Halogenated phenolic compounds in wild fish from Canadian Areas of Concern.

Concentrations of halogenated phenolic compounds were measured in the plasma of brown bullhead (Ameiurus nebulosus) from 4 Canadian Areas of Concern (AOCs), to assess exposure to suspected thyroid-disrupting chemicals. Hydroxylated polychlorinated biphenyls (OH-PCBs) were detected in every sample collected in 3 of the AOCs; the detection frequency was lower in samples from the Detroit River AOC. The OH-PCBs most frequently detected were pentachloro, hexachloro, and heptachloro congeners, which are structurally similar to thyroid hormones. Pentachlorophenol (PCP) was detected at highest concentrations (1.8 ng/g) in fish from Prince Edward Bay, the Bay of Quinte Lake reference site, and Hillman Marsh (the Wheatley Harbour reference site), suggesting local sources of contamination. Elevated PCP concentrations were also detected in the plasma of brown bullhead from exposed sites in the Toronto and Region AOC (0.4-0.6 ng/g). Triclosan was consistently detected in the Toronto and Region AOC (0.05-0.9 ng/g), consistent with wastewater emission. Greater concentrations were occasionally detected in the plasma of brown bullhead from the Bay of Quinte AOC. Concentrations of polybrominated diphenyl ethers were highest in the Toronto and Region AOC, and at 2 of the Bay of Quinte AOC exposed sites near Trenton and Belleville. Distribution patterns reflected the properties and usage of the compounds under investigation and the characteristics of each AOC. Environ Toxicol Chem 2017;36:2266-2273. © 2017 SETAC.

Maternal transfer of dioxin-like compounds in artificially matured European eels.

Several eel species of the genus Anguilla are considered endangered due to a severe decline in recruitment. Up to now, the reasons for this threatening development are not fully understood. The eel's highly specialized biology can lead to explicitly high accumulation of globally distributed organic lipophilic contaminants during its continental life. Because of this and due the particular toxicological sensitivity of early life stages of oviparous organisms towards dioxin-like compounds, it is crucial to improve our understanding concerning toxicokinetics and maternal transfer of organic contaminants in eels. This study presents analytical data on maternal transfer of dioxin-like (dl) compounds in relevant tissue samples taken from artificially matured and non-matured European silver eels (Anguilla anguilla) from German inland waters using gas chromatography coupled with mass spectrometry (GC/MS) and high-resolution mass spectrometry (GC/HRMS). Detected concentrations revealed a lipid-driven transfer of targeted compounds from muscle-fat-reserves to gonads and eggs respectively, with no distinct preferences concerning the chlorination degree of targeted compounds. Dl-PCBs were shown to contribute the major share of toxicity equivalents found in analysed eel tissues. Maternal muscle tissue to egg concentration ratios in wet weight-based samples had a mean of 6.95 ± 1.49 in accordance with the differences in total lipid content in the respective body matrices. Dioxins and furans in analysed samples were (from a toxicological point of view) of less relevance. Furthermore it was shown that muscle concentrations in silver eels could be used in future assessments to make conservative predictions for expected egg concentrations in female eels.