Oil Sands Process-affected Water Samples Research Articles

Photocatalytic treatment of diverse contaminants of potential concern in oil sands process-affected water

Oil sands process-affected water (OSPW), generated by surface mining in Canada's oil sands, require treatment of environmentally persistent dissolved organic compounds before release to the watershed. Conventional chemical and mechanical treatments have not proved suitable for treating the large quantities of stored OSPW, and the biological recalcitrance of some dissolved organics may not be adequately addressed by conventional passive treatment systems. Previous work has evaluated photocatalytic treatment as a passive advanced oxidation process (P-AOP) for OSPW remediation. This work expands upon this prior research to further characterize the effects of water chemistry on the treatment rate and detoxification threshold. Under artificial sunlight, buoyant photocatalysts (BPCs) detoxified all OSPW samples within 1 week of treatment time with simultaneous treatment of polycyclic aromatic hydrocarbons, naphthenic acid fraction components (NAFCs), and un-ionized ammonia. Overall, these results further demonstrate passive photocatalysis as an effective method for treatment of OSPW contaminants of potential concern (COPCs).

Treatment of oil sands process-affected water using a semi pilot-scale coalescing filter: Effect of fundamental conditions and water characteristics on filtration performance

The reuse of oil sands process-affected water (OSPW) generated during oil extraction is becoming essential due to oil extraction efficiency and stringent environmental regulations. This study investigates the efficacy of a coalescing filter (CF) in removing oil components from OSPW by exploiting coalescence, which involves merging small oil droplets into larger ones using fibers. Real-time, precise oil measurement systems were employed to evaluate the oil removal efficiency of the CF across synthetic OSPW samples with varying properties. Fundamental conditions and water quality components were systematically adjusted to elucidate the influencing factors on oil removal by the CF. Results showed that despite the diesel having significantly lower viscosity than the oil contents in OSPW, CF achieved a removal efficiency of over 60% within the first 10 min of operation time, regardless of oil concentration. Total suspended solids/turbidity exhibited a decreasing trend as it passed through the filter, indicating fouling occurring within the filter. On the other hands, its increase improved CF performance by 6% compared to baseline conditions, while an increase of alkalinity decreased performance by 10%. When each water quality component exists independently, they do not significantly impact the oil removal efficiency. However, when present together, there is a more decrease in removal efficiency due to the reduced interaction between oil and filter. CF was resistant to changes in water quality. Rather, changes in fundamental factors are more sensitive to CF performance. Filter characteristics and mechanisms make residence time the primary factor affecting oil removal by the CF, with variations exceeding 30% depending on conditions. Therefore, optimizing filter number and flow rate is essential to maximize the filtration performance.

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.

Examining the immunotoxicity of oil sands process affected waters using a human macrophage cell line

Oil sands process affected water (OSPW) is produced during the surface mining of the oil sands bitumen deposits in Northern Alberta. OSPW contains variable quantities of organic and inorganic components causing toxic effects on living organisms. Advanced Oxidation Processes (AOPs) are widely used to degrade toxic organic components from OSPW including naphthenic acids (NAs). However, there is no established biological procedure to assess the effectiveness of the remediation processes. Our previous study showed that human macrophage cells (THP-1) can be used as a bioindicator system to evaluate the effectiveness of OSPW treatments through examining the proinflammatory gene transcription levels. In the present study, we investigated the immunotoxicological changes in THP-1 cells following exposure to untreated and AOP-treated OSPW. Specifically, using proinflammatory cytokine protein secretion assays we showed that AOP treatment significantly abrogates the ability of OSPW to induce the secretion of IL-1β, IL-6, IL-8, TNF-α, IL-1Ra and MCP-1. By measuring transcriptional activity as well as surface protein expression levels, we also showed that two select immune cell surface markers, CD40 and CD54, were significantly elevated following OSPW exposure. However, AOP treatments abolished the immunostimulatory properties of OSPW to enhance the surface expression of these immune proteins. Finally, a transcriptome-based approach was used to examine the proinflammatory effects of OSPW as well as the abrogation of immunotoxicity following AOP treatments. Overall, this research shows how a human macrophage cell-based biomonitoring system serves as an effective in vitro tool to study the immunotoxicity of OSPW samples before and after targeted remediation strategies.

Profiling low molecular weight organic compounds from naphthenic acids, acid extractable organic mixtures, and oil sands process-affected water by SPME-GC-EIMS

Naphthenic acids (NAs) are complex mixtures of carboxylic acids from petroleum that have industrial applications and that may be released to the environment after oil spills. There is significant research on the chemical composition and toxicity of water-soluble NAs derived from oil sands mining in Alberta, Canada. Yet, little is known about low molecular weight organic compounds (LMWOC) from these sources. Headspace solid-phase microextraction coupled to gas chromatography-electron impact mass spectrometry was used for LMWOC profiling of commercial NA blends, and an acid-extractable organics (AEOs) mixture from a tailings pond. From Sigma 1, Sigma 2, Merichem NAs and the AEO extract, 54, 56, 40 and 4 compounds were identified, respectively. These include aliphatic and cyclic hydrocarbons, carboxylic acids, alkylbenzenes, phenols, naphthalene and alkyl-naphthalene, and decalin compounds. A sample of oil sands process-affected water (OSPW) and aqueous solutions of the NA blends were evaluated for matrix effects on LMWOC profiles. Principal component and clustering analyses revealed that LMWOC profiles of commercial extracts were closely related but distinct from the AEO and OSPW samples. Some of the identified LMWOC are reported to be genotoxic or carcinogenic, and therefore the NA mixtures and AEOs should be considered hazardous materials and further evaluated.

Diagnostic Ratio Analysis: A New Concept for the Tracking of Oil Sands Process-Affected Water Naphthenic Acids and Other Water-Soluble Organics in Surface Waters.

A diagnostic ratio forensics tool, similar to that recognized internationally for oil spill source identification, is proposed for use in conjunction with existing LC/QToF quantitative methodology for bitumen-derived water-soluble organics (WSOs). The concept recognizes that bitumen WSOs bear a chemical skeletal relationship to stearane and hopane oil biomarkers. The method uses response ratios for 50 selected WSOs compared between samples by their relative percent difference and adopted acceptance criteria. Oil sands process-affected water (OSPW) samples from different locations within a single tailings pond were shown to match, while those from different industrial sites did not. Acid extractable organic samples collected over 3 weeks from the same location within a single tailings pond matched with each other; as did temporal OSPW samples a year apart. Blind quality assurance samples of OSPW diluted in surface waters were positively identified to their corresponding OSPW source. No interferences were observed from surface waters, and there was no match between bitumen-influenced groundwater and OSPW samples, as expected for different sources. Proof of concept for OSPW source identification using diagnostic ratios was demonstrated, with anticipated application in the tracking of OSPW plumes in surface receiving waters, together with the potential for confirmation of source.

Advances in Distinguishing Groundwater Influenced by Oil Sands Process-Affected Water (OSPW) from Natural Bitumen-Influenced Groundwaters.

The objective of this study was to advance analytical methods for detecting oil sands process-affected water (OSPW) seepage from mining containments and discriminating any such seepage from the natural bitumen background in groundwaters influenced by the Alberta McMurray formation. Improved sampling methods and quantitative analyses of two groups of monoaromatic acids were employed to analyze OSPW and bitumen-affected natural background groundwaters for source discrimination. Both groups of monoaromatic acids showed significant enrichment in OSPW, while ratios of O2/O4 containing heteroatomic ion classes of acid extractable organics (AEOs) did not exhibit diagnostic differences. Evaluating the monoaromatic acids to track a known plume of OSPW-affected groundwater confirmed their diagnostic abilities. A secondary objective was to assess anthropogenically derived artificial sweeteners and per- and polyfluoroalkyl substances (PFAS) as potential tracers for OSPW. Despite the discovery of acesulfame and PFAS in most OSPW samples, trace levels in groundwaters influenced by general anthropogenic activities preclude them as individual robust tracers. However, their inclusion with the other metrics employed in this study served to augment the tiered, weight of evidence methodology developed. This methodology was then used to confirm earlier findings of OSPW migrations into groundwater reaching the Athabasca River system adjacent to the reclaimed pond at Tar Island Dyke.

Assessment of raw and ozonated oil sands process-affected water exposure in developing zebrafish: Associating morphological changes with gene expression

With the ever-increasing amounts of oil sands process-affected water (OSPW) accumulating from Canada's oil sands operations, its eventual release must be considered. As OSPW has been found to be both acutely and chronically toxic to aquatic organisms, remediation processes must be developed to lower its toxicity. Ozone treatment is currently being studied as a tool to facilitate the removal of organic constituents associated with toxicity. Biomarkers (e.g. gene expression) are commonly used when studying the effects of environmental contaminants, however, they are not always indicative of adverse effects at the whole organism level. In this study, we assessed the effects of OSPW exposure on developing zebrafish by linking gene expression to relevant cellular and whole organism level endpoints. We also investigated whether or not ozone treatment decreased biomarkers and any associated toxicity observed from OSPW exposure. The concentrations of classical naphthenic acids in the raw and ozonated OSPW used in this study were 16.9 mg/L and 0.6 mg/L, respectively. Ozone treatment reduced the total amount of naphthenic acids (NAs) in the OSPW sample by 92%. We found that exposure to both raw and ozonated OSPW had no effect on the survival of zebrafish embryos. The expression levels of biotransformation genes CYP1A and CYP1B were induced by raw OSPW exposure, with CYP1B being more highly expressed than CYP1A. In contrast, ozonated OSPW exposure did not increase the expression of CYP1A and only slightly induced CYP1B. A decrease in cardiac development and function genes (NKX2.5 and APT2a2a) was not associates with large changes in heart rate, arrhythmia or heart size. We did not find any indications of craniofacial abnormalities or of increased occurrence of apoptotic cells. Overall, our study found that OSPW was not overtly toxic to zebrafish embryos.

Profiling of dissolved organic compounds in the oil sands region using complimentary liquid–liquid extraction and ultrahigh resolution Fourier transform mass spectrometry

Understanding and characterizing organics in aquatic environments is a great challenge for environmental monitoring, especially for the oil sands industry due to the complexity and potential toxicity of dissolved organics in water. To date, significant efforts have been made in investigating the toxicity of naphthenic acids, although other compounds may also contribute to the toxicity of oil sands process-affected water (OSPW). Here, we present a case study showing a systematic approach for profiling the organic composition of OSPW and environmental water samples by concentrating and separating dissolved organics through complementary liquid–liquid extractions followed by positive- or negative-ion mode ultrahigh resolution mass detection. Our comparative investigation shows clear differences in the composition of dissolved organics (homologues particularly) not only between OSPW samples and environmental water samples, but also differences among oil sands operators. Sulfur-containing compounds (especially the SO n classes) appear to have great potential to be used for evaluating the impact of OSPW, while our understanding of oxygen-only containing compounds should not be limited to O2 (i.e., classic naphthenic acids), but rather can be broadened to include many other compound classes (for instance O n , n = 1–9). Systematic profiling of water samples should be more widely implemented for monitoring the origin and transport of organics in aquatic ecosystems of the oil sands development region, northeastern Alberta, Canada.

Characterization of dicarboxylic naphthenic acid fraction compounds utilizing amide derivatization: Proof of concept.

The characterization of naphthenic acid fraction compounds (NAFCs) in oil sands process affected water (OSPW) is of interest for both toxicology studies and regulatory reasons. Previous studies utilizing authentic standards have identified dicarboxylic naphthenic acids using two-dimensional gas chromatography hyphenated to time-of-flight mass spectrometry (GC×GC/TOFMS). The selective derivatization of hydroxyl groups has also recently aided in the characterization of oxy-NAFCs, and indirectly the characterization of dicarboxylic NAFCs. However, there has been no previous report of derivatization being used to directly aid in the standard-free characterization of NAFCs with multiple carboxylic acid functional groups. Herein we present proof-of-concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization. Carboxylic acid groups in OSPW extract and in a dicarboxylic acidstandard were derivatized to amides using a previously described method. The derivatized extract and derivatized standard were analyzed by direct-injection positive-mode electrospray ionization ((+)ESI) high-resolution mass spectrometry (HRMS), and the underivatized extract was analyzed by (-)ESI MS. Tandem mass spectrometry (MS/MS) was carried out on selected ions of the derivatized standard and derivatized OSPW. Data analysis was carried out using the Python programming language. The distribution of monocarboxylic NAFCs observed in the amide-derivatized OSPW sample by (+)ESI-MS was generally similar to that seen in underivatized OSPW by (-)ESI-MS. The dicarboxylic acid standard shows evidence of being doubly derivatized, although the second derivatization appears to be inefficient. Furthermore, a spectrum of potential diacid NAFCs is presented, identified by both charge state and derivatization mass. Interference due to the presence of multiple derivatization products is noted, but can be eliminated using on-line separation or an isotopically labelled derivatization reagent. Proof of concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization is demonstrated. Furthermore, (+)ESI-HRMS of the derivatized monocarboxylic NAFCS yields similar information to (-)ESI-MS analysis of underivatized NAFCs, with the benefit of added selectivity for carboxylic acid species and the characterization of diacids.

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.

Investigating the chronic effects of oil sands process-affected water on growth and fitness of Daphnia magna Straus 1820

The increasing amount of stored oil sands process-affected water (OSPW), a primary by-product of oil sands mining, is an environmental concern. In the present study, we investigated the chronic effects of OSPW on growth, reproduction, and macronutrient content in Daphnia magna. To do so, we exposed D. magna to 1 and 10% OSPW (a mixture of three OSPW samples provided by major oil sands mining operators in northern Alberta) for ten days. We measured the number of the neonates produced daily in each group throughout the exposure. At the end of the exposure, we measured the mass and length of the exposed daphniids and neonates. We also measured the carbohydrate, lipid, and protein content of exposed daphniids. In the 10% OSPW group, we observed a significant reduction in all of the measured endpoints except for body length and carbohydrate and protein content of exposed daphniids. In the 1% OSPW group, on the other hand, we found a reduction only in lipid content of exposed daphniids as compared to the control group. The results of the present study demonstrated that chronic exposure to 10% OSPW affects growth and fitness of D. magna, probably due to a reduction in energy intake that causes daphniids to deplete their energy reserves.

Comparison of biomass from integrated fixed-film activated sludge (IFAS), moving bed biofilm reactor (MBBR) and membrane bioreactor (MBR) treating recalcitrant organics: Importance of attached biomass

This study compared microbial characteristics and oil sands process-affected water (OSPW) treatment performance of five types of microbial biomass (MBBR-biofilm, IFAS-biofilm, IFAS-floc, MBR-aerobic-floc, and MBR-anoxic-floc) cultivated from three types of bioreactors (MBBR, IFAS, and MBR) in batch experiments. Chemical oxygen demand (COD), ammonium, acid extractable fraction (AEF), and naphthenic acids (NAs) removals efficiencies were distinctly different between suspended and attached bacterial aggregates and between aerobic and anoxic suspended flocs. MBR-aerobic-floc and MBR-anoxic-floc demonstrated COD removal efficiencies higher than microbial aggregates obtained from MBBR and IFAS, MBBR and IFAS biofilm had higher AEF removal efficiencies than those obtained using flocs. MBBR-biofilm demonstrated the most efficient NAs removal from OSPW. NAs degradation efficiency was highly dependent on the carbon number and NA cyclization number according to UPLC/HRMS analysis. Mono- and di-oxidized NAs were the dominant oxy-NA species in OSPW samples. Microbial analysis with quantitative polymerase chain reaction (q-PCR) indicated that the bacterial 16S rRNA gene abundance was significantly higher in the batch bioreactors with suspended flocs than in those with biofilm, the NSR gene abundance in the MBR-anoxic bioreactor was significantly lower than that in aerobic batch bioreactors, and denitrifiers were more abundant in the suspended phase of the activated sludge flocs.

Molecular profiling of naphthenic acids in technical mixtures and oil sands process-affected water using polar reversed-phase liquid chromatography-mass spectrometry.

In this work, a reversed-phase ultra-HPLC (UHPLC) ultrahigh resolution MS (UHRMS) method was evaluated for the comprehensive profiling of NAs containing two O atoms in each molecule (O2NAs; general formula Cn H2n + z O2 , where n is the number of carbon atoms and z represents hydrogen deficiency). Using a polar cyanopropyl-bonded phase column and negative-ion electrospray ionization mass spectrometric detection at 120,000 FWHM (m/z 400), 187 and 226 O2NA species were found in two naphthenic acid technical mixtures, and 424 and 198 species with molecular formulas corresponding to O2NAs were found in two oil sands process-affected water samples (one from a surface mining operation and the other from a steam-assisted gravity drainage operation), respectively. To our knowledge, these are the highest numbers of molecular compositions of O2NAs that have been profiled thus far in environmental samples. Assignments were based on accurate mass measurements (≤3 ppm) combined with rational molecular formula generation, correlation of chromatographic behavior of O2NA homologues with their elemental compositions, and confirmation with carboxyl group-specific chemical derivatization using 3-nitrophenylhydrazine. Application of this UHPLC-UHRMS method to the quantitation of O2NAs in the surface mining operation-derived water sample showed excellent linearity (R2 = 0.9999) with external calibration, a linear range of 256-fold in concentration, and quantitation accuracies of 64.9 and 69.4% at two "standard substance" spiking levels.

Effect of Lipid Partitioning on Predictions of Acute Toxicity of Oil Sands Process Affected Water to Embryos of Fathead Minnow (Pimephales promelas).

Dissolved organic compounds in oil sands process affected water (OSPW) are known to be responsible for most of its toxicity to aquatic organisms, but the complexity of this mixture prevents use of traditional bottom-up approaches for predicting toxicities of mixtures. Therefore, a top-down approach to predict toxicity of the dissolved organic fraction of OSPW was developed and tested. Accurate masses (i.e., m/z) determined by ultrahigh resolution mass spectrometry in negative and positive ionization modes were used to assign empirical chemical formulas to each chemical species in the mixture. For each chemical species, a predictive measure of lipid accumulation was estimated by stir-bar sorptive extraction (SBSE) to poly(dimethyl)siloxane, or by partitioning to solid-supported lipid membranes (SSLM). A narcosis mode of action was assumed and the target-lipid model was used to estimate potencies of mixtures by assuming strict additivity. A model developed using a combination of the SBSE and SSLM lipid partitioning estimates, whereby the accumulation of chemicals to neutral and polar lipids was explicitly considered, was best for predicting empirical values of LC50 in 96-h acute toxicity tests with embryos of fathead minnow (Pimephales promelas). Model predictions were within 4-fold of observed toxicity for 75% of OSPW samples, and within 8.5-fold for all samples tested, which is comparable to the range of interlaboratory variability for in vivo toxicity testing.

Assessing Risks of Shallow Riparian Groundwater Quality Near an Oil Sands Tailings Pond

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.

Determining the effect of oil sands process-affected water on grazing behaviour of Daphnia magna, long-term consequences, and mechanism

Oil sands process-affected water (OSPW) is a byproduct of the extraction of bitumen in the surface-mining oil sands industry and is currently stored in on-site tailings ponds. OSPW from three oil sands companies were studied to capture some of the variability associated with OSPW characteristics. To investigate the effect and mechanism(s) of effect of OSPW on feeding behaviour, Daphnia magna were exposed to low OSPW concentrations for 24 h and monitored for their feeding rate, olfactory response and swimming activity. The Al and Si content, which are indicators of suspended particulate matter in D. magna exposed to OSPW were investigated using energy-dispersive X-ray (EDX) spectroscopy. In long-term experiments, effects of exposure to OSPW for 21 days on feeding behaviour, growth, and reproduction of D. magna were evaluated. Feeding rates were similar among the three exposure populations, yielding a 24 h IC50 of 5.3% OSPW. Results of behavioural assays suggest that OSPW impairs the chemosensory function and reduces the total activity of D. magna. In EDX spectroscopy, Al and Si were detected in the body of the exposed D. magna, suggesting that D. magna filter clay particles from the OSPW solution. Results of the long-term exposure showed that OSPW significantly inhibits feeding behaviour, suppresses growth, and reduces reproductive output of D. magna. There were no differences in the toxicity of the three samples of OSPW, which was in agreement with the fact that there were no differences in the species of dissolved organic compounds in the OSPW samples.

An omic approach for the identification of oil sands process-affected water compounds using multivariate statistical analysis of ultrahigh resolution mass spectrometry datasets

Oil sands process-affected water (OSPW) is a major environmental issue due to its acute and chronic toxicity to aquatic life. Advanced oxidation processes are promising treatments to successfully degrade toxic OSPW compounds. This study applied high resolution mass spectrometry to detect over 1000 compounds in OSPW samples after treatments including general ozonation, and ozone with carbonate, tert-butyl-alcohol, carbonate/tert-butyl-alcohol, tetranitromethane, or iron. Hierarchal clustering analysis showed that samples clustered based on sampling time and principal component analysis corroborated these results while also providing information on significant markers responsible for the clustering. Some markers were uniquely present in certain treatment conditions, while others showed variable behaviors in two or more treatments due to the presence of scavengers/catalysts. This advanced approach to monitoring significant changes of markers by using multivariate analysis can be invaluable for future work on OSPW treatment by-products and their potential toxicity to receiving environment organisms.

Rapid characterization of naphthenic acids using differential mobility spectrometry and mass spectrometry.

To analyze the naphthenic acid content of environmental waters quickly and efficiently, we have developed a method that employs differential mobility spectrometry (DMS) coupled to mass spectrometry (MS). This technique combines the benefits of infusion-based MS experiments (parallel, on-demand access to individual components) with DMS's ability to provide liquid chromatography-like separations of isobaric and isomeric compounds in a fraction of the time. In this study, we have applied a DMS-MS workflow to the rapid gas-phase separation of naphthenic acids (NAs) within a technical standard and a real-world oil sands process-affected water (OSPW) extract. Among the findings provided by this workflow are the rapid characterization of isomeric NAs (i.e., same molecular formulas) in a complex OSPW sample, the ability to use DMS to isolate individual NA components (including isomeric NAs) for in-depth structural analyses, and a method by which NA analytes, background ions, and dimer species can be characterized by their distinct behaviors in DMS. Overall, the profiles of the NA content of the technical and OSPW samples were consistent with published values for similar samples, such that the benefits of DMS technology do not detract from the workflow's accuracy or quality.