Quenching residual H2O2 from UV/H2O2 with granular activated carbon: A significant impact of bicarbonate.

UV/H2O2 has been used as an advanced oxidation process to remove organic micropollutants from drinking water. It is essential to quench residual H2O2 to prevent increased chlorine demand during chlorination/chloramination and within distribution systems. Granular activated carbon (GAC) filter can quench the residual oxidant and eliminate some of the dissolved organic matter. However, knowledge on the kinetics and governing factors of GAC quenching of residual H2O2 from UV/H2O2 and the mechanism underlying the enhancement of the process by HCO3- is limited. Therefore, this study aimed to analyse the kinetics and influential factors, particularly the significant impact of bicarbonate (HCO3-). H2O2 decomposition by GAC followed first-order kinetics, and the rate constants normalised by the GAC dosage (kn) were steady (1.6 × 10-3 L g-1 min-1) with variations in the GAC dosage and initial H2O2 concentration. Alkaline conditions favour H2O2 quenching. The content of basic groups exhibited a stronger correlation with the efficiency of GAC in quenching H2O2 than did the acidic groups， with their specific kn values being 8.9 and 2.4 min-1 M-1, respectively. The presence of chloride, sulfate, nitrate, and dissolved organic matter inhibited H2O2 quenching, while HCO3- promoted it. The interfacial hydroxyl radical (HO•) zones were visualised on the GAC surface, and HCO3- addition increased the HO• concentration. HCO3- increased the concentration of persistent free radicals (PFRs) on the GAC surface, which mainly contributed to HO• generation. A significant enhancement of HCO3- on H2O2 quenching by GAC was also verified in real water. This study revealed the synergistic mechanism of HCO3- and GAC on H2O2 quenching and presents the potential applications of residual H2O2 in the H2O2-based oxidation processes.

Copper ion affects oxidant decay and combined aspartic acid transformation during chlorination in water pipes: Differentiated action on the yield of trihalomethanes and haloacetonitriles.

The chlorination of extracellular polymeric substances (EPS) secreted by biofilm often induces the formation of high-toxic disinfection byproducts (DBPs) in drinking water distribution systems. The protein components in EPS are the main precursors of DBPs, which mostly exist in the form of combined amino acids. The paper aimed to study the action of a pipe corrosion product (Cu2+) on the formation of DBPs (trihalomethanes, THMs; haloacetonitriles, HANs) with aspartic acid tetrapeptide (TAsp) as a precursor. Cu2+ mainly promoted the reaction of oxidants with TAsp (i.e., TAsp-induced decay) to produce DBPs, rather than self-decay of oxidants to generate BrO3‒ and ClO3‒. Cu2+ increased THMs yield, but decreased HANs yield due to the catalytic hydrolysis. Cu2+ was more prone to promote the reaction of TAsp with HOCl than with HOBr, leading to a DBPs shift from brominated to chlorinated species. The chemical characterizations of Cu2+-TAsp complexations demonstrate that Cu2+ combined with TAsp at the N and O sites in both amine and amide groups, and the intermediate identification suggests that Cu2+ enhanced the stepwise chlorination process by promoting the substitution of chlorine and the breakage of CC bonds. The effect of Cu2+ on THMs yield changed from promoting to inhibiting with the increase of pH, while that on HANs yield was inhibiting regardless of pH variation. Additionally, the impact of Cu2+ on the formation of DBPs was also affected by Cu2+ dose, Cl2/C ratio and Br- concentration. This study helps to understand the formation of EPS-derived DBPs in water pipes, and provides reference for formulating control strategies during biofilm outbreaks.

Adsorption, boiling or membrane filtration for disinfection by-product removal: How to make our drinking water safer?

Disinfection by-products (DBPs) generated in drinking water have become a global concern due to their potential harm to human health. Nevertheless, there are few studies about different point-of-use water treatments in household drinking water. The study aims to compare the effectiveness of three point-of-use water treatments: adsorption, boiling, and membrane filtration. The experimental results showed that the initial average concentration of volatile DBPs and non-volatile DBPs for tap water were 63.71 µg/L and 6.33 µg/L. The removal efficiency of DBPs for adsorption which were 75.6 % (the filter volumes from 0 L to 20 L) and 45.4 % (the filter volumes from 20 L to 50 L) during the service life of the filter element (50 L). Boiling had a high removal efficiency for volatile DBPs like trihalomethanes (THMs), haloacetaldehydes (HALs), haloacetonitriles (HANs), and haloketones (HKs) (90.5 %, 100 %, 100 %, and 100 %, respectively). However, boiling had a low removal efficiency which was 15 % in removing non-volatile DBPs like haloacetic acids (HAAs). Membrane filtration had a middle removal efficiency for THMs, HAAs, HALs, HKs, and HANs (45.3 %, 75.2 %, 46.5 %, 47.6 %, and 100 %, respectively). Through analysis of the correlation between dissolved organic matter (DOM) removal efficacy and DBP removal efficiency, it was found that the strongest correlation was observed between UV254 and DBP removal efficiency. Boiling showed a lower estimated cytotoxicity of DBPs compared to adsorption and membrane filtration. Cancer risk assessment of DBPs was below the specified risk range for three point-of-use water treatments. This study provides a reference for choosing point-of-use water treatments in household drinking water.

Accelerated degradation of micro-pollutant by combined UV and chlorine dioxide: Unexpected inhibition of chlorite formation.

UV/chlorine dioxide (ClO2) process can be intentionally or accidently conducted and is potentially effective in micro-pollutants degradation. UV irradiation can promote ClO2 decay and subsequently result in the formation of reactive radicals. Hence, the co-exposure of ClO2 and UV exhibited a synergetic effect on metribuzin (MET) degradation. The MET degradation was promoted by UV/ClO2 with a rate of 0.089 min-1 at pH 7.5, which was around 2.4 folds the total of rates caused by single ClO2 (0.004 min-1) and single UV (0.033 min-1). Reactive radicals mainly HO• and reactive chlorine species were involved in the acceleration effect, and contributed to 59%-67% of the total degradation rate of MET during UV/ClO2 under pHs 5.5-7.5. Among them, HO• was the predominant contributor and the contribution rate gradually rose under higher pH. Chlorite (ClO2-) and chlorate (ClO3-) formation has been the major concern of ClO2 oxidation. However, a comparison of their formation during UV/ClO2 and ClO2 oxidation is rarely reported. Herein, during MET degradation by ClO2, only ClO2- was identified with the highest amount of 1.17 mg L-1. Conversely, during MET degradation by UV/ClO2, only ClO3- was identified with the highest amount of 0.68 mg L-1, showing an upward trend with prolonging treatment time. Furthermore, organic halogenated DBPs formation after 24 h post-chlorination with UV/ClO2 and ClO2 pre-treatments was comparatively evaluated. Organic DBPs formation after post-chlorination was higher with UV/ClO2 pre-treatment compared to ClO2 pre-treatment. The overall concentration of DBPs produced with 30 min UV/ClO2 pre-treatment was about 4.5 times that with 1min UV/ClO2 pre-treatment. This study provided useful reference for the application of UV/ClO2 in micro-pollutants degradation.

Ethanol-diluted turbidimetry method for rapid and accurate quantification of low-density microplastics in synthetic samples.

Retention and transport behaviours of microplastics (MPs) and their associated pollutants in porous media are of great concern. The homogeneity of the studied MPs in artificially controlled lab-scale studies makes rapid and accurate MP quantification feasible. In this study, an economical ethanol-diluted turbidimetry method for polypropylene (PP) and polyethylene (PE) MPs was developed. With ethanol dilution, the MP dispersion system exhibited an excellent suspension performance. Strong linear relationships were observed between MP concentrations and turbidities in both low (<1.3 mg L-1) and high (<170 mg L-1) MP concentration ranges. Solution density and MP agglomeration governed the MP suspension performance. For low surface tension and high molecular mass, the addition of ethanol decreased the contact angles of PP-MPs with solutions from 81.73 to 15.5°, and consequently improved the MP suspension performance. The suspension system was optimised to an ethanol/water (v/v) ratio of 3:2 and 4:1 for PP- and PE-MPs, when the slopes of standard curves were determined to be 1.252 and 0.471 with the recovery of 100.54 ± 3.09% and 103.19 ± 1.66%, and the limit of detection and quantification values of 0.025 and 0.082 mg L-1, and 0.060 and 0.201 mg L-1, respectively. Solution pH, salinity, and dissolved organic matter in the selected range induced acceptable fluctuations in the MP recovery and matrix effect values. The Derjaguin-Landau-Verwey-Overbeek (DLVO) energy barriers were calculated to be > 20 kT, indicating excellent tolerance to the solution matrix. Additionally, applications in real water samples were validated to demonstrate the potential of the developed method.

Formation and transformation of pre-chlorination-formed disinfection byproducts in drinking water treatment process.

As pre-chlorination is increasingly adopted in drinking water treatment plant (DWTP), an attractive question emerged: how the disinfection by-products that formed during pre-chlorination (preformed DBPs) would be transformed in the drinking water treatment process? This study investigated the DBP formation kinetics and molecular characteristics in chlorinated source water, DBP transformation and removal in practical DWTP. It was found that the formation of trihalomethanes (THMs) followed pseudo first-order kinetic model and the intensified Br- exposure facilitated the transformation of TCM into TBM. As Br- concentration shifted from 0.5 mg L-1 to 2.0 mg L-1, the predicted maximum yield of TBM was doubled to 53.7 µg L-1 with the increase of formation rate constant (k-value) from 0.249 h-1 to 0.336 h-1. Besides known DBPs, the molecular-scale investigation unveiled that the preformed unknown Cl-DBPs were a cluster of unsaturated aromatic DBPs ((DBE-O)/Cwa = 0.16, AImod, wa = 0.36) with high H/C (H/Cwa = 1.25). Pre-ozonation exhibited a preferential removal pattern towards condensed aromatic preformed Cl-DBPs with high H/C (AImod ≥ 0.67, H/C > 1.2 and O/C < 0.3). However, the removal of Cl-DBPs in coagulation-clarification process was limited with 56 more unknown Cl-DBP formulas identified. O3-biological activated carbon process exhibited effective removal of preformed DBPs featured with low MW (carbon number ≤ 13), high unsaturation (DBE ≥ 7), condensed aromaticity (AImod ≥ 0.67), and higher H/C (H/C > 1.6). When the pre-chlorination process is adopted, the removal of preformed DBPs during the conventional treatment process is limited, while advanced treatment process can effectively remove these preformed DBPs.

Simple and Sensitive Method for Synchronous Quantification of Regulated and Unregulated Priority Disinfection Byproducts in Drinking Water.

Due to their elevated concentrations in drinking water, compared to other emerging environmental contaminants, disinfection byproducts (DBPs) have become a global concern. To address this, we have created a simple and sensitive method for simultaneously measuring 9 classes of DBPs. Haloacetic acids (HAAs) and iodo-acetic acids (IAAs) are determined using silylation derivatization, replacing diazomethane or acidic methanol derivatization with a more environmentally friendly and simpler treatment process that also offers greater sensitivity. Mono-/di-haloacetaldehydes (mono-/di-HALs) are directly analyzed without derivatization, along with trihalomethanes (THMs), iodo-THMs, haloketones, haloacetonitriles, haloacetamides, and halonitromethanes. Of the 50 DBPs studied, recoveries for most were 70-130%, LOQs for most were 0.01-0.05 µg/L, and relative standard deviations were <30%. We subsequently applied this method to 13 home tap water samples. Total concentrations of 9 classes of DBPs were 39.6-79.2 µg/L, in which unregulated priority DBPs contributed 42% of total DBP concentrations and 97% of total calculated cytotoxicity, highlighting the importance of monitoring their presence in drinking water. Br-DBPs were the dominant contributors to total DBPs (54%) and total calculated cytotoxicity (92%). Nitrogenous DBPs contributed 25% of total DBPs while inducing 57% of total calculated cytotoxicity. HALs were the most important toxicity drivers (40%), particularly four mono-/di-HALs, which induced 28% of total calculated cytotoxicity. This simple and sensitive method allows the synchronous analysis of 9 classes of regulated and unregulated priority DBPs and overcomes the weaknesses of some other methods especially for HAAs/IAAs and mono-/di-HALs, providing a useful tool for research on regulated and unregulated priority DBPs.

Start-up of solid-phase denitrification process for treatment of nitrate-rich water in recirculating mariculture system: Carbon source selection and nitrate removal mechanism.

Efficient nitrate removal from recirculating mariculture system (RMS) water is of significance since high concentration of nitrate would cause chronic health effects on aquatic organisms and eutrophication. Solid-phase denitrification (SPD) is a safer and more sustainable approach than conventional heterotrophic denitrification by dosing liquid carbon sources. Thus, its application for treating nitrate-rich RMS water was investigated in this study. Poly 3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) was identified with the best nitrate removal among four kinds of carbon sources. PHBV-filled reactors started with mariculture, municipal and mixing sludges (at the ratio of 1:1) and fed with 200 mg L-1 nitrate-rich RMS water all achieved over 81% nitrate removals with a HRT of 4 days. The dissolved organic carbon concentrations of the reactors were in the range of 3-9 mg L-1. Arcobacter, Halomonas, and Psedomonas were dominant genera responsible for nitrate removal in different reactors. Metagenomic analyses indicate that both denitrification and assimilatory nitrate reduction (ANR) are the main contributors to nitrate removals. Metagenomic results illustrated nirB/D cooperated with nasA may perform ANR pathway, which transformed nitrate to ammonia for biosynthesis. These results indicate that SPD could be a safer alternative for treating nitrate-rich RMS water, and provide new insights into nitrogen metabolism pathways in SPD process.

Degradation of micropollutants in flow-through VUV/UV reactors: Impact of internal diameter and baffle allocation.

Application of VUV/UV process for micropollutants removal in decentralized water supply systems (e.g., rural drinking water treatment) is promising while few researches by far paid attention to the performance of practical flow-through reactors. This study investigated the degradation of atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET) under different hydrodynamic conditions in reactors with varied internal diameters and baffle allocations. Results showed that the target micropollutants could be degraded efficiently in the flow-through VUV/UV reactors following basically the pseudo-first order kinetics (R2 ≥ 0.97). The largest degradation rate constants were found in the D35 reactor and incorporation of baffles in the D50 and D80 reactors accelerated obviously the micrpollutants degradation. The improved performances of the baffled reactors were due mainly to the elevated utilization of HO•, and a new parameter named UEHO (HO• utilization efficiency) was proposed accordingly. The calculated UEHO values of the reactors ranged between 30.2% and 69.2% with the largest found in the D50-5 reactor. This testified the usually insufficient utilization of radicals in flow-through reactors and the effectiveness of baffle implementation. Electrical energy per order (EEO) values of micropollutants degradation in the reactors were in the range of 0.104-0.263 kWh m-3 order-1. The degradation was inhibited significantly by high-concentration nitrate yet the formed nitrite concentration stayed consistently below the drinking water limitation. The acute toxicity of the micropollutant solutions increased first and leveled off afterwards during the VUV/UV treatment, as indicated by the inhibition ratios of luminescence intensity of Vibrio fischeri.

Electrical Energy Consumption of Multiscale UV-AOP Reactors for Micropollutant Removal in Drinking Water: Facilitated Prediction by Reaction Rate Constants Measured on a Mini-Fluidic Photoreaction System.

Electrical energy consumption per order (EEO) is an important figure-of-merit for the selection and optimization of ultraviolet (UV)-based advanced oxidation processes (UV-AOPs). However, EEO applications are limited by the lack of an accurate and facilitative evaluation method because EEO presents reactor property dependence. In this study, we developed an EEO prediction method for multiscale UV-AOP reactors for micropollutant removal in water. The method utilized the reaction rate constants determined in a reference reactor (e.g., mini-fluidic photoreaction system), complemented by a scale-up method that clarified the dependence of EEO on reactor properties. The predicted results of various UV-AOPs were verified experimentally in four bench/pilot-scale reactors in laboratory and a full-scale flow-through reactor (FFR) in field using sulfamethazine as a model micropollutant. For example, EEO values of 0.105 and 0.058 kWh m-3 order-1 were predicted in the FFR at H2O2 doses of 5 and 10 mg L-1, respectively, which generally agreed with verification results. Additionally, the developed method could assist the identification of appropriate reactors in the laboratory for EEO measurements, providing a valuable supplement for the EEO prediction in practice. The developed method presents acceptable accuracy, convenience, and low cost, which would significantly facilitate EEO evaluations for practical UV-AOP applications.

Priority screening of contaminants of emerging concern in drinking water sources of eastern China: Assessing risks based on exposure-activity ratios (EARs).

Increasing and widely detected contaminants of emerging concern (CECs) pose a threat to drinking water safety. Compared with traditional methods, the exposure-activity ratio (EAR) method based on the ToxCast database may have unique advantages in risk assessment of drinking water sources because it provides massive multi-target high-throughput screening toxicity effect data assessment for chemicals with missing traditional toxicity data. In this study, 112 CECs at 52 sampling sites in drinking water sources in Zhejiang Province of eastern China were investigated. Based on EARs and occurrence, priority chemicals were identified as difenoconazole (priority level 1), dimethomorph (priority level 2), acetochlor, caffeine, carbamazepine, carbendazim, paclobutrazol and pyrimethanil (priority level 3). Different from single observable biological effect in traditional methods, a variety of observable biological effects caused by high-risk targets were explored through adverse outcomes pathways (AOPs), revealing ecological risks as well as human health risks, for example, hepatocellular adenomas and carcinomas. Furthermore, the difference between the maximum EAR for a given chemical in a sample (EARmax) and the toxicity quotient (TQ) in priority screening of CECs was compared. The results show that screening priority CECs based on the EAR method is acceptable and more sensitive, suggesting the difference between in vitro and in vivo toxic effects and the necessity of incorporating the harm degree of biological effects into the EAR method to screen priority chemicals in the future.

Cascade capture, oxidization and inactivation for removing multi-species pollutants, antimicrobial resistance and pathogenicity from hospital wastewater.

As reservoirs of pathogens, antimicrobial resistant microorganisms and a wide variety of pollutants, hospital wastewaters (HWWs) need to be effectively treated before discharge. This study employed the functionalized colloidal microbubble technology as one-step fast HWW treatment. Inorganic coagulant (monomeric Fe(III)-coagulant or polymeric Al(III)-coagulant) and ozone were used as surface-decorator and gaseous core modifier, respectively. The Fe(III)- or Al(III)-modified colloidal gas (or, ozone) microbubbles (Fe(III)-CCGMBs, Fe(III)-CCOMBs, Al(III)-CCGMBs and Al(III)-CCOMBs) were constructed. Within 3 min, CCOMBs decreased CODCr and fecal coliform concentration to the levels meeting the national discharge standard for medical organization. Regrowth of bacteria was inhibited and biodegradability of organics was increased after the simultaneous oxidation and cell-inactivation process. The metagenomics analysis further reveals that Al(III)-CCOMBs performed best in capturing the virulence genes, antibiotic resistance genes and their potential hosts. The horizontal transfer of those harmful genes could be effectively hampered thanks to the removal of mobile genetic elements. Interestingly, the virulence factors of adherence, micronutrient uptake/acquisition and phase invasion could facilitate the interface-dominated capture. Featured as cascade processes of capture, oxidation and inactivation in the one-step operation, the robust Al(III)-CCOMB treatment is recommended for the HWW treatment and the protection of downstream aquatic environment.

Microbiome recognition of virulence-factor-governed interfacial mechanisms in antibiotic resistance and pathogenicity removal by functionalized microbubbles.

The frequent occurrence of epidemics around the world gives rise to increasing concerns of the pollution of pathogens and antibiotic resistant bacteria in water. This study investigated the impacts of virulence factors (VFs) on the removal of antibiotic resistant and pathogenic bacteria from municipal wastewater by ozone-free or ozone-encapsulated Fe(III)-coagulant-modified colloidal microbubbles (O3_free-CCMBs or O3-CCMBs). The highly interface-dependent process was initiated with cell-capture on the microbubble surface where the as-collected cells could be further inactivated with the bubble-released ozone and oxidative species if O3-CCMBs were used. The microbiome sequencing analyses denote that the O3_free-CCMB performance of antibiotic resistant and pathogenic bacteria removal was dependent on the virulence phenotypes related to cell-surface properties or structures. The adhesion-related VFs facilitated the effective attachment between cells and the coagulant-modified bubble-surface, which further enhanced cell inactivation by bubble-released ozone. On the contrary, the motility-related VFs might help cells to escape from the bubble capture by locomotion; however, this could be overcome by O3-CCMB-induced oxidative demolition of the movement structures. Besides, the microbubble performance was also impacted with the cell-membrane structure related to antibiotic resistance (i.e., efflux pumps) and the dissolved organic matter through promoting the surface-capture and decreasing the oxidation efficacy. The ozone-encapsulated microbubbles with surface functionalization are robust and promising tools in hampering antibiotic resistance and pathogenicity dissemination from wastewater to surface water environment; and awareness should be raised for the influence of virulence signatures on its performance.

Interactions between H2O2 and dissolved organic matter during granular activated carbon-based residual H2O2 quenching from the upstream UV/H2O2 process.

Granular activated carbon (GAC) filtration can be employed to synchronously quench residual H2O2 from the upstream UV/H2O2 process and further degrade dissolved organic matter (DOM). In this study, rapid small-scale column tests (RSSCTs) were performed to clarify the mechanisms underlying the interactions between H2O2 and DOM during the GAC-based H2O2 quenching process. It was observed that GAC can catalytically decompose H2O2, with a long-lasting high efficiency (>80% for approximately 50,000 empty-bed volumes). DOM inhibited GAC-based H2O2 quenching via a pore-blocking effect, especially at high concentrations (10 mg/L), with the adsorbed DOM molecules being oxidized by the continuously generated ·OH; this further deteriorated the H2O2 quenching efficiency. In batch experiments, H2O2 could enhance DOM adsorption by GAC; however, in RSSCTs, it deteriorated DOM removal. This observation could be attributed to the different ·OH exposure in these two systems. It was also observed that aging with H2O2 and DOM altered the morphology, specific surface area, pore volume, and the surface functional groups of GAC, owing to the oxidation effect of H2O2 and ·OH on the GAC surface as well as the effect of DOM. Additionally, the changes in the content of persistent free radicals in the GAC samples were insignificant following different aging processes. This work contributes to enhancing understanding regarding the UV/H2O2-GAC filtration scheme, and promoting the application in drinking water treatment.

Perfluorinated compound correlation between human serum and drinking water: Is drinking water a significant contributor?

Perfluorinated compounds (PFASs) are a new artificial chemical. Due to its substantial toxicity and complex degradation in the natural environment, monitoring PFASs has become a hot issue for many researchers. Currently, the relationship between the concentration of PFASs in serum and the concentration of PFASs in drinking water is unclear. This paper aims to study the concentration levels of PFASs in drinking water and residents' serum in a city in northern China and the relationship between them. The results show that the concentration of PFASs in drinking water is low, and the average concentrations of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) were 2.57 ± 0.69 ng/L and 0.30 ng/L, respectively, which were lower than the limits specified in China's newly introduced Standards for drinking water quality (GB 5749-2022). In the serum of residents, PFOA and PFOS were the two PFASs with the highest concentration. Spearman correlation analysis showed that perfluorohexane sulfonate (PFHxS) and PFOS concentrations were positively correlated with age, and PFHxS, PFOA, PFNA, and PFOS varied with sex. At the same time, the correlation analysis also showed no correlation between PFAS in drinking water and serum, indicating that drinking water was not the main factor causing the physical burden of PFAS in residents. The HI method was used to assess the health risks of PFASs to human beings. The risk entropy of all PFASs for human hepatotoxicity and reproductive toxicity is below 1.

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.

Accelerated transformation of sodium dodecylbenzene sulfonate surfactant in the UV/chlorine process: Kinetics and formation of chlorinated disinfection by-products.

The degradation kinetics of Sodium dodecylbenzene sulfonate (SDBS) surfactant in the UV/chlorine process was comprehensively investigated, and the formation of chlorinated disinfection by-products (Cl-DBPs) were determined. Results showed that the degradation of SDBS by UV, chlorine and UV/chlorine all followed pseudo-first-order kinetics. The rate constant by UV/chlorine in ultrapure water was approximately 3 times higher than the sum of those by UV and chlorine, and decreased from 0.297 to 0.063 min-1 with pH increasing from 5.0 to 9.0. Water matrices such as NO3-, HCO3- and natural organic matter (NOM) inhibited the degradation efficiency to a certain extent. The second-order rate constant of SDBS with HO• was determined as 2.84 × 109 M-1 s-1. Through using different probes, the main contributors to SDBS degradation were found to be UV, HO• and reactive chlorine species (RCS). Meanwhile, 64.0 µg L-1 trichloromethane (TCM) and 8.7 µg L-1 chloral hydrate (CH) were simultaneously formed within 30 min of UV/chlorine treatment. The concentration of total organic chlorine (TOCl) (424.0 µg L-1) was obviously higher than those of TCM and CH. In addition, 414 unknown by-products formed during UV/chlorine treatment were detected by mass spectrometry at a high confidence level, including 64 monochloro-DBPs and 2 dichloro-DBPs. Although UV/chlorine process accelerated SDBS degradation, the associated DBP formation deserves enough attention.

UV aging of microplastic polymers promotes their chemical transformation and byproduct formation upon chlorination.

The presence and accumulation of microplastics (MPs) in water and wastewater is a growing concern. When released to the water bodies, microplastics can be subject to surface weathering due to ultraviolet (UV) exposure. In this study, the effects of UV aging of six MP polymers from three groups (e.g., polyamide, polyester, and polyolefin) on their chlorine reactivity, chemical transformation, and formation of disinfection byproducts (DBPs) were studied. Polyamide (e.g., polyamide 6) in both virgin and UV-aged forms showed significantly higher chlorine demands than other MP polymers (915.5-947.9 versus 7.0-21.1 µmol/g MP in 24 h), and polyolefins were relatively inert to chlorine. UV aging enhanced the destructions of functional groups of polyamide and polyester upon chlorination, promoting the chlorine demands and leaching of organics by up to 1.7- and 2.4-fold, respectively. Polymer monomer and oligomers of polyamide 6 and toxic or endocrine disrupting additives (e.g., dimethyl phthalate and butyl octyl phthalate) were identified in leachates from chlorinated MP polymers by mass spectrometry. Meanwhile, up to >10-fold increases in the yields of trihalomethane, haloacetic acid, haloacetaldehyde, haloacetonitrile, and haloacetamide were observed from 30-day UV-aged MP polymers as compared to their virgin counterparts. Overall, this study reveals that UV aging can promote the reactivity and chemical transformation of MP polymers during chlorination, especially for polyamide and polyester, increase the release of polymer monomers, oligomers, and additives, and aggravate the role of MP polymers as DBP precursors.

Simultaneous oxidation of trace organic contaminant and Mn(II) by Mn(VII): Accelerating role of dissolved oxygen.

Permanganate (Mn(VII)) is a widely used oxidant in water treatment, which can oxidize trace organic contaminants (TrOCs) and Mn(II). Interestingly, this study found that presence of Mn(II) could accelerate the abatement of bisphenol A by Mn(VII) only under oxic condition. Herein, the effects of Mn(II) and dissolved oxygen (DO) on the abatement of TrOCs by Mn(VII) oxidation and the related mechanism were investigated. Results indicate that DO was involved in the Mn(VII)/Mn(II) reaction, with the reaction stoichiometry of Δ[Mn(VII)]:Δ[Mn(II)] determined to be 1:2 and 1:1.5 in the presence and absence of DO, respectively. Quenching and electron paramagnetic resonance tests verified that both superoxide radicals (O2•-) and reactive Mn species contributed to the accelerated abatement of TrOCs (bisphenol A, methyl phenyl sulfoxide, and methyl phenyl sulfone) in the Mn(VII)/Mn(II) process. Specifically, O2•- was produced through the one-electron reduction of DO and made an important contribution (32.4%-100%) to the abatement of selected TrOCs. This study reveals that Mn(II) could enhance TrOC abatement by Mn(VII) oxidation, and DO played a pivotal role in the Mn(VII)/Mn(II) process.

Degradation of micropollutants in flow-through UV/chlorine reactors: Kinetics, mechanism, energy requirement and toxicity evaluation.

The degradation of three micropollutants (i.e., atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET)) was comprehensively investigated in flow-through UV/chlorine reactors. Results showed that the micropollutants degradation fitted well with pseudo-first-order kinetics (R2 > 0.92) with the order of rate constants following SMX > MET > ATZ. The developed steady-state approximation (SSA) model was roughly applicable in flow-through UV/chlorine reactors with the predictions deviated within 44%. UV photolysis here stood as the major degradation pathway for ATZ while the contribution of non-radical processes (UV photolysis and chlorination) to SMX degradation increased as the reactor internal diameter enlarged. The degradation rates were reduced to varying extents with complex water matrices (chloride, bicarbonate and dissolved organic matter (DOM)) where the inhibition from the DOM was most prominent (up to 73.6%). Although reactors with a larger internal diameter resulted in reduced degradation rate constants, the energy requirements were also lowered. The EEO values of micropollutants degradation by UV/chlorine fell mostly within 1.0 kWh m-3 order-1 in deionized water and under different water matrices. The acute toxicity was observed to be higher after UV/chlorine treatment in tap water, but still stayed low in general. This study revealed the different kinetics and mechanisms of micropollutants degradation in flow-through reactors and demonstrated the potential of the UV/chlorine process in terms of low energy consumption and acute toxicity.