Raw Oil Sands Process-affected Water Research Articles

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.

Floating Photocatalysts for Passive Solar Degradation of Naphthenic Acids in Oil Sands Process-Affected Water

Oil sands process-affected water (OSPW), generated from bitumen extraction in the Canadian oil sands, may require treatment to enable safe discharge to receiving watersheds, as dissolved naphthenic acids (NAs) and other acid extractable organics (AEO), identified as the primary toxic components of OSPW, are environmentally persistent and poorly biodegradable. However, conventional advanced oxidation processes (AOPs) are impractically expensive to treat the volumes of OSPW stockpiled in the Athabasca region. Here we prepared floating photocatalysts (FPCs) by immobilizing TiO2 on glass microbubbles, such that the composite particles float at the air-water interface for passive solar photocatalysis. The FPCs were demonstrated to outperform P25 TiO2 nanoparticles in degrading AEO in raw OSPW under natural sunlight and gentle mixing conditions. The FPCs were also found to be recyclable for multiple uses through simple flotation and skimming. This paper thus demonstrates the concept of a fully passive AOP that may be scalable to oil sands water treatment challenges, achieving efficient NA reduction solely through the energy provided by sunlight and natural mixing processes (wind and waves).

The role of ozone pretreatment on optimization of membrane bioreactor for treatment of oil sands process-affected water

Previously, anoxic-aerobic membrane bioreactor (MBR) coupled with mild ozonation pretreatment has been applied to remove toxic naphthenic acids (NAs) in oil sands process-affected water (OSPW). To further improve MBR performance, the optimal operation conditions including hydraulic retention time (HRT) and initial ammonia nitrogen (NH4+-N) need to be explored. In this study, the role of ozone pretreatment on MBR optimization was investigated. Compared with MBR treating raw OSPW, MBR treating ozonated OSPW had the same optimal operation conditions (HRT of 12 h and NH4+-N concentration of 25 mg/L). Nevertheless, MBR performance benefited from HRT adjustment more after ozone pretreatment. HRT adjustment resulted in NA removal in the range of 33–50% for the treatment of ozonated OSPW whereas NA removal for raw OSPW only fluctuated between 27% and 38%. Compared with the removal of classical NAs, the degradation of oxidized NAs was more sensitive to the adjustment of operation conditions. Adjusting HRT increased the removal of oxidized NAs in ozonated OSPW substantially (from 6% to 35%). It was also noticed that microbial communities in MBR treating ozonated OSPW were more responsive to the adjustment of operation conditions as indicated by the noticeable increase of Shannon index and extended genetic distances.

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.

Fate and abundance of classical and heteroatomic naphthenic acid species after advanced oxidation processes: Insights and indicators of transformation and degradation

The toxicological effects from all components in oil sands process-affected water (OSPW) are not known. Alternatively, monitoring the variations and abundance of different classes and compounds after treatments might be a useful approach in OSPW remediation. In this study, the variations in the compositions of classical and heteroatomic naphthenic acids (NAs) after treatment using advanced oxidation processes (AOPs), mainly ozone and peroxone, and two different mass spectrometry methods; ultra-performance liquid chromatography time-of-flight (UPLC-TOFMS) and Fourier transform ion cyclotron resonance (FTICR-MS), were examined. Two markers (O2S:O3S:O4S and O2:O4 ratios) were used to reveal changes and similarities of the treated water characteristics with those in natural waters. Both ratios decreased after all treatments, from 2.7:4.8:2.1 and 3.59 in raw OSPW to 0:1.4:0.5 and 0.7, respectively, in peroxone (1:2), becoming close to the reported ratios in natural waters. Toxicity toward Vibrio fischeri showed residual toxic effects after AOPs, suggesting that part of OSPW toxicity may be caused by specific compounds of NAs (i.e., similar reduction (50%) was achieved in both toxicity and abundance in O2 species with carbon 15–26) and/or generated by-products (e.g., O3S classes at double bond equivalent (DBE) = 4 and C9H12O2 at DBE = 4). Although by-products were generated, the best biodegradability enhancement and chemical oxygen demand reduction were achieved in peroxone (1:2) compared to ozone, suggesting the possibility of using combined OSPW remediation approaches (i.e., peroxone coupled with biological process). The recommended indicators can assist in evaluating the treatments' performance and in examining the best removal levels to accomplish significant toxicity reduction.

Effects of ozone pretreatment and operating conditions on membrane fouling behaviors of an anoxic-aerobic membrane bioreactor for oil sands process-affected water (OSPW) treatment

Two identical anoxic-aerobic membrane bioreactors (MBRs) were operated in parallel for 742 consecutive days for raw and ozonated oil sands process-affected water (OSPW) treatment. The MBRs not only substantially degraded OSPW classical and oxidized NAs, but also demonstrated outstanding membrane fouling control performance (the MBR receiving raw OSPW experienced its first severe fouling with a transmembrane pressure (TMP) of −35 kPa on Day 433). The mild ozonation (30 mg O3/L) pretreatment of OSPW remarkably enhanced OSPW NA degradation, and improved the MBR's fouling control in terms of prolonged long-term slow TMP growth phase and reduced TMP jump frequency. Ozonation substantially altered the feed water organic composition, reshaped the microbial community (e.g., reduced growth of extracellular polymeric substances (EPS) producers and biofilm formation facilitators), and lowered EPS production and EPS protein/polysaccharides (PN/PS) ratio, consequently leading to the better fouling control. Examination on fouling behaviors at different HRTs of the raw OSPW MBR indicates that HRT also played a role in determining the dominating fouling mechanism during the sharp TMP rise phase. Therefore, the results of this study suggest that the low-dose ozone pretreatment is a good option to enhance organic contaminant degradation and alleviate membrane fouling in the MBR for OSPW treatment.

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.

Optimization of ozonation combined with integrated fixed-film activated sludge (IFAS) in the treatment of oil sands process-affected water (OSPW)

Effects of hydraulic retention time (HRT) and the chemical oxygen demand/nitrogen (COD/N) ratio on the microbial community composition of integrated fixed-film activated sludge (IFAS) and its ability to treat raw and ozonated oil sands process-affected water (OSPW) were evaluated. After 11 months of HRT and ammonium optimization, 54.56% of the COD and 30.20% of the acid extractable fraction (AEF) were removed in raw OSPW IFAS, and 56.83% of the COD and 51.51% of the AEF were removed in ozonated OSPW IFAS. Extension of the HRT in the IFAS had no significant effect on the removal of COD and nitrogen, whereas a lower COD/N ratio increased the removal of organics and total nitrogen. The quantitative polymerase chain reaction (q-PCR) indicated that the abundance of nitrifier and denitrifier genes decreased during HRT optimization, and increased significantly after ammonium optimization. Proteobacteria, Nitrospirae, Acidobacteria, and Bacteroidetes were the dominant phyla in IFAS flocs and biofilms according to 454 sequencing. Proteobacteria showed significant decreases in flocs and biofilms after HRT and ammonium IFAS optimization. Nitrospirae and Acidobacteria showed significant upward trends in all biomass forms in optimized IFAS systems compared to unoptimized IFAS systems.

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.

Treatment of oil sands process-affected water (OSPW) using ozonation combined with integrated fixed-film activated sludge (IFAS)

Two integrated fixed-film activated sludge (IFAS) reactors were operated continuously to treat raw (untreated) and ozonated (30 mg/L) oil sands process-affected water (OSPW). After 11 months, 12.1% of the acid extractable fraction (AEF) and 43.1% of the parent naphthenic acids (NAs) were removed in the raw OSPW IFAS, while 42.0% AEF and 80.2% of parent NAs were removed in the ozonated OSPW IFAS. UPLC/HRMS analysis showed that NA biodegradation significantly decreased as the NA cyclization number increased. Confocal laser scanning microscopy (CLSM) results showed that the biofilm in the ozonated OSPW IFAS was significantly thicker (94 ± 1.6 μm) than the biofilm in the raw OSPW IFAS (72 ± 2.8 μm) after 283 days of cultivation. The quantitative polymerase chain reaction (q-PCR) revealed that the abundance proportions of both nitrifier genes (AomA, NSR and Nitro) and denitrifier genes (narG, nirS, nirK and nosZ) within total bacteria were significantly higher in biofilms than in flocs in the raw OSPW IFAS system, but a different trend was observed in the ozonated OSPW IFAS system.

Coagulation/flocculation process with polyaluminum chloride for the remediation of oil sands process-affected water: Performance and mechanism study

This study investigated the application of polyaluminum chloride (PACl) for the treatment of the oil sands process-affected water (OSPW). These coagulants are commonly used in water treatment with the most effective species reported to be Al13. PACl with 83.6% Al13 was synthesized using the slow base titration method and compared with a commercially available PACl in terms of aluminum species distribution, coagulation/flocculation (CF) performance, floc morphology, and contaminant removal. Both coagulants were effective in removing suspended solids, achieving over 96% turbidity removal at all applied coagulant doses (0.5–3.0 mM Al). The removal efficiencies of metals varied among different metals depending on their pKa values with metal cations having pKa values (Fe, Al, Ga, and Ti) below OSPW pH of 6.9–8.1 (dose dependent) being removed by more than 90%, while cations with higher pKa values (K, Na, Ca, Mg and Ni) had removals of less than 40%. Naphthenic acids were not removed due to their low molecular weights, negative charges, and hydrophilic characteristics at the OSPW pH. At the highest applied coagulant dose of 3.0 mM Al, the synthetic PACl reduced Vibrio fischeri inhibition effect to 43.3 ± 3.0% from 49.5 ± 0.4% in raw OSPW. In contrast, no reduction of toxicity was found for OSPW treated with the commercial PACl. Based on water quality and floc analyses, the dominant CF mechanism for particle removal during OSPW treatment was considered to be enmeshment in the precipitates (i.e., sweep flocculation). Overall, the CF using synthesized PACl can be a valuable pretreatment process for OSPW to create wastewater that is more easily treated by downstream processes.

Granular activated carbon for simultaneous adsorption and biodegradation of toxic oil sands process-affected water organic compounds

Naphthenic acids (NAs) released into oil sands process-affected water (OSPW) during bitumen processing in Northern Alberta are problematic for oil sands industries due to their toxicity in the environment and resistance to degradation during conventional wastewater treatment processes. Granular activated carbon (GAC) has shown to be an effective media in removing biopersistent organics from wastewater using a combination of adsorption and biodegradation removal mechanisms. A simultaneous GAC (0.4 g GAC/L) adsorption and biodegradation (combined treatment) study was used for the treatment of raw and ozonated OSPW. After 28 days of batch treatment, classical and oxidized NAs removals for raw OSPW were 93.3% and 73.7%, and for ozonated OSPW were 96.2% and 77.1%, respectively. Synergetic effects of the combined treatment process were observed in removals of COD, the acid extractable fraction, and oxidized NAs, which indicated enhanced biodegradation and bioregeneration in GAC biofilms. A bacteria copy number >108 copies/g GAC on GAC surfaces was found using quantitative real time polymerase chain reaction after treatment for both raw and ozonated OSPW. A Microtox® acute toxicity test (Vibrio fischeri) showed effective toxicity removal (>95.3%) for the combined treatments. Therefore, the simultaneous GAC adsorption and biodegradation treatment process is a promising technology for the elimination of toxic OSPW NAs.

Impact of ozonation pre-treatment of oil sands process-affected water on the operational performance of a GAC-fluidized bed biofilm reactor.

Treatment of oil sands process-affected water (OSPW) using biodegradation has the potential to be an environmentally sound approach for tailings water reclamation. This process is both economical and efficient, however, the recalcitrance of some OSPW constituents, such as naphthenic acids (NAs), require the pre-treatment of raw OSPW to improve its biodegradability. This study evaluated the treatment of OSPW using ozonation followed by fluidized bed biofilm reactor (FBBR) using granular activated carbon (GAC). Different organic and hydraulic loading rates were applied to investigate the performance of the bioreactor over 120 days. It was shown that ozonation improved the adsorption capacity of GAC for OSPW and improved biodegradation by reducing NAs cyclicity. Bioreactor treatment efficiencies were dependent on the organic loading rate (OLR), and to a lesser degree, the hydraulic loading rate (HLR). The combined ozonation, GAC adsorption, and biodegradation process removed 62 % of chemical oxygen demand (COD), 88 % of acid-extractable fraction (AEF) and 99.9 % of NAs under optimized operational conditions. Compared with a planktonic bacterial community in raw and ozonated OSPW, more diverse microbial communities were found in biofilms colonized on the surface of GAC after 120 days, with various carbon degraders found in the bioreactor including Burkholderia multivorans, Polaromonas jejuensis and Roseomonas sp.

Application of a solar UV/chlorine advanced oxidation process to oil sands process-affected water remediation.

The solar UV/chlorine process has emerged as a novel advanced oxidation process for industrial and municipal wastewaters. Currently, its practical application to oil sands process-affected water (OSPW) remediation has been studied to treat fresh OSPW retained in large tailings ponds, which can cause significant adverse environmental impacts on ground and surface waters in Northern Alberta, Canada. Degradation of naphthenic acids (NAs) and fluorophore organic compounds in OSPW was investigated. In a laboratory-scale UV/chlorine treatment, the NAs degradation was clearly structure-dependent and hydroxyl radical-based. In terms of the NAs degradation rate, the raw OSPW (pH ∼ 8.3) rates were higher than those at an alkaline condition (pH = 10). Under actual sunlight, direct solar photolysis partially degraded fluorophore organic compounds, as indicated by the qualitative synchronous fluorescence spectra (SFS) of the OSPW, but did not impact NAs degradation. The solar/chlorine process effectively removed NAs (75-84% removal) and fluorophore organic compounds in OSPW in the presence of 200 or 300 mg L(-1) OCl(-). The acute toxicity of OSPW toward Vibrio fischeri was reduced after the solar/chlorine treatment. However, the OSPW toxicity toward goldfish primary kidney macrophages after solar/chlorine treatment showed no obvious toxicity reduction versus that of untreated OSPW, which warrants further study for process optimization.

Biodegradation of oil sands process affected water in sequencing batch reactors and microbial community analysis by high-throughput pyrosequencing

Two sequencing batch reactors (SBR) were constructed and filled with different inocula of activated sludge (AS) and mature fine tailings (MFT) to treat oil sands process-affected water (OSPW). The COD was reduced by 82% in the AS-SBR and 43% in the MFT-SBR during phase I using 10% OSPW and 90% synthetic wastewater as reactor feed. However, COD removal reached 12% and 20% in the AS-SBR and the MFT-SBR, respectively, when 100% raw OSPW was fed into the reactors. Maximum removal of acid-extractable organics (AEO) was 8.7% and 16.6% in the AS-SBR and the MFT-SBR, respectively with a hydraulic retention time of one day. Pyrosequencing analysis revealed that Proteobacteria was the dominant phylum and beta- and gamma-Proteobacteria were dominant classes in both reactors. Evidence of a microbial community change was observed when influent raw OSPW was switched from 50 to 100%. More significant changes in the AS-SBR community were detected.