RESUMEN
The St. Lawrence River, at Cornwall Ontario, has accumulated sediment contaminants, mainly mercury (Hg) and polychlorinated biphenyls (PCBs), from industrial point sources over many years. Although those sources are past, the river at Cornwall remains an Area of Concern (AOC). Because of remediation and other changes in the AOC, improved knowledge of contaminants in wild-fish and their putative links to health effects could help decision makers to better assess the AOC's state. Thus, we compared tissue concentrations of Hg, PCBs, morphometric measures of health, and biomarkers of exposure, metabolic-, and reproductive health in native brown bullhead (Ameiurus nebulosus) from the AOC to those of upstream reference fish. Linear discriminant analysis separated the adult fish of both sexes among upstream and downstream sites without misclassification. Burdens of total-Hg (all sites) and PCB toxic equivalents (downstream sites) exceeded the guidance for the protection of wildlife consumers. There were subtle effects of site on physiological variables, particularly in female fish. Total-Hg in tissue correlated negatively to plasma testosterone and 17ß-estradiol in female fish at Cornwall: moreover, concentrations of both hormones were lower within the AOC compared to reference site fish. A similar effect on vitellogenin, which was uncorrelated to E2/T at the downstream sites, indicated the potential for reproductive effects. Downstream fish also had altered thyroidal status (T3, TSH, and ratio of thyroid epithelial cell area to colloid area). Despite spatial and temporal variability of the endocrine-related responses, these subtle effects on fish health within the AOC warrant further study.
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Ictaluridae , Mercurio , Bifenilos Policlorados , Contaminantes Químicos del Agua , Animales , Monitoreo del Ambiente , Femenino , Masculino , OntarioRESUMEN
Oil sand operations in Alberta, Canada will eventually include returning treated process-affected waters to the environment. Organic constituents in oil sand process-affected water (OSPW) represent complex mixtures of nonionic and ionic (e.g., naphthenic acids) compounds, and compositions can vary spatially and temporally, which has impeded development of water quality benchmarks. To address this challenge, it was hypothesized that solid phase microextraction fibers coated with polydimethylsiloxane (PDMS) could be used as a biomimetic extraction (BE) to measure bioavailable organics in OSPW. Organic constituents of OSPW were assumed to contribute additively to toxicity, and partitioning to PDMS was assumed to be predictive of accumulation in target lipids, which were the presumed site of action. This method was tested using toxicity data for individual model compounds, defined mixtures, and organic mixtures extracted from OSPW. Toxicity was correlated with BE data, which supports the use of this method in hazard assessments of acute lethality to aquatic organisms. A species sensitivity distribution (SSD), based on target lipid model and BE values, was similar to SSDs based on residues in tissues for both nonionic and ionic organics. BE was shown to be an analytical tool that accounts for bioaccumulation of organic compound mixtures from which toxicity can be predicted, with the potential to aid in the development of water quality guidelines.
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Yacimiento de Petróleo y Gas , Contaminantes Químicos del Agua , Alberta , Ácidos Carboxílicos , Lípidos , Compuestos OrgánicosRESUMEN
RATIONALE: Characterising complex mixtures of organic compounds in polar fractions of heavy petroleum is challenging, but is important for pollution studies and for exploration and production geochemistry. Oil sands process-affected water (OSPW) stored in large tailings ponds by Canadian oil sands industries contains such mixtures. METHODS: A polar OSPW fraction was obtained by silver ion solid-phase extraction with methanol elution. This was examined by numerous methods, including electrospray ionisation (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) and ultra-high-pressure liquid chromatography (uHPLC)/Orbitrap MS, in multiple ionisation and MS/MS modes. Compounds were also synthesised for comparison. RESULTS: The major ESI ionisable compounds detected (+ion mode) were C15-28 SO3 species with 3-7 double bond equivalents (DBE) and C27-28 SO5 species with 5 DBE. ESI-MS/MS collision-induced losses were due to water, methanol, water plus methanol and water plus methyl formate, typical of methyl esters of hydroxy acids. Once the fraction was re-saponified, species originally detected by positive ion MS, could be detected only by negative ion MS, consistent with their assignment as sulphur-containing hydroxy carboxylic acids. The free acid of a keto dibenzothiophene alkanoic acid was added to an unesterified acid extract of OSPW in known concentrations as a putative internal standard, but attempted quantification in this way proved unreliable. CONCLUSIONS: The results suggest the more polar acidic organic SO3 constituents of OSPW include C15-28 S-containing, alicyclic and aromatic hydroxy carboxylic acids. SO5 species are possibly sulphone analogues of these. The origin of such compounds is probably via further biotransformation (hydroxylation) of the related S-containing carboxylic acids identified previously in a less polar OSPW fraction. The environmental risks, corrosivity and oil flow assurance effects should be easier to assess, given that partial structures are now known, although further identification is still needed.
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Yacimiento de Petróleo y Gas/química , Compuestos Orgánicos/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Compuestos de Azufre/química , Cromatografía Líquida de Alta Presión , Ésteres/química , Extracción en Fase SólidaRESUMEN
This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.
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Ácidos Carboxílicos/análisis , Monitoreo del Ambiente/métodos , Contaminantes Químicos del Agua/análisis , Espectrometría de Masas , Hidrocarburos Policíclicos Aromáticos/análisisRESUMEN
Understanding the toxicity of organic compounds in oil sands process-affected water (OSPW) is necessary to inform the development of environmental guidelines related to wastewater management in Canada's oil sands region. In the present study, we investigated the effects of naphthenic acid fraction compounds (NAFCs), one of the most toxic components of OSPW, on mating behaviour, fertility, and offspring viability in the wood frog (Rana sylvatica). Wild adult wood frogs were exposed separately from the opposite sex to 0, 5, or 10 mg/L of OSPW-derived NAFCs for 24 h and then combined in outdoor lake water mesocosms containing the same NAFC concentrations (n = 2 males and 1 female per mesocosm, n = 3 mesocosms per treatment). Mating events were recorded for 48 h and egg masses were measured to determine adult fertility. NAFC exposure had no significant effect on mating behaviour (probability of amplexus and oviposition, amplexus and oviposition latency, total duration of amplexus and number of amplectic events) or fertility (fertilization success and clutch size). Tadpoles (50 individuals per mesocosm at hatching, and 15 individuals per mesocosm from 42 d post-hatch) were reared in the same mesocosms under chronic NAFC exposure until metamorphic climax (61-85 d after hatching). Offspring exposed to 10 mg/L NAFCs during development were less likely to survive and complete metamorphosis, grew at a reduced rate, and displayed more frequent morphological abnormalities. These abnormalities included limb anomalies at metamorphosis, described for the first time after NAFC exposure. The results of this study suggest that NAFCs reduce wood frog reproductive success through declines in offspring viability and therefore raise the concern that exposure to NAFCs during reproduction and development may affect the recruitment of native amphibian populations in the oil sands region.
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Yacimiento de Petróleo y Gas , Contaminantes Químicos del Agua , Animales , Femenino , Masculino , Ácidos Carboxílicos/toxicidad , Ranidae , Reproducción , Agua , Contaminantes Químicos del Agua/toxicidad , Contaminantes Químicos del Agua/análisisRESUMEN
There is a growing need to develop analytical methods that can distinguish compounds found within industrially derived oil sands process water (OSPW) from those derived from natural weathering of oil sands deposits. This is a difficult challenge as possible leakage beyond tailings pond containments will probably be in the form of mixtures of water-soluble organics that may be similar to those leaching naturally into aquatic environments. We have evaluated the potential of negative ion electrospray ionization high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) for comparing oil sands polar organics from tailing ponds, interceptor wells, groundwater, river and lake surface waters. Principal component analysis was performed for all species observed. which included the O(2) class (often assumed to be monocarbxoylic naphthenic acids) along with a wide range of other species including humic substances in the river and lake samples: O(n) where n=1-16; NO(n) and N(2)O(n) where n=1-13; and O(n)S and O(n)S(2) where n=1-10 and 1-8, respectively. A broad range of species was investigated because classical naphthenic acids can be a small fraction of the 'organics' detected in the polar fraction of OSPW, river water and groundwater. Aquatic toxicity and environmental chemistry are attributed to the total organics (not only the classical naphthenic acids). The distributions of the oil sands polar organics, particularly the sulfur-containing species, O(n)S and O(n)S(2), may have potential for distinguishing sources of OSPW. The ratios of species containing O(n) along with nitrogen-containing species: NO(n), and N(2)O(n), were useful for differentiating organic components derived from OSPW from those found in river and lake waters. Further application of the FTICRMS technique for a diverse range of OSPW of varying ages and composition, as well as the surrounding groundwater wells, may be critical in assessing whether leakage from industrial sources to natural waters is occurring.
RESUMEN
In this study fathead minnow (Pimephales promelas) embryo-larval stages were exposed to two oil sands tailings pond sediments which had previously been shown to decrease the survival of embryo-larval larval stages of walleye (Sander vitreus) and northern pike (Esox lucius). Fathead minnow are standard test species and we wanted to compare their sensitivity to the other two species. Fathead minnow larvae were exposed for 20 days (5 days in the egg stage and 15 days in the larval stage) with daily renewal of sediments and waters. Sediments contained polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs (APAHs). Results from an earlier study showed that Sediment 1 contained 173 µg/g total PAHs + APAHs (97 % alkylated), and sediment 2 contained 401 µg/g total PAHs + APAHs (95 % alkylated). Fathead minnow larvae exposed to oil sands tailings pond sediments had decreased survival, decreased weight, and increased deformities. Fathead minnow survival was unaffected at the embryo stage and at hatch. Most deaths occurred at the larval stages 1-8 days after hatching, showing the importance of exposing the fish for at least a week after hatch. Toxicity was seen at 0.2 g/L of sediment, which was equivalent to the addition of 35 and 80 µg total PAHs + APAHs to 1 L of overlying water for sediment 1 and 2, respectively. When compared to embryo-larval northern pike and walleye results from previous studies, all three species of fish responded more strongly to sediment 2 compared to sediment 1. For effects on lethality, fathead minnow were equally sensitive to pike, but walleye were 5-28 times more sensitive to the lethal effects of the sediments compared to both fathead minnow and pike. The study (and comparisons to our previous studies) shows the difference in sensitivity between a model laboratory species (fathead minnow) and some species of wild fish that are highly relevant to the oil sands area of Alberta.
RESUMEN
The aim of this study was to investigate the long-term effects of a short exposure to natural sediments within the Athabasca oil sand formation to critical stages of embryo-larval development in fathead minnows (Pimephales promelas). Three different sediments were used: Ref sediment from the upper Steepbank River tested at 3â¯g/L (containing 12.2â¯ng/g ∑PAHs), and two bitumen-rich sediments tested at 1 and 3â¯g/L; one from the Ells River (Ells downstream, 6480â¯ng/g ∑PAHs) and one from the Steepbank River (Stp downstream, 4660â¯ng/g ∑PAHs). Eggs and larvae were exposed to sediments for 21 days, then transferred to clean water for a 5-month grow-out and recovery period. Larval fish had significantly decreased survival after exposure to 3â¯g/L sediment from Stp downstream, and decreased growth (length and weight at 16 days post hatch) in Ells and Stp downstream sediments at both 1 and 3â¯g/L. Decreased tail length was a sensitive endpoint in larval fish exposed to Ells and Stp downstream sediments for 21 days compared to Ref sediment. After the grow-out in clean water, all growth effects from the bitumen-containing sediments recovered, but adult fish from Stp downstream 3â¯g/L sediment had significant increases in jaw deformities. The study shows the potential for fish to recover from the decreased growth effects caused by sediments containing oil sands-related compounds, but that some effects of the early-life sediment exposure occur later on in adult fish.
Asunto(s)
Cyprinidae/fisiología , Hidrocarburos/toxicidad , Contaminantes Químicos del Agua/toxicidad , Animales , Sedimentos Geológicos , Larva/efectos de los fármacos , Yacimiento de Petróleo y Gas , Hidrocarburos Policíclicos Aromáticos/análisis , Ríos , Contaminantes Químicos del Agua/análisisRESUMEN
The surface mining of oil sands north of Fort McMurray, Alberta produces considerable tailings waste that is stored in large tailings ponds on industrial lease sites. Viable strategies for the detoxification of oil sands process affected water (OSPW) are under investigation. In order to assess the toxic potential of the suite of dissolved organics in OSPW, a method for their extraction and fractionation was developed using solid phase extraction. The method successfully isolated organic compounds from 180â¯L of an aged OSPW source. Using acidic- or alkaline-conditioned non-polar ENV+ resin and soxhlet extraction with ethyl acetate and methanol, three fractions (F1-F3) were generated. Chemical characterization of the generated fractions included infusion to electrospray ionization ultrahigh-resolution mass spectrometry (ESI-UHRMS), liquid chromatography quadrupole time-of-flight mass spectrometry, gas chromatography triple quadrupole time-of-flight mass spectrometry, and synchronous fluorescence spectroscopy (SFS). Additionally, ESI-UHRMS class distribution data and SFS identified an increased degree of oxygenation and aromaticity, associated with increased polarity. Method validation, which included method and matrix spikes with surrogate and labelled organic mono carboxylic acid standards, confirmed separation according to acidity and polarity with generally good recoveries (average 76%). Because this method is capable of extracting large sample volumes, it is amenable to thorough chemical characterization and toxicological assessments with a suite of bioassays. As such, this protocol will facilitate effects-directed analysis of toxic components within bitumen-influenced waters from a variety of sources.
RESUMEN
The process of surface mining and extracting bitumen from oil sand produces large quantities of tailings and oil sands process-affected water (OSPW). The industry is currently storing OSPW on-site while investigating strategies for their detoxification. One such strategy relies on the biodegradation of organic compounds by indigenous microbes, resulting in aged tailings waters with reduced toxicity. This study assessed the toxicity of OSPW aged statically for approximately 18â¯years. Dissolved organics in aged OSPW were fractionated using a preparative solid-phase extraction method that generated three organic fractions (F1-F3) of increasing polarity. Eight aquatic species from different trophic levels were exposed to whole OSPW (WW) and the derived OSPW organic fractions to assess toxicity: Pimephales promelas, Oryzias latipes, Vibrio fischeri, Daphnia magna, Lampsilis cardium, Hyalella azteca, Ceriodaphnia dubia, and Hexagenia spp. Broad comparisons revealed that P. promelas and H. azteca were most sensitive to dissolved organics within aged OSPW, while WW was most toxic to L. cardium and H. azteca. Three cases of possible contaminant interactions occurred within whole OSPW treatments, as toxicity was higher than organic fractions for H. azteca and L. cardium, and lower for P. promelas. As such, the drivers of toxicity appeared to be dependent on the species exposed. Of the organic fractions assessed, F3 (most polar) was the most toxic overall while F2 (intermediate polarity) displayed little toxicity to all species evaluated. This presents strong evidence that classical mono-carboxylic naphthenic acids, mostly present in F1 (least polar), are not primarily responsible for the toxicity in aged tailings. The current study indicates that although the aged tailings source (≥18â¯years) did not display acute toxicity to the majority of organisms assessed, inorganic components and polyoxygenated organics may pose a persistent concern to some aquatic organisms.
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Organismos Acuáticos/efectos de los fármacos , Yacimiento de Petróleo y Gas , Compuestos Orgánicos/toxicidad , Contaminación por Petróleo , Contaminantes Químicos del Agua/toxicidad , Aliivibrio fischeri , Anfípodos , Animales , Organismos Acuáticos/fisiología , Ácidos Carboxílicos , Cladóceros , Cyprinidae , Daphnia , Hidrocarburos , Minería , Oryzias , Pruebas de ToxicidadRESUMEN
To assess the toxicity of winter-time atmospheric deposition in the oil sands mining area of Northern Alberta, embryo-larval fathead minnow (Pimephales promelas) were exposed to snowmelt samples. Snow was collected in 2011-2014 near (<7km) oil sands open pit mining operations in the Athabasca River watershed and at sites far from (>25km) oil sands mining. Snow was shipped frozen back to the laboratory, melted, and amended with essential ions prior to testing. Fertilized fathead minnow eggs were exposed (<24h post-fertilization to 7-16days post-hatch) to a range of 25%-100% snowmelt. Snow samples far from (25-277km away) surface mining operations and upgrading facilities did not affect larval fathead minnow survival at 100%. Snow samples from sites near surface mining and refining activities (<7km) showed reduced larval minnow survival. There was some variability in the potencies of snow year-to-year from 2011 to 2014, and there were increases in deformities in minnows exposed to snow from 1 site on the Steepbank River. Although exposure to snowmelt from sites near oil sands surface mining operations caused effects in larval fish, spring melt water from these same sites in late March-May of 2010, 2013 and 2014 showed no effects on larval survival when tested at 100%. Snow was analyzed for metals, total naphthenic acid concentrations, parent PAHs and alkylated PAHs. Naphthenic acid concentrations in snow were below those known to affect fish larvae. Concentrations of metals in ion-amended snow were below published water quality guideline concentrations. Compared to other sites, the snowmelt samples collected close to mining and upgrading activities had higher concentrations of PAHs and alkylated PAHs associated with airborne deposition of fugitive dusts from mining and coke piles, and in aerosols and particles from stack emissions. CAPSULE: Snow collected close to oil sands surface mining sites is toxic to larval fathead minnows in the lab; however spring melt water samples from the same sites do not reduce larval fish survival.
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Cyprinidae , Yacimiento de Petróleo y Gas , Ríos/química , Nieve/química , Contaminantes Químicos del Agua/toxicidad , Alberta , Animales , Larva/efectos de los fármacos , Estaciones del Año , Pruebas de ToxicidadRESUMEN
The potential discharge of groundwater contaminated by oil sands process-affected water (OSPW) is a concern for aquatic ecosystems near tailings ponds. Groundwater in the area, but unaffected by OSPW, may contain similar compounds, complicating the assessment of potential ecological impacts. In this study, 177 shallow groundwater samples were collected from riparian areas along the Athabasca River and tributaries proximate to oil sands developments. For "pond-site" samples (71; adjacent to study tailings pond), Canadian aquatic life guidelines were exceeded for 11 of 20 assessed compounds. However, "non-pond" samples (54; not near any tailings pond) provided similar exceedances. Statistical analyses indicate that pond-site and non-pond samples were indistinguishable for all but seven parameters assessed, including salts, many trace metals, and fluorescence profiles of aromatic naphthenic acids (ANA). This suggests that, regarding the tested parameters, groundwater adjacent to the study tailings pond generally poses no greater ecological risk than other nearby groundwaters at this time. Multivariate analyses applied to the groundwater data set separated into 11 smaller zones support this conclusion, but show some variation between zones. Geological and potential OSPW influences could not be distinguished based on major ions and metals concentrations. However, similarities in indicator parameters, namely ANA, F, Mo, Se, and Na-Cl ratio, were noted between a small subset of samples from two pond-site zones and two OSPW samples and two shallow groundwater samples documented as likely OSPW affected. This indicator-based screening suggests that OSPW-affected groundwater may be reaching Athabasca River sediments at a few locations.
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Agua Subterránea , Yacimiento de Petróleo y Gas , Contaminantes Químicos del Agua , Canadá , EstanquesRESUMEN
Serotonin S1 and S2 receptors were studied in brains obtained at post-mortem from controls and patients with Huntington's disease. Significant reductions in serotonin S1 receptors were observed in putamen and hippocampus but not in frontal and temporal cortices. Serotonin S2 receptors were unchanged in all four brain regions. The results suggest that S1 receptors may be located on susceptible cells in both the putamen and hippocampus in Huntington's disease.
RESUMEN
White sucker (Catostomus commersoni) caged for 3 days in a bleached kraft mill effluent (BKME) stream had elevated mixed function oxygenase (MFO) activities 15-90 fold those of fish caged in a reference stream. Liver composites of male and female fish were ground and extracted with dichloromethane (DCM), methanol or 50% DCM/methanol, and tested for MFO activity in rat hepatoma cells (H4IIE). There was no difference in the potency of H4IIE EROD induction among the three solvents, so DCM extracts were split into 31 fractions using reverse phase high pressure liquid chromatography (HPLC). H4IIE MFO activity was elevated in several fractions, with three early peaks and several later peaks of induction, indicating several classes or compounds causing MFO induction were present in the fish livers. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and chlorinated diphenylethers (CDPEs) were detected in several late-eluting fractions, but concentrations were not high enough for these compounds to be solely responsible for the observed induction. Induction by liver extracts decreased as cell exposure times increased (24, 48 or 72 h), suggesting that some inducers were more easily metabolized and eliminated from the H4IIE cells. In contrast, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TCDD) had similar potency over 24, 48 and 72 h, as it was relatively resistant to metabolism.
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Peces/fisiología , Oxigenasas de Función Mixta/metabolismo , Contaminantes Químicos del Agua/efectos adversos , Animales , Benzofuranos/efectos adversos , Benzofuranos/análisis , Femenino , Industrias , Masculino , Oxigenasas de Función Mixta/efectos de los fármacos , Dibenzodioxinas Policloradas/efectos adversos , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análisis , Distribución Tisular , Eliminación de Residuos Líquidos , Contaminantes Químicos del Agua/análisisRESUMEN
The Bay of Quinte (BOQ) is an Area of Concern listed under the Great Lakes Water Quality Agreement. The presence of dioxins and dioxin-like PCBs in fish in the BOQ AOC has led to restrictions on fish consumption by humans, which is a beneficial use impairment. Adult yellow perch (Perca flavescens) and brown bullhead (Ameiurus nebulosus) were sampled from Trenton, Belleville, and Deseronto (reference site) in the BOQ. A suite of hormone assays and various measures of exposure and/or sublethal health effects were used to assess the health status of fish of both species and sex. Condition factor, hepatosomatic index, ethoxyresorufin-O-deethylase activity, circulating steroid and thyroid hormones, thyroid activation, oocyte size distribution, spermatogenic cell stages, and plasma vitellogenin were among the endpoints that were significantly (p < 0.05) affected by location. Many of those effects corresponded with significantly (p < 0.05) greater tissue concentrations of polychlorinated biphenyls (PCBs) at Belleville and Trenton. Hepatic extracts from brown bullhead sampled from Trenton had significantly (p < 0.05) greater binding activity to the androgen receptor and sex steroid binding protein. Taken together, these data and preliminary data from a concomitant study suggest that PCBs are likely being hydroxylated in vivo, resulting in enhanced bioactivity at endocrine receptors and measurable health responses. The present study supports the growing body of evidence that PCBs and their metabolites can affect fish thyroid and steroid hormone systems.
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Sistema Endocrino/efectos de los fármacos , Monitoreo del Ambiente , Peces/fisiología , Bifenilos Policlorados/análisis , Bifenilos Policlorados/toxicidad , Glándula Tiroides/química , Animales , Bahías , Biomarcadores/análisis , Canadá , Disruptores Endocrinos/análisis , Disruptores Endocrinos/toxicidad , Femenino , Peces/metabolismo , Hígado/química , Hígado/efectos de los fármacos , Masculino , Glándula Tiroides/efectos de los fármacos , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidadRESUMEN
To facilitate monitoring efforts, a forensic chemical fingerprinting methodology has been applied to characterize and differentiate pyrogenic (combustion derived) and biogenic (organism derived) hydrocarbons from petrogenic (petroleum derived) hydrocarbons in environmental samples from the Canadian oil sands region. Between 2009 and 2012, hundreds of oil sands environmental samples including water (snowmelt water, river water, and tailings pond water) and sediments (from river beds and tailings ponds) have been analyzed. These samples were taken from sites where assessments of wild fish health, invertebrate communities, toxicology and detailed chemistry are being conducted as part of the Canada-Alberta Joint Oil Sands Monitoring Plan (JOSMP). This study describes the distribution patterns and potential sources of PAHs from these integrated JOSMP study sites, and findings will be linked to responses in laboratory bioassays and in wild organisms collected from these same sites. It was determined that hydrocarbons in Athabasca River sediments and waters were most likely from four sources: (1) petrogenic heavy oil sands bitumen; (2) biogenic compounds; (3) petrogenic hydrocarbons of other lighter fuel oils; and (4) pyrogenic PAHs. PAHs and biomarkers detected in snowmelt water samples collected near mining operations imply that these materials are derived from oil sands particulates (from open pit mines, stacks and coke piles).
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Contaminantes Ambientales/análisis , Hidrocarburos/análisis , Yacimiento de Petróleo y Gas , Alberta , Monitoreo del Ambiente , Agua Dulce/análisis , Aceites Combustibles , Sedimentos Geológicos/análisis , Residuos Industriales , Minería , Nieve/químicaRESUMEN
The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic. In the present study we therefore assayed the acute toxicity to larval fish, of a whole acidified OSPW extract and an esterifiable naphthenic acids fraction, de-esterified with alkali: both fractions were toxic (LC50 â¼5-8mgL(-1)). We then fractionated the acids by argentation solid phase extraction of the esters and examined the acute toxicity of two fractions: a de-esterified alicyclic acids fraction, which contained, for example, adamantane and diamantane carboxylic acids, and an aromatic acids fraction. The alicyclic acids were toxic (LC50 13mgL(-1)) but the higher molecular weight aromatic acids fraction was somewhat more toxic, at least on a weight per volume basis (LC50 8mgL(-1); P<0.05) (for comparison, the monoaromatic dehydroabietic acid had a LC50 of â¼1mgL(-1)). These results show how toxic naphthenic acids of OSPW are to these larval fish and that on a weight per volume basis, the aromatic acids are at least as toxic as the 'classical' alicyclic acids. The environmental fates and other toxic effects, if any, of the fractions remain to be established.
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Ácidos Carboxílicos/química , Ácidos Carboxílicos/toxicidad , Petróleo/análisis , Dióxido de Silicio/química , Pruebas de Toxicidad Aguda , Agua/química , Pez Cebra , Acetatos/química , Animales , Ácidos Carboxílicos/aislamiento & purificación , Esterificación , Concentración de Iones de Hidrógeno , Larva/efectos de los fármacosRESUMEN
The oil sands region of northern Alberta represents the world's largest reserves of bitumen, and the accelerated pace of industrial extraction activity has raised concern about the possible impacts on the Athabasca River and its tributaries. An ecotoxicogenomic study was undertaken on Oncorhynchus mykiss trout hepatocytes exposed to extracts of water samples near the oil sand development area, as well as to oil sands process-affected water (OSPW) extracts using the quantitative reverse transcriptase polymerase chain reaction technique. The expression of the following genes (mRNA) was monitored to track changes in xenobiotic biotransformation (CYP1A1, CYP3A4, glutathione S-transferase, multi-drug resistance transporter), estrogenicity (estrogen receptor and vitellogenin), oxidative stress (superoxide dismutase and metallothionein) and DNA repair activity (DNA ligase). The extent of DNA-aromatic hydrocarbon adducts was also determined in cells by immuno-staining. A comparative analysis of gene expression between the river/lake and OSPW samples revealed that CYP3A4, metallothioneins, DNA ligase and GST genes, were specifically expressed by OSPW. Cells exposed to OSPW, commercial naphthenic acids, and benzo(a)pyrene showed increased polyaromatic hydrocarbon DNA-adducts, as determined by cell immunofluorescence analysis. Other genes were induced by all types of water samples, although the induction potential was stronger in OSPW most of the time (e.g., VTG gene was expressed nearly 15-fold by surface waters from the lake and river samples but increased to a maximum of 31-fold in OSPW). A multivariate discriminant function analysis revealed that the lake and river water samples were well discriminated from the OSPW. The CYP3A4 gene was the most highly expressed gene in cells exposed to OSPW and responded less to the lake or river water in the Athabasca River area. This study identified a suite of gene targets that responded specifically to OSPW extracts, which could serve as toxicogenomic fingerprints of OSPW contamination.
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Regulación Enzimológica de la Expresión Génica/efectos de los fármacos , Hepatocitos/efectos de los fármacos , Hidrocarburos/toxicidad , Residuos Industriales , Oncorhynchus mykiss , Contaminantes Químicos del Agua/toxicidad , Animales , Citocromo P-450 CYP3A/genética , ADN/química , Aductos de ADN/análisis , ADN Ligasas/genética , Análisis Discriminante , Monitoreo del Ambiente , Agua Dulce , Glutatión Transferasa/genética , Hepatocitos/metabolismo , Hidrocarburos/química , Metalotioneína/genética , Hidrocarburos Policíclicos Aromáticos/análisis , RíosRESUMEN
The impacts of pulp mill effluents on white sucker (Catostomus commersoni) have been studied at Jackfish Bay, ON, Canada since the late 1980s. The site receives effluent from a large bleached kraft pulp mill which is the only source of chemical contamination in the area. Many laboratory studies have looked at the toxicological consequences of pulping process changes, but the benefit of these changes have not been looked at in wild fish. Jackfish Bay white sucker showed impacts on sexual maturity, gonad size, secondary sexual characteristics and circulating steroids hormone levels in the early years of the studies, and impacts were evaluated after installation of secondary treatment (1989), major pulping process changes (1995) and after the mill ceased pulp production and effluent release (2006). The addition of secondary treatment resulted in minor improvements in wild fish health, and the conversion to elemental chlorine free (ECF) bleaching at the mill was associated with more recovery in liver and gonad size. While some impacts persist at the exposure site, reproductive parameters showed further improvement during the mill shutdown period demonstrating that biologically active chemicals are still being discharged from modernized mills.
Asunto(s)
Cipriniformes/fisiología , Residuos Industriales/efectos adversos , Lignina/química , Contaminantes Químicos del Agua/toxicidad , Animales , Cloro/química , Gónadas/efectos de los fármacos , Gónadas/metabolismo , Hígado/efectos de los fármacos , Hígado/metabolismo , Maduración Sexual/efectos de los fármacos , Maduración Sexual/fisiología , Esteroides/metabolismo , Factores de TiempoRESUMEN
The presence of unidentified estrogens and androgens in effluents from pulp and paper mills is well documented. However, their role in effluent effects on fish reproduction remains unclear. The objective of this study was to investigate the hypothesis that reproductive impacts of a modern pulp mill effluent are mediated by androgens and/or estrogens in the effluent. Male and female threespine stickleback were exposed to biologically treated Canadian bleached kraft mill effluent under flow-through conditions in the laboratory at 0, 1, 10 and 100% (v/v) dilutions. After 7 and 21 d of exposure, steroidogenesis was assessed using in vitro incubations of gonadal tissue in both males and females. mRNA expression of the estrogen-regulated gene vitellogenin, and the androgen-responsive gene spiggin were assessed using quantitative RT-PCR in the livers of male and posterior kidneys of female stickleback, respectively. Hepatic 7-ethoxyresorufin-O-deethylase (EROD) activity was assessed in both sexes. Effluent extracts were examined for estrogenic and androgenic bioactivity using receptor binding bioassays, and were screened for pulp and paper related extractives and steroidal androgens using GC-MS. This effluent up-regulated spiggin mRNA in the kidney of female stickleback at 10% and 100% (v/v) effluent at 21 d, but not at 7 d of exposure. This change at the mRNA expression of the gene was associated with an increase in cell height in kidney proximal tubule epithelial cells at 100% effluent after both 7 and 21 d. Liver vitellogenin mRNA in male stickleback was not induced at either 7 or 21 d. EROD was induced at 10 and 100% after 21 d of exposure in both sexes, but not after 7 d of exposure. Despite evidence of exposure to androgens, there was no reduction in steroidogenic capacity at any effluent dilution. Effluent extracts were capable of eliciting the displacement of androgens and estrogens from receptors, but androgenic potency was 4-fold greater. A screen of more than 30 androgenic androstane steroids showed no detections. Hence, the androgenic constituents in this particular effluent remain unknown.