Comprehensive characterization of organics in oil sands process water in constructed mesocosms utilizing multiple analytical methods.

This study aims to provide a thorough characterization of dissolved organics in oil sands process water (OSPW) in field-based aquatic mesocosms at both molecular and bulk measurement levels using multiple analytical methods. In a 3-year outdoor mesocosm experiment, the analysis of naphthenic acid (NA) species was conducted using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). The results revealed the removal of both total NAs (38% and 35%) and classical NAs (O2-NAs, 58% and 49%) in undiluted and half-diluted OSPW, respectively. The increased ratios of oxidized NAs (O3-O6 NAs) to classical NAs suggested a transformation trend. The results also indicated that O2-NAs with higher carbon number and lower double bond equivalent (DBE) were more easily degraded in the mesocosm systems. Biomimetic extraction using solid-phase microextraction (BE-SPME) measurement displayed 26% (undiluted OSPW) and 30% (half-diluted OSPW) decrease in total bioavailable organics over 3 years. Naphthenic acids fraction compounds (NAFCs) obtained by liquid-liquid extraction (LLE) were also determined using Fourier transform infrared spectroscopy (FTIR). Reduction in acute toxicity for undiluted (43%) and half-diluted (26%) OSPW was observed over 3 years, which are well correlated with the decreases of NAs and BE-SPME concentrations. Moreover, BE-SPME values were found to be linearly correlated with total NAs concentrations (r = 0.96) and NAFCs (r = 0.96). Additionally, the linear relationships of individual O2-O6 NA species and BE-SPME concentrations unveiled the changes in the relative abundances of O2-O6 NA species in total bioavailable organics over time in the mesocosms. The present study has provided comprehensive insights by integrating various analytical methods, contributing valuable information for assessing the effectiveness of aquatic mesocosm systems in studying the temporal changes of organics in OSPW.

Survival strategies and assembly mechanisms of microbial communities in petroleum-contaminated soils.

This study analyzed petroleum-contaminated soils from south and north locations in China to explore the structure, diversity, functional genes and assembly processes of microbial communities' . Compared with soils from south locations, soils from northern regions exhibited elevated pH, total nitrogen (TN), and total petroleum hydrocarbon (TPH) levels. Among these, TN and TPH were the most influential on the microbial community. The dominant phyla for bacteria, archaea, and fungi were Proteobacteria, Thaumarchaeota, and Ascomycota, respectively. Among them, Proteobacteria was strongly correlated with various functional genes including alkB and many aromatics degradation and denitrification genes (r > 0.9, p < 0.01), suggesting that Proteobacteria play an important role in petroleum-contaminated soils. Metabolism in northern regions was more active than that in southern regions. The northern regions showed a pronounced tendency for denitrification, while the southern regions were characterized by acetoclastic methanogenesis. The assembly of microbial communities exhibited regional patterns, the deterministic assembly was more prominent in the northern soils, while the stochastic assembly was evident in the southern soils. Overall, these findings provide a new conceptual framework to understand the biosphere in petroleum-contaminated soil, potentially guiding improved management practices in the environmental remediation.

Experimental and theoretical insight into carbamazepine degradation by chlorine-based advanced oxidation processes: Efficiency, energy consumption, mechanism and DBPs formation.

Chlorine has been widely used in different advanced oxidation processes (AOPs) for micropollutants removal. In this study, different chlorine-based AOPs, namely medium pressure (MP) UV/chlorine, low pressure (LP) UV/chlorine, and in-situ chlorination, were compared for carbamazepine (CBZ) removal efficiency, energy consumption, and disinfection by-products (DBPs) formation. All three processes could achieve nearly 100% CBZ removal, while the reaction time needed by in-situ chlorination was double the time required by UV/chlorine processes. The energy consumed per magnitude of CBZ removed (EE/O) of MP UV/chlorine was 13 times higher than that of LP UV/chlorine, and relative to that of in-situ chlorination process. Accordingly, MP and LP UV/chlorine processes generated one to two orders of magnitude more hydroxyl radicals (•OH) and reactive chlorine species (RCS) than in-situ chlorination. Besides, RCS were the dominant reactive species, contributing to 78.3%, 75.6%, and 71.6% of CBZ removal in MP, LP UV/chlorine, and in-situ chlorination, respectively. According to the Gibbs free energy barriers between CBZ and RCS/•OH calculated based on density functional theory (DFT), RCS had more reaction routes with CBZ and showed lower energy barrier in the main CBZ degradation pathways like epoxidation and formation of iminostilbene. When applied to secondary wastewater effluent, UV/chlorine and in-situ chlorination produced overall DBPs ranging from 104.77 to 135.41 µg/L. However, the production of chlorate during UV/chlorine processes was 15 times higher than that during in-situ chlorination.

A novel biochar composite derived from oil-based drill sludge and cuttings: Structural characterization and electrochemical properties.

How to dispose of large quantities of hazardous shale gas drilling waste is an important worldwide problem facing the oil and gas industry. In this study, we report an environmentally friendly and low energy consumption approach (carbonization followed by activation) to convert oil-based drill sludge (OBDS) and oil-based drill cuttings (OBDCs) into biochar composites and investigate the effect of hydrofluoric acid (HF) acidification on them. The biochar composites were prepared using the OBDS, OBDCs, the mixtures of OBDS and OBDCs, and HF treatment the mixtures were named OS, OC, OSC, and OSC-HF, respectively. The characterization result of synthesized biochar composites indicated that the OSC had a larger specific surface area and a higher degree of graphitization. The composites mainly consisted of SiO2 and BaSO4, except for biochar. The OSC electrode exhibited the highest oxygen evolution potential (1.72 V vs Ag/AgCl) and the lowest charge transfer resistance compared with OS, OC, and OSC-HF electrodes, implying that SiO2 plays an important role in electrochemical performance. Using the OSC electrode as an anode, the chemical oxygen demand removal efficiency of the OBDS supernatant was 79.4 ± 0.95%. Further, the OSC electrode could maintain higher degradation efficiency and stability after the fifth reuse. The study provides a promising route for the proper disposal and resource utilization of OBDS and OBDCs and proposes a novel biochar compound as an electrode for the efficient treatment of wastewater. Moreover, this work highlights the important significance of the simultaneous resource utilization of waste and the treatment of wastewater using waste materials.

Review on carbon-based adsorbents from organic feedstocks for removal of organic contaminants from oil and gas industry process water: Production, adsorption performance and research gaps.

Large amounts of process water with considerable concentrations of recalcitrant organic contaminants, such as polycyclic aromatic hydrocarbon (PAHs), phenolic compounds (PCs), and benzene, toluene, ethylbenzene, and xylene (BTEX), are generated by several segments of oil and gas industries. These segments include refineries, hydraulic fracturing (HF), and produced waters from the extraction of shale gas (SGPW), coalbed methane (CBMPW) and oil sands (OSPW). In fact, the concentration of PCs and PAHs in process water from refinery can reach 855 and 742 mg L-1, respectively. SGPW can contain BTEX at concentrations as high as 778 mg L-1. Adsorption can effectively target those organic compounds for the remediation of the process water by applying carbon-based adsorbents generated from organic feedstocks. Such organic feedstocks usually come from organic waste materials that would otherwise be conventionally disposed of. The objective of this review paper is to cover the scientific progress in the studies of carbon-based adsorbents from organic feedstocks that were successfully applied for the removal of organic contaminants PAHs, PCs, and BTEX. The contributions of this review paper include the important aspects of (i) production and characterization of carbon-based adsorbents to enhance the efficiency of organic contaminant adsorption, (ii) adsorption properties and mechanisms associated with the engineered adsorbent and expected for certain pollutants, and (iii) research gaps in the field, which could be a guidance for future studies. In terms of production and characterization of materials, standalone pyrolysis or hybrid procedures (pyrolysis associated with chemical activation methods) are the most applied techniques, yielding high surface area and other surface properties that are crucial to the adsorption of organic contaminants. The adsorption of organic compounds on carbonaceous materials performed well at wide range of pH and temperatures and this is desirable considering the pH of process waters. The mechanisms are frequently pore filling, hydrogen bonding, π-π, hydrophobic and electrostatic interactions, and same precursor material can present more than one adsorption mechanism, which can be beneficial to target more than one organic contaminant. Research gaps include the evaluation of engineered adsorbents in terms of competitive adsorption, application of adsorbents in oil and gas industry process water, adsorbent regeneration and reuse studies, and pilot or full-scale applications.

Alkaline fermentation of refinery waste activated sludge mediated by refinery spent caustic for volatile fatty acids production.

Volatile fatty acids (VFA), produced from waste activated sludge (WAS), provide unique opportunities for resource recovery in wastewater treatment plants. This study investigates the potential of refinery spent caustic (RSC) on VFA production during refinery WAS (RWAS) alkaline fermentation. The highest VFA yield was 196.3 mg/g-VS at a sludge retention time of 6 days. Amplicon sequencing revealed the enrichment of Soehngenia (20.21%), Bacilli (11.86%), and Brassicibacter (4.17%), which was associated with improved activities of protease (626%) and α-glucosidase (715%). Function prediction analysis confirmed that acetyl-CoA production and fatty acid biosynthesis were enhanced, while fatty acid degradation was inhibited. Accordingly, hydrolysis, acidogenesis, and acetogenesis were improved by 6.87%, 10.67%, and 28.50%, respectively; whereas methanogenesis was inhibited by 28.87%. The sulfate and free ammonia in RSC likely contributed to increased acetic acid production. This study showcases that RWAS alkaline fermentation mediated by RSC for VFA production is the practicable approach.

Bifunctional Fe for Induced Graphitization and Catalytic Ozonation Based on a Fe/N-Doped Carbon-Al2O3 Framework: Theoretical Calculations Guided Catalyst Design and Optimization.

Heterogeneous catalytic ozonation is regarded as a feasible technology in advanced wastewater treatment. Catalytic performance, mass transfer, and mechanical strength are the key elements for large-scale applications of catalysts. To optimize those elements, Fe was selected for its dual role in graphitization and catalytic ozonation. A Fe/N-doped micron-scale carbon-Al2O3 framework (CAF) was designed and applied to a fluidized catalytic process for the treatment of secondary effluent from coal gasification. The chemical oxygen demand removal rate constant and the hydroxyl radical generation efficiency (Rct) of the Fe/N-doped CAF were 190% and 429% higher than those of pure ozone, respectively. Theoretical calculations revealed that higher Fe valence promoted ozone decomposition, which implied increasing FeIII content for further catalyst optimization. The rate constant and Rct with a higher FeIII-proportion catalyst were increased by 13% and 16%, respectively, compared to those with the lower one. Molecular dynamics and density functional theory calculations were performed to analyze the reaction kinetics qualitatively and quantitatively. The energy barrier corresponding to FeIII configuration was 1.32 kcal mol-1, 27% lower than that for FeII configuration. These theoretical calculations guided the catalyst optimization and provided a novel solution for designing ozonation catalysts. The Fe/N-doped CAF demonstrated a great potential for practical applications.

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.

Enhanced primary treatment during wet weather flow using ferrate as a coagulant, coagulant aid and disinfectant.

This study evaluated the dual-function of ferrate as a coagulant and disinfectant for chemically-enhanced primary treatment during wet weather flow (WWF). For the first time, ferrate was thoroughly examined as a coagulant aid with aluminum sulfate (alum) to minimize the organic and inorganic contents along with microbial level during WWF. Ferrate as a coagulant was evaluated based on a two-level factorial design. At an optimized condition, a ferrate dose of 0.5 mg/L Fe with a cationic polymer (1.25 mg/L) removed 83% of turbidity, 87% of total suspended solids (TSS), 70% of chemical oxygen demand (COD), and 23% of ortho-phosphate (OP). Linear models were developed and used to adequately predict the removals. Ferrate as a coagulant aid added with alum showed better removal of TSS while no improvement was observed in the removals of turbidity and COD. The disinfection capacity of ferrate was evaluated at different dosing points when it was used as a coagulant, coagulant aid and as post dosed as a disinfectant. In particular, ferrate dose of 8 mg/L Fe removed only 2 logs of E. coli when it was used as a coagulant compared to more than 3-log removal of E. coli when ferrate was used as a coagulant aid and as a disinfectant. At optimal ferrate dose of 10 mg/L Fe as a coagulant aid with 6 mg/L Al achieved the target levels of turbidity (<8 NTU), TSS (<25 mg/L), and ferrate-induced iron particles (<0.6 mg/L) along with 5-log removal of E. coli within 31 min. This study suggested that using ferrate as a coagulant aid/disinfectant might be considered an effective approach for treating the wastewater during WWF.

An enhanced disintegration using refinery spent caustic for anaerobic digestion of refinery waste activated sludge.

Alkali-mediated disintegration is efficient to improve the anaerobic digestion of waste activated sludge (WAS). In the present study, the role and potential of refinery spent caustic (RSC), an alkaline hazardous waste, in enhancing the disintegration of refinery waste activated sludge (RWAS) was investigated. The high alkalinity and free ammonia of RSC destroyed the microbial cell wall and promoted the release of intracellular substances. The contents of N-acetylglucosamine and proteins in the disintegrated liquid greatly increased to 0.41 mg/L and 1147 mg/L, respectively, relative to no disintegration (0.04 mg/L and 3.3 mg/L). The methane production (66.1 mL/g-VS) from RWAS anaerobic digestion increased by 226% compared to without disintegration (20.3 mL/g-VS). This study provides a newly developed "wastes-treat-wastes" management approach of refinery wastewater using combined treatment processes for RWAS and RSC using a cost-efficient and environmentally friendly disintegration of RWAS.

Influences of integrated coagulation-ozonation pretreatment on the characteristics of dissolved organic pollutants (DOPs) of heavy oil electric desalting wastewaters.

The quality of heavy oil electric desalting wastewaters (HO-EDWs) affects the effectiveness of refinery wastewater treatment plants. In this study, an integrated coagulation-ozonation (ICO) process was used to pretreat HO-EDWs and the influences on the characteristics of dissolved organic pollutants (DOPs) were investigated. Coagulation using aluminum sulfate removed 39% of soluble chemical oxygen demand (SCOD), 21% of dissolved organic carbon (DOC), 57% of petroleum hydrocarbons and 38% of polar oils from Liaohe HO-EDWs and the biodegradability was greatly improved. Ozonation removed 33% of SCOD and 88% of polar oils from the coagulated HO-EDWs. Most species of aromatic compounds, phenols, aliphatic acids, anilines and naphthenic acids with high C numbers and ring numbers were degraded and the unsaturation degrees of DOPs significantly decreased under ozonation. As a result, the biodegradability was further improved and the acute toxicity towards Vibrio fischeri was substantially reduced. Some OxS1 species and organic nitrogen compounds in HO-EDWs were penetrated through ozonation and caused the residual biotoxicity. The results demonstrate the potential of ICO pretreatment for improving the quality of refractory HO-EDWs.

The removal of Cu(II)-EDTA chelates using green rust adsorption combined with ferrite formation process.

Classical adsorbents such as activated carbon are inefficient to remove Cu(II)-EDTA in solution. Moreover, the heavy metals in the generated sludge can easily be dissolved back into solution. In this research, a novel strategy developed by coupling green rust adsorption and ferrite formation technology was proposed for Cu(II)-EDTA chelate removal. At the adsorption stage, green rust sulfate (GRME(SO42-)) showed a high adsorption efficiency of chelated copper, with a capacity of 126.41 mg g-1, compared to other classical adsorbents. During the ferrite formation stage, GRME(SO42-)-based precipitate with high moisture content and slow settling rate could be transformed into ferrite-based precipitate with low moisture content and rapid settling rate. The volume and moisture content of ferrite were 2.20 and 1.45 times lower than those of GRME(SO42-) and the sedimentation velocity of ferrite was also 1.23 times higher than that of GRME(SO42-), which strongly demonstrated the necessity of the ferrite formation process. Toxicity characteristic leaching procedure (TCLP) test results showed that the metallic copper of GRME(SO42-) sludge could be more easily dissolved back into solution than that of ferrite precipitate under weak-acid conditions, indicating the stability of ferrite. In addition, after the ferrite process, the generated sludge exhibited soft magnetism and could be quickly separated within few seconds using an external magnetic field. All these results showed that the combined green rust adsorption with ferrite formation method was an efficient, recyclable and eco-friendly method for the treatment of wastewater containing Cu(II)-EDTA.

Coagulation-flocculation followed by catalytic ozonation processes for enhanced primary treatment during wet weather conditions.

Combined sewer overflows (CSO), generated during the wet weather flow from the combination of the inflow and stormwater runoff in sewer system, result in an overflow of untreated wastewater from sewer system, which might ultimately contain different micropollutants (MPs). In this study, a coagulation-flocculation-sedimentation (CFS) pretreated CSO spiked with MPs was treated by catalytic ozonation using carbon, iron, and peroxide-based catalysts. The catalysts were characterized and their activity on MPs removal was studied at two different ozone (O3) doses (5 and 10 mg L-1). The effect of the treatment on the spiked CSO effluent was also assessed from the acute toxicity of the effluent using Microtox®, Yeast, and Macrophage cell-line toxicity assay tests. All the carbon-based catalysts showed large surface area, which was strongly influenced by the activation technique in the preparation of the catalysts. The CFS treatment strongly reduced the turbidity (≥60%) but had marginal effect on the UV254, dissolved organic carbon (DOC), and pH. Sludge Based Carbon (SBC) showed strong adsorption capacity (≥60% removal efficiency) for all MPs studied compared to other carbon and iron-based catalysts. Ozonation alone was effective for the degradation of easily oxidizable MPs (sulfamethoxazole, mecoprop, and 2,4-dichlorophenoxyl acetic acid), achieving more than 80% degradation efficiency at 10 mg L-1 of ozone, but not effective for atrazine (≤60% degradation efficiency) at similar O3 dose. Catalytic ozonation (at 10 mg L-1 O3 dose) improved the degradation of the MPs at low catalyst dosage but higher dosage strongly inhibited their degradation. In all cases, the effluents showed negligible acute toxicity, indicating the suitability of the process for the treatment of CSO.

Exposure to Organic Fraction Extracted from Oil Sands Process-Affected Water Has Negligible Impact on Pregnancy and Lactation of Mice.

Dissolved organic compounds are major contaminants in oil sands process-affected water (OSPW), of which naphthenic acids (NAs) are one of the main persistent toxicants. In the present study, we explore the toxic effects of the organic fraction extracted from OSPW (OSPW-OF) in mice during pregnancy and lactation. Here, we report that acute oral exposure of female Balb/c mice during gestation, and subchronic exposure throughout gestation and lactation to OSPW-OF (containing naturally occurring levels of NAs found in tailings ponds), had negligible effects on their reproductive performance. Specifically, mating behavior, pregnancy success, embryonic implantation, gestation period, litter size, and offspring viability were not affected by OSPW-OF containing up to 55 mg/L NAs. OSPW-OF exposure also did not affect plasma concentrations of pregnancy-associated hormones or pro- and anti-inflammatory cytokines, and it had minimal effects on liver stress gene expression. This study presents the first comprehensive in vivo analysis of mammalian toxicity associated with OSPW-OF exposure. Overall, our results suggest that the risk of acute and subchronic toxicity to mice exposed to OSPW-OF at environmentally relevant concentrations of NAs in contaminated drinking water is likely negligible.

Comparison of the Acute Immunotoxicity of Nonfractionated and Fractionated Oil Sands Process-Affected Water Using Mammalian Macrophages.

OSPW is a complex mixture of inorganic and organic substances and its principal toxic components have yet to be fully characterized. Previously, we showed in vitro that the oil sands process-affected water (OSPW) organic fraction (OF) caused a concentration-dependent immunotoxicity in mammals. In the present study we further explore the immunotoxicological properties of OSPW in mammals using a series of in vitro bioassays. Specifically, using the RAW 264.7 mouse macrophage cell line we show that whole OSPW containing naphthenic acid (NA) concentrations ranging from 12 to 18 mg/L, significantly inhibited cell proliferation, reduced cell viability, and was directly cytotoxic, whereas the exposure of cells to equivalent doses of the OSPW-OF had no measurable effects. Whole OSPW exposures also caused morphological changes in RAW 264.7 cells, and at sublethal doses (i.e., 10 mg/L) it induced the early expression of the stress genes hmox1 and gadd45. In addition, at NA concentrations of 10 mg/L, whole OSPW but not the OSPW-OF had significant effects on pro-inflammatory cytokine mRNA levels and cytokine protein secretion activities. Finally, whole OSPW also impaired the ability of RAW 264.7 cells to perform phagocytosis. Overall, we demonstrate that exposure to whole OSPW (at NA doses ranging from 10 to 20 mg/L), but not the OSPW-OF caused both cytotoxic and immunomodulatory changes in mouse macrophages. This suggests that the complex mixture of inorganic and organic components found in whole OSPW are acutely toxic at much lower doses than we previously reported for the OSPW-OF (i.e., 50 mg/L) due to unknown additive and/or synergistic interactions that likely occur between the various components present in whole OSPW.

Sensory and Behavioral Responses of a Model Fish to Oil Sands Process-Affected Water with and without Treatment.

If oil sands process-affected water (OSPW) is to be returned to the environment, a desire is that it not adversely affect aquatic life. We investigated whether a relevant model fish (rainbow trout, Oncorhynchus mykiss) could detect OSPW using its olfactory sense (smell) and whether exposure to it would result in behavioral changes. We also investigated whether ozonation of OSPW, which lowers the concentration of organic compounds attributed with toxicity (naphthenic acids), would ameliorate any observed adverse effects. We found that OSPW, regardless of ozonation, evoked olfactory tissue responses similar to those expected of natural odorants, suggesting that fish could smell OSPW. In 30 min OSPW exposures, olfactory responses to a food odorant and a pheromone were reduced to a similar degree by OSPW, again regardless of ozonation. However, olfactory responses returned within minutes of exposure cessation. In contrast, in longer (7 d) exposures, olfactory responses remained impaired, but not in fish that had received ozone-treated OSPW. In the behavioral assay, fish avoided an introduced plume of OSPW, and this response was not affected by ozonation. Taken together, our data suggest that fish smell OSPW, that they may use this sense to mount an avoidance response, and that, if they cannot avoid it, their sensory responses may be impaired, unless the OSPW has received some remediation.

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.

Silver-Ion Solid Phase Extraction Separation of Classical, Aromatic, Oxidized, and Heteroatomic Naphthenic Acids from Oil Sands Process-Affected Water.

The separation of classical, aromatic, oxidized, and heteroatomic (sulfur-containing) naphthenic acid (NA) species from unprocessed and ozone-treated oil sands process-affected water (OSPW) was performed using silver-ion (Ag-ion) solid phase extraction (SPE) without the requirement of pre-methylation for NAs. OSPW samples before SPE and SPE fractions were characterized using ultra performance liquid chromatography ion mobility time-of-flight mass spectrometry (UPLC-IM-TOFMS) to corroborate the separation of distinct NA species. The mass spectrum identification applied a mass tolerance of ±1.5 mDa due to the mass errors of NAs were measured within this range, allowing the identification of O2S-NAs from O2-NAs. Moreover, separated NA species facilitated the tandem mass spectrometry (MS/MS) characterization of NA compounds due to the removal of matrix and a simplified composition. MS/MS results showed that classical, aromatic, oxidized, and sulfur-containing NA compounds were eluted into individual SPE fractions. Overall results indicated that the separation of NA species using Ag-ion SPE is a valuable method for extracting individual NA species that are of great interest for environmental toxicology and wastewater treatment research, to conduct species-specific studies. Furthermore, the separated NA species on the milligram level could be widely used as the standard materials for environmental monitoring of NAs from various contamination sites.

Oxidation of Oil Sands Process-Affected Water by Potassium Ferrate(VI).

This paper investigates the oxidation of oil sands process-affected water (OSPW) by potassium ferrate(VI). Due to the selectivity of ferrate(VI) oxidation, two-ring and three-ring fluorescing aromatics were preferentially removed at doses <100 mg/L Fe(VI), and one-ring aromatics were removed only at doses ≥100 mg/L Fe(VI). Ferrate(VI) oxidation achieved 64.0% and 78.4% removal of naphthenic acids (NAs) at the dose of 200 mg/L and 400 mg/L Fe(VI) respectively, and NAs with high carbon number and ring number were removed preferentially. (1)H nuclear magnetic resonance ((1)H NMR) spectra indicated that the oxidation of fluorescing aromatics resulted in the opening of some aromatic rings. Electron paramagnetic resonance (EPR) analysis detected signals of organic radical intermediates, indicating that one-electron transfer is one of the probable mechanisms in the oxidation of NAs. The inhibition effect of OSPW on Vibrio fischeri and the toxicity effect on goldfish primary kidney macrophages (PKMs) were both reduced after ferrate(VI) oxidation. The fluorescing aromatics in OSPW were proposed to be an important contributor to this acute toxicity. Degradation of model compounds with ferrate(VI) was also investigated and the results confirmed our findings in OSPW study.

Comparison of Nitrilotriacetic Acid and [S,S]-Ethylenediamine-N,N'-disuccinic Acid in UV-Fenton for the Treatment of Oil Sands Process-Affected Water at Natural pH.

The application of UV-Fenton processes with two chelating agents, nitrilotriacetic acid (NTA) and [S,S]-ethylenediamine-N,N'-disuccinic acid ([S,S]-EDDS), for the treatment of oil sands process-affected water (OSPW) at natural pH was investigated. The half-wave potentials of Fe(III/II)NTA and Fe(III/II)EDDS and the UV photolysis of the complexes in Milli-Q water and OSPW were compared. Under optimum conditions, UV-NTA-Fenton exhibited higher efficiency than UV-EDDS-Fenton in the removal of acid extractable organic fraction (66.8% for the former and 50.0% for the latter) and aromatics (93.5% for the former and 74.2% for the latter). Naphthenic acids (NAs) removals in the UV-NTA-Fenton process (98.4%, 86.0%, and 81.0% for classical NAs, NAs + O (oxidized NAs with one additional oxygen atom), and NAs + 2O (oxidized NAs with two additional oxygen atoms), respectively) under the experimental conditions were much higher than those in the UV-H2O2 (88.9%, 48.7%, and 54.6%, correspondingly) and NTA-Fenton (69.6%, 35.3%, and 44.2%, correspondingly) processes. Both UV-NTA-Fenton and UV-EDDS-Fenton processes presented promoting effect on the acute toxicity of OSPW toward Vibrio fischeri. No significant change of the NTA toxicity occurred during the photolysis of Fe(III)NTA; however, the acute toxicity of EDDS increased as the photolysis of Fe(III)EDDS proceeded. NTA is a much better agent than EDDS for the application of UV-Fenton process in the treatment of OSPW.