Quantifying the effects of chlorine disinfection on microplastics by time-resolved inductively coupled plasma-mass spectrometry.

Using current water treatment systems, significant amounts of microplastics (MPs) are passing through and being released into the aquatic environment. However, we do not clearly know what effects disinfection processes have had on these particles. In this study, we applied inductively coupled plasma-mass spectrometry (ICP-MS) operating in time-resolved analysis (TRA) mode for quantifying changes in the chlorine (Cl) content of MPs under a variety of water treatment scenarios. Our results illustrated that time-resolved ICP-MS offers a potential method for sensitive and direct analysis of Cl content, including Cl mass and chlorine association (%Cl/C), of discrete particles in the MP suspension by the fast sequential measurements of signals from 35Cl1H2 and 12C1H. Our research, across various water treatment scenarios, also showed that polystyrene (PS) MPs exhibited greater reactivity to Cl disinfectant after being pre-disinfected with UV light and in mildly acidic to neutral pH environments. It is noteworthy that about half of the particles in MP suspension exposed to 10 mg Cl2/L, a typical Cl dose applied in water treatment, were chlorinated, and had a Cl content comparable to that of particles subjected to extreme conditions. Of even greater concern is the fact that our cell viability tests revealed that chlorinated MPs induced considerably higher rates of cell death in both human A549 and Caco-2 cells, and that the effects were Cl dose- and polymer type-dependent. Overall, this study demonstrates the potential of time-resolved ICP-MS as a valuable technique for quantifying the Cl content of MP particles, which is crucial to assessing the fate and transformation of MPs in our water supply and treatment systems.

Effects of Fe(III) on the formation and toxicity alteration of halonitromethanes, dichloroacetonitrile, and dichloroacetamide from polyethyleneimine during UV/chlorine disinfection.

Trace iron ions (Fe(III)) are commonly found in water and wastewater, where free chlorine is very likely to coexist with Fe(III) affecting the disinfectant's stability and N-DBPs' fate during UV/chlorine disinfection, and yet current understanding of these mechanisms is limited. This study investigates the effects of Fe(III) on the formation and toxicity alteration of halonitromethanes (HNMs), dichloroacetonitrile (DCAN), and dichloroacetamide (DCAcAm) from polyethyleneimine (PEI) during UV/chlorine disinfection. Results reveal that the maxima concentrations of HNMs, DCAN, and DCAcAm during UV/chlorine disinfection with additional Fe(III) were 1.39, 1.38, and 1.29 times higher than those without additional Fe(III), instead of being similar to those of Fe(III) inhibited the formation of HNMs, DCAN and DCAcAm during chlorination disinfection. Meanwhile, higher Fe(III) concentration, acidic pH, and higher chlorine dose were more favorable for forming HNMs, DCAN, and DCAcAm during UV/chlorine disinfection, which were highly dependent on the involvement of HO· and Cl·. Fe(III) in the aquatic environment partially hydrolyzed to the photoactive Fe(III)­hydroxyl complexes Fe(OH)2+ and [Fe(H2O)6]3+, which undergone UV photoactivation and coupling reactions with HOCl to achieve effective Fe(III)/Fe(II) interconversion, a process that facilitated the sustainable production of HO·. Extensive product analysis and comparison verified that the HO· production enhanced by the Fe(III)/Fe(II) internal cycle played a primary role in increasing HNMs, DCAN, and DCAcAm productions during UV/chlorine disinfection. Note that the incorporation of Fe(III) increased the cytotoxicity and genotoxicity of HNMs, DCAN, and DCAcAm formed during UV/chlorine disinfection, and yet Fe(III) did not have a significant effect on the acute toxicity of water samples before, during, and after UV/chlorine disinfection. The new findings broaden the knowledge of Fe(III) affecting HNMs, DCAN, and DCAcAm formation and toxicity alteration during UV/chlorine disinfection.

Dissolved oxygen facilitates efficiency of chlorine disinfection for antibiotic resistance.

Controlling the dissemination of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) is a global concern. While commonly used chlorine disinfectants can damage or even kill ARB, dissolved oxygen (DO) may affect the formation of reactive chlorine species. This leads to the hypothesis that DO may play roles in mediating the effectiveness of chlorine disinfection for antibiotic resistance. To this end, this study investigated the impacts of DO on the efficiency of chlorine disinfection for antibiotic resistance. The results revealed that DO could increase the inactivation efficiency of ARB under chloramine and free chlorine exposure at practically relevant concentrations. Reactive species induced by DO, including H2O2, O2-, and OH, inactivated ARB strains by triggering oxidative stress response and cell membrane damage. In addition, the removal efficiency of extracellular ARGs (i.e. tetA and blaTEM) was enhanced with increasing dosage of free chlorine or chloramine under aerobic conditions. DO facilitated the fragmentation of plasmids, contributing to the degradation of extracellular ARGs under exposure to chlorine disinfectants. The findings suggested that DO facilitates disinfection efficiency for antibiotic resistance in water treatment systems.

Formation potential of disinfection byproducts during chlorination of petroleum hydrocarbon-contaminated drinking water.

Recent leaks of underground fuel storage tanks in the Pearl Harbor region have led to direct release of un-weathered petroleum hydrocarbons (PHCs) into drinking water sources, which then directly underwent chlorination disinfection treatment. Since the control of disinfection byproducts (DBPs) traditionally focuses natural organic matters (NOM) from source water and little is known about the interactions between free chlorine and un-weathered PHCs, laboratory chlorination experiments in batch reactors were conducted to determine the formation potential of DBPs during chlorination of PHC-contaminated drinking water. Quantitative analysis of regulated DBPs showed that significant quantities of THM4 (average 3,498 µg/L) and HAA5 (average 355.4 µg/L) compounds were formed as the result of chlorination of un-weathered PHCs. Amongst the regulated DBPs, THM4, which were comprised primarily of chloroform and bromodichloromethane, were more abundant than HAA5. Numerous unregulated DBPs and a large diversity of unidentified potentially halogenated organic compounds were also produced, with the most abundant being 1,1-dichloroacetone, 1,2-dibromo-3-chloropropane, chloropicrin, dichloroacetonitrile, and trichloracetonitrile. Together, the results demonstrated the DBP formation potential when PHC-contaminated water undergoes chlorination treatment. Further studies are needed to confirm the regulated DBP production and health risks under field relevant conditions.

Metabolic response of bacterial community to sodium hypochlorite and ammonia nitrogen affected the antibiotic resistance genes in pipelines biofilm.

The biofilm is important for the antibiotic resistance genes (ARGs) propagation in drinking water pipelines. This study investigated the influence of chlorine disinfection and ammonia nitrogen on the ARGs in pipelines biofilm using metagenomic and metabolomics analysis. Chlorine disinfection reduced the relative abundance of unclassified_c_Actinobacteria, Acidimicrobium, and Candidatus_Pelagibacter to 394-430 TPM, 114-123 TPM, and 49-54 TPM, respectively. Correspondingly, the ARGs Saur_rpoC_DAP, macB, and mfd was reduced to 8-12 TPM, 81-92 TPM and 30-35 TPM, respectively. The results of metabolomics suggested that chlorine disinfection suppressed the pathways of ABC transporters, fatty acid biosynthesis, biosynthesis of unsaturated fatty acids, and biosynthesis of amino acids. These pathways were related to the cell membrane integrality and extracellular polymeric substances (EPS) secretion. Chlorine disinfection induced the decrease of EPS-related genes, resulting in the lower relative abundance of bacterial community and their antibiotic resistance. However, added approximately 0.5 mg/L NH3-N induced up-regulation of these metabolic pathways. In addition, NH3-N addition increased the relative abundance of enzymes related to inorganic and organic nitrogen metabolic pathway significantly, such as ammonia monooxygenase, glutamine synthetase, and glutamate synthase. Due to the EPS protection and nitrogen metabolism, the relative abundance of the main bacterial genera and the related ARGs increased to the level equal to that in pipelines biofilm with no disinfection. Therefore, NH3-N reduced the ARGs removal efficiency of chlorine disinfection. It is necessary to take measures to improve the removal rate of NH3-N and ARGs for preventing their risks in drinking water.

Introducing bacterial community turnover times to elucidate temporal and spatial hotspots of biological instability in a large Austrian drinking water distribution network.

Ensuring biological stability in drinking water distribution systems (DWDSs) is important to reduce the risk of aesthetic, operational and hygienic impairments of the distributed water. Drinking water after treatment often changes in quality during transport due to interactions with pipe-associated biofilms, temperature increases and disinfectant residual decay leading to potential biological instability. To comprehensively assess the potential for biological instability in a large chlorinated DWDS, a tool-box of bacterial biomass and activity parameters was applied, introducing bacterial community turnover times (BaCTT) as a direct, sensitive and easy-to-interpret quantitative parameter based on the combination of 3H-leucine incorporation with bacterial biomass. Using BaCTT, hotspots and periods of bacterial growth and potential biological instability could be identified in the DWDS that is fed by water with high bacterial growth potential. A de-coupling of biomass from activity parameters was observed, suggesting that bacterial biomass parameters depict seasonally fluctuating raw water quality rather than processes related to biological stability of the finished water in the DWDS. BaCTT, on the other hand, were significantly correlated to water age, disinfectant residual, temperature and a seasonal factor, indicating a higher potential of biological instability at more distant sampling sites and later in the year. As demonstrated, BaCTT is suggested as a novel, sensitive and very useful parameter for assessing the biological instability potential. However, additional studies in other DWDSs are needed to investigate the general applicability of BaCTT depending on water source, applied treatment processes, biofilm growth potential on different pipe materials, or size, age and complexity of the DWDS.

Environmental fate and risk evolution of calcium channel blockers from chlorine-based disinfection to sunlit surface waters.

Organic micropollutants present in disinfected wastewater and discharged to sunlit surface waters may be transformed by multiple processes, such as chlorination due to the presence of chlorine residuals, solar irradiation as well as solar-irradiated chlorine residues. This study reports, for the first time, the multi-scenario degradation kinetics, transformation products, and risk evolution of calcium channel blockers (CCBs), a class of emerging pharmaceutical contaminants with worldwide prevalence in natural waters and wastewater. It was found that the chlorination of the studied CCBs (amlodipine (AML) and verapamil (VER)) was dominated by the reaction of HOCl with their neutral species, with second-order rate constants of 6.15×104 M-1 s-1 (AML) and 7.93×103 M-1 s-1 (VER) at pH 5.0-11.0. Bromination is much faster than chlorination, with the measured kapp,HOBr values of 2.94×105 M-1 s-1 and 6.58×103 M-1 s-1 for AML and VER, respectively, at pH 7.0. Furthermore, both CCBs would undergo photolytic attenuations with hydroxyl and carbonate radicals as the dominant reactive species in water. Notably, free chlorine mainly contributed to their abatement during the solar/chlorine treatment. Additionally, the halogen addition on the aromatic ring was observed during chlorination and bromination of the two CCBs. Cyclization was observed under solar irradiation only, while the aromatic ring was opened in the solar/chlorine system. Some products generated by the three transformation processes exhibited non-negligible risks of high biodegradation recalcitrance and toxicity, potentially threatening the aquatic environment and public health. Overall, this study elucidated the environmental fate of typical CCBs under different transformation processes to better understand the resulting ecological risks in these environmental scenarios.

Synergistic disinfection effects and reduction of disinfection by-products in water treatment using magnetic quaternized cyclodextrin polymer combined with chorine disinfection process.

Disinfection is vital in ensuring water safety. However, the traditional chlorine disinfection process is prone to producing toxic and harmful disinfection by-products (DBPs). The combination of quaternary ammonium polymer and the chlorine disinfection process can solve this shortcoming. Currently, research on the control of DBPs through the combined process is not systematic and the control effect between reducing the dosage of disinfectants and DBPs remains to be studied. Quaternized cyclodextrin polymers have attracted increasing attention due to their excellent adsorption and antibacterial properties, but their synergistic effect with chlorine disinfection is still unclear. In this study, a magnetic quaternized cyclodextrin polymer (MQCDP) is synthesized in an ionic liquid green system, and a combined process of MQCDP treatment and chlorine disinfection is established. The disinfection performance of the combined process on the actual water body along with its reducing effect on the amount of chlorine disinfectant as well as the trihalomethanes (THMs) and haloacetic acids (HAAs) DBPs are explored. MQCDP has a porous structure with a specific surface area of 825 m2 g-1 and is easily magnetically separated. MQCDP can remove most of the natural organic matter (UV254 absorbance decreased by 97 %) in the water at the dosage of 1 g L-1 and kill bacteria with a sterilization rate of 85 %. Compared with disinfection using chlorine alone, the combined process has higher disinfection efficiency and significantly reduces the amount of disinfectant used. A concentration of 5 mg/L of NaClO was needed to meet the standard by chlorine disinfectant alone, while only 2 mg/L of NaClO can meet the standard for the combined process, indicating 60 % of the chlorine demand was reduced. More importantly, the combined process can significantly reduce the generation potential of DBPs. When 10 mg/L of NaClO is added, the THMs and HAAs generated by the combined process decreased by 65 % and 34 %, respectively, compared with the levels produced by single chlorine disinfection. The combined process can reduce the dosage of chlorine disinfectant and MQCDP can adsorb humic acid DBP precursors in raw water, thus lowering the generation of DBPs during disinfection. In summary, MQCDP has excellent separation and antibacterial ability, and its synergistic effects combined with the chlorine disinfection process are of great significance for controlling the amount of disinfectant and the formation potential of DBPs, which has potential applications in actual water treatment.

Formation of halonitromethanes from glycine during LED-UV265/chlorine disinfection.

LED-UV265/chlorine is a promising alternative disinfection technology that emits mono-wavelength light for high germicidal efficiency. Halonitromethanes (HNMs) are highly cytotoxic and genotoxic disinfection byproducts that can be formed during LED-UV265/chlorine disinfection. Thus, this work aimed to investigate the HNMs formation from glycine (Gly) during LED-UV265/chlorine disinfection. The results indicated that the concentrations of chlorinated-HNMs (Cl-HNMs) increased first and then decreased as the reaction proceeded. Besides, the effects of operating parameters (UV intensity, free chlorine dosage, and pH) and coexisting ions (Cu2+ and Br-) on HNMs formation were investigated. It was found that the formation concentrations of Cl-HNMs increased with the increase of LED-UV265 intensity and free chlorine dosage but decreased with increased pH. The presence of Cu2+ promoted the formation of Cl-HNMs. The total concentration of HNMs (at 3 min) with adding 1.5 mg/L Cu2+ was 30.90% higher than that without Cu2+. Notably, nine species of HNMs were detected after adding Br-, and the total concentrations of HNMs were enhanced. Moreover, Cl-HNMs were gradually transformed into brominated (chlorinated)-HNMs and brominated-HNMs as Br- concentration increased. According to the findings, the possible formation mechanism of HNMs from Gly during LED-UV265/chlorine disinfection was deduced. Finally, it was demonstrated that the formation laws of HNMs from Gly in real water samples were basically consistent with those in simulated water. Insights obtained in this study help to comprehend the HNMs formation from Gly and provide strategies for controlling the production of HNMs during LED-UV265/chlorine disinfection.

Self-repair and resuscitation of viable injured bacteria in chlorinated drinking water: Achromobacter as an example.

Chlorine disinfection for the treatment of drinking water can cause injury to the membrane and DNA of bacterial cells and may induce the surviving injured bacteria into a viable but non-culturable (VBNC) state. It is difficult to monitor viable injured bacteria by heterotrophic plate counting (HPC), and their presence is also easily miscalculated in flow cytometry intact cell counting (FCM-ICC). Viable injured bacteria have a potential risk of resuscitation in drinking water distribution systems (DWDSs) and pose a threat to public health when drinking from faucets. In this study, bacteria with injured membranes were isolated from chlorinated drinking water by FCM cell sorting. The culture rate of injured bacteria varied from 0.08% to 2.6% on agar plates and 0.39% to 6.5% in 96-well plates. As the dominant genus among the five identified genera, as well as an opportunistic pathogen with multiple antibiotic resistance, Achromobacter was selected and further studied. After treatment with chlorine at a concentration of 1.2 mg/L, Achromobacter entered into the intermediate injured state on the FCM plot, and the injury on the bacterial surface was observed by electron microscopy. However, the CTC respiratory activity assay showed that 75.0% of the bacteria were still physiologically active, and they entered into a VBNC state. The injured VBNC Achromobacter in sterile drinking water were resuscitated after approximately 25 h. The cellular repair behavior of injured bacteria was studied by Fourier transform infrared attenuated total reflectance (FTIR-ATR) and comet assays. It was found that DNA injury rather than membrane injury was repaired first. The expression of Ku and ligD increased significantly during the DNA repair period, indicating that non-homologous end-joining (NHEJ) played an important role in repairing DNA double-strand breaks. This study deepened the understanding of the effect of chlorine disinfection on bacterial viability in drinking water and will provide support for the improvement of the chlorine disinfection process for the treatment of drinking water.

Aquifer clogging caused by chlorine disinfection during the reclaimed water recharge.

Aquifer clogging plays a critical role in the efficiency of reclaimed water recharge. While chlorine disinfection is commonly used for reclaimed water, its impact on clogging has seldom been discussed. Thus, this study aimed to investigate the mechanism of chlorine disinfection on clogging by establishing a lab-scale reclaimed water recharge system that utilized chlorine-treated secondary effluent as feed water. The findings indicated that increasing the chlorine concentration led to a surge in the total amount of suspended particles, and the median particle size increased from 2.65 µm to 10.58 µm. Furthermore, the fluorescence intensity of dissolved organic matter decreased by 20%, with 80% of these compounds, including humic acid, becoming entrapped within the porous media. Additionally, the formation of biofilms was also found to be promoted. Microbial community structure analysis unveiled a consistent dominance of Proteobacteria consistently exceeded 50% in relative abundance. Moreover, the relative abundance of Firmicutes increased from 0.19% to 26.28%, thereby verifying their strong tolerance to chlorine disinfection. These results showed that higher chlorine concentrations could stimulate microorganisms to secrete an increased quantity of extracellular polymeric substance (EPS) and form a coexistence system with the trapped particles and natural organic matter (NOM) within the porous media. Consequently, this supported the formation of biofilms, thereby potentially elevating the risk of aquifer clogging.

Identification of significant live bacterial community shifts in different reclaimed waters during ozone and chlorine disinfection.

Ozone and chlorine are the most widely used disinfectants for water and wastewater disinfection. They play important role in microbial inactivation but could also pose a considerable selection effect on the microbial community of reclaimed water. Classical culture-based methods that rely on the assessment of conventional bacterial indicators (e.g., coliform bacteria) could hardly reflect the survival of disinfection residual bacteria (DRB) and hidden microbial risks in disinfected effluents. Hence, this study investigated the shifts of live bacterial community during ozone and chlorine disinfection in three reclaimed waters (i.e., two secondary effluents and one tertiary effluent), adopting Illumina Miseq sequencing technology in combination with a viability assay, propidium monoazide (PMA) pretreatment. Notably, statistical analyses of Wilcoxon rank-sum test confirmed the existance of distinct differences in bacterial community structure between samples with or without PMA pretreatment. On the phylum level, Proteobacteria commonly dominated in three undisinfected reclaimed waters, while ozone and chlorine disinfection posed varied effects on its relative abundance among different influents. On the genus level, ozone and chlorine disinfection significantly changed the bacterial composition and dominant species in reclaimed waters. Specifically, the typical DRB identified in ozone disinfected effluents were Pseudomonas, Nitrospira and Dechloromonas, while for chlorine disinfected effluents, Pseudomonas, Legionella, Clostridium, Mycobacterium and Romboutsia were recognized as typical DRB, which call for much attention. The Alpha and Beta diversity analysis results also suggested that different influent compositions greatly affected the bacterial community structure during disinfection processes. Since the experiments in present study were conducted in a short period and the dataset was relatively limited, prolonged experiment under different operational conditions are needed in future to illustrate the potential long-term effects of disinfection on the microbial community structure. The findings of this study could provide insights into microbial safety concern and control after disinfection for sustainable water reclamation and reuse.

Toxicity Evaluation and Effect-Based Identification of Chlorine Disinfection Products of the Anti-COVID-19 Drug Chloroquine Phosphate.

Antiviral transformation products (TPs) generated during wastewater treatment are an environmental concern, as their discharge, in considerable amounts, into natural waters during a pandemic can pose possible risks to the aquatic environment. Identification of the hazardous TPs generated from antivirals during wastewater treatment is important. Herein, chloroquine phosphate (CQP), which was widely used during the coronavirus disease-19 (COVID-19) pandemic, was selected for research. We investigated the TPs generated from CQP during water chlorination. Zebrafish (Danio rerio) embryos were used to assess the developmental toxicity of CQP after water chlorination, and hazardous TPs were estimated using effect-directed analysis (EDA). Principal component analysis revealed that the developmental toxicity induced by chlorinated samples could be relevant to the formation of some halogenated TPs. Fractionation of the hazardous chlorinated sample, along with the bioassay and chemical analysis, identified halogenated TP387 as the main hazardous TP contributing to the developmental toxicity induced by chlorinated samples. TP387 could also be formed in real wastewater during chlorination in environmentally relevant conditions. This study provides a scientific basis for the further assessment of environmental risks of CQP after water chlorination and describes a method for identifying unknown hazardous TPs generated from pharmaceuticals during wastewater treatment.

Glyoxylate cycle maintains the metabolic homeostasis of Pseudomonas aeruginosa in viable but nonculturable state induced by chlorine stress.

Bacteria enter a viable but non-culturable (VBNC) state with low metabolic activity to cope with environmental stress (e.g., chlorine disinfection). Elucidating the mechanism and key pathway of VBNC bacteria maintaining low metabolic competence is of great significance to realize their effective control and reduce their environmental and health risks. This study discovered that the glyoxylate cycle is a key metabolic pathway for VBNC bacteria, but not for culturable bacteria. And blocking the glyoxylate cycle pathway inhibited the reactivation and led to the death of VBNC bacteria. The main mechanisms involved the breakdown of material and energy metabolism and the antioxidant system. Gas chromatography-tandem mass spectrometry analysis showed that blocking the glyoxylate cycle led to a disruption of carbohydrate metabolism and fatty acid catabolism in VBNC bacteria. As a result, the energy metabolism system of VBNC bacteria collapsed and the abundance of energy metabolites (ATP, NAD+ and NADP+) decreased significantly. Moreover, the decrease in the level of quorum sensing signaling molecules (quinolinone and N-Butanoyl-D-homoserine lactone) inhibited the synthesis of extracellular polymeric substances (EPSs) and biofilm formation. And the downregulation of glycerophospholipid metabolic competence increased the permeability of cell membranes, leading to the entry of large amounts of hypochlorous acid (HClO) into the bacteria. In addition, the down-regulation of nucleotide metabolism, glutathione metabolism, and the reduction of antioxidant enzyme content resulted in the inability to scavenge reactive oxygen species (ROS) generated by chlorine stress. The large production of ROS and the reduction of antioxidants together led to the breakdown of the antioxidant system of VBNC bacteria. In short, the glyoxylate cycle is the key metabolism pathway of VBNC bacteria for stress resistance and maintaining cellular metabolic balance, and targeting the glyoxylate cycle represents an attractive strategy for developing new and efficient disinfection methods for the control of VBNC bacteria.

Quantitative models and potential surrogates for rapid evaluation and surveillance of chlorine disinfection efficacy in reclaimed water.

Chlorine disinfection has become the most widely applied and indispensable technology in wastewater treatment and reuse to mitigate microbial risk and guarantee water safety. However, owing to complexities and high concentrations of contaminants in reclaimed water, rapid evaluation of chlorine disinfection efficacy is a crucial but challenging issue. Based on intensive experimental and statistical analyses, this study has established kinetic models and potential surrogates for rapid indication of the inactivation of microbial indicators and opportunistic pathogens during chlorine disinfection in different reclaimed waters. Overall, the constructed Selleck models performed very well to simulate log removal values (LRVs) of fecal coliforms, Pseudomonas aeruginosa and heterotrophic plate counts in all reclaimed water samples (R2 = 0.877-0.990). Moreover, total and Peak A fluorescence intensity as well as fluorescence integral intensities in Regions II and IV were found to have high response sensitivities during the chlorination process. Nevertheless, their effectiveness to act as potential surrogates of LRVs of microbial indicators needs to be further validated. The results from this study can provide valuable information on microbial safety surveillance of disinfection toward sustainable and long-term water reuse.

Occurrence and removal of psychiatric pharmaceuticals in the Tehran South Municipal Wastewater Treatment Plant.

Psychiatric drugs released by humans in wastewater have received more attention because of their potential risks for aquatic organisms. In this study, the occurrence of the two most common groups of psychiatric drugs (sedatives-hypnotics-anxiolytics and antidepressants) were evaluated in the Tehran South Municipal Wastewater Treatment Plant. All the target sedatives-hypnotics-anxiolytics (alprazolam, phenobarbital, and thioridazine) and antidepressants (fluoxetine, citalopram, sertraline, and venlafaxine) were observed in influent and secondary clarification (SC) effluent. Thioridazine (164.25 ± 218.74 ng/L) and citalopram (672.53 ± 938.56 ng/L) had the highest mean concentrations in the influent, while alprazolam (5.09 ± 2.33 ng/L) and citalopram (776.97 ± 1088.01 ng/L) had the highest concentrations in the SC effluent. The higher concentrations of the psychiatric drugs, except thioridazine, were detected in the SC effluent compared to the concentrations in the influent. The increased drugs concentrations, with negative removal efficiencies, were more distinctive in the cold season samples. Psychiatric drugs processed in the chlorination unit followed a completely different pattern compared to the drugs in the biological treatment unit. All the drugs' concentrations, except thioridazine, decreased in the chlorination unit, ranging between 27 ± 14% for alprazolam and 75 ± 10% for citalopram. However, the mean concentrations of the detected drugs were as follows: sertraline (11.96 ± 11.62 ng/L) and venlafaxine (184.94 ± 219.74 ng/L) which could cause environmental and ecological concerns.

Chlorination of L-tyrosine and metal complex: degradation kinetics and disinfection by-products generation.

The presence of metal ions in drinking water treatment and distribution systems may affect the disinfection process of organic matter, which had aroused people's concern. L-tyrosine can complex with metal ions through carboxyl, carbonyl, and amino groups and affect its chemical reactions. In this paper, the complexation of L-tyrosine with common metal ions was studied and the influence of complexation on chlorination with different experimental factors was investigated. It was inferred that L-tyrosine complexed with metal ions by single dentate ligand or double dentate chelation in a ratio of 2:1. The degradation of L-tyrosine-metal complex followed the pseudo-first-order reaction kinetic. TCM, DCAA, and TCAA were the main species DBPs in the chlorination of L-tyrosine. Compared with L-tyrosine, the reaction rate constants of complex increased by 5.6%, the formation of trihalomethane production decreased by 21.5% and the formation of haloacetic acids production increased by 26.9% at the state of metal complexation. The effect of metal complexation on chlorination was more obvious than that of metal coexistence. For different metal complexation, the order of inhibition on trihalomethane production was Ca2+> Fe3+> Mn2+ and the order of promotion on haloacetic acids production was Mn2+> Fe3+> Ca2+. Moreover, it was found that alkaline conditions were favorable for the formation of DBPs due to the hydroxyl radical. The combination of ultraviolet and chlorine disinfection promoted L-Tyrosine degradation and DBPs generation, and the promotion efficiency follow the order: UV/Cl2> UV-Cl2> Cl2.

Occurrence and removal of conventional pollutants, estrogenicities, and fecal coliform in village sewage treatment plants along the Yangtze River, China.

The present study investigated the occurrence and removal efficiency of some conventional pollutants, estrogenic effects, and fecal coliform in influents and/or effluents of village sewage treatment plants (STPs) in the upper, middle, and lower reaches of the Yangtze River Basin. The water quality of sewage from the village STPs showed significant seasonal and spatial variability. The removal rates of conventional pollutants by the village STPs were mostly lower than urban STPs, thereby resulting in that the water quality compliance rate of the effluents was only 33.3%. In addition, the average removal rate of estrogenic compounds was only 22.2%, which caused the estrogenicity of effluent to exceed the safety threshold. And E2 was determined to be the main estrogenic component. Moreover, ultraviolet (UV) disinfection, as the main disinfection treatment process of sewage along the Yangtze River Basin, was unable to meet the discharge standard of fecal coliform. The sequential chlorine (10 mg L-1)-UV (20 mJ cm-2) disinfection was found to both achieve up-to-standard discharge of fecal coliform and increase the removal rate of estrogenic effect from 3.78 to 9.86%. Overall, the present study provides valuable information on the conventional pollutants, estrogenic effects, and fecal coliform in sewage from village STPs along the Yangtze River Basin, and practical suggestions for basin-wide pollution control.

Virus inactivation by sequential ultraviolet-chlorine disinfection: Synergistic effect and mechanism.

The COVID-19 outbreak has raised concerns about the efficacy of the disinfection process followed in water treatment plants in preventing the spread of viruses. Ultraviolet (UV) and chlorine multi-barrier disinfection processes are commonly used in water treatment plants; however, their effects on virus inactivation are still unclear. In this study, the effects of different disinfection processes (i.e., UV, free chlorine, and their combination) on waterborne viruses were analyzed using bacteriophage surrogates (i.e., MS2 and PR772) as alternative indicators. The results showed that the inactivation rates of PR772 by either UV or free chlorine disinfection were higher than those of MS2. PR772 was approximately 1.5 times more sensitive to UV disinfection and 8.4 times more sensitive to chlorine disinfection than MS2. Sequential UV-chlorine disinfection had a synergistic effect on virus inactivation, which was enhanced by an increase in the UV dose. As compared with single free chlorine disinfection, UV irradiation at 40 mJ cm-2 enhanced MS2 and PR772 inactivation significantly with a 2.7-fold (MS2) and a 1.7-fold (PR772) increase in the inactivation rate constants on subsequent chlorination in phosphate buffered saline. The synergistic effect was also observed in real wastewater samples, in which the MS2 inactivation rate increased 1.4-fold on subsequent chlorination following UV irradiation at 40 mJ cm-2. The mechanism of the synergistic effect of sequential UV-chlorine disinfection was determined via sodium dodecyl sulfate-polyacrylamide gel electrophoresis, using MS2 as an indicator. The results showed that the synergistic effect was due to damage to MS2 surface proteins caused by previous UV disinfection, which enhanced the sensitivity of MS2 to chlorination. This study provides a feasible approach for the efficient inactivation of viruses in water supply and drainage.

Comparison of disinfection by-products formed by preoxidation of sulfamethazine by K2FeO4 and O3 and the influence on cytotoxicity and biological toxicity.

This study researched the formation of disinfection by-products (DBPs) in sulfamethazine (SMZ) chlorination after preoxidation by K2FeO4 and O3 and the influence of preoxidation on cytotoxicity and biological toxicity. Then, the study emphatically analyzed the influencing factors such as NaClO dosage, pH value, reaction temperature, fulvic acid (FA), and bromide and iodide ions. The results showed that preoxidation by K2FeO4 effectively inhibited the formation of DBPs of haloketones (HKS) and trihalomethanes (THMs), with an average inhibition rate of over 60%. The formation of DBPs after preoxidation by O3 was higher than that by K2FeO4; preoxidation by K2FeO4 reduced the influence of NaClO dosage, temperature, and pH value on the production of DBPs after SMZ chlorination. The cytotoxicity and biological toxicity of SMZ chlorination after preoxidation were evaluated and compared by calculating the LC50 value of DBPs and the luminescent bacteria method. The results of both calculation methods showed that the toxicity of DBPs after preoxidation by K2FeO4 was lower than that by O3 preoxidation. K2FeO4 and O3 preoxidation improved the SMZ removal efficiency by 8.41 and 10.49%, respectively, and inhibited the formation of most DBPs, but the preoxidation promoted the formation of highly toxic DBPs (HANs). The toxicity of DBPs formed in SMZ chlorination after preoxidation by K2FeO4 and O3 was slightly higher than that of chlorination disinfection alone, but it was still within the safe range. This study provides more new details about the formation and toxicity changes of DBPs in the process of SMZ chlorination after preoxidation.