Oil Sands Process-affected Water Research Articles

Sorption of copper(II) from synthetic oil sands process-affected water (OSPW) by pine sawdust biochars: effects of pyrolysis temperature and steam activation

Remediate metal contamination is a fundamental step prior to reclaim oil sands tailing ponds, and copper (Cu(II)) is the most abundant metal in the tailings water or oil sands process-affected water (OSPW). Biochars produced at four pyrolysis conditions were evaluated for sorption of Cu(II) in synthetic OSPW to explore different biochar potentials in removing Cu(II) from the contaminated water. Pine sawdust biochars pyrolyzed at 300 and 550 °C with and without steam activation were investigated by batch sorption experiments. Isotherm and kinetic studies were conducted to compare the sorption capacities of the four biochars and to examine potential mechanisms involved. For all the biochars, Langmuir and pseudo-second order models were the best-fit for isotherm and kinetic studies, respectively. According to the Langmuir parameters, the maximum adsorption capacities of the biochars produced at 550 °C were around 2.5 mg Cu(II) g−1, which were 30-folds higher than those produced at 300 °C. However, steam activation did not cause any significant difference in the biochars’ sorption performance. The kinetic study suggested that chemisorption involving valence forces was the limiting factor of the sorption. In addition, ion exchange and precipitation were likely the primary mechanisms for Cu(II) sorption which outweigh complexation with functional groups on the biochars’ surface. Pine sawdust biochar produced at 550 °C without steam activation could be utilized as a sustainable and cost-effective material to remove Cu(II) from the OSPW.

Suspended solids in an end pit lake: potential mixing mechanisms

The production of crude oil from the Canadian oil sands has generated tailings ponds that contain oil sands process-affected water and oil sands fluid fine tailings (FFT). One remediation strategy is to backfill a mined out pit with FFT and cap this with a mix of oil sands process-affected water and fresh water to form a lake, called an end pit lake. Here we discuss various mechanisms governing the vertical mixing of suspended solids in an end pit lake. Depending on the depth of the water cap, wind waves can cause mixing between the water cap and the FFT. Other potential mixing mechanisms include: convection due to salt-water exclusion during ice formation, penetrative convection due to surface cooling, gas emission from the FFT, and internal wave activity. Data collected at Syncrude Canada Limited’s Base Mine Lake in 2013 and 2014 are used to demonstrate the effects of some of these processes.

Surface amination of activated carbon and petroleum coke for the removal of naphthenic acids and treatment of oil sands process-affected water (OSPW)

To enhance the removal of model naphthenic acids (NA) from synthetic wastewater and removal of organics in oil sands process-affected water (OSPW) by adsorption, surfaces of commercial charcoal-derived activated carbon (AC) and proprietary petroleum coke-derived activated carbon (PAC) were modified. Two different amination processes including a single stage treatment with ammonia gas at an elevated temperature and a two-step treatment of nitration followed by reduction were adopted. All adsorbents showed excellent capacity for the model NAs and OSPW at low pH (⩽4.0). Ammonia treatment was more effective on improvement of adsorption capacity than the nitration followed by reduction method. The effect was more significant for commercial activated carbon compared to PAC, especially for multi-component adsorption at pH 8.0. The kinetics of adsorption improved significantly by the surface modification methods indicating great potential for these adsorbents in continuous column operation.

Diamondoid naphthenic acids cause in vivo genetic damage in gills and haemocytes of marine mussels.

Diamondoids are polycyclic saturated hydrocarbons that possess a cage-like carbon skeleton approaching that of diamond. These 'nano-diamonds' are used in a range of industries including nanotechnologies and biomedicine. Diamondoids were thought to be highly resistant to degradation, but their presumed degradation acid products have now been found in oil sands process-affected waters (OSPW) and numerous crude oils. Recently, a diamondoid-related structure, 3-noradamantane carboxylic acid, was reported to cause genetic damage in trout hepatocytes under in vitro conditions. This particular compound has never been reported in the environment but led us to hypothesise that other more environmentally relevant diamondoid acids could also be genotoxic. We carried out in vivo exposures (3 days, semi-static) of marine mussels to two environmentally relevant diamondoid acids, 1-adamantane carboxylic acid and 3,5-dimethyladamantane carboxylic acid plus 3-noradamantane carboxylic acid with genotoxic damage assessed using the Comet assay. An initial screening test confirmed that these acids displayed varying degrees of genotoxicity to haemocytes (increased DNA damage above that of controls) when exposed in vivo to a concentration of 30 μmol L(-1). In a further test focused on 1-adamantane carboxylic acid with varying concentrations (0.6, 6 and 30 μmol L(-1)), significant (P < 0.05%) DNA damage was observed in different target cells (viz. gills and haemocytes) at 0.6 μmol L(-1). Such a level of induced genetic damage was similar to that observed following exposure to a known genotoxin, benzo(a)pyrene (exposure concentration, 0.8 μmol L(-1)). These findings may have implications for a range of worldwide industries including oil extraction, nanotechnology and biomedicine.

Photocatalytic degradation of commercially sourced naphthenic acids by TiO2-graphene composite nanomaterial

Naphthenic acids (NAs) are a major contributor to the toxicity in oil sands process-affected water (OSPW), which is produced by hot water extraction of bitumen. NAs are extremely difficult to be degraded due to its complex ring and side chain structure. Photocatalysis is recognized as a promising technology in the removal of refractory organic pollutants. In this work, TiO2-graphene (P25-GR) composites were synthesized by means of solvothermal method. The results showed that P25-GR composite exhibited better photocatalytic activity than pure P25. The removal efficiency of naphthenic acids in acid solution was higher than that in neutral and alkaline solutions. It was the first report ever known on the photodegradation of NAs based on graphene, and this process achieved a higher removal rate than other photocatalysis degradation of NAs in a shorter reaction time. LC/MS analysis showed that macromolecular NAs (carbon number 17–22, z value −2) were easy to be degraded than the micromolecular ones (carbon number 11–16, z value −2). Furthermore, the reactive oxygen species that play the main role in the photocatalysis system were studied. It was found that holes and ·OH were the main reactive species in the UV/P25-GR photocatalysis system. Given the high removal efficiency of refractory organic pollutants and the short degradation time, photodegradation based on composite catalysts has a broad and practical prospect. The study on the photodegradation of commercially sourced NAs may provide a guidance for the degradation of OSPW NAs by this method.

Application of forward osmosis membrane technology for oil sands process-affected water desalination.

The extraction process used to obtain bitumen from the oil sands produces large volumes of oil sands process-affected water (OSPW). As a newly emerging desalination technology, forward osmosis (FO) has shown great promise in saving electrical power requirements, increasing water recovery, and minimizing brine discharge. With the support of this funding, a FO system was constructed using a cellulose triacetate FO membrane to test the feasibility of OSPW desalination and contaminant removal. The FO systems were optimized using different types and concentrations of draw solution. The FO system using 4 M NH4HCO3 as a draw solution achieved 85% water recovery from OSPW, and 80 to 100% contaminant rejection for most metals and ions. A water backwash cleaning method was applied to clean the fouled membrane, and the cleaned membrane achieved 77% water recovery, a performance comparable to that of new FO membranes. This suggests that the membrane fouling was reversible. The FO system developed in this project provides a novel and energy efficient strategy to remediate the tailings waters generated by oil sands bitumen extraction and processing.

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.

Effect of ozone pretreatment on naphthenic acid biodegradation and fouling behavior in a membrane bioreactor receiving oil sands process-affected water

Effect of ozone pretreatment on naphthenic acid biodegradation and fouling behavior in a membrane bioreactor receiving oil sands process-affected water

Investigation of the impact of organic solvent type and solution pH on the extraction efficiency of naphthenic acids from oil sands process-affected water

Naphthenic acids (NAs) from oil sand process-affected water (OSPW) were liquid-liquid extracted using six organic solvents (n-pentane, n-hexane, cyclohexane, dichloromethane, ethyl ether, and ethyl acetate) at three pHs (2.0, 8.5, and 12.0). The NAs exist in ionic (ions) and non-ionic (molecules) forms in the water phase depending on their dissociation constants and the solution pH. Results showed the extractability of NA molecules depends on the solvent polarity and the extractability of NA ions on the water solubility in solvent. The organic solvent type and solution pH were found to not only impact the extracted amounts of each NA species, but also the NAs distribution in terms of molecule carbon number and hydrogen deficiency. Overall, it is concluded that ethyl ether can be used as an alternative to dichloromethane (DCM) given their similar extraction efficiencies and extracted NA profiles. This is important since DCM is known to have metabolic toxicity and transitioning to the safer ethyl ether would eliminate laboratory DCM exposures and risk to human health. Despite the higher extraction efficiency of NAs at pH 2.0, extraction at pH 12.0 could be useful for targeted extraction of low-concentration nonpolar organic compounds in OSPW. This knowledge may assist in the determination of the specific NAs species that are known to have chronic, sub-chronic and acute toxicity to various organisms, and the potential targeting of treatment to these NAs species.

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.

Anaerobic biodegradation of surrogate naphthenic acids

Surface bitumen extraction from the Alberta's oil sands region generates large settling basins known as tailings ponds. The oil sands process-affected water (OSPW) stored in these ponds contain solid and residual bitumen-associated compounds including naphthenic acids (NAs) that can potentially be biodedgraded by indigenous tailings microorganisms. While the biodegradation of some NAs is known to occur under aerobic conditions, little is understood about anaerobic NA biodegradation even though tailings ponds are mainly anoxic. Here, we investigated the potential for anaerobic NA biodegradation by indigenous tailings microorganisms. Enrichment cultures were established from anoxic tailings that were amended with 5 single-ringed surrogate NAs or acid-extractable organics (AEO) from OSPW and incubated under nitrate-, sulfate-, iron-reducing, and methanogenic conditions. Surrogate NA depletion was observed under all anaerobic conditions tested to varying extents, correlating to losses in the respective electron acceptor (sulfate or nitrate) or the production of predicted products (Fe(II) or methane). Tailings-containing cultures incubated under the different electron-accepting conditions resulted in the enrichment and putative identification of microbial community members that may function in metabolizing surrogate NAs under the various anoxic conditions. In addition, more complex NAs (in the form of AEO) was observed to drive sulfate and iron reduction relative to controls. Overall, this study has shown that simple surrogate NAs can be biodegraded under a variety of anoxic conditions, a key first step in understanding the potential anaerobic metabolism of NAs in oil sands tailings ponds and other industrial wastewaters.

The effect of oil sands process-affected water and model naphthenic acids on photosynthesis and growth in Emiliania huxleyi and Chlorella vulgaris.

Naphthenic acids (NAs) are among the most toxic organic pollutants present in oil sands process waters (OSPW) and enter marine and freshwater environments through natural and anthropogenic sources. We investigated the effects of the acid extractable organic (AEO) fraction of OSPW and individual surrogate NAs, on maximum photosynthetic efficiency of photosystem II (PSII) (FV/FM) and cell growth in Emiliania huxleyi and Chlorella vulgaris as representative marine and freshwater phytoplankton. Whilst FV/FM in E. huxleyi and C. vulgaris was not inhibited by AEO, exposure to two surrogate NAs: (4'-n-butylphenyl)-4-butanoic acid (n-BPBA) and (4'-tert-butylphenyl)-4-butanoic acid (tert-BPBA), caused complete inhibition of FV/FM in E. huxleyi (≥10 mg L(-1)n-BPBA; ≥50 mg L(-1)tert-BPBA) but not in C. vulgaris. Growth rates and cell abundances in E. huxleyi were also reduced when exposed to ≥10 mg L(-1)n- and tert-BPBA; however, higher concentrations of n- and tert-BPBA (100 mg L(-1)) were required to reduce cell growth in C. vulgaris. AEO at ≥10 mg L(-1) stimulated E. huxleyi growth rate (p ≤ 0.002), yet had no apparent effect on C. vulgaris. In conclusion, E. huxleyi was generally more sensitive to NAs than C. vulgaris. This report provides a better understanding of the physiological responses of phytoplankton to NAs which will enable improved monitoring of NA pollution in aquatic ecosystems in the future.

Inhibition of ABC transport proteins by oil sands process affected water

The ATP-binding cassette (ABC) superfamily of transporter proteins is important for detoxification of xenobiotics. For example, ABC transporters from the multidrug-resistance protein (MRP) subfamily are important for excretion of polycyclic aromatic hydrocarbons (PAHs) and their metabolites. Effects of chemicals in the water soluble organic fraction of relatively fresh oil sands process affected water (OSPW) from Base Mine Lake (BML-OSPW) and aged OSPW from Pond 9 (P9-OSPW) on the activity of MRP transporters were investigated in vivo by use of Japanese medaka at the fry stage of development. Activities of MRPs were monitored by use of the lipophilic dye calcein, which is transported from cells by ABC proteins, including MRPs. To begin to identify chemicals that might inhibit activity of MRPs, BML-OSPW and P9-OSPW were fractionated into acidic, basic, and neutral fractions by use of mixed-mode sorbents. Chemical compositions of fractions were determined by use of ultrahigh resolution orbitrap mass spectrometry in ESI+ and ESI− mode. Greater amounts of calcein were retained in fry exposed to BML-OSPW at concentration equivalents greater than 1× (i.e., full strength). The neutral and basic fractions of BML-OSPW, but not the acidic fraction, caused greater retention of calcein. Exposure to P9-OSPW did not affect the amount of calcein in fry. Neutral and basic fractions of BML-OSPW contained relatively greater amounts of several oxygen-, sulfur, and nitrogen-containing chemical species that might inhibit MRPs, such as O+, SO+, and NO+ chemical species, although secondary fractionation will be required to conclusively identify the most potent inhibitors. Naphthenic acids (O2−), which were dominant in the acidic fraction, did not appear to be the cause of the inhibition. This is the first study to demonstrate that chemicals in the water soluble organic fraction of OSPW inhibit activity of this important class of proteins. However, aging of OSPW attenuates this effect and inhibition of the activity of MRPs by OSPW from Base Mine Lake does not occur at environmentally relevantconcentrations.

The Challenge: Safe release and reintegration of oil sands process-affected water.

The Challenge: Safe release and reintegration of oil sands process-affected water.

Solar photocatalytic degradation of naphthenic acids in oil sands process-affected water.

Bitumen mining in the Canadian oil sands creates large volumes of oil sands process-affected water (OSPW), the toxicity of which is due in part to naphthenic acids (NAs) and other acid extractable organics (AEO). The objective of this work was to evaluate the potential of solar photocatalysis over TiO2 to remove AEO from OSPW. One day of photocatalytic treatment under natural sunlight (25 MJ/m(2) over ∼14 h daylight) eradicated AEO from raw OSPW, and acute toxicity of the OSPW toward Vibrio fischeri was eliminated. Nearly complete mineralization of organic carbon was achieved within 1-7 day equivalents of sunlight exposure, and degradation was shown to proceed through a superoxide-mediated oxidation pathway. High resolution mass spectrometry (HRMS) analysis of oxidized intermediate compounds indicated preferential degradation of the heavier and more cyclic NAs (higher number of double bond equivalents), which are the most environmentally persistent fractions. The photocatalyst was shown to be recyclable for multiple uses, and thus solar photocatalysis may be a promising "green" advanced oxidation process (AOP) for OSPW treatment.

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.

Treatment of oil sands process-affected water (OSPW) using a membrane bioreactor with a submerged flat-sheet ceramic microfiltration membrane

The release of oil sands process-affected water (OSPW) into the environment is a concern because it contains persistent organic pollutants that are toxic to aquatic life. A modified Ludzack–Ettinger membrane bioreactor (MLE-MBR) with a submerged ceramic membrane was continuously operated for 425 days to evaluate its feasibility on OSPW treatment. A stabilized biomass concentration of 3730 mg mixed liquor volatile suspended solids per litre and a naphthenic acid (NA) removal of 24.7% were observed in the reactor after 361 days of operation. Ultra Performance Liquid Chromatography/High Resolution Mass Spectrometry analysis revealed that the removal of individual NA species declined with increased ring numbers. Pyrosequencing analysis revealed that Betaproteobacteria were dominant in sludge samples from the MLE-MBR, with microorganisms such as Rhodocyclales and Sphingobacteriales capable of degrading hydrocarbon and aromatic compounds. During 425 days of continuous operation, no severe membrane fouling was observed as the transmembrane pressure (TMP) of the MLE-MBR never exceeded −20 kPa given that the manufacturer's suggested critical TMP for chemical cleaning is −35 kPa. Our results indicated that the proposed MLE-MBR has a good potential for removing recalcitrant organics in OSPW.

Effects-Directed Analysis of Dissolved Organic Compounds in Oil Sands Process-Affected Water.

Acute toxicity of oil sands process-affected water (OSPW) is caused by its complex mixture of bitumen-derived organics, but the specific chemical classes that are most toxic have not been demonstrated. Here, effects-directed analysis was used to determine the most acutely toxic chemical classes in OSPW collected from the world's first oil sands end-pit lake. Three sequential rounds of fractionation, chemical analysis (ultrahigh resolution mass spectrometry), and acute toxicity testing (96 h fathead minnow embryo lethality and 15 min Microtox bioassay) were conducted. Following primary fractionation, toxicity was primarily attributable to the neutral extractable fraction (F1-NE), containing 27% of original organics mass. In secondary fractionation, F1-NE was subfractionated by alkaline water washing, and toxicity was primarily isolated to the ionizable fraction (F2-NE2), containing 18.5% of the original organic mass. In the final round, chromatographic subfractionation of F2-NE2 resulted in two toxic fractions, with the most potent (F3-NE2a, 11% of original organic mass) containing predominantly naphthenic acids (O2(-)). The less-toxic fraction (F3-NE2b, 8% of original organic mass) contained predominantly nonacid species (O(+), O2(+), SO(+), NO(+)). Evidence supports naphthenic acids as among the most acutely toxic chemical classes in OSPW, but nonacidic species also contribute to acute toxicity of OSPW.

Mechanistic investigation of industrial wastewater naphthenic acids removal using granular activated carbon (GAC) biofilm based processes

Naphthenic acids (NAs) found in oil sands process-affected waters (OSPW) have known environmental toxicity and are resistant to conventional wastewater treatments. The granular activated carbon (GAC) biofilm treatment process has been shown to effectively treat OSPW NAs via combined adsorption/biodegradation processes despite the lack of research investigating their individual contributions. Presently, the NAs removals due to the individual processes of adsorption and biodegradation in OSPW bioreactors were determined using sodium azide to inhibit biodegradation. For raw OSPW, after 28 days biodegradation and adsorption contributed 14% and 63% of NA removal, respectively. For ozonated OSPW, biodegradation removed 18% of NAs while adsorption reduced NAs by 73%. Microbial community 454-pyrosequencing of bioreactor matrices indicated the importance of biodegradation given the diverse carbon degrading families including Acidobacteriaceae, Ectothiorhodospiraceae, and Comamonadaceae. Overall, results highlight the ability to determine specific processes of NAs removals in the combined treatment process in the presence of diverse bacteria metabolic groups found in GAC bioreactors.

Ozonation of Naphthenic Acids in Water: Kinetic Study

The large amount of oil sands process-affected water (OSPW), produced from the extraction of oil from oil sands in Alberta, Canada, has demonstrated both acute and chronic toxicity to many species due to the presence of naphthenic acids (NAs). The “zero discharge” policy posted by the Alberta government presents a major challenge for the oil sands industries. In this study, ozonation was used to remove model NAs from water. It was found that the removal of NAs increased with the temperature. The kinetics of direct ozonation between molecular ozone and NAs was investigated in the presence of a radical scavenger, sodium bicarbonate. The rate constants of the direct ozonation at 5, 15 and 25 °C were determined to be 0.67, 2.71 and 8.85 M−1 s−1, respectively, and the activation energy of the direct ozonation was found to be 88.85 kJ mol−1. The kinetics of indirect ozonation was also studied. By using pCBA as a hydroxyl radical probe compound to determine the hydroxyl radical concentration and applying the ratio of hydroxyl radical concentration to dissolved ozone concentration, R ct, the rate constants of the indirect ozonation of NAs were found to be 1.12 × 108, 1.78 × 108 and 2.33 × 108 M−1 s−1 at 5, 15 and 25 °C, respectively. In addition, from the Arrhenius plot of the rate constants, the activation energy of the indirect ozonation was found to be 25.41 kJ mole−1.