Toxicity Of Oil Sands Process-affected Water Research Articles

The effect of rhizosphere pH on removal of naphthenic acid fraction compounds from oil sands process-affected water in a willow hydroponic system

The extraction and processing of bitumen from the oil sands in northern Alberta, Canada generates large volumes of oil sands process-affected water (OSPW). OSPW contains a complex mixture of inorganic and organic compounds, including naphthenic acid fraction compounds (NAFCs) that are of particular concern due to their toxicity to aquatic organisms. Phytoremediation is a cost-effective, scalable approach that has the potential to remove NAFCs from OSPW and reduce OSPW toxicity. Environmental pH influences the chemical form and bioavailability of NAFCs. However, little is known about the influence of pH on the uptake of NAFCs in plant systems. This study sought to elucidate the impact of rhizosphere pH on the uptake of NAFCs using a sandbar willow (Salix interior) hydroponic system. To mimic and maintain the naturally low pH conditions of the root, OSPW solutions in these systems were adjusted to a low pH level (pH 5.0) and their NAFC uptake from solution was compared to that of OSPW at native pH (pH 8.0). Our findings revealed that the lower pH hydroponic systems demonstrated enhanced NAFC removal from solution as determined by LC-MS analysis, where up to 26% of NAFCs were removed from OSPW over 72 h at pH 5.0 compared to 8% removed at pH 8.0. Similarly, analysis of spike-in 13C-labeled NAs demonstrated that the OSPW hydroponic system rapidly removed a relatively labile NA (13C-cyclohexane carboxylic acid) from solution at both pH levels, whereas near complete removal of a recalcitrant NA (13C-1-adamantane carboxylic acid) was observed in pH 5.0 solutions only. These results provide insight into the importance of rhizosphere pH on efficient NAFC uptake by plant root systems. Further research will determine whether OSPW phytoremediation efficiency can be enhanced using field treatment conditions that promote low rhizosphere pH levels.

A multi-step approach: Coupling of biodegradation and UV photocatalytic oxidation TiO2 for the treatment of naphthenic acid fraction compounds in oil sands process-affected water

Bitumen extraction in Alberta's oil sands region uses large volumes of water, leading to an abundance of oil sands process-affected water (OSPW). OSPW contains naphthenic acid fraction compounds (NAFCs) which have been found to contribute to OSPW toxicity. This study utilized a multistep treatment, coupling biological degradation with UV photocatalytic oxidation, and nutrient addition to boost the native microbial community's degradation capacity. OSPW initially contained 40–42 mg/L NAFCs with a toxicity of 3.8–3.9 TU. Initial biodegradation (Step 1) was used to remove the easily biodegradable NAFCs (11–25% removal), followed by a light or heavy dose of oxidation (Step 2) to breakdown the recalcitrant NAFCs (66–82% removal). Lastly, post-oxidation biodegradation with nutrients (Step 3) removed the residual bioavailable NAFCs (16–31% removal). By the end of the multistep treatment, the final NAFC concentrations and toxicity ranged from 5.3 to 6.8 mg/L and 1.1–1.2 TU. Analysis showed that OPSW was limited in phosphorus (below detection limit), and the addition of nutrients improved the degradation of NAFCs. Two treatments throughout the multistep treatment never received nutrients and showed minimal NAFC degradation post-oxidation. The native microbial community survived the stress from UV photocatalytic oxidation as seen by the post-oxidation NAFC biodegradation. Microbial community diversity was reduced considerably following oxidation, but increased with nutrient addition. The microbial community consisted predominately of Proteobacteria (Gammaproteobacteria and Alphaproteobacteria), and the composition shifted depending on the level of oxidation received. Possible NAFC-degrading microbes identified after a light oxidation dose included Pseudomonas, Acinetobacter and Xanthomonadales, while Xanthobacteracea and Rhodococcus were the dominant microbes after heavy oxidation. This experiment confirms that the microbial community is capable of degrading NAFCs and withstanding oxidative stress, and that degradation is further enhanced with the addition of nutrients.

A Light Touch: Solar Photocatalysis Detoxifies Oil Sands Process-Affected Waters Prior to Significant Treatment of Naphthenic Acids.

Environmental reclamation of Canada's oil sands tailings ponds is among the single largest water treatment challenges globally. The toxicity of oil sands process-affected water (OSPW) has been associated with its dissolved organics, a complex mixture of naphthenic acid fraction components (NAFCs). Here, we evaluated solar treatment with buoyant photocatalysts (BPCs) as a passive advanced oxidation process (P-AOP) for OSPW remediation. Photocatalysis fully degraded naphthenic acids (NAs) and acid extractable organics (AEO) in 3 different OSPW samples. However, classical NAs and AEO, traditionally considered among the principal toxicants in OSPW, were not correlated with OSPW toxicity herein. Instead, nontarget petroleomic analysis revealed that low-polarity organosulfur compounds, composing <10% of the total AEO, apparently accounted for the majority of waters' toxicity to fish, as described by a model of tissue partitioning. These findings have implications for OSPW release, for which a less extensive but more selective treatment may be required than previously expected.

Biodegradation in oil sands process-affected water: A comprehensive laboratory analysis of the in situ biodegradation of dissolved organic acids

Oil sands process-affected water (OSPW) is a by-product of the extraction of bitumen, and volumes of OSPW have accumulated across the Alberta oil sands region due to the governments zero-discharge policy. Some dissolved organics in OSPW, including toxic naphthenic acids (NAs), can be biodegraded in oxic conditions, thereby reducing the toxicity of OSPW. While there has been much focus on degradation of NAs, the biodegradation of other dissolved organic chemicals by endogenous organisms remains understudied. Here, using the HPLC–ultrahigh resolution Orbitrap mass spectrometry, we examined the microbial biodegradation of dissolved organic acids in OSPW. Non-targeted analysis enabled the estimation of biodegradation rates for unique heteroatomic chemical classes detected in negative ion mode. The microcosm experiments were conducted with and without nutrient supplementation, and the changes in the microbial community over time were investigated. Without added nutrients, internal standard–adjusted intensities of all organics, including NAs, were largely unchanged. The addition of nutrients increased the biodegradation rate of O2− and SO2− chemical classes. While anoxic biodegradation can occur in tailings ponds and end pit lakes, microbial community analyses confirmed that the presence of oxygen stimulated biodegradation of the OSPW samples studied. We detected several aerobic hydrocarbon-degrading microbes (e.g., Pseudomonas and Brevundimonas), and microbes capable of degrading sulfur-containing hydrocarbons (e.g., Microbacterium). Microbial community diversity decreased over time with nutrient addition. Overall, the results from this study indicate that toxic dissolved organics beyond NAs can be biodegraded by endogenous organisms in OSPW, but reaffirms that biological treatment strategies require careful consideration of how nutrients and dissolved oxygen may impact efficacy.

Evaluating the attenuation of naphthenic acids in constructed wetland mesocosms planted with Carex aquatilis

Surface oil sands mining and extraction in northern Alberta’s Athabasca oil sands region produce large volumes of oil sands process–affected water (OSPW). OSPW is a complex mixture containing major contaminant classes including trace metals, polycyclic aromatic hydrocarbons, and naphthenic acid fraction compounds (NAFCs). Naphthenic acids (NAs) are the primary organic toxicants in OSPW, and reducing their concentrations is a priority for oil sands companies. Previous evidence has shown that constructed wetland treatment systems (CWTSs) are capable of reducing the concentration of NAs and the toxicity of OSPW through bioremediation. In this study, we constructed greenhouse mesocosms with OSPW or lab process water (LPW) (i.e., water designed to mimic OSPW minus the NAFC content) with three treatments: (1) OSPW planted with Carex aquatilis; (2) OSPW, no plants; and (3) LPW, no plants. The OSPW–C. aquatilis treatment saw a significant reduction in NAFC concentrations in comparison to OSPW, no plant treatments, but both changed the distribution of the NAFCs in similar ways. Upon completion of the study, treatments with OSPW saw fewer high-molecular-weight NAs and an increase in the abundance of O3- and O4-containing formulae. Results from this study provide invaluable information on how constructed wetlands can be used in future remediation of OSPW in a way that previous studies were unable to achieve due to uncontrollable environmental factors in field experiments and the active, high-energy processes used in CWTSs pilot studies.

Persistent Cytotoxicity and Endocrine Activity in the First Oil Sands End-Pit Lake.

Oil sands process-affected water (OSPW) is a byproduct of bitumen extraction that has persistent toxicity owing to its complex mixture of organics. A prominent remediation strategy that involves aging OSPW in end-pit lakes and Base Mine Lake (BML) is the first full-scale test. Its effectiveness over the first 5 years was investigated here using real-time cell analysis, yeast estrogenic and androgenic screens (YES/YAS), and ultra-high-resolution mass spectrometry. HepG2 cytotoxicity per volume of BML organics extracted decreased with age; however, the toxic potency (i.e., toxicity per mass of extract) was not significantly different between years. This was consistent with mass spectral evidence showing no difference in chemical profiles, yet lower total abundance of organics in field-aged samples, suggestive that dilution explains the declining cytotoxicity in BML. The IC50's of BML extracts for YES/YAS antagonism were at environmental concentrations and were similar despite differences in field-age. Persistent YES/YAS antagonism and cytotoxicity were detected in experimental pond OSPW field-aged >20 years, and while organic acids were depleted here, non-acid chemical classes were enriched compared to BML, suggesting these contribute to persistent toxicity of aged OSPW. To avoid a legacy of contaminated sites, active water treatment may be required to accelerate detoxification of end-pit lakes.

Detection of naphthenic acid uptake into root and shoot tissues indicates a direct role for plants in the remediation of oil sands process-affected water

Bitumen extraction from surface-mined oil sands deposits results in the accumulation of large volumes of oil sands process-affected water (OSPW). Naphthenic acids (NAs) are primary contributors to OSPW toxicity and have been a focal point for the development of OSPW remediation strategies. Phytoremediation is an approach that utilizes plants and their associated microbes to remediate contaminants from soil and groundwater. While previous evidence has indicated a role for phytoremediation in OSPW treatment through the transformation and degradation of NAs, there are no reports that demonstrate the direct uptake of NAs into plant tissue. Using NAs labelled with 14C radioisotopes (14C-NAs) paired with whole-plant autoradiography, we show that NAs representing aliphatic (linear), single-ring, and diamondoid compounds were effectively removed from hydroponic solution and OSPW-treated soil by sandbar willow (Salix interior) and slender wheatgrass (Elymus trachycaulus) and their associated microbiomes. The NA-derived 14C label accumulated in root and shoot tissues of both plant species and was concentrated in vascular tissue and rapidly growing sink tissues, indicating that 14C-NAs or their metabolic derivatives were incorporated into physiological processes within the plants. Slender wheatgrass seedlings grown under axenic (sterile) hydroponic and soil conditions also effectively removed all 14C-NAs, including a highly stable diamondoid NA, demonstrating that plants can directly take up simple and complex NAs without the assistance of microbes. Furthermore, root and shoot tissue fractionation into major biomolecule groups suggests that NA-derived carbon is allocated toward biomolecule synthesis rapidly after NA treatment. These findings provide evidence of plant-mediated uptake of NAs and support a direct role for plants and their associated microbes in the development of future large-scale OSPW phytoremediation strategies.

The Appropriateness of Using Aquatic Snails as Bioindicators of Toxicity for Oil Sands Process-Affected Water

Canada’s oil sands mining activity produces large volumes of oil sands process-affected water (OSPW), and there have been increasing concerns regarding the potential environmental impacts associated with this material. Developing an understanding of the toxicity of OSPW is critical to anticipating and mitigating the potential risks and effects of the oil sands industry on surrounding ecosystems. The composition of OSPW is highly variable and is influenced by a range of factors. While numerous research projects have been conducted on the toxicity of OSPW, much remains unknown about its impact on various biota. Freshwater gastropods (snails and slugs) are an ecologically crucial aquatic group, and members of this taxa have been used as bioindicators in a range of ecological settings. The literature suggests freshwater snails could be used as an indicator of toxicity in monitoring programs associated with oil sands development. This mini-review explores the use of snails as bioindicators in aquatic systems affected by oil sands development, focusing on how snails may respond to potential constituents of concern in systems exposed to OSPW.

Oil sands process affected water sourced Trichoderma harzianum demonstrates capacity for mycoremediation of naphthenic acid fraction compounds

Development of Alberta’s oil sands requires large volumes of water, leading to the abundance of oil sands process affected water (OSPW) that must be remediated prior to discharge or reuse. OSPW contains a variety of dissolved organic compounds, however naphthenic acids (NAs) have been found to contribute significantly to the toxicity of OSPW. A fungus, Trichoderma harzianum, isolated directly from OSPW, has previously demonstrated a high tolerance and capacity for growth in the presence of commercial NAs. This study conducted microcosm experiments to elucidate and characterize the capacity of T. harzianum to degrade labile commercial NAs (Merichem), and OSPW-sourced naphthenic acid fraction compounds (NAFCs). Additionally, two model NA compounds, the simple single ring cyclohexane carboxylic acid (CHCA) and complex diamondoid 1-adamanatane carboxylic acid (ADA), were utilized to determine the influence of NA structure on degradation. T. harzianum degraded 14% of CHCA, 13% of ADA, and 23–47% of Merichem NAs. Additionally, Orbitrap mass spectrometry revealed a large change in Z-series within NAFCs. This removal and shift in composition correlated to a 59% and 52% drop in toxicity as per Microtox, for Merichem NAs and NAFCs respectively. This proof of concept experiment confirms that the fungal species T. harzianum can contribute to the biodegradation of complex dissolved organics found in OSPW, including cyclic and diamondoid structures.

Tolerance and cytotoxicity of naphthenic acids on microorganisms isolated from oil sands process-affected water

The expansion of oil sands has made remediation of oil sands process-affected water (OSPW) critical. As naphthenic acids (NAs) are the primary contributors to toxicity, remediation is required. Bioremediation by native microorganisms is potentially effective, however, toxicity of NAs towards native microorganisms is poorly understood. The aim of this study was to isolate microorganisms from OSPW, assess tolerance to stressors, including naturally sourced NAs and examine exposure effect of NAs on cell membranes. Microorganisms were isolated from OSPW, including the first reported isolation of a fungus (Trichoderma harzianum) and yeast (Rhodotorula mucilaginosa). Isolates tolerated alkaline pH, high salinity, and NA concentrations far exceeding those typical of OSPW indicating toxic effects of OSPW are likely the result of interactions between OSPW components. Comparisons of toxicity determined that OSPW exhibited higher cytotoxicity than NAs. The fungal isolate was able to grow using commercial NAs as its sole carbon source, indicating high resistance to NAs' cytotoxic effects. Future studies will focus on the organisms' ability to degrade NAs, and subsequent effects on toxicity. Characterization of OSPW constituents should be investigated with focus on the synergistic toxic effects of dissolved compounds. A better understanding of OSPW toxicity would enable more effective and targeted bioremediation schemes by native microorganisms.

Transcriptome Profiling in Larval Fathead Minnow Exposed to Commercial Naphthenic Acids and Extracts from Fresh and Aged Oil Sands Process-Affected Water.

Surface mining and extraction of oil sands results in the generation of and need for storage of large volumes of oil sands process-affected water (OSPW). More structurally complex than classical naphthenic acids (NAs), naphthenic acid fraction components (NAFCs) are key toxic constituents of OSPW, and changes in the NAFC profile in OSPW over time have been linked to mitigation of OSPW toxicity. Molecular studies targeting individual genes have indicated that NAFC toxicity is likely mediated via oxidative stress, altered cell cycles, ontogenetic differentiation, endocrine disruption, and immunotoxicity. However, the individual-gene approach results in a limited picture of molecular responses. This study shows that NAFCs, from aged or fresh OSPW, have a unique effect on the larval fathead minnow transcriptome and provides initial data to construct adverse outcome pathways for skeletal deformities. All three types of processed NAs (fresh, aged, and commercial) affected the immunome of developing fish. These gene networks included immunity, inflammatory response, B-cell response, platelet adhesion, and T-helper lymphocyte activity. Larvae exposed to both NAFCs and commercial NA developed cardiovascular and bone deformities, and transcriptomic networks reflected these developmental abnormalities. Gene networks found only in NAFC-exposed fish suggest NAFCs may alter fish cardiovascular health through altered calcium ion regulation. This study improves understanding regarding the molecular perturbations underlying developmental deformities following exposure to NAFCs.

Petroleomic analysis of the treatment of naphthenic organics in oil sands process-affected water with buoyant photocatalysts

The persistence of toxicity associated with the soluble naphthenic organic compounds (NOCs) of oil sands process-affected water (OSPW) implies that a treatment solution may be necessary to enable safe return of this water to the environment. Due to recent advances in high-resolution mass spectrometry (HRMS), the majority of the toxicity of OSPW is currently understood to derive from a subset of toxic classes, comprising only a minority of the total NOCs. Herein, oxidative treatment of OSPW with buoyant photocatalysts was evaluated under a petroleomics paradigm: chemical changes across acid-, base- and neutral-extractable organic fractions were tracked throughout the treatment with both positive and negative ion mode electrospray ionization (ESI) Orbitrap MS. Elimination of detected OS+ and NO+ classes of concern in the earliest stages of the treatment, along with preferential degradation of high carbon-numbered O2− acids, suggest that photocatalysis may detoxify OSPW with higher efficiency than previously thought. Application of petroleomic level analysis offers unprecedented insights into the treatment of petroleum impacted water, allowing reaction trends to be followed across multiple fractions and thousands of compounds simultaneously.

Isotherm and kinetic studies on adsorption of oil sands process-affected water organic compounds using granular activated carbon

The production of oil from oil sands in northern Alberta has led to the generation of large volumes of oil sands process-affected water (OSPW) that was reported to be toxic to aquatic and other living organisms. The toxicity of OSPW has been attributed to the complex nature of OSPW matrix including the inorganic and organic compounds primarily naphthenic acids (NAs: CnH2n+ZOx). In the present study, granular activated carbon (GAC) adsorption was investigated for its potential use to treat raw and ozonated OSPW. The results indicated that NA species removal increased with carbon number (n) for a fixed Z number; however, the NA species removal decreased with Z number for a fixed carbon number. The maximum adsorption capacities obtained from Langmuir adsorption isotherm based on acid-extractable fraction (AEF) and NAs were 98.5 mg and 60.9 mg AEF/g GAC and 60 mg and 37 mg NA/g GAC for raw and ozonated OSPW, respectively. It was found that the Freundlich isotherm model best fits the AEF and NA equilibrium data (r2 ≥ 0.88). The adsorption kinetics showed that the pseudo-second order and intraparticle diffusion models were both appropriate in modeling the adsorption kinetics of AEF and NAs to GAC (r2 ≥ 0.97). Although pore diffusion was the rate limiting step, film diffusion was still significant for assessing the rate of diffusion of NAs. This study could be helpful to model, design and optimize the adsorption treatment technologies of OSPW and to assess the performance of other adsorbents.

Effects of Seasonal Changes on the Toxic Impacts of Oil Sands Process-Affected Water on Daphnia magna.

Oil sands process-affected water (OSPW), which can be potentially toxic to aquatic biota, is a major by-product of bitumen mining in northern Alberta. The effects of environmental factors on the toxicity of OSPW are understudied. In the present study, the impacts of seasonal changes in water quality on the toxic effects of OSPW (1 and 10%) on Daphnia magna was examined. Animals were chronically exposed to OSPW under conditions that represented water quality of a cold or warm seasonal condition. At each seasonal scenario survival, growth (length and mass) and reproduction of exposed D. magna were investigated. Survival and length of D. magna were only affected by OSPW in the cold-season treatment. Exposure to OSPW reduced the mass of D. magna in both cold and warm season scenarios. Daphnia magna in the cold-season treatment did not reproduce or produce eggs during the course of the experiment. The results of the present study suggest that seasonal changes in water quality may alter the toxicity of OSPW on D. magna.

Using ultrahigh-resolution mass spectrometry and toxicity identification techniques to characterize the toxicity of oil sands process-affected water: The case for classical naphthenic acids.

Previous assessments of oil sands process-affected water (OSPW) toxicity were hampered by lack of high-resolution analytical analysis, use of nonstandard toxicity methods, and variability between OSPW samples. We integrated ultrahigh-resolution mass spectrometry with a toxicity identification evaluation (TIE) approach to quantitatively identify the primary cause of acute toxicity of OSPW to rainbow trout (Oncorhynchus mykiss). The initial characterization of OSPW toxicity indicated that toxicity was associated with nonpolar organic compounds, and toxicant(s) were further isolated within a range of discrete methanol fractions that were then subjected to Orbitrap mass spectrometry to evaluate the contribution of naphthenic acid fraction compounds to toxicity. The results showed that toxicity was attributable to classical naphthenic acids, with the potency of individual compounds increasing as a function of carbon number. Notably, the mass of classical naphthenic acids present in OSPW was dominated by carbon numbers ≤16; however, toxicity was largely a function of classical naphthenic acids with ≥17 carbons. Additional experiments found that acute toxicity of the organic fraction was similar when tested at conductivities of 400 and 1800 μmhos/cm and that rainbow trout fry were more sensitive to the organic fraction than larval fathead minnows (Pimephales promelas). Collectively, the results will aid in developing treatment goals and targets for removal of OSPW toxicity in water return scenarios both during operations and on mine closure. Environ Toxicol Chem 2017;36:3148-3157. © 2017 SETAC.

Fate and abundance of classical and heteroatomic naphthenic acid species after advanced oxidation processes: Insights and indicators of transformation and degradation

The toxicological effects from all components in oil sands process-affected water (OSPW) are not known. Alternatively, monitoring the variations and abundance of different classes and compounds after treatments might be a useful approach in OSPW remediation. In this study, the variations in the compositions of classical and heteroatomic naphthenic acids (NAs) after treatment using advanced oxidation processes (AOPs), mainly ozone and peroxone, and two different mass spectrometry methods; ultra-performance liquid chromatography time-of-flight (UPLC-TOFMS) and Fourier transform ion cyclotron resonance (FTICR-MS), were examined. Two markers (O2S:O3S:O4S and O2:O4 ratios) were used to reveal changes and similarities of the treated water characteristics with those in natural waters. Both ratios decreased after all treatments, from 2.7:4.8:2.1 and 3.59 in raw OSPW to 0:1.4:0.5 and 0.7, respectively, in peroxone (1:2), becoming close to the reported ratios in natural waters. Toxicity toward Vibrio fischeri showed residual toxic effects after AOPs, suggesting that part of OSPW toxicity may be caused by specific compounds of NAs (i.e., similar reduction (50%) was achieved in both toxicity and abundance in O2 species with carbon 15–26) and/or generated by-products (e.g., O3S classes at double bond equivalent (DBE) = 4 and C9H12O2 at DBE = 4). Although by-products were generated, the best biodegradability enhancement and chemical oxygen demand reduction were achieved in peroxone (1:2) compared to ozone, suggesting the possibility of using combined OSPW remediation approaches (i.e., peroxone coupled with biological process). The recommended indicators can assist in evaluating the treatments' performance and in examining the best removal levels to accomplish significant toxicity reduction.

A risk-based approach for identifying constituents of concern in oil sands process-affected water from the Athabasca Oil Sands region

Mining leases in the Athabasca Oil Sands (AOS) region produce large volumes of oil sands process-affected water (OSPW) containing constituents that limit beneficial uses and discharge into receiving systems. The aim of this research is to identify constituents of concern (COCs) in OSPW sourced from an active settling basin with the goal of providing a sound rational for developing mitigation strategies for using constructed treatment wetlands for COCs contained in OSPW. COCs were identified through several lines of evidence: 1) chemical and physical characterization of OSPW and comparisons with numeric water quality guidelines and toxicity endpoints, 2) measuring toxicity of OSPW using a taxonomic range of sentinel organisms (i.e. fish, aquatic invertebrates, and a macrophyte), 3) conducting process-based manipulations (PBMs) of OSPW to alter toxicity and inform treatment processes, and 4) discerning potential treatment pathways to mitigate ecological risks of OSPW based on identification of COCs, toxicological analyses, and PBM results. COCs identified in OSPW included organics (naphthenic acids [NAs], oil and grease [O/G]), metals/metalloids, and suspended solids. In terms of species sensitivities to undiluted OSPW, fish ≥ aquatic invertebrates > macrophytes. Bench-scale manipulations of the organic fractions of OSPW via PBMs (i.e. H2O2+UV254 and granular activated charcoal treatments) eliminated toxicity to Ceriodaphnia dubia (7–8 d), in terms of mortality and reproduction. Results from this study provide critical information to inform mitigation strategies using passive or semi-passive treatment processes (e.g., constructed treatment wetlands) to mitigate ecological risks of OSPW to aquatic organisms.

Molecular responses of Walleye (Sander vitreus) embryos to naphthenic acid fraction components extracted from fresh oil sands process-affected water

Naphthenic acid fraction components (NAFCs) are constituents of oil sands process-affected water (OSPW), which is generated as a result of unconventional oil production via surface mining in the Athabasca oil sands region. NAFCs are often considered to be major drivers of OSPW toxicity to various taxa, including fishes. However, the molecular targets of these complex mixtures are not fully elucidated. Here we examined the effects in walleye (Sander vitreus) embryos after exposure to NAFCs extracted from fresh OSPW. Eleutheroembryos (exposed to 0, 4.2 or 8.3mg/L NAFCs from 1day post-fertilization to hatch) were subsampled, measured for growth and deformities, and molecular responses were assessed via real-time polymerase chain reaction (PCR). Fourteen genes were evaluated, with a focus on the aryl-hydrocarbon receptor (AhR) − cytochrome P450 pathway (arnt, cyp1a1), the oxidative stress axis (cat, gst, sod, gpx1b), apoptosis (e.g. casp3, bax and p53), growth factor signaling (e.g. insulin-like growth factors igf1, igf1b, and igf1bp), and tissue differentiation (vim). NAFC exposure was associated with an increase in the expression of cyp1a1, and a decrease in gpx1b and ribosomal protein rps40. These results indicate that NAFC effects on walleye early-life stages may be mediated through oxidative stress via pathways that include AhR.

Comparison of Nitrilotriacetic Acid and [S,S]-Ethylenediamine-N,N'-disuccinic Acid in UV-Fenton for the Treatment of Oil Sands Process-Affected Water at Natural pH.

The application of UV-Fenton processes with two chelating agents, nitrilotriacetic acid (NTA) and [S,S]-ethylenediamine-N,N'-disuccinic acid ([S,S]-EDDS), for the treatment of oil sands process-affected water (OSPW) at natural pH was investigated. The half-wave potentials of Fe(III/II)NTA and Fe(III/II)EDDS and the UV photolysis of the complexes in Milli-Q water and OSPW were compared. Under optimum conditions, UV-NTA-Fenton exhibited higher efficiency than UV-EDDS-Fenton in the removal of acid extractable organic fraction (66.8% for the former and 50.0% for the latter) and aromatics (93.5% for the former and 74.2% for the latter). Naphthenic acids (NAs) removals in the UV-NTA-Fenton process (98.4%, 86.0%, and 81.0% for classical NAs, NAs + O (oxidized NAs with one additional oxygen atom), and NAs + 2O (oxidized NAs with two additional oxygen atoms), respectively) under the experimental conditions were much higher than those in the UV-H2O2 (88.9%, 48.7%, and 54.6%, correspondingly) and NTA-Fenton (69.6%, 35.3%, and 44.2%, correspondingly) processes. Both UV-NTA-Fenton and UV-EDDS-Fenton processes presented promoting effect on the acute toxicity of OSPW toward Vibrio fischeri. No significant change of the NTA toxicity occurred during the photolysis of Fe(III)NTA; however, the acute toxicity of EDDS increased as the photolysis of Fe(III)EDDS proceeded. NTA is a much better agent than EDDS for the application of UV-Fenton process in the treatment of OSPW.

Biostimulation of Oil Sands Process-Affected Water with Phosphate Yields Removal of Sulfur-Containing Organics and Detoxification.

The ability to mitigate toxicity of oil sands process-affected water (OSPW) for return into the environment is an important issue for effective tailings management in Alberta, Canada. OSPW toxicity has been linked to classical naphthenic acids (NAs), but the toxic contribution of other acid-extractable organics (AEOs) remains unknown. Here, we examine the potential for in situ bioremediation of OSPW AEOs by indigenous algae. Phosphate biostimulation was performed in OSPW to promote the growth of indigenous photosynthetic microorganisms and subsequent toxicity and chemical changes were determined. After 12 weeks, the AEO fraction of phosphate-biostimulated OSPW was significantly less toxic to the fission yeast Schizosaccharomyces pombe than unstimulated OSPW. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis of the AEO fraction in phosphate-biostimulated OSPW showed decreased levels of SO3 class compounds, including a subset that may represent linear arylsulfonates. A screen with S. pombe transcription factor mutant strains for growth sensitivity to the AEO fraction or sodium dodecylbenzenesulfonate revealed a mode of toxic action consistent with oxidative stress and detrimental effects on cellular membranes. These findings demonstrate a potential algal-based in situ bioremediation strategy for OSPW AEOs and uncover a link between toxicity and AEOs other than classical NAs.