Degradation of ambroxol by UV/chloramine process: Kinetics, degradation pathway, and control of the risk of highly toxic disinfection by-products.

Ambroxol (AMB) is a commonly used bromine-containing organic compound in medical applications and has been frequently found in water environments, which might pose risks of forming brominated disinfection by-products (Br-DBPs) in water treatment systems. The degradation kinetics as well as the degradation mechanism of AMB in the UV/chloramine process were investigated in this study. It was determined that reactive chlorine species (RCS) and the reactive nitrogen species (RNS) were the dominant free radicals for AMB degradation. Debromination occurred mainly in the initial stage of the degradation process, with a debromination rate of 34.5% at 10 min. Four possible degradation pathways of AMB were proposed based on liquid chromatography mass spectrometry (LC-MS) analysis as well as density functional theory (DFT) calculations, meanwhile the ECOSAR model was used to predict the toxicity risk of AMB and its degradation intermediates. Furthermore, after assessing the formation of DBPs during the UV/chloramine pre-oxidation process and conducting a toxicity risk analysis based on the results, it has been verified that this method can effectively remove AMB while reducing the formation potential of DBPs in the water environment. This suggests that the UV/chloramine process shows promise for treating bromine-containing organic compounds in real-world water treatment applications.

Halogenation of Anilines: Formation of Haloacetonitriles and Large-Molecule Disinfection Byproducts.

Aniline-related structures are common in anthropogenic chemicals, such as pharmaceuticals and pesticides. Compared with the widely studied phenolic compounds, anilines have received far less assessment of their disinfection byproduct (DBP) formation potential, even though anilines and phenols likely exhibit similar reactivities on their respective aromatic rings. In this study, a suite of 19 aniline compounds with varying N- and ring-substitutions were evaluated for their formation potentials of haloacetonitriles and trihalomethanes under free chlorination and free bromination conditions. Eight of the aniline compounds formed dichloroacetonitrile at yields above 0.50%; the highest yields were observed for 4-nitroaniline, 3-chloroaniline, and 4-(methylsulfonyl)aniline (1.6-2.3%). Free bromination generally resulted in greater haloacetonitrile yields with the highest yield observed for 2-ethylaniline (6.5%). The trihalomethane yields of anilines correlated with their haloacetonitrile yields. Product analysis of aniline chlorination by liquid chromatography-high-resolution mass spectrometry revealed several large-molecule DBPs, including chloroanilines, (chloro)hydroxyanilines, (chloro)benzoquinone imines, and ring-cleavage products. The product time profiles suggested that the reaction pathways include initial ring chlorination and hydroxylation, followed by the formation of benzoquinone imines that eventually led to ring cleavage. This work revealed the potential of aniline-related moieties in micropollutants as potent precursors to haloacetonitriles and other emerging large-molecule DBPs with the expected toxicity.

Persistent free radicals in natural organic matter activated by iron particles enhanced disinfection byproduct formation.

The widespread presence of iron (Fe) particles and natural organic matter (NOM) in drinking water distribution systems (DWDS) can significantly affect tap water quality, contributing to aesthetic issues and potentially generating harmful disinfection byproducts (DBPs). This study revealed that Fe particles, when combined with humic acid (HA), substantially increased DBP formation during chlorination. Fe particles (particularly preformed Fe particles) significantly increased haloacetic acid (HAA) formation by activating the persistent free radicals (PFRs) in the HA. Compared with the control system without Fe particles, greater than 2 times of HAA increase were observed for the system with Fe pariticles. PFRs accumulated on Fe particle surface could generate hydroxyl radicals, facilitating the decomposition of HA into smaller molecules, which were more reactive with chlorine disinfectants, thus elevated the DBP formation including both known and unknown N-DBPs and Cl-DBPs. The DBP promotion effect of in-situ formed Fe particles was much less than that of preformed Fe particles although both in-situ formed and preformed Fe particles could accumulate PFRs from HA. In-situ formed particles primarily accumulated carbon-centered PFRs, while preformed particles accumulated oxygen-centered PFRs. To mitigate the Fe particle induced water quality risks, it is crucial to control iron pipe corrosion and iron release in DWDS. In addtion, the optimization of treatment processes such as coagulation and filtration to more completely remove NOM and Fe particles could help minimize the DBP formation.

Evaluation of distribution system water quality during a free chlorine conversion.

Chloraminated drinking water systems commonly use free chlorine conversions (FCCs) to prevent or control nitrification, but unintended water quality changes may occur, including increased disinfection by-product and metal concentrations. This study evaluated water quality in a chloraminated drinking water system and residential locations before, during, and after their annual, planned FCC. Water quality alternated between relatively consistent and variable periods when switching disinfectants. During the FCC, regulated four trihalomethane and five haloacetic acid concentrations increased by four and seven times, respectively, and exceeded corresponding maximum contaminant levels. Implications of disinfection by-product sampling during an FCC were assessed, and an approach to account for increased FCC disinfection by-product concentrations was proposed. For metals, the FCC had minor impacts on distribution system concentrations and did not appear to impact residential concentrations. Overall, observed variable water quality appeared primarily associated with switching disinfectants and depended on distribution system hydraulics.

Health Risk Assessment of Employees Exposed to Chlorination By-products of Recreational Water in Large Amusement Parks in Shanghai.

Objective: Chlorination is often used to disinfect recreational water in large amusement parks; however, the health hazards of chlorination disinfection by-products (DBPs) to occupational populations are unknown. This study aimed to assess the exposure status of chlorinated DBPs in recreational water and the health risks to employees of large amusement parks. Methods: Exposure parameters of employees of three large amusement parks in Shanghai were investigated using a questionnaire. Seven typical chlorinated DBPs in recreational water and spray samples were quantified by gas chromatography, and the health risks to amusement park employees exposed to chlorinated DBPs were evaluated according to the WHO's risk assessment framework. Results: Trichloroacetic acid, dibromochloromethane, bromodichloromethane, and dichloroacetic acid were detected predominantly in recreational water. The carcinogenic and non-carcinogenic risks of the five DBPs did not exceed the risk thresholds. In addition, the carcinogenic and non-carcinogenic risks of mixed exposure to DBPs were within the acceptable risk limits. Conclusion: Typical DBPs were widely detected in recreational water collected from three large amusement parks in Shanghai; however, the health risks of DBPs and their mixtures were within acceptable limits.

The impact of PAC-loaded polymer membrane thickness on chloroform removal and comparison of solvent and thermal membrane regeneration methods.

Powdered activated carbon (PAC) has better adsorption performance than granular activated carbon (GAC) and is widely used in water purification. In most cases, PAC is dosed into water directly, then precipitated as sludge, and landfilled. In this study, PAC was mixed with a polymer and dissolved in dimethylformamide (DMF) solvent to form a PAC-loaded membrane, which was then tested for chloroform removal. The chloroform adsorption capacity of the PAC membrane increased with increasing membrane thickness because of higher carbon loading. However, regardless of membrane thickness, the flux of the PAC membranes was similar since flux resistance predominantly occurred at the top dense polymer surface. This dense surface can be removed by sandpaper polishing, where the adsorption capacity of the polished PAC membranes was 20% higher than the unpolished membranes because of more even distribution of feed water on the polished surface. Removal of the dense surface via polishing increased the flux by 97% to 130%, exceeding the flux of typical household carbon block filters. Using DMF to regenerate the membrane recovered 48% to 66% of the initial adsorption capacity. Thermal regeneration of the exhausted PAC membrane at 250°C was more effective than DMF regeneration (both in terms of cost and performance), with 83% to 94% PAC membrane regeneration efficiency over four regeneration recycles. After four thermal regeneration cycles, flux increased by 300% and the membrane became brittle because of thermal aging of the polymer, indicating that a total of 6 h of regeneration time (equivalent to three cycles in this study) was the limit for effective PAC membrane performance. PRACTITIONER POINTS: Powdered activated carbon was immobilized on a membrane to remove chloroform from water. Thicker membranes increased adsorption capacity but did not impact flux. Flux and capacity increased using polishing to remove the dense polymer surface and more evenly distribute flow across the membrane. Thermal regeneration of the membrane at 250°C was effective for up to three cycles and outperformed solvent-based regeneration. PAC-loaded filters are relevant for applications such as household carbon block filtration.

Influence of biodegradable plastics on the generation of disinfection byproducts in the chlorination process.

Biodegradable plastics (BPs) have seen a continuous increase in annual production and application due to their environmentally sustainable characteristics. However, research on the formation of disinfection byproducts (DBPs) from biodegradable microplastics (BMPs) during chlorination is limited, and the effects of aqueous solution chemistry on this process have yet to be explored. Therefore, two biodegradable microplastics, polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT), were investigated in this study to examine the changes in their physicochemical properties before and after chlorination, and the formation of DBPs under different environmental conditions. The results showed that PLA was more chlorine-responsive, and generated more DBPs. The pH converted some of the intermediates into more stable DBPs by affecting the concentration of HClO and base-catalyzed reactions, whereas ionic strength slightly reduced DBP concentration by ion adsorption and promoting the aggregation of BMPs. Finally, since PLA has a slightly greater volume of mesopores and micropores compared to PBAT, it may more effectively adsorb DBP precursors beyond natural organic matter (NOM), such as some anthropogenic pollutants, thus potentially decreasing the formation of chlorinated DBPs in surface water. This research explored the potentiality for DBP formation by BMPs under different water quality conditions during the disinfection process, which is useful for assessing the environmental hazards of BMPs.

Bacterial dealkylation of benzalkonium chlorides in wastewater produces benzyldimethylamine, a potent N-nitrosodimethylamine precursor.

N-nitrosodimethylamine (NDMA) is a carcinogenic disinfection byproduct that forms during chloramine disinfection of municipal wastewater effluents which are increasingly used to augment drinking water supplies due to growing water scarcity. Knowledge of wastewater NDMA precursors is limited and the known pool of NDMA precursors has not closed the mass balance between precursor loading, precursor NDMA yield, and formed NDMA. Benzalkonium chlorides (BACs) are the most prevalent quaternary ammonium surfactants and have antimicrobial properties. The extensive utilization of BACs in household, commercial and industrial products has resulted in their detection in wastewater at elevated concentrations. We report the formation of a potent NDMA precursor, benzyldimethylamine (BDMA) from the biodegradation of BACs during activated sludge treatment. BDMA formation and NDMA formation potential (FP) were functions of BAC and mixed liquor suspended solids concentration at circumneutral pH, and the microbial community source. Sustained exposure to microorganisms reduced NDMA FP through successive dealkylation of BDMA to less potent precursors. BAC alkyl chain length (C8 - C16) had little impact on NDMA FP and BDMA formation because chain cleavage occurred at the C-N bond. Wastewater effluents collected from three facilities contained BDMA from 15 to 106 ng/L, accounting for an estimated 4 to 38 % of the NDMA precursor pool.

Harnessing bromide ions to boost peroxymonosulfate for reactive yellow 145 dye degradation.

Bromide (Br-) was found in the fresh waters at concentrations from 0.1 to 1 mg/L and can be used to activate peroxymonosulfate (PMS) as a widely used chemical oxidation agent. In the present study, the reaction between PMS and Br- ions (PMS/Br- process) for the effective degradation of reactive yellow 145 (RY-145) dye was investigated by changing operational parameters vis solution pH, dosage of Br- ions and PMS, RY-145 concentration, and reaction time. Based on the results, the simultaneous presence of PMS and Br- ions in the solution led to efficient degradation of RY-145 with a synergistic index of 11.89. The degradation efficiency of RY-145 was decreased in severe basic pH and the presence of CO32- ions as a coexisting anion. Likewise, 4 mg/L of humic acid (HA), used as a classic scavenger, led to a 26.53% decrease in the RY-145 degradation efficiency. The free bromine (HOBr/OBr-), superoxide radical (●O2-), and singlet oxygen (1O2) was the dominant oxidation agents in RY-145 degradation, which confirmed the nonradical degradation pathway. In addition, PMS/Br- process showed excellent ability in mineralizing RY-145 in different aqueous solutions (total organic carbon (TOC) decreased 86.39% in deionized water and 78.23% in tap water). Although pollutants such as azo dyes can be effectively removed in the PMS/Br- process, the formation of byproducts should be strategically controlled and special attention should be paid when the PMS-based advance oxidation process is applied to treat Br- containing solutions.

Sulfonamide disinfection byproducts exhibited severe toxicity to human commensal bacteria.

Many antibiotic disinfection byproducts have been detected but their toxicity has not been evaluated adequately. In this report, the chlorination reaction kinetics of five common sulfamides (SAs), reaction intermediates and their toxicity were investigated. Chlorination of sulfapyridine (SPD), sulfamethazine (SMT), sulfathiazole (STZ), and sulfisoxazole (SIZ) followed the second-order kinetics, and were degraded completely within 10 min. A large number of reaction intermediates were deteced by LC-MS, among which a total of 16 intermediates were detected for the first time. Toxicity of the five SAs chlorination solutions was evaluated separately by examining their effects on the growth rate of S. salivarius K12, a commensal bacterium in the human digestive system. After 30 min chlorination, solutions of SMT, STZ and sulfadiazine (SDZ) each exhibited severe toxicity by inhibiting the bacteria growth completely, whereas the inhibition was only 50 % and 20  % by SIZ and SPD respectively. Based on the comparison between toxicity test results and mass spectra, three SA chlorination intermediates, m/z 187.2 (C10H10N4), m/z 287.2 (C9H7N3O4S2) and m/z 215 (C7H10N4O2S/C12H14N4) were proposed to be the primary toxicants in the chlorination products. Our study demonstrated the power of combined approach of chemical analysis and toxicity testing in identifying toxic disinfection byproducts, and highlighted the ne ed for more research on the toxicity evaluation and risk assessment of antibiotic disinfection byproducts.

Degradation of carbamazepine in ice with bromate and nitrite: Role of reactive nitrogen species.

Seasonal freezing of waters occurs during winter in cold regions. Bromate ( [Formula: see text] ) is a disinfection by-product generated during water treatment, its interaction with emerging contaminants may be affected by freezing. Nitrite ( [Formula: see text] ) is widely distributed in the environment, whereas its effect on the interaction of emerging contaminants and [Formula: see text] in ice may have been overlooked. Herein carbamazepine (CBZ) was selected as a model emerging contaminant to elucidate the role of reactive nitrogen species (RNS) in contaminant transformation during the reduction of [Formula: see text] by [Formula: see text] in ice. Results indicated that freezing significantly enhanced CBZ degradation by [Formula: see text] . The CBZ degradation by [Formula: see text] and [Formula: see text] in ice was 25.4 %-27.8 % higher than that by [Formula: see text] . Contributions of hydroxyl radical (•OH), bromine radical (•Br), and RNS to CBZ degradation in freezing/dark or sunlight systems were 8.1 % or 15.9 %, 25.4 % or 7.2 %, and 66.5 % or 76.9 %, respectively. Most CBZ was degraded by RNS generated during the reduction of [Formula: see text] by [Formula: see text] in ice, resulting in 16.4 % of transformation products being nitro-containing byproducts. Hybrid toxicity of CBZ/ [Formula: see text] / [Formula: see text] system was reduced effectively after the freezing-sunlight process. This study can provide new insights into the environmental fate of emerging contaminants, [Formula: see text] , and [Formula: see text] in cold regions.

Natural Disinfection-like Process Unveiled in Soil Microenvironments by Enzyme-Catalyzed Chlorination.

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.

Climate change and future water demand: Implications for chlorine and trihalomethanes management in water distribution systems.

The global change in surface water quality calls for increased preparedness of drinking water utilities. The increasing frequency of extreme climatic events combined with global warming can impact source and treated water characteristics such as temperature and natural organic matter. On the other hand, water saving policies in response to water and energy crisis in some countries can aggravate the situation by increasing the water residence time in the drinking water distribution system (DWDS). This study investigates the individual and combined effect of increased dissolved organic carbon (DOC), increased temperature, and reduced water demand on fate and transport of chlorine and trihalomethanes (THMs) within a full-scale DWDS in Canada. Chlorine and THM prediction models were calibrated with laboratory experiments and implemented in EPANET-MATLAB toolkit for prediction in the DWDS under different combinations of DOC, temperature, and demand. The duration of low chlorine residuals (<0.2 mg/L) and high THM (>80 µg/L) periods within a day in each scenario was reported using a reliability index. Low-reliability zones prone to microbial regrowth or high THM exposure were then delineated geographically on the city DWDS. Results revealed that water demand reduction primarily affects chlorine availability, with less concern for THM formation. The reduction in nodal chlorine reliability was gradual with rising temperature and DOC of the treated water and reducing water demand. Nodal THM reliability remained unchanged until certain thresholds were reached, i.e., temperature >25 °C for waters with DOC <1.52 mg/L, and DOC >2.2 mg/L for waters with temperature = 17 °C. At these critical thresholds, an abrupt network-wide THM exceedance of 80 µg/L occurred. Under higher DOC and temperature levels in future, employing the proposed approach revealed that increasing the applied chlorine dosage (which is a conventional method used to ensure sufficient chlorine coverage) results in elevated exposure toTHMs and is not recommended. This approach aids water utilities in assessing the effectiveness of different intervention measures to solve water quality problems, identify site-specific thresholds leading to major decreases in system reliability, and integrate climate adaptation into water safety management.

Impact of changes in biofilm composition response following chlorine and chloramine disinfection on nitrogenous disinfection byproduct formation and toxicity risk in drinking water distribution systems.

In practical drinking water treatment, chlorine and chloramine disinfection exhibit different mechanisms that affect biofilm growth. This study focused on the influence of biofilm composition changes, especially extracellular polymeric substance (EPS) fractions, on the potential formation and toxicity of nitrogenous disinfection by-products (N-DBP). Significant differences in microbial diversity and community structure were observed between the chlorine and chloramine treatments. Notably, the biofilms from the chloramine-treated group had higher microbial dominance and greater accumulation of organic precursors, as evidenced by the semi-quantitative confocal laser-scanning microscopy assay of more concentrated microbial aggregates and polysaccharide proteins in the samples. Additionally, the chloramine-treated group compared with chlorine had a higher EPS matrix content, with a 13.5 % increase in protein. Furthermore, the protein distribution within the biofilm differed; in the chlorine group, proteins were concentrated in the central region, whereas in the chloramine group, proteins were primarily located at the water-biofilm interface. Notably, functional prediction analyses of protein fractions in biofilms revealed specific functional regulation patterns and increased metabolism-related abundance of proteins in the chlorine-treated group. This increase was particularly pronounced for proteins such as dehydrogenases, reductases, transcription factors, and acyl-CoA dehydrogenases. By combining the Fukui function and density functional calculations to further analyse the effect of biofilm component changes on N-DBP production under chlorine/chloramine and by assessing the toxicity risk potential of N-DBP, it was determined that chloramine disinfection is detrimental to biofilm control and the accumulation of protein precursors has a higher formation potential of N-DBPs and toxicity risk, increasing the health risk of drinking water.

Degradation kinetics and disinfection by-products formation of benzophenone-4 during UV/persulfate process.

The degradation kinetics, reaction pathways, and disinfection by-products formation of an organic UV filter, benzophenone-4 (BP4) during UV/persulfate oxidation were investigated. BP4 can hardly be degraded by UV alone, but can be effectively decomposed by UV/persulfate following pseudo-first order kinetics. BP4 degradation rate was enhanced with increasing persulfate dosage and decreasing pH from 8 to 5. However, the degradation rate of BP4 at pH 9 was higher than that at pH 8 because of the presence of phenolic group in BP4 structure. and SO4-⋅ were confirmed as the major contributors to BP4 decomposition in radical scavenging experiments, and the second-order rate constants between HO⋅ and BP4 as well as those between SO4-⋅ and BP4 were estimated by establishing and solving a kinetic model. The presence of Br- and humic acid inhibited the decomposition of BP4, while NO3- promoted it. The mineralisation of BP4 was only 9.1% at the persulfate concentration of 50 µM. Six degradation intermediates were identified for the promulgation of the reaction pathways of BP4 during UV/persulfate oxidation were proposed as a result. In addition, the formation of DBP in the sequential chlorination was evaluated at different persulfate dosages, pH values, and water matrix. The results of this study can provide essential knowledge for the effective control of DBP formation with reducing potential hazard to provide safe drinking water to the public.

BP4 can be effectively degraded by UV/persulfate process, following pseudo-first order kinetics.OH⋅ and SO4−⋅ were identified as the main contributors to BP4 degradation during UV/persulfate process.The degradation pathways of BP4 during UV/persulfate process were proposed.Initial persulfate concentration and solution pH both affected the yield of DBPs.The higher toxic DBPs can be generated in the presence of Br− or NO3−.

Closing Dichloramine Decomposition Nitrogen and Oxygen Mass Balances: Relative Importance of End-Products from the Reactive Nitrogen Species Pathway.

In drinking water chloramination, monochloramine autodecomposition occurs in the presence of excess free ammonia through dichloramine, the decay of which was implicated in N-nitrosodimethylamine (NDMA) formation by (i) dichloramine hydrolysis to nitroxyl which reacts with itself to nitrous oxide (N2O), (ii) nitroxyl reaction with dissolved oxygen (DO) to peroxynitrite or mono/dichloramine to nitrogen gas (N2), and (iii) peroxynitrite reaction with total dimethylamine (TOTDMA) to NDMA or decomposition to nitrite/nitrate. Here, the yields of nitrogen and oxygen-containing end-products were quantified at pH 9 from NHCl2 decomposition at 200, 400, or 800 µeq Cl2·L-1 with and without 10 µM-N TOTDMA under ambient DO (∼500 µM-O) and, to limit peroxynitrite formation, low DO (≤40 µM-O). Without TOTDMA, the sum of free ammonia, monochloramine, dichloramine, N2, N2O, nitrite, and nitrate indicated nitrogen recoveries ±95% confidence intervals were not significantly different under ambient (90 ± 6%) and low (93 ± 7%) DO. With TOTDMA, nitrogen recoveries were less under ambient (82 ± 5%) than low (97 ± 7%) DO. Oxygen recoveries under ambient DO were 88-97%, and the so-called unidentified product of dichloramine decomposition formed at about three-fold greater concentration under ambient compared to low DO, like NDMA, consistent with a DO limitation. Unidentified product formation stemmed from peroxynitrite decomposition products reacting with mono/dichloramine. For a 2:2:1 nitrogen/oxygen/chlorine atom ratio and its estimated molar absorptivity, unidentified product inclusion with uncertainty may close oxygen recoveries and increase nitrogen recoveries to 98% (ambient DO) and 100% (low DO).

Divergent Fate and Roles of Dissolved Organic Matter from Spatially Varied Grassland Soils in China During Long-Term Biogeochemical Processes.

Terrestrial dissolved organic matter (DOM) is critical to global carbon and nutrient cycling, climate change, and human health. However, how the spatial and compositional differences of soil DOM affect its dynamics and fate in water during the carbon cycle is largely unclear. Herein, the biodegradation of DOM from 14 spatially distributed grassland soils in China with diverse organic composition was investigated by 165 days of incubation experiments. The results showed that although the high humified fraction (high-HS) regions were featured by high humic-like fractions of 4-25 kDa molecular weight, especially the abundant condensed aromatics and tannins, they unexpectedly displayed greater DOM degradation during 45-165 days. In contrast, the unique proteinaceous and 25-100 kDa fractions enriched in the low humified fraction (low-HS) regions were drastically depleted and improved the decay of bulk DOM but only during 0-45 days. Together, DOM from the high-HS regions would cause lower CO2 outgassing to the atmosphere but higher organic loads for drinking water production in the short term than that from the low-HS regions. However, this would be reversed for the two regions during the long-term transformation processes. These findings highlight the importance of spatial and temporal variability of DOM biogeochemistry to mitigate the negative impacts of grassland soil DOM on climate, waters, and humans.

Highly efficient reduction of bromate by vacuum UV/sulfite system.

Bromate (BrO3-), a worldwide regulated by-product after ozone disinfection, is often detected in bromide-containing water, and has a strict limit of 10 µg L-1 in potable water. BrO3- degradation by advanced reduction processes (ARPs) has gained much attention because of efficient removal and easy integration with ultraviolet disinfection (UV at 254 nm). In the vacuum UV (VUV, 185/254 nm)/sulfite system, the elimination kinetics of BrO3- increased by 9-fold and 15-fold comparing with VUV alone and UV/sulfite system. This study further demonstrated the hydrated electron (eaq-) works as the dominant species in BrO3- degradation in alkaline solution, while in the acidic solution the H• became a secondary reactive species besides eaq-. Hence, the influences of pH, sulfite concentration, dissolved gas and water matrix on effectiveness of degradation kinetics of BrO3- was explored in details. With increasing pH, the proportion of SO32- species increased and even became the major ones, which also correlated well with the kobs (min-1) of BrO3- degradation. The stability of eaq- also climbs with increasing pH, while that of H• drops significantly. Higher sulfite dosage favored a more rapid degradation of BrO3-. The presence of dissolved oxygen inhibited BrO3- removal due to the scavenging effect of O2 toward eaq- and transformed VUV/sulfite-based ARP to an advanced oxidation process (AOP), which was ineffective for BrO3- removal. BrO3- removal was inhibited to varying degrees after anions (e.g., bicarbonate (HCO3-), chloride (Cl-), nitrate (NO3-)) and humic acid (HA) being added.

Dibromoacetonitrile induced autophagy by mediating the PERK signalling pathway and ROS interaction in HT22 cell.

Dibromoacetonitrile (DBAN) is a high-risk haloacetonitrile (HAN) generated as a byproduct of chloramine disinfection in drinking water. DBAN-induced neurotoxicity in mouse hippocampal neuronal cells (HT22) and mammals was observed to be related to reactive oxygen species (ROS). ROS, endoplasmic reticulum stress (ERS) and autophagy play crucial roles in regulating a variety of cellular processes. However, whether ERS and autophagy are associated with HAN-responsive apoptosis remains unclear. This study indicated that DBAN (10 µM, 24 h) activated the ERS protein kinase like endoplasmic reticulum kinase (PERK) signaling pathway. The ERS inhibitor 4-phenylbutyric acid (4-PBA) reversed DBAN-inhibited cell viability and alleviated DBAN-induced apoptosis in HT22 cell, indicating that activation of the ERS PERK pathway mediates DBAN induced cytotoxicity. Moreover, DBAN activated autophagy. The autophagy inhibitor 3-methyladenine(3-MA) reversed DBAN-inhibited cell viability and alleviated DBAN-induced apoptosis in HT22 cell, suggesting that autophagy activation mediates DBAN-induced cell toxicity. Notably, the results showed that 4-PBA inhibited DBAN-activated autophagy, demonstrating that ERS-PERK promotes DBAN-induced cellular autophagy. Pretreatment with antioxidant N-acetylcysteine (NAC) inhibited the increase in ROS production and the activation of ERS, and protected cells from toxicity. Furthermore, 4-PBA pretreatment reduced the increase in ROS production, indicating that the ROS and PERK promote each other and form a positive feedback loop. ROS also promoted DBAN-induced autophagy. In summary, our findings indicate that DBAN induced autophagy by mediating the PERK signalling pathway and ROS interaction, leading to HT22 cell damage. Accordingly, targeting these pathogenic mechanisms may provide a potential target and theoretical basis for preventing and improving HAN-induced neurotoxicity.

Fluorescence spectroscopy in the detection and management of disinfection by-product precursors in drinking water treatment processes: A review.

Monitoring and prevention of the formation of disinfection by-products (DBPs) is paramount in drinking water treatment plants (DWTP) to ensure human health safety. This review provides an overview of how fluorescence techniques are developed to predict DBP formation and to evaluate the reduction of fluorescence components and DBPs following individual DWTP processes. Evidence has shown that common DBPs, nitrogenous DBPs and specific emerging DBPs exhibit positive linear relationships with terrestrial, anthropogenic, tryptophan-like, and eutrophic humic-like fluorescence. Due to the interrelationships of both regulated and emerging DBP types with fluorescence components, the limitations arise when attempting to predict emerging DBPs solely through linear relationships. Monitoring the reduction of DBP precursors after each treatment process can be achieved by studying the relationship between fluorescence components and DBPs. During the coagulation process, highest reduction rates are observed for terrestrial humic-like fluorescence. Advanced treatments such as granular, powdered, silver-impregnated activated carbon, magnetic ion exchange resins, and reverse osmosis, have revealed a significant reduction of fluorescent DBP precursors, ranging from 53% to 100%. During chlorination, the reduction rate follows the order: terrestrial humic-like > microbial humic-like > protein/tryptophan-like fluorescence. This review provides insights into the reduction of fluorescence signatures following individual DWTP processes, which offers information regarding DBP formation. These insights could assist in optimizing the treatment process to more effectively manage DBP formation. For the identification of emerging DBP generation, the utilization of advanced models is imperative to precisely predict emerging DBPs and to more accurately trace DBP precursors within DWTPs.