Large volumes of toxic aqueous tailings containing a complex mixture of naphthenic acids (NAs; CnH2n+ZO2) are produced in northern Alberta by the oil sands industry. Because of their persistence and contribution to toxicity, there is an urgent need to understand the fate of NAs under a variety of remediation scenarios. In a previous study, we developed a highly specific HPLC-high resolution mass spectrometry method for the analysis of NAs. Here we apply this method to determine quantitative structure-persistence relationships and kinetics for commercial NAs and NAs in oil sands process water (OSPW) during aerobic microbial biodegradation. Biodegradation of commercial NAs revealed thatthe mixture contained a substantial labile fraction, which was rapidly biodegraded, and a recalcitrant fraction composed of highly branched compounds. Conversely, NAs in OSPW were predominantly recalcitrant, and degraded slowly by first-order kinetics. Carbon number (n) had little effect on the rate of biodegradation, whereas a general structure-persistence relationship was observed indicating that increased cyclization (Z) decreased the biodegradation rate for NAs in both mixtures. Time to 50% biodegradation ranged from 1 to 8 days among all NAs in the commercial mixture, whereas half-lives for OSPW NAs ranged from 44 to 240 days, likely a result of relatively high alkyl branching among OSPW NAs. It is anticipated that these data will facilitate development of strategic solutions for remediating billions of cubic meters of OSPW stored, or predicted to be generated, in Northern Alberta.

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Ozonation can degrade toxic naphthenic acids (NAs) in oil sands process-affected water (OSPW), but even after extensive treatment a residual NA fraction remains. Here we hypothesized that mild ozonation would selectively oxidize the most biopersistent NA fraction, thereby accelerating subsequent NA biodegradation and toxicity removal by indigenous microbes. OSPW was ozonated to achieve approximately 50% and 75% NA degradation, and the major ozonation byproducts included oxidized NAs (i.e., hydroxy- or keto-NAs). However, oxidized NAs are already present in untreated OSPW and were shown to be formed during the microbial biodegradation of NAs. Ozonation alone did not affect OSPW toxicity, based on Microtox; however, there was a significant acceleration of toxicity removal in ozonated OSPW following inoculation with native microbes. Furthermore, all residual NAs biodegraded significantly faster in ozonated OSPW. The opposite trend was found for ozonated commercial NAs, which are known to contain no significant biopersistent fraction. Thus, we suggest that ozonation preferentially degraded the most biopersistent OSPW NA fraction, and that ozonation is complementary to the biodegradation capacity of microbial populations in OSPW. The toxicity of ozonated OSPW to higher organisms needs to be assessed, but there is promise that this technique could be applied to accelerate the bioremediation of large volumes of OSPW in Northern Alberta, Canada.

The oil sands regions of Northern Alberta, Canada, contain an estimated 1.7 trillion barrels of oil in the form of bitumen, representing the second largest deposit of crude oil in the world. A rapidly expanding industry extracts surface-mined bitumen using alkaline hot water, resulting in large volumes of oil sands process water (OSPW) that must be contained on site due to toxicity. The toxicity has largely been attributed to naphthenic acids (NAs), a complex mixture of naturally occurring aliphatic and (poly-)alicyclic carboxylic acids. Research has increasingly focused on the environmental fate and remediation of OSPW NAs, but an understanding of these processes necessitates an analytical method that can accurately characterize and quantify NA mixtures. Here we report results of an interlaboratory comparison for the analysis of pure commercial NAs and environmental OSPW NAs using direct injection electrospray ionization mass spectrometry (ESI-MS) and high-pressure liquid chromatography/high-resolution mass spectrometry (HPLC/HRMS). Both methods provided very similar characterization of pure commercial NA mixture; however, the m/z selectivity of HPLC/HRMS was essential to prevent substantial false-positive detections and misclassifications in OSPW NA mixtures. For a range of concentrations encompassing those found in OSPW (10-100 mg/L), both methods produced linear response, although concentrations of commercial NAs above 50 mg/L resulted in slight non-linearity by HPLC/HRMS. A three-fold lower response factor for total OSPW NAs by HPLC/HRMS was largely attributable to other organic compounds in the OSPW, including hydroxylated NAs, which may explain the substantial misclassification by ESI-MS. For the quantitative analysis of unknown OSPW samples, both methods yielded total NA concentrations that correlated with results from Fourier transform infrared (FTIR), but the coefficients of determination were not high. Quantification by either MS method should therefore be considered semi-quantitative at best, albeit either method has substantial value in environmental fate experiments where relative concentration changes are the desired endpoints rather than absolute concentrations.

Mass spectrometry is a common tool for studying the fate of complex organic compound mixtures in oil sands processed water (OSPW), but a comparison of low-, high- ( approximately 10 000), and ultrahigh-resolution ( approximately 400 000) instrumentation for this purpose has not previously been made. High-resolution quadrupole time-of-flight mass spectrometry (QTOF MS) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), with negative-ion electrospray ionization, provided evidence for the selective dissipation of components in OSPW. Dissipation of oil sands naphthenic acids (NAs with general formula C(n)H(2n+z)O(2) where n is the number of carbon atoms, and Z is zero or a negative even number describing the number of rings) was masked (by components such as fatty acids, O(3), O(5), O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) species) at low resolution (1000) when using a triple quadrupole mass spectrometer. Changes observed in the relative composition of components in OSPW appear to be due primarily to the presence of plants, specifically cattails (Typha latifolia) and their associated microorganisms. The observed dissipation included a range of heteratomic species containing O(2), O(3), O(4), and O(5), present in Athabasca oil sands acid extracts. For the heteratomic O(2) species, namely naphthenic acids, an interesting structural relationship suggests that low and high carbon number NAs are dissipated by the plants preferentially, with a minimum around C(14)/C(15). Other heteratomic species containing O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) appear to be relatively recalcitrant to the cattails and were not dissipated to the same extent in planted systems.