Nitrogen removal intensification of aerobic granular sludge through bioaugmentation with "heterotrophic nitrification-aerobic denitrification" consortium during petroleum wastewater treatment.

The bioaugmentation potential of aerobic granular sludge (AGS) was investigated using heterotrophic nitrification-aerobic denitrification (HN-AD) bacterial consortium to improve nitrogen removal during petroleum wastewater treatment. An efficient HN-AD consortium was constructed by mixing Pseudomonas mendocina K0, Brucella sp. K1, Pseudomonas putida T4 and Paracoccus sp. T9. AGS bioaugmented by immobilized HN-AD consortium enhanced nitrogen removal, which showed NH4+-N and TN removal efficiency of 92.4% and 79.8%, respectively. The immobilized consortium addition facilitated larger AGS formation, while granules > 2.0 mm accounted for 16.7% higher than that of control (6.7%). Further, the abundance of napA gene was 4-times higher in the bioaugmented AGS as compared to the control, which demonstrated the long-term stability of HN-AD consortium in the bioreactor. The bioaugmented AGS also showed a higher abundance of xenobiotics biodegradation and nitrogen metabolism. These results highlight that bioaugmentation of AGS technology could be effectively used for enhanced denitrification of petroleum wastewater.

Aerobic naphthenic acid-degrading bacteria in petroleum-coke improve oil sands process water remediation in biofilters: DNA-stable isotope probing reveals methylotrophy in Schmutzdecke.

There is an increasing interest in treatment of oil sands process water (OSPW) via biofiltration with petroleum coke (PC) as a substratum. In fixed bed biofilters (FBBs) with PC, the dominance of anaerobic digestion of dissolved organics results in poor removal of naphthenic acids (NAs) along with a high degree of methanogenesis. In this study, the operation of FBBs was modified to improve OSPW remediation by supporting the filtering bed with aerobic naphthenic acid-degrading bacteria treating aerated OSPW (FBBbioaugmentation). The results were compared with a biofilter operated under controlled conditions (FBBcontrol). To this end, a consortium of three aerobic NAs-degrading bacterial strains was immobilized on PC as a top layer (10 cm). These bacteria were pre-screened for growth on 15 different NAs surrogates as a sole carbon source, and for the presence of catabolic genes coding alkane hydroxylase (CYP153) and alkane monooxygenase (alkB) enzymes. The results illustrated that biofiltration in FBBbioaugmentation removed 32% of classical NAs in 15 days; while in the FBBcontrol, degradation was limited to 19%. The degradation of fluorophore (aromatic) compounds was also improved from 16% to 39% for single ring (OI), 22% to 29% for double ring (OII), and 15% to 23% for three rings (OIII) compounds. DNA-Stable Isotope Probing revealed that potential hydrocarbons degraders such as Pseudomonas (inoculated), Pseudoxanthomonas (indigenous) were present up to 9.0% in the 13C-labelled DNA fraction. Furthermore, a high abundance of methylotrophs was observed in the Schmutzdecke, with Methylobacillus comprising more than two-third of the total community. This study shows that bioaugmentation rapidly improved OSPW remediation. Aeration mostly contributed to methane consumption in the top layer, thus minimizing its release into the environment.

Bacterial diversity in petroleum coke based biofilters treating oil sands process water.

Adopting nature-based solutions for the bioremediation of oil sands process water (OSPW) is of significant interest, which requires a thorough understanding of how bacterial communities behave within treatment systems operated under natural conditions. This study investigates the OSPW remediation potential of delayed petroleum-coke (PC), which is a byproduct of bitumen upgrading process and is readily available at oil refining sites, in fixed-bed biofilters particularly for the degradation of naphthenic acids (NAs) and aromatics. The biofilters were operated continuously and total and active bacterial communities were studied by DNA and RNA-based amplicon sequencing in a metataxonomic fashion to extrapolate the underlying degradation mechanisms. The results of total community structure indicated a high abundance of aerobic bacteria at all depths of the biofilter, e.g., Porphyrobacter, Legionella, Pseudomonas, Planctomyces. However, redox conditions within the biofilters were anoxic (-153 to -182 mV) that selected anaerobic bacteria to actively participate in the remediation of OSPW, i.e., Ruminicoccus, Eubacterium, Faecalibacterium, Dorea. After 15 days of operation, the removal of classical NAs was recorded up to 20% whereas oxidized NAs species were poorly removed, i.e., O3-NAs: 4.8%, O4-NAs: 1.2%, O5-NAs: 1.7%, and O6-NAs: 0.5%. Accordingly, monoaromatics, diaromatics, and triaromatics were removed up to 16%, 22%, and 15%, respectively. The physiology of the identified genera suggested that the degradation in the PC-based biofilters was most likely proceeded in a scheme similar to beta-oxidation during anaerobic digestion process. The presence of hydrogenotrophic methanogens namely Methanobrevibacter and Methanomassiliicoccus and quantification of mcrA gene (2.4 × 102 to 8.7 × 102 copies/mg of PC) revealed that methane production was likely occurring in a syntrophic mechanism during the OSPW remediation. A slight reduction in toxicity was also observed. This study suggests that PC-based biofilters may offer some advantages in the remediation of OSPW; however, the production of methane could be of future concerns if operated at field-scale.

Treatment of oil sands process water using petroleum coke: Field pilot.

This is the first large-scale field pilot study that examined the feasibility and effectiveness of petroleum coke (PC), produced by a Fluid Coking Process, as an adsorbent for oil sands process water (OSPW) treatment. The pilot program consisted of an inline series of two reactors (pipeline reactor 1, and batch reactor 2) and lasted for approximately 4 months. The quality of treated OSPW as a function of residence time in the PC deposit under natural climatic conditions was assessed by looking at changes in organic compounds (acid extractable fraction (AEF), dissolved organic carbon (DOC), etc.), vanadium, and other trace element concentrations, major ions, conductivity, total suspended solids (TSS), pH and toxicity. The results indicated that the AEF adsorption by PC followed pseudo-second order kinetics and the overall combined removal efficiency of AEF was greater than 80%. Reactor 1 showed higher AEF removal than Reactor 2. DOC decreased about 50% after 4 weeks of retention in the PC deposit. An increase of vanadium concentration after PC contact indicated that vanadium leaching occurred. However, with increased residence time in the PC deposit, vanadium concentration decreased in the cells and tanks by 42% and 98%, respectively. Filtration through the PC deposit reduced the TSS in OSPW to less than laboratory detectable limits. Unlike untreated OSPW, treated OSPW did not show an acute toxic response based on whole effluent toxicity testing using trout, zooplankton, and bacteria. This study demonstrated that PC adsorption is a potentially commercially viable technology for highly efficient treatment of OSPW.

Influences of coagulation pretreatment on the characteristics of crude oil electric desalting wastewaters.

Highly polluted crude oil electric desalting wastewaters (EDWs) severely affect the efficiency of refinery wastewater treatment plants (WWTPs). Coagulation is an efficient pretreatment to reduce the impacts of EDWs. In the present study, the influences of coagulation pretreatment on the characteristics of EDWs of three typical Chinese crude oils, Liaohe heavy oil (LHO), Karamay heavy oil (KHO) and Daqing light oil (DLO), were investigated. The stability of three raw EDWs was broken and the contents of organic pollutants were significantly reduced by aluminum sulfate coagulation. More soluble COD and polar oils were removed from LHO-EDW (1241 and 98 mg L-1) and KHO-EDW (779 and 57 mg L-1) compared to DLO-EDW (417 and 11 mg L-1). Coagulation significantly changed the compositions of the organic pollutants of two heavy oil EDWs; however, slightly influenced DLO-EDW, particularly the polar organic pollutants. Most types of aromatic compounds, aliphatic acids and Ox polar compounds were removed from two heavy oil EDWs, but mainly alkanes were removed from DLO-EDW. As such, the differences in the types of dominant polar compounds became insignificant among treated heavy oil and light oil EDWs. Coagulation notably decreased the acute biotoxicity and improved the biodegradability of all treated EDWs. The residual organic nitrogen compounds in treated KHO-EDW contributed to a higher residual biotoxicity compared to treated LHO-EDW. The results demonstrate that coagulation can effectively improve the qualities of heavy oil EDWs by lowering the contents of organic pollutants and removing recalcitrant compounds, thus guaranteeing the efficiency of refinery WWTPs.

Ferrate oxidation of distinct naphthenic acids species isolated from process water of unconventional petroleum production.

Distinct naphthenic acid (NA) species were isolated from oil sands process water (OSPW) into 20 fractions via silver-ion solid phase extraction, prior to treatment using potassium ferrate(VI). Untreated and treated fractions F1-F20 were characterized using ultra performance liquid chromatography traveling-wave ion mobility time-of-flight mass spectrometry to identify classical NAs (aliphatic O2-NAs mainly found in fractions F1-F4), aromatic NAs (aromatic O2-NAs in F6-F9), oxidized NAs (O3-, O4-, and O5-NAs in F14-F17), and sulfur-containing NAs (F16-F19). The Fe(VI) oxidation reactivity of individual NA species was studied with minimized confounding effects from the complicated OSPW matrix. Aliphatic and aromatic O2-NAs were found to have different reactivity towards Fe(VI) oxidation, with removals ranging from <50% up to 90% at 200 mg/L ferrate dose. The O3-NAs and O4-NAs from raw OSPW were recalcitrant species with slight degradation under Fe(VI) oxidation conditions. The Fe(VI) oxidation of O2-NAs generated new O3-NAs as byproducts or intermediate byproducts which finally resulted in more oxygen-rich Ox-NAs as the final byproducts depending on the Fe(VI) doses. Besides the obtained knowledge on chemical reactivity, current methodology (i.e., treatment of Ag-ion fractions of OSPW versus raw OSPW) could be applied to evaluate other treatment approaches as well as toxicity of distinct NA species for environmental applications.

Bioreactors for oil sands process-affected water (OSPW) treatment: A critical review.

Canada has the world's largest oil sands reservoirs. Surface mining and subsequent caustic hot water extraction of bitumen lead to an enormous quantity of tailings (volumetric ratio bitumen:water=9:1). Due to the zero-discharge approach and the persistency of the complex matrix, oil producers are storing oil sands tailings in vast ponds in Northern Alberta. Oil sands tailings are comprised of sand, clay and process-affected water (OSPW). OSPW contains an extremely complex matrix of organic contaminants (e.g., naphthenic acids (NAs), residual bitumen, and polycyclic aromatic hydrocarbons (PAHs)), which has proven to be toxic to a variety of aquatic species. Biodegradation, among a variety of examined methods, is believed to be one of the most cost effective and practical to treat OSPW. A number of studies have been published on the removal of oil sands related contaminants using biodegradation-based practices. This review focuses on the treatment of OSPW using various bioreactors, comparing bioreactor configurations, operating conditions, performance evaluation and microbial community dynamics. Effort is made to identify the governing biotic and abiotic factors in engineered biological systems receiving OSPW. Generally, biofilms and elevated suspended biomass are beneficial to the resilience and degradation performance of a bioreactor. The review therefore suggests that a hybridization of biofilms and membrane technology (to ensure higher suspended microbial biomass) is a more promising option to remove OSPW organic constituents.

Dynamics of microbial community structure and nutrient removal from an innovative side-stream enhanced biological phosphorus removal process.

Biological phosphorous (P) and nitrogen (N) removal from municipal wastewater was studied using an innovative anoxic-aerobic-anaerobic side-stream treatment system. The impact of influent water quality including chemical oxygen demand (COD), ammonium and orthophosphate concentrations on the reactor performance was evaluated. The results showed the system was very effective at removing both COD (>88%) and NH4+-N (>96%) despite varying influent concentrations of COD, NH4+-N, and total PO43--P. In contrast, it was found that the removal of P was sensitive to influent NH4+-N and PO43--P concentrations. The maximum PO43--P removal of 79% was achieved with the lowest influent NH4+-N and PO43--P concentration. Quantitative PCR (qPCR) assays showed a high abundance and diversity of phosphate accumulating organisms (PAO), nitrifiers and denitrifiers. The MiSeq microbial community structure analysis showed that the Proteobacteria (especially ß-Proteobacteria, and γ-Proteobacteria) were the dominant in all reactors. Further analysis of the bacteria indicated the presence of diverse PAO genera including Candidatus Accumulibacter phosphatis, Tetrasphaera, and Rhodocyclus, and the denitrifying PAO (DPAO) genus Dechloromonas. Interestingly, no glycogen accumulating organisms (GAOs) were detected in any of the reactors, suggesting the advantage of proposed process in term of PAO selection for enhanced P removal compared with conventional main-stream processes.

Comparison of biomass from integrated fixed-film activated sludge (IFAS), moving bed biofilm reactor (MBBR) and membrane bioreactor (MBR) treating recalcitrant organics: Importance of attached biomass.

This study compared microbial characteristics and oil sands process-affected water (OSPW) treatment performance of five types of microbial biomass (MBBR-biofilm, IFAS-biofilm, IFAS-floc, MBR-aerobic-floc, and MBR-anoxic-floc) cultivated from three types of bioreactors (MBBR, IFAS, and MBR) in batch experiments. Chemical oxygen demand (COD), ammonium, acid extractable fraction (AEF), and naphthenic acids (NAs) removals efficiencies were distinctly different between suspended and attached bacterial aggregates and between aerobic and anoxic suspended flocs. MBR-aerobic-floc and MBR-anoxic-floc demonstrated COD removal efficiencies higher than microbial aggregates obtained from MBBR and IFAS, MBBR and IFAS biofilm had higher AEF removal efficiencies than those obtained using flocs. MBBR-biofilm demonstrated the most efficient NAs removal from OSPW. NAs degradation efficiency was highly dependent on the carbon number and NA cyclization number according to UPLC/HRMS analysis. Mono- and di-oxidized NAs were the dominant oxy-NA species in OSPW samples. Microbial analysis with quantitative polymerase chain reaction (q-PCR) indicated that the bacterial 16S rRNA gene abundance was significantly higher in the batch bioreactors with suspended flocs than in those with biofilm, the NSR gene abundance in the MBR-anoxic bioreactor was significantly lower than that in aerobic batch bioreactors, and denitrifiers were more abundant in the suspended phase of the activated sludge flocs.

Removal of organic compounds and trace metals from oil sands process-affected water using zero valent iron enhanced by petroleum coke.

The oil production generates large volumes of oil sands process-affected water (OSPW), referring to the water that has been in contact with oil sands or released from tailings deposits. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. Zero valent iron alone (ZVI) and in combination with petroleum coke (CZVI) were investigated as environmentally friendly treatment processes for the removal of naphthenic acids (NAs), acid-extractable fraction (AEF), fluorophore organic compounds, and trace metals from OSPW. While the application of 25 g/L ZVI to OSPW resulted in 58.4% removal of NAs in the presence of oxygen, the addition of 25 g petroleum coke (PC) as an electron conductor enhanced the NAs removal up to 90.9%. The increase in ZVI concentration enhanced the removals of NAs, AEF, and fluorophore compounds from OSPW. It was suggested that the electrons generated from the oxidation of ZVI were transferred to oxygen, resulting in the production of hydroxyl radicals and oxidation of NAs. When OSPW was de-oxygenated, the NAs removal decreased to 17.5% and 65.4% during treatment with ZVI and CZVI, respectively. The removal of metals in ZVI samples was similar to that obtained during CZVI treatment. Although an increase in ZVI concentration did not enhance the removal of metals, their concentrations effectively decreased at all ZVI loadings. The Microtox(®) bioassay with Vibrio fischeri showed a decrease in the toxicity of ZVI- and CZVI-treated OSPW. The results obtained in this study showed that the application of ZVI in combination with PC is a promising technology for OSPW treatment.

Desalination of oil sands process-affected water and basal depressurization water in Fort McMurray, Alberta, Canada: application of electrodialysis.

The high content of inorganic species in water used to extract bitumen from the Alberta oil sands and in the groundwater below the oil sands is an increasing environmental concern. These water matrices require treatment before they can be reused or safely discharged. Desalination of the oil sands process-affected water (OSPW) and groundwater, or basal depressurization water (BDW), can be accomplished with deionization techniques such as electrodialysis (ED). In order to achieve the effective ED treatment, OSPW and BDW were pretreated with coagulation-flocculation-sedimentation to remove solid species and turbidity. We demonstrated that a conductivity range for industrial reuse of OSPW and BDW can be achieved with the ED treatment and showed the possibility of applying ED in the oil sands industry. A continuous ED system that reuses the diluate stream as a source for the concentrate stream was designed. The cost of a hypothetical ED water treatment plant in Fort McMurray, Alberta, was estimated to be C$10.71 per cubic meter of treated water.

Impact of peroxydisulfate in the presence of zero valent iron on the oxidation of cyclohexanoic acid and naphthenic acids from oil sands process-affected water.

Large volumes of oil sands process-affected water (OSPW) are produced during the extraction of bitumen from oil sands in Alberta, Canada. The degradation of a model naphthenic acid, cyclohexanoic acid (CHA), and real naphthenic acids (NAs) from OSPW were investigated in the presence of peroxydisulfate (S(2)O(8)(2-)) and zerovalent iron (ZVI). For the model compound CHA (50 mg/L), in the presence of ZVI and 500 mg/L S(2)O(8)(2-), the concentration decreased by 45% after 6 days of treatment at 20 °C, whereas at 40, 60, and 80 °C the concentration decreased by 20, 45 and 90%, respectively, after 2 h of treatment. The formation of chloro-CHA was observed during ZVI/S(2)O(8)(2-) treatment of CHA in the presence of chloride. For OSPW NAs, in the presence of ZVI alone, a 50% removal of NAs was observed after 6 days of exposure at 20 °C. The addition of 100 mg/L S(2)O(8)(2-) to the solution increased the removal of OSPW NAs from 50 to 90%. In absence of ZVI, a complete NAs removal from OSPW was observed in presence of 2000 mg/L S(2)O(8)(2-) at 80 °C. The addition of ZVI increased the efficiency of NAs oxidation by S(2)O(8)(2-) near room temperature. Thus, ZVI/S(2)O(8)(2-) process was found to be a viable option for accelerating the degradation of NAs present in OSPW.

Petroleum coke adsorption as a water management option for oil sands process-affected water.

Water is integral to both operational and environmental aspects of the oil sands industry. A water treatment option based on the use of petroleum coke (PC), a by-product of bitumen upgrading, was examined as an opportunity to reduce site oil sands process-affected water (OSPW) inventories and net raw water demand. Changes in OSPW quality when treated with PC included increments in pH levels and concentrations of vanadium, molybdenum, and sulphate. Constituents that decreased in concentration after PC adsorption included total acid-extractable organics (TAO), bicarbonate, calcium, barium, magnesium, and strontium. Changes in naphthenic acids (NAs) speciation were observed after PC adsorption. A battery of bioassays was used to measure the OSPW toxicity. The results indicated that untreated OSPW was toxic towards Vibrio fischeri and rainbow trout. However, OSPW treated with PC at appropriate dosages was not acutely toxic towards these test organisms. Removal of TAO was found to be an adsorption process, fitting the Langmuir and Langmuir-Freundlich isotherm models. For TAO concentrations of 60 mg/L, adsorption capacities ranged between 0.1 and 0.46 mg/g. This study demonstrates that freshly produced PC from fluid cokers provides an effective treatment of OSPW in terms of key constituents' removal and toxicity reduction.

Naphthenic acids speciation and removal during petroleum-coke adsorption and ozonation of oil sands process-affected water.

The Athabasca Oil Sands industry produces large volumes of oil sands process-affected water (OSPW) as a result of bitumen extraction and upgrading processes. Constituents of OSPW include chloride, naphthenic acids (NAs), aromatic hydrocarbons, and trace heavy metals, among other inorganic and organic compounds. To address the environmental issues associated with the recycling and/or safe return of OSPW into the environment, water treatment technologies are required. This study examined, for the first time, the impacts of pretreatment steps, including filtration and petroleum-coke adsorption, on ozonation requirements and performance. The effect of the initial OSPW pH on treatment performance, and the evolution of ozonation and its impact on OSPW toxicity and biodegradability were also examined. The degradation of more than 76% of total acid-extractable organics was achieved using a semi-batch ozonation system at a utilized ozone dose of 150 mg/L. With a utilized ozone dose of 100 mg/L, the treated OSPW became more biodegradable and showed no toxicity towards Vibrio fischeri. Changes in the NA profiles in terms of carbon number and number of rings were observed after ozonation. The filtration of the OSPW did not improve the ozonation performance. Petroleum-coke adsorption was found to be effective in reducing total acid-extractable organics by a 91%, NA content by an 84%, and OSPW toxicity from 4.3 to 1.1 toxicity units. The results of this study indicate that the combination of petroleum-coke adsorption and ozonation is a promising treatment approach to treat OSPW.

Structure-reactivity of naphthenic acids in the ozonation process.

Large volumes of oil sands process-affected water (OSPW) are produced in northern Alberta by the surface mining oil sands industry. Naphthenic acids (NAs) are a complex mixture of persistent organic acids that are believed to contribute to the toxicity of OSPW. In situ microbial biodegradation strategies are slow and not effective at eliminating chronic aquatic toxicity, thus there is a need to examine alternative remediation techniques. NAs with multiple rings and alkyl branching are most recalcitrant to microbial biodegradation, but here we hypothesized that these same structural features may lead to preferential degradation in the ozonation process. Total NA degradation increased with increasing pH for commercial NA solutions, suggesting a hydroxyl radical mechanism and that naturally alkaline OSPW would unlikely require pH adjustment prior to treatment. For commercial NAs and OSPW, NAs with more rings and more carbon (and more H atoms) were depleted most rapidly in the process. Relative rate measurements with binary mixtures of model NA compounds not only confirmed this structure reactivity but also indicated that alkyl branching patterns were an additional factor determining NA reactivity. The results demonstrate that ozonation is complementary to microbial biodegradation, and the process remains a promising water reclamation strategy for the oil sands industry.