Classical Naphthenic Acids Research Articles

Solar-activated tin oxide photocatalysis for efficient naphthenic acids removal and toxicity reduction in oil sands process water

This research studied, for the first time, the effect of activating tin oxide (SnO2) under simulated solar light for treating real oil sands process water (OSPW). The solar/SnO2 system effectively eliminated fluorophore organic contaminants, classical naphthenic acids (O2-NAs), and oxidized NAs (Oxy-NAs) from OSPW. The best experimental conditions to remove over 90 % of O2-NAs were found to be 0.5 g/L SnO2 under 8 h of irradiation. HO• and O2•– species identified by electron paramagnetic resonance (EPR) analysis played an important role in the degradation of NAs and other contaminants in real OSPW. The initial toxic effects of untreated OSPW were noticeably reduced after treatment, with a reduction of approximately 50 % in acute toxicity using Microtox® bioassay and over 80 % in the level of bioavailable hydrocarbons. In addition, the process also demonstrated a significant reduction in immunotoxicity as measured using an immune cell bioassay and reduced the toxic effects on Staphylococcus warneri using an adapted bacterial minimal inhibitory concentration (MIC) viability assay. These results suggest that treated OSPW by SnO2 under solar light has high environmental compatibility, indicating it is safe for reuse in further applications.

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.

UVA LED-assisted breakdown of persulfate oxidants for the treatment of real oil sands process water: Removal of naphthenic acids and evaluation of residual toxicity

This study investigated for the first time the synergistic effect of coupling persulfate (PDS) and peroxymonosulfate (PMS) with UVA LED light for the treatment of real oil sands process water (OSPW). The performance of the UVA LED/PDS and UVA LED/PMS processes was studied at different oxidant concentrations to remove fluorophore organic compounds and naphthenic acids (NAs), commonly considered significant contributors to the toxicity of raw OSPW. Both systems were highly efficient in eliminating fluorophore organic contaminants and classical NAs (O2-NAs) from the matrix; however, concentrations of 1 and 2 mM of PDS and PMS, respectively, were the most suitable conditions to achieve one order of magnitude removal of O2-NAs (i.e., 90 %). In addition, oxidized NAs (O3- and O4-NAs) were moderately degraded under these conditions. Considering economic factors, the UVA LED/PDS (1 mM) system proved to be more cost-effective than the UVA LED/PMS (2 mM) process and a viable alternative to other advanced treatments for OSPW remediation. Moreover, the pre-existing toxic effect of raw OSPW was markedly mitigated after treatment with UVA LED/PDS (1 mM), reducing by 80 % the ability of the matrix to induce pro-inflammatory cytokines in human leukemic monocytic and without significantly affecting the viability of the Staphylococcus epidermidis bacteria. Specifically for the microbial viability assay, the exposure period of the microorganism was exceptionally more extended than those considered in standard bioassays, reinforcing the scientific relevance of the obtained results. Finally, these results suggest a high environmental compatibility of the treated OSPW, making its reuse in further applications safe.

Z-scheme plasmonic Ag decorated Bi2WO6/NiO hybrids for enhanced photocatalytic treatment of naphthenic acids in real oil sands process water under simulated solar irradiation

A novel photocatalyst, Bi2WO6/NiO/Ag, with hierarchical flower-like Z-scheme heterojunction, which exhibited excellent stability and photocatalytic activity over a wide light spectrum, was firstly synthesized and used in the remediation of real oil sands process water (OSPW) and achieved complete removal of aromatics, classical naphthenic acids (NAs), and heteroatomic NAs after 6 h of photocatalytic treatment. The acute toxicity of OSPW was completely eliminated after only 2 h of treatment. h+ and ∙OH were found to be the major oxidative species in the photocatalytic system. The enhanced photocatalytic efficiency is the result of the unique Z-scheme electron transfer among electron mediators Ag, NiO, and Bi2WO6, which was supported by the in-situ irradiated XPS. The study benefits the design of engineered passive treatment approach for OSPW remediation through solar light-driven catalyst.

Treatment of oil sands process water by the ferric citrate under visible light irradiation

An environmental-friendly treatment method based on photochemical reactions of ferricarboxylate complexes was developed for the treatment of oil sands process water (OSPW). Without using H2O2, the classical naphthenic acids (NAs), one of the organic compounds present in OSPW, can be effectively degraded by ferric citrate under visible light irradiation. Photochemical reaction activity of ferric citrate was greatly affected by the initial pH of OSPW. In acidic conditions, ferric citrate exhibited an extremely high degradation ratio of classical NAs, 98.3% (initial pH 3) and 96.8% (initial pH 5). Once initial pH exceeded 5, the degradation ratio of classical NAs in OSPW decreased quickly, and the degradation ratio of classical NAs could reach 65.7% (initial pH 7) and 42.4% (without adjusting pH, initial pH 8.9), respectively. It was found that the structure of NAs had little impact on the removal efficiency of NAs. It was also confirmed through scavenger experiments and reaction mechanism study that hydroxyl radical was the dominant reactive species in the process. The study demonstrated that ferric citrate possesses excellent visible light absorption ability and the photochemical reactions of ferric citrate can produce both Fe2+ and H2O2in situ, Fenton reagent, which non-selectively degrade NAs of OSPW.

Persulfate Oxidation Coupled with Biodegradation by Pseudomonas fluorescens Enhances Naphthenic Acid Remediation and Toxicity Reduction.

The extraction of bitumen from the Albertan oilsands produces large amounts of oil sands process-affected water (OSPW) that requires remediation. Classical naphthenic acids (NAs), a complex mixture of organic compounds containing O2− species, are present in the acid extractable organic fraction of OSPW and are a primary cause of acute toxicity. A potential remediation strategy is combining chemical oxidation and biodegradation. Persulfate as an oxidant is advantageous, as it is powerful, economical, and less harmful towards microorganisms. This is the first study to examine persulfate oxidation coupled to biodegradation for NA remediation. Merichem NAs were reacted with 100, 250, 500, and 1000 mg/L of unactivated persulfate at 21 °C and 500 and 1000 mg/L of activated persulfate at 30 °C, then inoculated with Pseudomonas fluorescens LP6a after 2 months. At 21 °C, the coupled treatment removed 52.8–98.9% of Merichem NAs, while 30 °C saw increased removals of 99.4–99.7%. Coupling persulfate oxidation with biodegradation improved removal of Merichem NAs and chemical oxidation demand by up to 1.8× and 6.7×, respectively, and microbial viability was enhanced up to 4.6×. Acute toxicity towards Vibrio fischeri was negatively impacted by synergistic interactions between the persulfate and Merichem NAs; however, it was ultimately reduced by 74.5–100%. This study supports that persulfate oxidation coupled to biodegradation is an effective and feasible treatment to remove NAs and reduce toxicity.

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.

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.

Molecular transformation of dissolved organic matter in process water from oil and gas operation during UV/H2O2, UV/chlorine, and UV/persulfate processes

This paper reported the impact of UV/H2O2, UV/chlorine, and UV/persulfate advanced oxidation processes on the molecular transformations of dissolved organic matter (DOM), removal of naphthenic acids (NAs) and acute toxicity in oil sands process water (OSPW). The UV/persulfate process exhibited the highest removal (81.2% with 2 mM dose) towards classical NAs and highest reduction in acute toxicity to Vibrio fischeri among the three processes. The fraction of DOM such as CHOS class species decreased along with the increase of the oxidant doses in all processes. The increase in O/C ratio and lack of change in the H/C and double bond equivalence indicated that H-abstraction followed by the OH-addition was the main reaction pathway for all processes. This observation aligned with previous studies using model compounds and proved that OSPW DOM reacted similarly to model compounds. Sulfur containing organic matters were the most liable compounds in OSPW NOM, while UV/chlorine was the most effective process to oxidize nitrogen containing organic matters. Overall results revealed that the UV/persulfate process could be used as a promising technique for the removal of OSPW NA and reduction of acute toxicity towards Vibrio fischeri. In addition, this DOM characterization approach could be utilized to investigate the transformation of complicated OSPW DOM and to identify the byproducts generated during different water treatment processes.

Direct analysis of naphthenic acids in constructed wetland samples by condensed phase membrane introduction mass spectrometry.

The application of direct mass spectrometry techniques to the analysis of complex samples has a number of advantages including reduced sample handling, higher sample throughput, in situ process monitoring, and the potential for adaptation to on-site analysis. We report the application of a semi-permeable capillary hollow fibre membrane probe (immersed directly into an aqueous sample) coupled to a triple quadrupole mass spectrometer by a continuously flowing methanol acceptor phase for the rapid analysis of naphthenic acids with unit mass resolution. The intensity of the naphthenic acid-associated peaks in the mass spectrum are normalized to an internal standard in the acceptor phase for quantitation and the relative abundance of the peaks in the mass spectrum are employed to monitor compositional changes in the naphthenic acid mixture using principle component analysis. We demonstrate the direct analysis of a synthetic oil sands process-affected water for classical naphthenic acids (CnH2n+zO2) as they are attenuated through constructed wetlands containing sedge (Carex aquatilis), cattail (Typha latifolia), or bulrush (Schoenoplectus acutus). Quantitative results for on-line membrane sampling compare favourably to those obtained by solid-phase extraction high-resolution mass spectrometry. Additionally, chemometric analysis of the mass spectra indicates a clear discrimination between naphthenic acid-influenced and natural background waters. Furthermore, the compositional changes within complex naphthenic acid mixtures track closely with the degree of attenuation. Overall, the technique is successful in following changes in both the concentration and composition of naphthenic acids from synthetic oil sands process-affected waters, with the potential for high throughput screening and environmental forensics.

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.

Integrated mild ozonation with biofiltration can effectively enhance the removal of naphthenic acids from hydrocarbon-contaminated water

An innovative biofiltration-ozonation-biofiltration process was established and applied for the treatment of oil sands process water (OSPW). With an equivalent hydraulic retention time (HRT) of 8 h, the biofiltration pretreatment removed 24.4% of classical naphthenic acids (NAs) and 3.3% of oxidized NAs from raw OSPW with removal rate of 0.4 mg/L/h and 0.1 mg/L. Oxidized NAs showed higher resistance to the biofiltration process than classical NAs. The mild ozonation process (with utilized ozone dose of 30 mg/L) removed 84.8% of classical NAs and 11.5% of oxidized NAs from the biofiltrated OSPW with a degradation efficiency of 0.3 mg classical NAs/mg O3 and 0.1 mg oxidized NAs/mg O3. However, by using the same utilized ozone dose, the degradation of classical NAs and oxidized NAs from raw OSPW was 32.1% and 3.9% with ozonation efficiency of 0.1 mg classical NAs/mg O3 and 0.0 mg oxidized NAs/mg O3, respectively. Compared with the biofiltration pretreatment, the post biofiltration process (with HRT of 8 h) showed higher degradation effect on oxidized NAs with removal ratio of 22.9% and removal rate of 0.4 mg/L/h, but showed lower degradation effect on classical NAs with removal ratio of 6.7% and removal rate of 0.0 mg/L/h. After biofiltration-ozonation-biofiltration treatment, the microbial community structure in the biofilter was investigated by next generation sequencing. Proteobacteria and Rhodococcus were dominant bacterial phyla and genus in the biofilter, the abundance of which were 47.21% and 9.50% which were different from those in raw OSPW (62.88% and 0.72%). The change of microbial community structure could be resulted from the interaction between microbial community and the circulating OSPW. The ozonation integrated biodegradation process removed 89.3% and 34.0% of classical and oxidized NAs from OSPW which shows high potential to be applied by the oil and gas industry.

Electro-oxidation by graphite anode for naphthenic acids degradation, biodegradability enhancement and toxicity reduction

Electro-oxidation (EO) by using graphite anode and at relatively low current densities was successfully applied for the degradation of commercial naphthenic acids (NAs) mixture in water samples. At current densities of 0.5, 2.5, and 5 mA/cm2, acid extractable fraction (AEF) was removed by 42.2%, 57.0% and 67.9%, respectively, while classical NAs were degraded by 76.9%, 77.6% and 82.4%, respectively. EO reactivity towards NAs increased with increasing the carbon number (n) and was higher for cyclic NAs compared to the acyclic component. Oxidized NAs containing O3 and O4 were also degraded effectively during EO. The biodegradability of organics in the NA mixture was clearly improved by 1.7, 2.5 and 2.7 folds when the samples were pre-treated with EO at current densities of 0.5, 2.5, and 5 mA/cm2, respectively. The aromatic fraction in the commercial NA mixture consisted mainly of single-ring aromatics and was degraded effectively by EO. Biodegradation alone was able to reduce the toxicity of the commercial NA mixture towards Vibrio fischeri; however, the combination of EO with biodegradation resulted in a complete removal of the toxicity, showing a synergistic effect of combining these two processes. Coupling EO with aerobic biodegradation can result in an effective and energy-efficient treatment option for NA-bearing waters such as oil sands process water (OSPW) and refinery effluents.

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.

Degradation of recalcitrant naphthenic acids from raw and ozonated oil sands process-affected waters by a semi-passive biofiltration process

In this study, a fixed-bed biofiltration system (biofilter) that utilized indigenous microorganisms was developed for the reclamation of oil sands process-affected water (OSPW). With the assistance of quantitative polymerase chain reaction (qPCR) and confocal laser scanning microscopy (CLSM), indigenous microorganisms from OSPW were able to attach to the surface of sand media and form biofilms. The number of total bacteria on the biofilter media reached a steady state (109/g) after 23 days of operation. Ultra Performance Liquid Chromatography/High Resolution Mass Spectrometry (UPLC/HRMS) analysis showed that 21.8% of the classical naphthenic acids (NAs) removal was achieved through the circulation of raw OSPW on the biofilter for 8 times (equivalent to a hydraulic retention time of 16 h). When ozonation with utilized ozone dose of 30 mg/L was applied as pretreatment, the classical NAs in the ozonated OSPW were removed by 89.3% with an accelerated biodegradation rate of 0.5 mg/L/h. Compared with other biofilm reactors such as moving bed biofilm reactor (MBBR), ozonation pretreatment could benefit the biodegradation of NAs in the biofilter more (classical NA removal: 89.3% vs. 34.4%), especially for those with high carbon number and cyclicity. The combined ozonation-biofiltration process could remove 92.7% of classical NAs from raw OSPW in 16 h. Although both ozonation and biofiltration alone did not show degradation of oxidized NAs from raw OSPW, the combined process led to a 52.9% and 42.6% removal for O3-NAs and O4-NAs, respectively, which were the dominant oxidized NA species in OSPW. Metagenomic sequencing analysis showed that Rhodococcus was the dominant bacterial genus on the sand media, which may play a crucial role during the NA biodegradation. With the advantage of high NA removal efficiency, the combined ozonation-biofiltration process is a promising approach for NA degradation and shows high potential to be scaled up for in-situ OSPW treatment.

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.

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.

Treatment of oil sands process-affected water using membrane bioreactor coupled with ozonation: A comparative study

The huge amount of toxic oil sands process-affected water (OSPW) stored in northern Alberta is of great concern to the public health and aquatic life. Therefore, cost-effective and more efficient approaches for OSPW treatment are urgently needed. In this study, mild ozonation followed by a modified Luzack–Ettinger membrane bioreactor (MLE-MBR) were employed for the treatment of OSPW. It was shown that with a utilized ozone dose of 30mg/L, 42.5–47.4% of classical naphthenic acids (NAs) were removed with toxicity reduction towards Vibrio fischeri. While ozonation targeted the heteroatomic NAs and classical NAs with high cyclicity and carbon number, MBR showed its advantages in removing oxidized NAs and classical NAs with less hydrogen deficiency. With excellent nitrification and denitrification performance, MBR achieved the removal of 46% for classical NAs, indicating the success of sludge acclimation in the MBR. Thauera became the most dominating bacterial genus in MBR, revealing its potentials in OSPW treatment. Compared with MBR treating raw OSPW, ozone pretreatment contributed to improved denitrification and NA removal in MBR. Moreover, it altered microbial community structure, thus delaying the occurrence of membrane fouling. During 426days of continuous operation, no severe membrane fouling was observed as the transmembrane pressure (TMP) of the MLE-MBR never exceeded −12kPa. With a reduction of classical NAs by around 70%, our results indicated that the MLE-MBR coupled with ozonation, is a promising approach for removing recalcitrant organics in 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.

Evaluation of biologically mediated changes in oil sands naphthenic acid composition by Chlamydomonas reinhardtii using negative-ion electrospray orbitrap mass spectrometry.

Industrial activity associated with oil-sands extraction in Canada's Athabasca region produces a variety of contaminants of concern, including naphthenic acid fraction components (NAFCs). NAFCs are a complex mixture of organic compounds that are poorly understood both in terms of their chemical composition and effects on the environment. NAFC toxicity in the unicellular green algae Chlamydomonas reinhardtii P.A.Dangeard was correlated with the presence of the algal cell wall. It was suggested that the toxicity of NAFCs in C.reinhardtii was due to surfactant effects. Surfactant-cell wall interactions are specific and governed by the compound class and structure, and by the nature of the biological material. Here, we investigate the effects of wildtype (WT) C.reinhardtii and two cell-wall mutants on specific classes of NAFCs when growing cultures were treated with a 100mg·L(-1) solution of NAFCs. Changes in the NAFC composition in the media were examined using high resolution mass spectrometry over a period of 4d. Algal mediated changes in the NAFCs were limited to specific classes of NAFCs. In particular, the removal of large, classical naphthenic acids, with a double bond equivalent of 8, was observed in WT C.reinhardtii cultures. The observed algal mediated changes in NAFC composition would have been masked by low resolution mass spectrometry and highlight the importance of this tool in examining bioremediation of complex mixtures of NAFCs.