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The global need for clean water requires sustainable technology for purifying contaminated water. Highly efficient solar-driven photodegradation is a sustainable strategy for wastewater treatment. In this work, we demonstrate that the photodegradation efficiency of micropollutants in water can be improved by ~2-24 times by leveraging polymeric microlenses (MLs). These microlenses (MLs) are fabricated from the in-situ polymerization of surface nanodroplets. We found that photodegradation efficiency ({\eta}) in water correlates approximately linearly with the sum of the intensity from all focal points of MLs, although no difference in the photodegradation pathway is detected from the chemical analysis of the byproducts. With the same overall power over a given surface area, {\eta} is doubled by using ordered arrays, compared to heterogeneous MLs on an unpatterned substrate. Higher {\eta} from ML arrays may be attributed to a coupled effect from the focal points on the same plane that creates high local concentrations of active species to further speed up the rate of photodegradation. As a proof-of-concept for ML-enhanced water treatment, MLs were formed on the inner wall of glass bottles that were used as containers for water to be treated. Three representative micropollutants (norfloxacin, sulfadiazine, and sulfamethoxazole) in the bottles functionalized by MLs were photodegraded by 30% to 170% faster than in normal bottles. Our findings suggest that the ML-enhanced photodegradation may lead to a highly efficient solar water purification approach without a large solar collector size. Such an approach may be particularly suitable for portable transparent bottles in remote regions., Comment: Preprint for ACS ES&T Water

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.

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 (p0.05) 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 (R

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.

A fully automated solid-phase extraction (SPE) coupled ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was developed for analysis of antibiotics (sulfonamides, quinolones, and macrolide) in water matrices. Sample preparation optimization included the selection of the best SPE material and configuration (HLB disks), sample volume (500−1000 mL water sample (pH = 3)) with a flow rate at 1−2 mL min− 1, and an elution procedure with 2 ⋅ 6 mL methanol, 2 ⋅ 6 mL acetone-methanol (V/V = 1/1). Meanwhile, the parameters for UPLC-MS/S detection of each analyte was 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 good linear correlation (R2 > 0.995) and precision (− 1 in WWEs and BQL−15.47 ng L− 1 in SW in the lower reaches of the Yangtze River Basin.

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.

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., Graphical abstract Image 1, Highlights • Cannabinoids in wastewater are expected to increase due to legalisation. • SPE-LC-MS is most commonly used for cannabinoids analysis. • Adsorption was the main mechanism of removal in wastewater treatment plants. • Transformation products predicted to have negative impact on the environment. • Possible pollutants in recreation waters are expected after legalisation.

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.

This paper reported the impact of UV/H

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.

Naphthenic acids (NAs) are a mixture of aliphatic and alicyclic carboxylic acids which are persistent in the environment. In this study, a sludge-based biochar/iron oxide (B-FeOx) catalyst with 3D flower-like shaped structure was prepared through a facile hydrothermal method. For the first time, the B-FeOx catalyst was employed to activate peroxymonosulfate (PMS) for the removal of two model NA compounds (1-adamantanecarboxylic acid (ACA) and 4-methylheptanoic acid) at pH 8.50. Compared to biochar or FeOx alone, a higher degradation efficiency (96.1%) and faster degradation rate (k = 0.100 min−1) of ACA were obtained by the B-FeOx composite at a catalyst dose of 2.0 g/L and PMS dose of 2.5 mM. The higher degradation efficiency of B-FeOx was attributed to the improved surface area and pore volume as well as the abundant reactive sites induced by the flower-like structure. Furthermore, the hydroxyl radical (•OH) generated in the B-FeOx/PMS system was the dominant radical for both ACA and 4-methylheptanoic acid degradation as demonstrated through radical quenching experiments. The presence of chloride ions in the B-FeOx/PMS system showed a suppression effect on the degradation of ACA and 4-methylheptanoic acid at Cl− concentrations between 5 and 20 mM. No significant difference in the degradation rates of ACA and 4-methylheptanoic acid was observed at different Cl− concentrations. Overall, the results of this study showed that the sludge (waste material)-based B-FeOx composite may have the potential to be utilized as PMS catalyst for the removal of NAs that are especially abundant in oil sands process water.

An environmental-friendly treatment method based on photochemical reactions of ferricarboxylate complexes was developed for the treatment of oil sands process water (OSPW). Without using H2O2, the classical naphthenic acids (NAs), one of the organic compounds present in OSPW, can be effectively degraded by ferric citrate under visible light irradiation. Photochemical reaction activity of ferric citrate was greatly affected by the initial pH of OSPW. In acidic conditions, ferric citrate exhibited an extremely high degradation ratio of classical NAs, 98.3% (initial pH 3) and 96.8% (initial pH 5). Once initial pH exceeded 5, the degradation ratio of classical NAs in OSPW decreased quickly, and the degradation ratio of classical NAs could reach 65.7% (initial pH 7) and 42.4% (without adjusting pH, initial pH 8.9), respectively. It was found that the structure of NAs had little impact on the removal efficiency of NAs. It was also confirmed through scavenger experiments and reaction mechanism study that hydroxyl radical was the dominant reactive species in the process. The study demonstrated that ferric citrate possesses excellent visible light absorption ability and the photochemical reactions of ferric citrate can produce both Fe2+ and H2O2 in situ, Fenton reagent, which non-selectively degrade NAs of OSPW.

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.

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.

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.

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 (

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.

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.

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.

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.

The formation of odorous aldehydes and N-chloraldimines, and also nitriles, which are potentially hazardous to human health, was investigated in studies of the chlorination of amino acids (AAs) in both operational drinking water treatment plants and laboratory-based experiments. In the drinking water treatment plants studied, the concentration of total free AAs did not significantly change after treatment, even though good removal of DOC was observed. However, free AAs still contributed less than 3% of total nitrogen in the treated drinking waters, and no aldehydes, N-chloraldimines or nitriles of interest were detected in the treated waters, presumably due to the low concentrations of the precursor AAs in these water samples. Laboratory formation potential experiments showed that carboxylic acids can form from the degradation of aldehydes and nitriles. Volatile carboxylic acids could result in odour issues and some carboxylic acids may be of potential health concern. Therefore, carboxylic acids should also be considered as potential by-products of interest in distribution systems with long contact times of ≥ 7days. A higher proportion of nitrile formation, and promotion of carboxylic acid formation, was observed when the chlorine to AA ratio was greater than 4 compared to when this ratio was 2.8, indicating that the Cl:AA ratio is an important factor in DBP formation pathways. This suggests that results from laboratory formation studies undertaken at these low Cl:AA ratios cannot be directly applied to 'real' water systems, which typically have Cl:AA ratios that are orders of magnitude higher than 4. Laboratory formation potential experiments also showed that the short-term rate of formation of aldehydes and N-chloraldimines was reduced in the presence of ammonia, although formation over longer timescales (e.g. 7 days) was not significantly different between chlorination and chloramination experiments. Therefore, the use of chloramination instead of chlorination does not appear to reduce the formation of these by-products from AAs.

Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected byproducts. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modeling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4 × 104 M-1 s-1) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9 × 102 M-1 s-1), although some N-monochlorovaline degraded into isobutyraldehyde (1.0 × 10-4 s-1). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3 × 10-4 s-1) and N-chloroisobutyraldimine (1.2 × 10-4 s-1). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odor threshold concentration, resulting in aesthetic challenges and an unknown health risk.

Oil sands process water (OSPW) contains complex components of inorganics and organics. This is the first study that separated OSPW inorganic and organic fractions and examined their relative acute toxicity when compared with the original whole OSPW using an in-vitro cell-based bio-indicator system. The separation of OSPW inorganic and organic fractions would be conducive to the understanding of the toxic contribution of organic and inorganic fractions as well as the identification and treatment of organic fractions. In this research, we demonstrated that the highest organic fraction extraction was obtained using HLB solid phase extraction with 95.4 ± 0.7% of dissolved organic carbon (DOC) and 90.0 ± 5.3% of naphthenic acid (NA) recovered from OSPW, which were higher than those obtained using the traditional dichloromethane liquid-liquid extraction (48.8 ± 0.2% of DOC and 81.0 ± 2.6% of NA recovery) or other SPE cartridges tested. We also reported the first isolation method for OSPW inorganic fraction by removing 96.1 ± 0.2% of DOC in OSPW using granular activated carbon. The difference of other parameters such as pH, alkalinity, conductivity, and concentration of detected ions between OSPW and isolated inorganic fraction was negligible. The acute toxicity of whole OSPW, separated OSPW inorganic fraction and organic fraction, and the reconstituted fractions were assessed using in-vitro bioassays with RAW 264.7 mouse macrophage cell lines. OSPW organic fraction demonstrated significant cytotoxicity at 14 mg/L O2-NA and affected the cellular metabolic activity at 10 mg/L of O2-NAs. No significant cytotoxicity or effect on cellular metabolic activity was observed for whole OSPW, OSPW inorganic fraction and the reconstituted fractions. Overall, this study provides the procedure for the isolation of the major components of OSPW (i.e., organics and inorganics), which allows the assessment of their relative toxicological effects using a standard in-vitro bioassay and would allow more accurate characterization and treatment study for each fraction in OSPW.

In this paper, the degradation of Acid Orange 7 (AO7), by persulfate activated from in situ electrochemically generated Cu+ (EC-Cu-PDS) was studied. The influence of key parameters such as pH, current density, copper concentration and electrode size were investigated, with the optimal operation condition being pH 2 with cathode to anode area of 4:1. The degradation efficiency of the EC-Cu-PDS after 30 min was compared to the efficiency of other electrocatalysis system using iron, cobalt or silver. The proposed EC-Cu-PDS process has a higher degradation efficiency of 70%, as compare to 56% of the EC-Fe-PDS process. Although the EC-Cu-PDS process has a lower degradation efficiency compared to 100% of Co-PMS and 80% of the EC-Ag-PDS processes, the EC-Cu-PDS process would be cheaper and safer to operate than the latter processes. The estimated electrical energy consumption of the EC-Cu-PDS processes was significantly lower than other electrocatalysis processes, ranging from 0.008 to 2.42 kW h m−3. The degradation of AO7 by the EC-Cu-PDS process was via oxidization of AO7 by both hydroxyl radicals generated at the anode and sulfate radicals generated by both electrochemically at the anode and Cu+ activation of PDS.

This paper is a critical review of current knowledge of organic chloramines in water systems, including their formation, stability, toxicity, analytical methods for detection, and their impact on drinking water treatment and quality. The term organic chloramines may refer to any halogenated organic compounds measured as part of combined chlorine (the difference between the measured free and total chlorine concentrations), and may include N-chloramines, N-chloramino acids, N-chloraldimines and N-chloramides. Organic chloramines can form when dissolved organic nitrogen or dissolved organic carbon react with either free chlorine or inorganic chloramines. They are potentially harmful to humans and may exist as an intermediate for other disinfection by-products. However, little information is available on the formation or occurrence of organic chloramines in water due to a number of challenges. One of the biggest challenges for the identification and quantification of organic chloramines in water systems is the lack of appropriate analytical methods. In addition, many of the organic chloramines that form during disinfection are unstable, which results in difficulties in sampling and detection. To date research has focussed on the study of organic monochloramines. However, given that breakpoint chlorination is commonly undertaken in water treatment systems, the formation of organic dichloramines should also be considered. Organic chloramines can be formed from many different precursors and pathways. Therefore, studying the occurrence of their precursors in water systems would enable better prediction and management of their formation.

Organic chloramines have been found to form in drinking water systems and they have been reported to potentially cause cytotoxic and genotoxic effects even at micromolar concentration levels. However, little information on the occurrence and toxicity of organic chloramines in drinking water is currently available. In this study, a triiodide colorimetric method, which was a modified standard iodometric method for colorimetric measurement, was used to determine the formation of organic chloramines that were not suitable for direct UV detection due to interference peaks in the 250 to 280 nm range. The triiodide colorimetric and direct UV methods were successfully applied to determine the rate of degradation of N-chloroglycine, N-chloroserine, N-chloroasparagine and N-chlorophenylalanine. The stability of these organic chloramines was found to vary, with their half-life ranging from 15 to 5775 min. The stability of the organic chloramines appeared to increase with increasing basicity of the amine nitrogen. The half-life values found for some of the organic chloramines investigated in this study suggest that their presence and persistence may be relevant in drinking water systems. In order to better characterise the risk associated with the occurrence of organic chloramines in drinking water, the stabilities of a wider range of organic chloramines should be investigated.

Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N-chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N-chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable.

This paper reports a new analytical method for the analysis of 18 amino acids in natural waters using solid-phase extraction (SPE) followed by liquid chromatography-electrospray tandem mass spectrometry (LC–MS/MS) operated in multiple reaction monitoring mode. Two different preconcentration methods, solid-phase extraction and concentration under reduced pressure, were tested in development of this method. Although concentration under reduced pressure provided better recoveries and method limits of detection for amino acids in ultrapure water, SPE was a more suitable extraction method for real samples due to the lower matrix effects for this method. Even though the strong cation exchange resin used in SPE method introduced exogenous matrix interferences into the sample extracts (inorganic salt originating from the acid–base reaction during the elution step), the SPE method still incorporates a broad sample clean-up and minimised endogenous matrix effects by reducing interferences originating from real water samples. The method limits of quantification (MLQ) for the SPE LC–MS/MS method in ultrapure water ranged from 0.1 to 100 μg L−1 as N for the different amino acids. The MLQs of the early eluting amino acids were limited by the presence of matrix interfering species, such as inorganic salts in natural water samples. The SPE LC–MS/MS method was successfully applied to the analysis of amino acids in 3 different drinking water source waters: the average total free amino acid content in these waters was found to be 19 μg L−1 as N, while among the 18 amino acids analysed, the most abundant amino acids were found to be tyrosine, leucine and isoleucine.