Hundreds of Unrecognized Halogenated Contaminants Discovered in Polar Bear Serum

Liu Y; Richardson ES; Derocher AE; Lunn NJ; Lehmler H-J; Li X; Zhang Y; Yue Cui J; Cheng L; Martin JW
2018 | Angew. Chem. Int. Ed. Engl. | 57 (50) (16401-16406)

Prolonged Exposure to Bisphenol A from Single Dermal Contact Events

Liu, JY; Martin, JW
2017 | Environ. Sci. Technol. | 51 (17) (9940-9949)
behavior , bpa concentrations , cashiers , cord serum , occupational exposure , penetration , pregnant-women , thermal paper receipts , urinary , widespread exposure

Bisphenol A (BPA) is an endocrine disruptor frequently detected in human biofluids. Dermal absorption of BPA from thermal paper receipts occurs but BPA pharmacokinetics following dermal exposure is not understood. To compare the pharmacokinetics of dermal and dietary BPA exposure, six male participants handled simulated receipts containing relevant levels of BPA (isotope-labeled BPA-d(16)) for 5 min, followed by hand-washing 2 h later. Urine (0-48 h) and serum (0-7.5 h) were monitored for free and total BPA-d16. One week later, participants returned for a dietary administration with monitoring as above. One participant repeated the dermal administration with extended monitoring of urine (9 days) and serum (2 days). After dietary exposure, urine total BPA-d16 peaked within 5 h and quickly cleared within 24 h. After dermal exposure, cumulative excretion increased linearly for 2 days, and half the participants still had detectable urinary total BPA-d(16) after 1 week. The participant repeating the dermal exposure had detectable BPA-d(16) in urine for 9 days, showed linear cumulative excretion over 5 days, and had detectable free BPA-d(16) in serum. Proportions of free BPA-d(16) in urine following dermal exposure (0.71%-8.3% of total BPA-d(16)) were generally higher than following the dietary exposure (0.29%-1.4%). Compared to dietary BPA exposure, dermal absorption of BPA leads to prolonged exposure and may lead to higher proportions of unconjugated BPA in systemic circulation.

Effects on Biotransformation, Oxidative Stress, and Endocrine Disruption in Rainbow Trout (Oncorhynchus mykiss) Exposed to Hydraulic Fracturing Flowback and Produced Water

He, YH; Folkerts, EJ; Zhang, YF; Martin, JW; Alessi, DS; Goss, GG
2017 | Environ. Sci. Technol. | 51 (2) (940-947)
contamination , drinking water , gas development , groundwater , marcellus , minnow pimephales-promelas , molecular biomarkers , oil , pollutants , surface waters

The effects of hydraulic fracturing (HF) flowback and produced water (HF-FPW), a complex saline mixture of injected HF fluids and deep formation water that return to the surface, was examined in rainbow trout (Oncorhynchus mykiss). Exposure to HF-FPWs resulted in significant induction of ethoxyresorufin-O-deethylase (EROD) activity in both liver and gill tissues. Increased lipid peroxidation via oxidative stress was also detected by thiobarbituric acid reactive substances (TBARS) assay. The mRNA expressions of a battery of genes related to biotransformation, oxidative stress, and endocrine disruption were also measured using quantitative real-time polymerase chain reaction (Q-RT-PCR). The increased expression of cyp1a (2.49 +/- 0.28-fold), udpgt (2.01 +/- 0.31-fold), sod (1.67 +/- 0.09-fold), and gpx (1.58 +/- 0.10-fold) in raw sample exposure group (7.5%) indicated elevated metabolic enzyme activity, likely through the aryl hydrocarbon receptor pathway, and generation of reactive oxygen species. In addition, the elevated vtg and era2 expression demonstrated endocrine disrupting potential exerted by HF-FPW in rainbow trout. The overall results suggested HF-FPW could cause significant adverse effects on fish, and the organic contents might play the major role in its toxicity. Future studies are needed to help fully determine the toxic mechanism(s) of HF-FPW on freshwater fish, and aid in establishing monitoring, treatment, and remediation protocols for HF-FPW.

Pesticide exposures and respiratory health in general populations

Ye, M; Beach, J; Martin, JW; Senthilselvan, A
2017 | J. Environ. Sci. | 51 (361-370)
agricultural health , airway smooth-muscle , canadian health measures survey , cancer incidence , chronic-bronchitis , environmental , general population , lung-function , occupational exposure , organophosphate pesticides , pesticides , pyrethroid insecticides , respiratory health , syncytial-virus bronchiolitis , urinary concentrations

Human exposures to pesticides can occur in the workplace, in the household and through the ambient environment. While several articles have reviewed the impact of pesticide exposures on human respiratory health in occupational settings, to the best of our knowledge, this article is the first one to review published studies on the association between pesticide exposures and human respiratory health in the general populations. In this article, we critically reviewed evidences up to date studying the associations between non-occupational pesticide exposures and respiratory health in general populations. This article also highlighted questions arising from these studies, including our recent analyses using the data from the Canadian Health Measures Survey (CHMS), for future research. We found few studies have addressed the impact of environmental pesticide exposures on respiratory health, especially on lung function, in general populations. In the studies using the data from CHMS Cycle 1, exposures to OP insecticides, pyrethroid insecticides, and the organochlorine pesticide DDT were associated with impaired lung function in the Canadian general population, but no significant associations were observed for the herbicide 2,4-D. Future research should focus on the potential age-specific and pesticide-specific effect on respiratory health in the general population, and repeated longitudinal study design is critical for assessing the temporal variations in pesticide exposures. Research findings from current studies of non-occupational pesticide exposures and their health impact in general populationwill help to improve the role of regulatory policies in mitigating pesticide-related public health problems, and thereafter providing greater benefit to the general population. (C) 2016 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

Elucidating mechanisms of toxic action of dissolved organic chemicals in oil sands process-affected water (OSPW)

Morandi, GD; Wiseman, SB; Guan, M; Zhang, XWW; Martin, JW; Giesy, JP
2017 | Chemosphere | 186 (893-900)
chironomus-dilutus , dna , escherichia-coli , genomics , live cell array , liver , mechanism of toxicity , minnow pimephales-promelas , naphthenic acids , ospw , oxidative stress , pentose-phosphate pathway , phospholipids , transcriptional responses
Oil sands process-affected water (OSPW) is generated during extraction of bitumen in the surface-mining oil sands industry in Alberta, Canada, and is acutely and chronically toxic to aquatic organisms. It is known that dissolved organic compounds in OSPW are responsible for most toxic effects, but knowledge of the specific mechanism(s) of toxicity, is limited. Using bioassay-based effects-directed analysis, the dissolved organic fraction of OSPW has previously been fractionated, ultimately producing refined samples of dissolved organic chemicals in OSPW, each with distinct chemical profiles. Using the Escherichia coli K-12 strain MG1655 gene reporter live cell array, the present study investigated relationships between toxic potencies of each fraction, expression of genes and characterization of chemicals in each of five acutely toxic and one non-toxic extract of OSPW derived by use of effects-directed analysis. Effects on expressions of genes related to response to oxidative stress, protein stress and DNA damage were indicative of exposure to acutely toxic extracts of OSPW. Additionally, six genes were uniquely responsive to acutely toxic extracts of OSPW. Evidence presented supports a role for sulphur- and nitrogen-containing chemical classes in the toxicity of extracts of OSPW. (C) 2017 Elsevier Ltd. All rights reserved.

Stream invertebrate community structure at Canadian oil sands development is linked to concentration of bitumen-derived contaminants

Gerner, NV; Kone, M; Ross, MS; Pereira, A; Ulrich, AC; Martin, JW; Liess, M
2017 | Sci. Total Environ. | 575 (1005-1013)
athabasca oil sands , athabasca river , invertebrate monitoring , naphthenic acids , pahs , polycyclic aromatic hydrocarbons , process-affected water , sediment , sensitivity , spear bioindicator , species traits , technical basis , toxicity , tributaries

In Canada, the Athabasca oil sands deposits are a source of bitumen-derived contaminants, reaching the aquatic environment via various natural and anthropogenic pathways. The ecological effects of these contaminants are under debate. To quantify the effects of bitumen-derived contaminants we monitored the aquatic exposure of polycyclic aromatic hydrocarbons (PAHs), metals, and naphthenic acids as well as the invertebrate community in the Athabasca River and its tributaries. PAH concentrations over 3 consecutive years were related to discharge and were highest in the year with high autumn rainfall. In the year with the highest PAH concentrations, these were linked with adverse effects on the aquatic invertebrate communities. We observed relative effects of the composition and concentration of contaminants on the invertebrate fauna. This is reflected by the composition and abundance of invertebrate species via the use of the species' traits "physiological sensitivity" and "generation time". Applying the SPEAR approach we observed alterations of community structure in terms of an increased physiological sensitivity and a decrease of generation time for the average species. These effects were apparent at concentrations 100 times below the acute sensitivity of the standard test organism Daphnia magna. To rapidly identify oil sands related effects in the field we designed a biological indicator system, SPEAR(oil), applicable for future routine monitoring. (C) 2016 Elsevier B.V. All rights reserved.

Characterization of Naphthenic Acids and Other Dissolved Organics in Natural Water from the Athabasca Oil Sands Region, Canada. (COVER ARTICLE)

Sun, CX; Shotyk, W; Cuss, CW; Donner, MW; Fennell, J; Javed, M; Noernberg, T; Poesch, M; Pelletier, R; Sinnatamby, N; Siddique, T; Martin, JW
2017 | Environ. Sci. Technol. | 51 (17) (9524-9532)
atmospheric-pressure photoionization , electrospray-ionization , groundwaters , industrial developments , mixtures , northern alberta , resonance mass-spectrometry , river , source identification

With growth of the Canadian oil sands industry, concerns have been raised about possible seepage of toxic oil sands process-affected water (OSPW) into the Athabasca River (AR). A sampling campaign in fall 2015 was undertaken to monitor for anthropogenic seepage while also considering natural sources. Naphthenic acids (NAs) and thousands of bitumen-derived organics were characterized in surface water, groundwater, and OSPW using a highly sensitive online solid phase extraction-HPLC-Orbitrap method. Elevated NA concentrations and bitumen-derived organics were detected in McLean Creek (30.1 mu g/L) and Beaver Creek (190 mu g/L), two tributaries that are physically impacted by tailings structures. This was suggestive of OSPW seepage, but conclusive differentiation of anthropogenic and natural sources remained difficult. High NA concentrations and bitumen-derived organics were also observed in natural water located far north of the industry, including exceedingly high concentrations in AR groundwater (A5w-GW, 2000 mu g/L) and elevated concentration in a tributary river (Pierre River, 34.7 mu g/L). Despite these evidence for both natural and anthropogenic seepage, no evidence of any bitumen-derived organics was detected at any location in AR mainstem surface water. The chemical significance of any bitumen-derived seepage to the AR was therefore minimal, and focused monitoring in tributaries will be valuable in the future.

Role of Snow Deposition of Perfluoroalkylated Substances at Coastal Livingston Island (Maritime Antarctica)

Casal, P; Zhang, YF; Martin, JW; Pizarro, M; Jimenez, B; Dachs, J
2017 | Environ. Sci. Technol. | 51 (15) (8460-8470)
acids , atmospheric transport , food-web , global survey , king george island , ocean , perfluorinated alkyl substances , perfluorooctane sulfonate (pfos) , polyfluoroalkyl substances , water
Perfluoroalkyl substances (PFAS) are ubiquitous in the environment, including remote polar regions. To evaluate the role of snow deposition as an input of PFAS to Maritime Antarctica, fresh snow deposition, surface snow, streams from melted snow, coastal seawater, and plankton samples were collected over a three-month period (December 2014 February 2015) at Livingston Island. Local sources of PFASs were significant for perfluoroalkyl sulfonates (PFSAs) and C7-14 perfluoroalkyl carboxylates (PFCAs) in snow but limited to the transited areas of the research station. The concentrations of 14 ionizable PFAS (Sigma PFAS) in freshly deposited snow (760-3600 pg L-1) were 1 order of magnitude higher than those in background surface snow (82-430 pg L-1). Sigma PFAS ranged from 94 to 420 pg L-1 in seawater and from 3.1 to 16 ng g(d)(-1) in plankton. Ratios of individual PFAS concentrations in freshly deposited snow relative to surface snow (C-SD/C-Snow), snowmelt (C-SD/C-SM), and seawater (C-SD/C-SW) were close to 1 (from 0.44 to 1.4) for all perfluorooctanesulfonate (PFOS) isomers, suggesting that snowfall does not contribute significantly to PFOS in seawater. Conversely, these ratios for PFCAs ranged from 1 to 33 and were positively correlated with the number of carbons in the PFCA alkylated chain. These trends suggest that snow deposition, scavenging sea-salt aerosol bound PFAS, plays a role as a significant input of PFCAs to the Maritime Antarctica.

Prenatal bisphenol a exposure and dysregulation of infant hypothalamic-pituitary-adrenal axis function: findings from the APrON cohort study

Giesbrecht, GF; Ejaredar, M; Liu, JY; Thomas, J; Letourneau, N; Campbell, T; Martin, JW; Dewey, D
2017 | Environ Health | 16
behavior , bisphenol a , children , cortisol , cortisol response , developmental exposure , estrogen-receptor-alpha , fetal exposure , glucocorticoid exposure , hypothalamic-pituitary-adrenal axis , infant stress reactivity , phthalate metabolite , pregnant-women , sexual-differentiation , stress-response

Background: Animal models show that prenatal bisphenol A (BPA) exposure leads to sexually dimorphic disruption of the neuroendocrine system in offspring, including the hypothalamic-pituitary-adrenal (HPA) neuroendocrine system, but human data are lacking. In humans, prenatal BPA exposure is associated with sex-specific behavioural problems in children, and HPA axis dysregulation may be a biological mechanism. The objective of the current study was to examine sex differences in associations between prenatal maternal urinary BPA concentration and HPA axis function in 3 month old infants. Methods: Mother-infant pairs (n = 132) were part of the Alberta Pregnancy Outcomes and Nutrition study, a longitudinal birth cohort recruited (2010-2012) during pregnancy. Maternal spot urine samples collected during the 2nd trimester were analyzed for total BPA and creatinine. Infant saliva samples collected prior to and after a blood draw were analyzed for cortisol. Linear growth curve models were used to characterize changes in infant cortisol as a function of prenatal BPA exposure. Results: Higher maternal BPA was associated with increases in baseline cortisol among females (beta = 0.13 log mu g/dL; 95% CI: 0.01, 0.26), but decreases among males (beta= -0.22 log mu g/dL; 95% CI: -0.39, -0.05). In contrast, higher BPA was associated with increased reactivity in males (beta =.30 log mu g/dL; 95% CI: 0.04, 0.56) but decreased reactivity in females (beta = -0.15 log mu g/dL; 95% CI: -0.35, 0.05). Models adjusting for creatinine yielded similar results. Conclusions: Prenatal BPA exposure is associated with sex-specific changes in infant HPA axis function. The biological plausibility of these findings is supported by their consistency with evidence in rodent models. Furthermore, these data support the hypotheses that sexually dimorphic changes in children's behaviour following prenatal BPA exposure are mediated by sexually dimorphic changes in HPA axis function.

Athabasca Oil Sands Petcoke Extract Elicits Biochemical and Transcriptomic Effects in Avian Hepatocytes

Crump, D; Williams, KL; Chiu, S; Zhang, YF; Martin, JW
2017 | Environ. Sci. Technol. | 51 (10) (5783-5792)
2 , 3 , 7 , 8-tetrachlorodibenzo-p-dioxin , chicken embryonic hepatocytes , cultures , cytochrome-p4501a induction , egg extracts , flame retardants , in-vitro , messenger-rna expression , polycyclic aromatic hydrocarbons , sensitivity

Petroleum coke or "petcoke" is a granular carbonaceous material produced during the upgrading of heavy crude oils, including bitumen. Petcoke dust was recently reported as an environmental contaminant in the Athabasca oil sands region, but the ecotoxicological hazards posed by this complex bitumen-derived material-including those to avian species-have not been characterized. In this study, solvent extracts (x) of delayed and fluid petcoke (xDP and xFP) were prepared and dissolved in dimethyl sulfoxide. A water accommodated fraction of delayed petcoke (waDP) was also prepared. Graded concentrations of xDP, xFP, and waDP were administered to chicken and double-crested cormorant hepatOcytes to determine effects on 7-ethoxyresorufin-O-deethylase (EROD) activity, porphyrin accumulation, and mRNA expression. Polycyclic aromatic compounds (PACs) were characterized, and xDP, xFP, and waDP had total PAC concentrations of 93 000, 270, and 5.3 ng/mL. The rank order of biochemical and transcriptomic responses was xDP > xFP > waDP (e.g., EROD EC50s, were lower for xDP compared to xFP and waDP). A total of 22, 18, and 4 genes were altered following exposure to the highest concentrations of xDP, xFP, and waDP, respectively, using a chicken PCR array comprising 27 AhR-related genes. To provide more exhaustive coverage of potential toxicity pathways being impacted, two avian ToxChip PCR-arrays chicken and double-crested cormorant-were utilized, and xDP altered the expression of more genes than xFP. Traditional PAC-related toxicity pathways and novel mechanisms of action were identified in two avian species following petcoke extract exposure. Extrapolation to real-world exposure scenarios must consider the bioavailability of the extracted PACs compared to those in exposed organisms.

SCREENING OF GENOTOXICITY AND MUTAGENICITY IN EXTRACTABLE ORGANICS FROM OIL SANDS PROCESS-AFFECTED WATER

Zetouni, NC; Siraki, AG; Weinfeld, M; Pereira, AD; Martin, JW
2017 | Environ. Toxicol. Chem. | 36 (5) (1397-1404)
assay , contaminants of emerging concern , genetic toxicology , genotoxicity , goldfish , mixture toxicology , naphthenic acids , oil sands , region , responses , sos chromotest , subchronic exposures , tailings , toxicity , yellow perch

Large volumes of oil sands process-affected water (OSPW) are produced by the oil sands surface mining industry during alkaline hot-water extraction of bitumen. It is well documented that the acid extractable organics (AEOs) in OSPW, a highly complex mixture of acidic and polar neutral substances, are acutely toxic; but few studies have examined the genotoxicity or mutagenicity of this mixture. In the present study, the in vitro SOS Chromotest and the Ames test (TA98 and TA100 strains) were used to evaluate genotoxicity and mutagenicity for whole OSPW AEOs in the presence and absence of biotransformation by rat S9 liver enzymes. Two subfractions were also examined in the same assays: neutral extractable fraction (F1-NE), and the subsequent acid extractable fraction (F2-AE). In the SOS assay, whole AEO was cytotoxic when concentrated 2 x (i.e., twice as concentrated as the environmental sample) and showed increasing genotoxic response above 6x. Co-exposure with S9 had a protective effect on the cell SOS-inducing factor and survival but did not eliminate genotoxicity above 6 x concentrations. Most of the cytotoxicity was attributable to F2-AE, but both F1-NE and F2-AE had similar genotoxic dose-responses above 6 x. In the Ames test without S9, whole AEO was mutagenic in both strains above 10x concentrations. Co-incubation with S9 had little effect on the TA100 strain but with TA98 resulted in bioactivation at midlevel doses (1.5-6.3x) and protection at higher doses (10-25x). The 2 subfractions were mutagenic in both strains but with different dose-responses. Further research in vivo or in more relevant cells is warranted to investigate the carcinogenic risks of OSPW. (C) 2016 SETAC

Chemical and toxicological characterizations of hydraulic fracturing flowback and produced water

He, YH; Flynn, SL; Folkerts, EJ; Zhang, YF; Ruan, DL; Alessi, DS; Martin, JW; Goss, GG
2017 | Water Res. | 114 (78-87)
acid , aquatic toxicity , aryl phosphate esters , drinking water , gas operations , hydraulic fracturing flowback and produced , marcellus , oil , oxidative stress , pah , polycyclic aromatic hydrocarbons , sands process water , synergistic effect , toxicity , trout oncorhynchus-mykiss , water (hf-fpw)

Hydraulic fracturing (HF) has emerged as a major method of unconventional oil and gas recovery. The toxicity of hydraulic fracturing flowback and produced water (HF-FPW) has not been previously reported and is complicated by the combined complexity of organic and inorganic constituents in HF fluids and deep formation water. In this study, we characterized the solids, salts, and organic signatures in an HF-FPW sample from the Duvernay Formation, Alberta, Canada. Untargeted HPLC-Orbitrap revealed numerous unknown dissolved polar organics. Among the most prominent peaks, a substituted tri-phenyl phosphate was identified which is likely an oxidation product of a common polymer antioxidant. Acute toxicity of zebrafish embryo was attributable to high salinity and organic contaminants in HF-FPW with LC50 values ranging from 0.6% to 3.9%, depending on the HF-FPW fractions and embryo developmental stages. Induction of ethoxyresorufin-O-deethylase (EROD) activity was detected, due in part to polycyclic aromatic hydrocarbons (PAHs), and suspended solids might have a synergistic effect on EROD induction. This study demonstrates that toxicological profiling of real HF-FPW sample presents great challenges for assessing the potential risks and impacts posed by HF-FPW spills. (C) 2017 Elsevier Ltd. All rights reserved.

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