Low adsorption affinity of athabasca oil sands naphthenic acid fraction compounds to a peat-mineral mixture.

Much of the toxicity in oil sands process-affected water in Athabasca oil sands tailings has been attributed to naphthenic acids (NAs) and associated naphthenic acid fraction compounds (NAFCs). Previous work has characterized the environmental behaviour and fate of these compounds, particularly in the context of constructed treatment wetlands. There is evidence that wetlands can attenuate NAFCs in natural and engineered contexts, but relative contributions of chemical, biotic, and physical adsorption with sequestration require deconvolution. In this work, the objective was to evaluate the extent to which prospective wetland substrate material may adsorb NAFCs using a peat-mineral mix (PMM) sourced from the Athabasca Oil Sands Region (AOSR). The PMM and NAFCs were first mixed and then equilibrated across a range of NAFC concentrations (5-500 mg/L) with moderate ionic strength and hardness (∼200 ppm combined Ca2+ and Mg2+) that approximate wetland water chemistry. Under these experimental conditions, low sorption of NAFCs to PMM was observed, where sorbed concentrations of NAFCs were approximately zero mg/kg at equilibrium. When NAFCs and PMM were mixed and equilibrated together at environmentally relevant concentrations, formula diversity increased more than could be explained by combining constituent spectra. The TOC present in this PMM was largely cellulose-derived, with low levels of thermally recalcitrant carbon (e.g., lignin, black carbon). The apparent enhancement of the concentration and diversity of components in PMM/NAFCs mixtures are likely related to aqueous solubility of some PMM-derived organic materials, as post-hoc combination of dissolved components from PMM and NAFCs cannot replicate enhanced complexity observed when the two components are agitated and equilibrated together.

Evaluations of Weathering of Polar and Nonpolar Petroleum Components in a Simulated Freshwater-Oil Spill by Orbitrap and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

The comprehensive chemical characterization of crude oil is important for the evaluation of the transformation and fate of components in the environment. Molecular-level speciation of naphthenic acid fraction compounds (NAFCs) was investigated in a mesoscale spill tank using both negative-ion electrospray ionization (ESI) Orbitrap mass spectrometry (MS) and positive-ion atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI-FT-ICR-MS). Both ionization techniques are coupled to high-resolution mass spectrometric detectors (ESI: Orbitrap MS; APPI: FT-ICR-MS at 9.4 T), enabling insight into the behavior and fate of petrogenic compounds during a simulated freshwater crude oil spill. Negative-ion ESI Orbitrap-MS reveals that oxygen-containing (Ox) classes are detected early in the spill, whereby species with more oxygen per molecule evolve later in the simulated spill. The O2-containing species gradually decreased in relative abundance, while O3 and O4 species increased in relative abundance throughout the simulated spill, which could correspond to a relative degree of oxygen incorporation. Nonpolar speciation by positive-ion APPI 9.4 T FT-ICR-MS allowed for the identification of water-soluble nonpolar and less polar acidic species. Molecular-level graphical representation of elemental compositions derived from simulated spill water-soluble and oil-soluble species suggest that biological activity is the primary degradation mechanism and that biodegradation was the dominant mechanism based on the negative-ion ESI Orbitrap-MS results.

Site-specific spatiotemporal occurrence and molecular congener distributions of naphthenic acids in Athabasca oil sands wetlands of Alberta, Canada.

The Athabasca oil sands region (AOSR) of Alberta, Canada is notable for its considerable unconventional petroleum extraction projects, where bitumen is extracted from naturally-occurring oil sands ore. The large scale of these heavy crude oil developments raises concerns because of their potential to distribute and/or otherwise influence the occurrence, behaviour, and fate of environmental contaminants. Naphthenic acids (NAs) are one such contaminant class of concern in the AOSR, so studies have examined the occurrence and molecular profiles of NAs in the region. We catalogued the spatiotemporal occurrence and characteristics of NAs in boreal wetlands in the AOSR over a 7-year period, using derivatized liquid chromatography-tandem mass spectrometry (LC-MS/MS). Comparing median concentrations of NAs across these wetlands revealed a pattern of NAs suggesting NAs in surface waters derived from oil sands deposits. Opportunistic wetlands that formed adjacent to reclaimed overburden and other reclamation activities had the highest concentrations of NAs and consistent patterns suggestive of bitumen-derived inputs. However, similar patterns in the occurrence of NAs were also observed in undeveloped natural wetlands located above the known surface-mineable oil sands deposit that underlies the region. Intra-annual sampling results along with inter-annual comparisons across wetlands demonstrated that differences in the spatial and temporal NA concentrations were dependent on local factors, particularly when naturally occurring oil sands ores were observed in the wetland or drainage catchment.

Fathead Minnows Exposed to Organic Compounds from Oil Sands Tailings as Embryos Have Reduced Survival, Impaired Development, and Altered Behaviors That Persist into Larval Stages.

Our study evaluated whether exposure to naphthenic acid fraction compounds (NAFCs) extracted from oil sands process-affected waters (OSPW) has adverse effects on fish embryos that persist into later life. We exposed fathead minnow (Pimephales promelas) embryos to concentrations of NAFCs found in OSPW (2.5-54 mg/L) for 7 days (1 day postfertilization to hatch), then raised surviving larvae in outdoor mesocosms of uncontaminated lake water for 1 month. Embryos exposed to NAFCs were more likely to exhibit malformations (by up to 8-fold) and had slower heart rates (by up to 24%) compared to controls. Fish raised in uncontaminated lake water following exposure to NAFCs as embryos, were 2.5-fold less likely to survive during the larval stage than control fish. These fish also showed up to a 45% decrease in swim activity and a 36% increase in swim burst events during behavioral tests relative to controls. We conclude that exposure to NAFCs during the embryonic stage can have lasting effects on fish survival, physiology, and behavior that persist at least through the larval stage. These findings of delayed mortalities and persistent sublethal effects of embryonic NAFC exposure are relevant to informing the development of regulations on treated OSPW releases from mining operations. Environ Toxicol Chem 2022;41:1319-1332. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Transformation of bitumen-derived naphthenic acid fraction compounds across surface waters of wetlands in the Athabasca Oil Sands region.

Bitumen is extracted from oil sands in the Athabasca Oil Sands region (AOSR) of Alberta, Canada. Much of the bitumen-derived toxicity in mine waste is attributable to naphthenic acid fraction compounds (NAFCs). Mines in the AOSR are required to be returned to a natural state after closure; thus, cost-effective strategies are needed to reduce toxicity from NAFCs. Previous studies have demonstrated the capability of constructed wetlands to attenuate NAFCs. However, the capacity of wetlands in the natural environment to degrade and transform NAFCs to less toxic components is poorly understood. To better understand the spatial distribution and fate of NAFCs in natural wetlands, samples were collected across the surfaces of two mature opportunistic wetlands near active oil sands mines. The first wetland has a well-defined surface flow pathway and inflows affected by overburden containing lean bitumen ore. The second wetland, in contrast, is a stagnant water body with raw bitumen visible along its edges. For the wetland with a well defined flow path, NAFCs decreased in concentration down gradient, while oxidized NAFCs constituted a greater proportion of NAFCs with increase in flow path. Likewise there was a decrease in the molecular weights of NAFCs, similar to trends observed in constructed wetland treatment systems. In comparison, NAFCs were more uniformly distributed across the relatively stagnant wetland. Overall, these data provide new evidence that mature opportunistic wetlands in the AOSR can promote the degradation and oxidation of bitumen-derived naphthenic acids into less toxic compounds.

High resolution Orbitrap mass spectrometry analysis of oxidized hydrocarbons found in freshwater following a simulated spill of crude oil.

Negative ion electrospray Orbitrap mass spectrometry was used to analyze water samples taken from a pilot-scale spill tank test of conventional crude oil on freshwater. A 56-day spill test was performed, and water samples were taken at regular intervals throughout the test to determine what changes in water chemistry occur with time. Orbitrap mass spectrometry was used to measure oxidized species in water samples, and oxidized species are analyzed by carbon number, double bond equivalent and hydrocarbon class. Emphasis is placed on changes with time over the course of the spill test, to examine changes by weathering processes that could occur naturally in a field spill scenario. Results demonstrate that while the concentrations of polycyclic aromatic hydrocarbons decrease in the water phase over time, the concentrations of total organic carbon and oxidized species in the water increase with time, where quantities of O2 and O3 species have the highest abundance. Measurement of increasing concentrations and changing relative abundances of these oxidized compounds can be used to assess how oil behaves in a freshwater aquatic environment after a spill.

Characterization of naphthenic acid fraction compounds in water from Athabasca oil sands wetlands by Orbitrap high-resolution mass spectrometry.

Classical naphthenic acids (NAs) are known to be primary aquatic toxicants of concern in the Athabasca oil sands region (AOSR), and are a component of naphthenic acid fraction compounds (NAFCs). Recent studies conducted in the AOSR have examined metals and polycyclic aromatic hydrocarbons in regional wetlands. However, few studies have described NAs and/or NAFCs in AOSR wetlands. To address this gap, we examined NAFC profiles in the water of different wetlands in the AOSR, including naturalized borrow pits (i.e., abandoned pits created by excavation of road-building materials), and opportunistically-formed wetlands associated with reclamation activities. For comparison, NAFC profiles from these wetlands were compared to an opportunistic wetland formed from tailings pond dyke seepage. Samples were prepared using solid-phase extraction and analyzed using negative-ion high-resolution Orbitrap mass spectrometry. Principal component analyses (PCA) revealed patterns to the NAFC profiles in the wetlands. The first distinct grouping of wetlands included water bodies associated with reclamation activities that are located on and/or adjacent to mining overburden. One other wetland, HATS5w, separated from all other wetlands during PCA, and had a unique NAFC profile; detailed examination of NAFCs revealed HATS5w contained the heaviest (i.e., high m/z components) and most unsaturated NAFCs among study locations, demonstrating the usefulness of high-resolution mass spectrometry for characterizing individual wetlands. The NAFCs of HATS5w are also substantially different from bitumen-derived inputs in overburden-adjacent opportunistic wetlands. Collectively, the NAFC profiles presented provide new information on background levels of polar bitumen-derived organics in AOSR wetlands.

Treatment of oil sands process affected waters by constructed wetlands: Evaluation of designs and plant types.

Constructed wetland treatment systems (CWTS)s can be used to treat various wastewaters. The main constituent in oil sands process-affected water (OSPW) with uncertain treatment by CWTS are naphthenic acid fraction compounds (NAFC)s. The NAFCs are also among the primary contributors of toxicity to aquatic organisms. While there is preliminary evidence that some CWTSs are capable of treating OSPW for future potential discharge, there is little information comparing the effectiveness and efficiencies of different CWTS designs. Obtaining large volumes of OSPW for testing can be difficult, and while it is known that synthetic NAFCs are simpler and have different toxicity than OSPW-NAFCs, it is unknown whether they could serve as a proxy for optimization of CWTS design and operation. This study presents a comprehensive comparison of CWTS performance operated with both synthetic OSPW and OSPW for four CWTS designs differing in plant type, aeration, flow path, water depth, and substrate type. This study evaluated the potential biodegradation of NAFCs including: (1) decrease in total NAFC concentration, (2) shifts in Ox-NAFC fractions from O2- to O3-, O4-, and O5-NAFC, (3) decrease in carbon number, (4) decrease of the double bond equivalencies (DBE), and (5) change in toxicity of the waters to test organisms. CWTS planted with Sedge achieved the greatest extent of NAFC treatment and detoxification regardless of design. Although CWTSs planted with Cattail and Bulrush also degraded NAFCs and decreased toxicity, a greater hydraulic retention time was required, and the total extent of treatment was less than the CWTSs planted with Sedge. While synthetic OSPW was more toxic and experienced faster degradation rates, it showed similar trends to OSPW in terms of CWTS design efficiencies and function. Although synthetic OSPW would not be appropriate for modelling or scaling of CWTSs, it can be useful for testing designs and operating conditions.

Molecular profiles of naphthenic acid fraction compounds from mine lease wetlands in the Athabasca Oil Sands Region.

Naphthenic acid fraction compounds (NAFCs) are a toxicologically relevant component of oil sands process-affected materials (OSPM). For the first time, we report on differences in the concentrations and distribution of NAFCs from wetlands on an Athabasca oil sands mine site with varied histories of solid and liquid OSPM input. Sampling locations included natural and naturalized reference wetlands, a reclaimed tailings pond, wetlands supplemented with OSPM, opportunistic wetlands, and tailings ponds. Samples were prepared using solid-phase extraction, and analyzed by high-resolution Orbitrap mass spectrometry; NAFC concentrations and characteristics were evaluated for all locations. The NAFCs from tailings ponds were dominated by O3-NAFCs and classical naphthenic acids (NAs; i.e., O2 species) with double bond equivalences of 3 and 4. Reference wetlands had no dominant species, and relatively little NAFC content. The heteroatomic species in opportunistic wetlands were dominated by highly-oxidized NAFC species, where Σ [O3:O6] species constituted 55-75% of the assignable spectrum and 3-4% NAs; in tailings ponds NAs constituted 47-51%. A relatively young (4-year-old) wetland built on a former tailings pond had NAFC concentrations between 65 and 80 mg/L, and NAs constituted 47% of the assignable spectrum. There was thus little apparent oxidation of NAFCs at this young wetland. The composition of NAFCs from one wetland (≥15 years old) supplemented with OSPM contained a greater proportion of oxidized species than tailings, suggesting NAFC transformation therein. These data suggest that while NAFCs are persistent in some wetlands, there is preliminary evidence for oxidation in mature wetlands.

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.

Distinguishing Natural from Anthropogenic Sources of Acid Extractable Organics in Groundwater near Oil Sands Tailings Ponds.

Distinguishing between naphthenic acids (NAs) associated with oil sands process-affected water (OSPW) and those found naturally in groundwaters in contact with the bituminous McMurray Formation poses a considerable analytical challenge to environmental research in Canada's oil sands region. Previous work addressing this problem combined high-resolution Orbitrap mass spectrometry with carbon isotope values generated by online pyrolysis (δ13Cpyr) to characterize and quantify the acid extractable organics (AEOs) fraction containing NAs in the subsurface near an oil sands tailings pond. Here, we build upon this work through further development and application of these techniques at two different study sites near two different tailings ponds, in conjunction with the use of an additional isotopic tool-sulfur isotope analysis (δ34S) of AEOs. The combined use of both δ13Cpyr and δ34S allowed for discrimination of AEOs into the three end-members relevant to ascertaining the NA environmental footprint within the region: (1) OSPW; (2) McMurray Formation groundwater (i.e., naturally occurring bitumen), and; (3) naturally occurring non-bitumen. A Bayesian isotopic mixing model was used to determine the relative proportions of these three sources in groundwater at both study sites. Although background levels of OSPW-derived AEOs were generally low, one sample containing 49-99% (95% credibility interval) OSPW-derived AEOs was detected within an inferred preferential flow-path, highlighting the potential for this technique to track tailings pond seepage.

Naphthenic Acid Mixtures and Acid-Extractable Organics from Oil Sands Process-Affected Water Impair Embryonic Development of Silurana (Xenopus) tropicalis.

Naphthenic acids (NAs) are carboxylic acids naturally occurring in crude oils and bitumen and are suspected to be the primary toxic substances in wastewaters associated with oil refineries and mining of oil sands. Oil sands process-affected water (OSPW) generated by the extraction of bitumen from oil sands are a major source of NAs and are currently stored in tailings ponds. We report on the acute lethality and teratogenic effects of aquatic exposure of Silurana (Xenopus) tropicalis embryos to commercial NA extracts and from the acid extractable organics (AEOs) fraction of a Canadian OSPW. Using electrospray ionization-high resolution mass spectrometry, we determined that the O2 species proportion were 98.8, 98.9 and 58.6% for commercial mixtures Sigma 1 (S1M) and Sigma 2 (S2M), and AEOs, respectively. The 96h LC50 estimates were 10.4, 11.7, and 52.3 mg/L for S1M, S2M, and the AEOs, respectively. The 96h EC50 estimates based on frequencies of developmental abnormalities were 2.1, 2.6, and 14.2 mg/L for S1M, S2M, and the AEOs, respectively. The main effects observed were reduced body size, edema, and cranial, heart, gut and ocular abnormalities. Increasing concentrations of the mixtures resulted in increased severity and frequency of abnormalities ( p < 0.05). The rank-order potency was S1M > S2M > AEO based on LC50 and EC50 estimates. These data provide insight into the effects NAs in amphibian embryos and can contribute to the development of environmental guidelines for the management of OSPW.

Monitoring of classical, oxidized, and heteroatomic naphthenic acids species in oil sands process water and groundwater from the active oil sands operation area.

The classical, oxidized, and heteroatomic naphthenic acids (NAs) species were monitored in the oil sands process water (OSPW) and groundwater from the active oil sands operation area, using solid phase extraction sample preparation and high resolution mass spectrometry analysis. Groundwater samples include Pleistocene channel aquifer groundwater (PLCA) and oil sands basal aquifer groundwater (OSBA) from different depth of underground. The concentrations of Ox-NAs decreased from OSPW to PLCA, and then increased from PLCA to OSBA, which is deeper than PLCA. The NAs in PLCA mainly comprised of Ox-NAs and N-NAs and the percentage of S-NAs was negligible. Results revealed relative abundances of individual NA species in total NAs varies among different water layers and the potential environmental impacts are expected to be variable. Principal component analysis results of O2-NAs or O4-NAs could be used for differentiation of water types. O2-NAs with n = 12-16 and |Z| = 4-6, and O4-NAs with n = 14-20 and |Z| = 6-8, were identified as marker compounds that could serve as surrogates of the larger complex NA mixture for source differentiation. This work utilized a combination of sample preparation, instrumental analysis, and statistical analysis methods to obtain knowledge of the occurrence, composition, and transfer of NAs in the groundwater of the Alberta oil sands operation area.

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.

Fate and behavior of oil sands naphthenic acids in a pilot-scale treatment wetland as characterized by negative-ion electrospray ionization Orbitrap mass spectrometry.

Large volumes of oil sands process-affected water (OSPW) are generated during the extraction of bitumen from oil sands in the Athabasca region of northeastern Alberta, Canada. As part of the development of treatment technologies, molecular characterization of naphthenic acids (NAs) and naphthenic acid fraction compounds (NAFC) in wetlands is a topic of research to better understand their fate and behavior in aquatic environments. Reported here is the application of high-resolution negative-ion electrospray Orbitrap-mass spectrometry for molecular characterization of NAs and NAFCs in a non-aerated constructed treatment wetland. The effectiveness of the wetlands to remove OSPW-NAs and NAFCs was evaluated by monitoring the changes in distributions of NAFC compounds in the untreated sample and non-aerated treatment system. After correction for measured evapotranspiration, the removal rate of the classical NAs followed approximately first-order kinetics, with higher rates observed for structures with relatively higher number of carbon atoms. These findings indicate that constructed wetland treatment is a viable method for removal of classical NAs in OSPW. Work is underway to evaluate the effects of wetland design on water quality improvement, preferential removal of different NAFC species, and reduction in toxicity.

Characterization of Athabasca lean oil sands and mixed surficial materials: Comparison of capillary electrophoresis/low-resolution mass spectrometry and high-resolution mass spectrometry.

RATIONALE: Oil sands mining in Alberta, Canada, requires removal and stockpiling of considerable volumes of near-surface overburden material. This overburden includes lean oil sands (LOS) which cannot be processed economically but contain sparingly soluble petroleum hydrocarbons and naphthenic acids, which can leach into environmental waters. In order to measure and track the leaching of dissolved constituents and distinguish industrially derived organics from naturally occurring organics in local waters, practical methods were developed for characterizing multiple sources of contaminated water leakage. METHODS: Capillary electrophoresis/positive-ion electrospray ionization low-resolution time-of-flight mass spectrometry (CE/LRMS), high-resolution negative-ion electrospray ionization Orbitrap mass spectrometry (HRMS) and conventional gas chromatography/flame ionization detection (GC/FID) were used to characterize porewater samples collected from within Athabasca LOS and mixed surficial materials. GC/FID was used to measure total petroleum hydrocarbon and HRMS was used to measure total naphthenic acid fraction components (NAFCs). HRMS and CE/LRMS were used to characterize samples according to source. RESULTS: The amounts of total petroleum hydrocarbon in each sample as measured by GC/FID ranged from 0.1 to 15.1 mg/L while the amounts of NAFCs as measured by HRMS ranged from 5.3 to 82.3 mg/L. Factors analysis (FA) on HRMS data visually demonstrated clustering according to sample source and was correlated to molecular formula. LRMS coupled to capillary electrophoresis separation (CE/LRMS) provides important information on NAFC isomers by adding analyte migration time data to m/z and peak intensity. CONCLUSIONS: Differences in measured amounts of total petroleum hydrocarbons by GC/FID and NAFCs by HRMS indicate that the two methods provide complementary information about the nature of dissolved organic species in a soil or water leachate samples. NAFC molecule class Ox Sy is a possible tracer for LOS seepage. CE/LRMS provides complementary information and is a feasible and practical option for source evaluation of NAFCs in water.

Naphthenic acids in groundwater overlying undeveloped shale gas and tight oil reservoirs.

The acid extractable organics (AEOs) containing naphthenic acids (NAs) in groundwater overlying undeveloped shale gas (Saint-Édouard region) and tight oil (Haldimand sector, Gaspé) reservoirs in Québec, Canada, were analysed using high resolution Orbitrap mass spectrometry and thermal conversion/elemental analysis - isotope ratio mass spectrometry. As classically defined by CnH2n+ZO2, the most abundant NAs detected in the majority of groundwater samples were straight-chain (Z = 0) or monounsaturated (Z = -2) C16 and C18 fatty acids. Several groundwater samples from both study areas, however, contained significant proportions of presumably alicyclic bicyclic NAs (i.e., Z = -4) in the C10-C18 range. These compounds may have originated from migrated waters containing a different distribution of NAs, or are the product of in situ microbial alteration of shale organic matter and petroleum. In most groundwater samples, intramolecular carbon isotope values generated by pyrolysis (δ13Cpyr) of AEOs were on average around 2-3‰ heavier than those generated by bulk combustion (δ13C) of AEOs, providing further support for microbial reworking of subsurface organic carbon. Although concentrations of AEOs were very low (<2.0 mg/L), the detection of potentially toxic bicyclic acids in groundwater overlying unconventional hydrocarbon reservoirs points to a natural background source of organic contaminants prior to any large-scale commercial hydrocarbon development.

Characterization and determination of naphthenic acids species in oil sands process-affected water and groundwater from oil sands development area of Alberta, Canada.

This work reports the monitoring and assessment of naphthenic acids (NAs) in oil sands process-affected water (OSPW), Pleistocene channel aquifer groundwater (PLCA), and oil sands basal aquifer groundwater (OSBA) from an active oil sands development in Alberta, Canada, using ultra performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) analysis with internal standard (ISTD) and external standard (ESTD) calibration methods and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) for compositional analysis. PLCA was collected at 45-51 m depth and OSBA was collected at 67-144 m depth. Results of Ox-NA concentrations follow an order as OSPW > OSBA > PLCA, indicating that occurrences of NAs in OSBA were likely related to natural bitumen deposits instead of OSPW. Liquid-liquid extraction (LLE) was applied to avoid the matrix effect for the ESTD method. Reduced LLE efficiency accounted for the divergence of the ISTD and ESTD calibrated results for oxidized NAs. Principle component analysis results of O2 and O4 species could be employed for differentiation of water types, while classical NAs with C13-15 and Z (-4)-(-6) and aromatic O2-NAs with C16-18 and Z (-14)-(-16) could be measured as marker compounds to characterize water sources and potential temporal variations of samples, respectively. FTICR-MS results revealed that compositions of NA species varied greatly among OSPW, PLCA, and OSBA, because of NA transfer and transformation processes. This work contributed to the understanding of the concentration and composition of NAs in various types of water, and provided a useful combination of analytical and statistical tools for monitoring studies, in support of future safe discharge of treated OSPW.

Comparison of methods for determination of total oil sands-derived naphthenic acids in water samples.

There are several established methods for the determination of naphthenic acids (NAs) in waters associated with oil sands mining operations. Due to their highly complex nature, measured concentration and composition of NAs vary depending on the method used. This study compared different common sample preparation techniques, analytical instrument methods, and analytical standards to measure NAs in groundwater and process water samples collected from an active oil sands operation. In general, the high- and ultrahigh-resolution methods, namely high performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) and Orbitrap mass spectrometry (Orbitrap-MS), were within an order of magnitude of the Fourier transform infrared spectroscopy (FTIR) methods. The gas chromatography mass spectrometry (GC-MS) methods consistently had the highest NA concentrations and greatest standard error. Total NAs concentration was not statistically different between sample preparation of solid phase extraction and liquid-liquid extraction. Calibration standards influenced quantitation results. This work provided a comprehensive understanding of the inherent differences in the various techniques available to measure NAs and hence the potential differences in measured amounts of NAs in samples. Results from this study will contribute to the analytical method standardization for NA analysis in oil sands related water samples.

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.