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.

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

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

Can short-term data accurately model long-term environmental exposures? Investigating the multigenerational adaptation potential of Daphnia magna to environmental concentrations of organic ultraviolet filters.

Organic ultraviolet filters (UVFs) are contaminants of concern, ubiquitously found in many aquatic environments due to their use in personal care products to protect against ultraviolet radiation. Research regarding the toxicity of UVFs such as avobenzone, octocrylene and oxybenzone indicate that these chemicals may pose a threat to invertebrate species; however, minimal long-term studies have been conducted to determine how these UVFs may affect continuously exposed populations. The present study modeled the effects of a 5-generation exposure of Daphnia magna to these UVFs at environmental concentrations. Avobenzone and octocrylene resulted in minor, transient decreases in reproduction and wet mass. Oxybenzone exposure resulted in > 40% mortality, 46% decreased reproduction, and 4-fold greater reproductive failure over the F0 and F1 generations; however, normal function was largely regained by the F2 generation. These results indicate that Daphnia are able to acclimate over long-term exposures to concentrations of 6.59 µg/L avobenzone, ∼0.6 µg/L octocrylene or 16.5 µg/L oxybenzone. This suggests that short-term studies indicating high toxicity may not accurately represent long-term outcomes in wild populations, adding additional complexity to risk assessment practices at a time when many regions are considering or implementing UVF bans in order to protect these most sensitive invertebrate species.

Transformation and toxicity studies of UV filter diethylamino hydroxybenzoyl hexyl benzoate in the swimming pools.

Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), an ultraviolet (UV) filter, can be found in sunscreens and other personal care products and thus can be introduced into swimming pools through the swimmers. In outdoor pools, DHHB will inevitably interact with free chlorine and sunlight. Therefore, the mechanism of solar­chlorine chemical transformation of DHHB, as well as the environmental risk, were investigated in this work. In chlorinated with solar (Cl + solar) process, free chlorine was the dominant contributor to 85% of the DHHB degradation, while hydroxyl radicals and reactive chlorine species contributed only 15% because of low free radical generation and fast DHHB and free chlorine reaction rates. Scavenging matrices, such as Cl-, NH4+, and dissolved organic matter (DOM), inhibited the degradation of DHHB in the Cl + solar process, while Br-, HCO3-, NO3-, and urea promoted DHHB degradation. DHHB degradation was inhibited in tap water swimming pool samples, while it was enhanced in seawater pool samples by the Cl + solar process. Seven transformation by-products (TBPs) including mono-, dichlorinated, dealkylate, and monochloro-hydroxylated TBPs were identified. Three degradation pathways, chlorine substitution, chlorine and hydroxyl substitution, and dealkylation were proposed for DHHB transformation in the Cl + solar process. Both Quantitative structure-activity relationship and Aliivibrio fischeri toxicity tests demonstrated increased toxicity for the chlorinated TBPs. A risk assessment of the DHHB and its TBPs suggested that both DHHB and its chlorinated TBPs pose a significant health risk.

Using immune cell-based bioactivity assays to compare the inflammatory activities of oil sands process-affected waters from a pilot scale demonstration pit lake.

In this study, we provide evidence that oil sands process-affected waters (OSPW) contain factors that activate the antimicrobial and proinflammatory responses of immune cells. Specifically, using the murine macrophage RAW 264.7 cell line, we establish the bioactivity of two different OSPW samples and their isolated fractions. Here, we directly compared the bioactivity of two pilot scale demonstration pit lake (DPL) water samples, which included expressed water from treated tailings (termed the before water capping sample; BWC) as well as an after water capping (AWC) sample consisting of a mixture of expressed water, precipitation, upland runoff, coagulated OSPW and added freshwater. Significant inflammatory (i.e. macrophage activating) bioactivity was associated with the AWC sample and its organic fraction (OF), whereas the BWC sample had reduced bioactivity that was primarily associated with its inorganic fraction (IF). Overall, these results indicate that at non-toxic exposure doses, the RAW 264.7 cell line serves as an acute, sensitive and reliable biosensor for the screening of inflammatory constituents within and among discrete OSPW samples.

Aerobic degradation of anionic polyacrylamide in oil sands tailings: Impact factor, degradation effect, and mechanism.

An investigation was carried out to study the degradation of anionic polyacrylamide (A-PAM) under different temperature and microorganism conditions as well as to assess its effects on water chemistry and toxicity in oil sands tailings. The maximum removal efficiency of A-PAM was 41.0 % in tailings water with augmented microorganisms at 20 °C. No acrylamide (AMD) monomer was released during the A-PAM degradation, while residual AMD, from the manufacturing process to make A-PAM, was completely removed within 4 weeks. Both temperature and microorganisms showed significant effects (p < 0.05) on the degradation of A-PAM and residual AMD. Gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) analyses showed that biodegradation could be the active pathway for A-PAM degradation in oil sands tailings. These analyses also indicated that macromolecular A-PAM was degraded into lower molecular weight organic compounds. No remarkable changes of the total concentration of naphthenic acids (NAs) were observed in A-PAM treated tailings water. However, low concentrations of fatty acids (<2.5 mg/L), which fit the NAs formula, were detected in pure polymer solution, indicating that A-PAM degradation would not affect the total concentration of NAs in tailings water but affect their distribution. Our results also showed that total organic carbon (TOC) and chemical oxygen demand (COD) could be used as indicators of A-PAM degradation in tailings water due to their strong linear correlations (R2 > 0.90). Only slight increases in zeta potential and pH were found during A-PAM degradation. Limited effect on acute toxicity and no genotoxicity were found in A-PAM treated tailings water. Furthermore, the results suggest that A-PAM undergoes hydrolysis of amide groups by amidase enzymes, releasing ammonia and smaller molecules like organic acids. This research provides valuable information regarding the stability and impacts of A-PAM and thus will be beneficial for the management of oil sands tailings in long period of time.

Fully-automated SPE coupled to UHPLC-MS/MS method for multiresidue analysis of 26 trace antibiotics in environmental waters: SPE optimization and method validation.

Achieving simultaneous determination of antibiotic multiresidues in environmental waters by solid phase extraction (SPE) coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) with detection limits ≤ ng L-1 is still a huge challenge. Moreover, the offline SPE procedure was performed manually, costly, and time-consuming, while the online SPE required precision pretreatment instruments that require highly-skilled personnel. In this paper, a fully automated SPE coupled with UHPLC-MS/MS method was developed for analysis of antibiotics (sulfonamides, quinolones, and macrolides) in water matrices. Sample preparation optimization included SPE materials and configuration (HLB disks), sample volume (500-1000 mL), and pH (pH = 3) with a flow rate at 2~5 mL min-1, and an elution procedure with 2 × 6 mL methanol, and 2 × 6 mL acetone. Meanwhile, the parameters for UHPLC-MS/S detection of analytes were optimized, including LC retention time, and MS parameters. The instrumental limits of detection (LOD) and quantification (LOQ) of analytes ranged from 0.01-0.72 µg L-1 and 0.05-2.39 µg L-1, respectively, with satisfactory linear calibration (R2 > 0.995) and precision (< 9.9%). Recoveries in spike samples ranged between 77.5-104.9% in pure water, 59.4-97.8% in surface water (SW), and 58.2-108.6% in wastewater effluent (WWE) with relative standard deviations ≤ 12.8%. The matrix effects observed for most analytes were suppression (0-28.1%) except for five analytes having presented enhancement (0-14.6 %) in SW or WWE. This method can basically meet the needs of trace antibiotic residues detection in waters, with examples of concentrations of detected antibiotics being lower than LOQ (LLQ) -94.47 ng L-1 in WWEs and LLQ-15.47 ng L-1 in SW in the lower reaches of the Yangtze River Basin.

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.

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.

Solar photocatalytic treatment of model and real oil sands process water naphthenic acids by bismuth tungstate: Effect of catalyst morphology and cations on the degradation kinetics and pathways.

Bitumen extraction from oil sands produces large quantities of oil sands process water (OSPW), which contains recalcitrant naphthenic acids (NAs). In this study, three different morphologies of bismuth tungstate (Bi2WO6) photocatalysts were prepared by hydrothermal method. The prepared catalyst was characterized to obtain its structural, textural and chemical properties and tested for the degradation of model NAs and real OSPW under simulated solar irradiation. Nanoplate, flower-like and swirl-like Bi2WO6 were prepared and the results showed that the flower-like structure exhibited the highest specific surface area and total pore volume. The highest photocatalytic activity for the degradation of NAs was also demonstrated by the flower-like Bi2WO6, achieving complete degradation of cyclohexanoic acid (CHA) at fluence-based rate constant of 0.0929 cm2/J. Superoxide radicals (O2•-) and holes were identified as the major reactive species generated during the photocatalytic process. The effect of metallic ions on the degradation rates of S-containing and N-containing NAs differed and the heteroatom was found to be the main reactive site. The by-products of heteroatomic NAs were identified and degradation pathways were reported for the first time. The concentration changes of each byproduct were further estimated by mass balance. This research provides valuable information for the treatment of NAs by engineered passive solar-based approaches.

Advancing the treatment of primary influent and effluent wastewater during wet weather flow by single versus powdered activated carbon-catalyzed ozonation for the removal of trace organic compounds.

For the first time, single and PAC-catalyzed ozonation were explored for the wastewater treatment during wet weather flow in a prompt and efficient process. The effect of varying the ozone (O3) specific dose on the removal of micropollutants (MPs) was first investigated with a mixture of pharmaceuticals, herbicides and perfluorinated compounds in clean water. Most MPs showed higher affinity towards catalytic ozonation. Carbamazepine and Atrazine were found to be good surrogates for fast and slow reacting compounds, respectively. Applying single or PAC-catalyzed ozonation for 1 min only after coagulation was more efficient than applying them simultaneously. PAC-catalyzed ozonation was more efficient for the removal of organics and O3-resistant MPs. Both single and PAC-catalyzed ozonation achieved 4 log removal of E. coli, reduced the acute and genetic toxicity, and estrogenic activity of the wastewater. A detailed cost analysis revealed that applying single ozonation after coagulation costs between 0.06 and 0.32 $/m3 while applying PAC-catalyzed ozonation costs between 0.32 and 0.63 $/m3 for a flow rate between 100 and 600 MLD. Through a comprehensive performance assessment, PAC-catalyzed ozonation was deemed superior with one drawback related to the disposal of PAC.

Characterization of raw and ozonated oil sands process water utilizing atmospheric pressure gas chromatography time-of-flight mass spectrometry combined with solid phase microextractionun.

This work describes a novel application of atmospheric pressure gas chromatography time-of-flight mass spectrometry (APGC-TOF-MS) combined with solid-phase microextraction (SPME) for the simultaneous analysis of hydrocarbons and naphthenic acids (NAs) species in raw and ozone-treated oil sands process water (OSPW). SPME method using polydimethylsiloxane (PDMS)-coated fibers was validated using gas chromatography with flame ionization detector (GC-FID) to ensure the SPME extractions were operated appropriately. The ionization pathways of the hydrocarbon species in OSPW in the APGC source were verified by analyzing a mixture of eight polyaromatic hydrocarbons which were ionized primarily via charge transfer to produce [M+] while NAs in OSPW were found to be ionized through protonation to generate [MH+] in the wet APGC source. SPME/APGC-TOF-MS analysis demonstrated a different composition profile in OSPW #1, with 74.5% of hydrocarbon species, 23.4% of O2-NAs, and 2.1% of the oxidized NA species at extraction pH 2.0 compared with that obtained by UPLC-TOF-MS analysis (36.9% of O2-NAs, 26.8% of O3-NAs, 24.9% of O4-NAs, 9.1% of O5-NAs, 2.3% of O6-NAs). Moreover, the peak areas of the total NAs and the total peak areas of NAs + hydrocarbons measured by SPME/APGC-TOF-MS correlated excellently with the total NA concentration determined by UPLC-TOF-MS (R2 = 0.90) and the concentrations of the total acid-extractable organics determined by SPME/GC-FID (R2 = 0.98), respectively. APGC-TOF-MS integrated with the SPME techniques could extend the range of target compounds and be a promising alternative to evaluate and characterize NAs and hydrocarbon in different water types.

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.

A critical review on the detection, occurrence, fate, toxicity, and removal of cannabinoids in the water system and the environment.

Cannabinoids are a group of organic compounds found in cannabis. Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), the two major constituents of cannabinoids, and their metabolites are contaminants of emerging concern due to the limited information on their environmental impacts. As well, their releases to the water systems and environment are expected to increase due to recent legalization. Solid-phase extraction is the most common technique for the extraction and pre-concentration of cannabinoids in water samples as well as a clean-up step after the extraction of cannabinoids from solid samples. Liquid chromatography coupled with mass spectrometry is the most common technique used for the analysis of cannabinoids. THC and its metabolites have been detected in wastewater, surface water, and drinking water. In particular, 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) has been detected at concentrations up to 2590 and 169 ng L-1 in untreated and treated wastewater, respectively, 79.9 ng L-1 in surface water, and 1 ng L-1 in drinking water. High removal of cannabinoids has been observed in wastewater treatment plants; this is likely a result of adsorption due to the low aqueous solubility of cannabinoids. Based on the estrogenicity and cytotoxicity studies and modelling, it has been predicted that THC and THC-COOH pose moderate risk for adverse impact on the environment. While chlorination and photo-oxidation have been shown to be effective in the removal of THC-COOH, they also produce by-products that are potentially more toxic than regulated disinfection by-products. The potential of indirect exposure to cannabinoids and their metabolites through recreational water is of great interest. As cannabinoids and especially their by-products may have adverse impacts on the environment and public health, more studies on their occurrence in various types of water and environmental systems, as well as on their environmental toxicity, would be required to accurately assess their impact on the environment and public health.

Degradation of cyclohexanecarboxylic acid as a model naphthenic acid by the UV/chlorine process: Kinetics and by-products identification.

Degradation kinetics, by-products identification and pathways of a model naphthenic acid, cyclohexanecarboxylic acid (CHA), by the UV/Chlorine process were investigated in this study. Mathematical modeling indicated that the initial CHA decay rate increased rapidly with the chlorine dose when the chlorine dose was lower than 45 mg/L and decreased with further chlorine dose increases. Increasing the chlorine dose from 400 to 800 mg/L resulted in a steady increase in the total removal of CHA after 60 min of UV photolysis. By dividing the 700 mg/L chlorine dose into five separated doses (140 mg/L each) added at 10 min intervals, the total CHA removal increased from 72% to 91%. This implies that the ideal condition of the UV/Chlorine process in degrading CHA is to add chlorine continuously at a constant rate to compensate any chlorine consumption to reduce the radical scavenging effect. It was found that the CHA decay was mainly attributed to the hydroxyl radical (OH) attack and the reactive chlorine species (RCS) contribution was relatively small. Various by-products, including the mono-chlorinated and di-chlorinated by-products, were identified and the reaction pathway for CHA degradation during UV/Chlorine treatment was proposed.

A burning issue: The effect of organic ultraviolet filter exposure on the behaviour and physiology of Daphnia magna.

Ultraviolet (UV) filters are compounds utilized in many manufacturing processes and personal care products such as sunscreen to protect against UV-radiation. These highly lipophilic compounds are emerging contaminants of concern in aquatic environments due to their previously observed potential to bioaccumulate and exert toxic effects in marine ecosystems. Currently, research into the toxic effects of UV filter contamination of freshwater ecosystems is lacking, thus the present study sought to model the effects of acute and chronic developmental exposures to UV filters avobenzone, oxybenzone and octocrylene as well as a mixture of these substances in the freshwater invertebrate, Daphnia magna, at environmentally realistic concentrations. Median 48-hour effect and lethal concentrations were determined to be in the low mg/L range, with the exception of octocrylene causing 50% immobilization near environmental concentrations. 48-hour acute developmental exposures proved to behaviourally impair daphnid phototactic response; however, recovery was observed following a 19-day post-exposure period. Although no physiological disruptions were detected in acutely exposed daphnids, delayed mortality was observed up to seven days post-exposure at 200 µg/L of avobenzone and octocrylene. 21-day chronic exposure to 7.5 µg/L octocrylene yielded complete mortality within 7 days, while sublethal chronic exposure to avobenzone increased Daphnia reproductive output and decreased metabolic rate. 2 µg/L oxybenzone induced a 25% increase in metabolic rate of adult daphnids, and otherwise caused no toxic effects at this dose. These data indicate that UV filters can exert toxic effects in freshwater invertebrates, therefore further study is required. It is clear that the most well-studied UV filter, oxybenzone, may not be the most toxic to Daphnia, as both avobenzone and octocrylene induced behavioural and physiological disruption at environmentally realistic concentrations.

Fourier transform infrared spectroscopy as a surrogate tool for the quantification of naphthenic acids in oil sands process water and groundwater.

Naphthenic acid fraction compounds (NAFCs), defined herein as the polar organic compounds extracted from the acidified oil sands process water (OSPW) samples using dichloromethane, are becoming the research hotspot due to their presence in large amount in OSPW and along with other potentially NA-contaminated water streams from the mining site. Fourier transform infrared spectroscopy (FTIR) method is commonly used to quantify NAFCs and assumes that the total NA concentration is measured as the sum of the responses for all carboxylic acid functional groups. In this study, the NAFCs in various OSPW and groundwater (GW) samples from an active oil sands mining site were analyzed using FTIR. All water samples were pretreated using either solid-phase extraction (SPE) or liquid-liquid extraction (LLE) methods before analysis. The results showed that SPE produced higher recoveries of NAFCs than LLE for most water samples under current experimental conditions. For the quantification of NAFCs, commercial Fluka NA mixture and a pre-calibrated OSPW extract were employed as the calibration standards. The NAFCs calibrated with Fluka NA mixture and OSPW extract had clear linear relationships. The concentrations of NAFCs obtained using OSPW extract standard curve were 2.5 times the NAFC concentrations obtained using the Fluka NA mixture standard curve. Additionally, good linear correlations were observed between the total NAs and O2-O6 NA species determined by ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC-TOFMS) and the NAFCs measured by FTIR. According to these correlations, the NA compositions in NAFCs were developed, and the relative abundances of O2-O6 NA species in NAFCs were similar for SPE and LLE pretreated samples. The findings of this study demonstrated that FTIR could be used as a promising tool to monitor total NA species and to estimate the NA profile in different environmental water samples.

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

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

Comprehensive chemical analysis and characterization of heavy oil electric desalting wastewaters in petroleum refineries.

Large quantities of highly polluted point-source wastewaters (EDWs) are generated from electric desalting process of heavy oils (HOs), resulting in severe impacts on the efficiency of wastewater treatment plants in petroleum refineries. In the present study, a comprehensive chemical analysis and characterization of EDWs of two typical Chinese heavy oils, Liaohe heavy oil (LHO) and Karamy heavy oil (KHO), were investigated using Daqing light oil (DLO) as a control. The HO-EDWs (LHO-EDW and KHO-EDW) show high pollutants contents with complicated compositions, more polar dissolved organic pollutants (DOPs), strong emulsion stability and high acute biotoxicity towards Vibrio fischeri, compared to DLO-EDW. LHO-EDW and KHO-EDW have nearly equal pollutants contents but different compositions and distributions, where more types of DOPs exist in KHO-EDW. Large amounts of biologically recalcitrant aromatic compounds, as well as heteroatomic compounds such as CHO, CHOS and CHON species, extensively distribute in HO-EDWs. The organic nitrogen compounds (e.g., anilines and N2-3Ox, N1OxS1) in KHO-EDW most probably contribute to and thus leading to elevated levels of acute biotoxicity. Additionally, highly dispersed colloidal, micron-sized particles and polar compounds promote the emulsification and stabilization of HO-EDWs. These results can guide the development of pretreatment technologies for HO-EDWs, thus improving the treatment and management of heavy oil refineries' wastewater streams.

Photodegradation of naphthenic acids induced by natural photosensitizer in oil sands process water.

Utilization of renewable solar energy driven advanced oxidation processes for oil sands process water (OSPW) remediation has received extensive attention. Naturally existing inorganic photosensitizer in OSPW was investigated in this work to provide information about the application of indirect photolysis treatment of organic contaminants in OSPW. OSPW and OSPW organic fraction were exposed under UV irradiance with fluence of 10 J/cm2 to investigate the effect of OSPW inorganic fraction (OSPW-IF) on the non-catalytic photolysis of naphthenic acids (NAs) in OSPW. The results indicated that the inorganic fraction in OSPW enhanced the photodegradation of NAs, with 24.3% of total NA removal in OSPW, while only 12.4% of total NAs were removed in OSPW organic fraction. Moreover, the photodegradation of 1-adamantanecarboxylic acid (ACA) dissolved in OSPW-IF or carbonate buffer was conducted to verify the enhanced photodegradation of NAs by OSPW-IF. The results showed that 30.9% of ACA was removed in the OSPW-IF, while no ACA degradation was observed in carbonate buffer after 60 min of UV exposure, indicating that the OSPW-IF induced the photodegradation of ACA. In addition, nitrate was identified to be the photosensitizer in OSPW-IF responsible for the indirect photolysis of ACA. In the presence of nitrate, both hydroxyl radicals (•OH) and reactive nitrogen species were generated, where •OH was the dominant reactive species that contributed to the degradation of ACA. Ten possible by-products ranging from single to multiple hydroxyl, nitroso, nitro and carbonyl substituted products were proposed to be produced from the nitrate-induced photodegradation process through three different pathways. This study demonstrated that the photolysis of NAs in OSPW due to the presence of natural photosensitizers and nitrate could act as a natural photosensitizer for the remediation of OSPW by the photo-oxidation process.