Removal of antibiotic resistant bacteria and antibiotic resistance genes by an electrochemically driven UV/chlorine process for decentralized water treatment.

The UV/chlorine (UV/Cl2) process is a developing advanced oxidation process and can efficiently remove antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs). However, the transportation and storage of chlorine solutions limit the application of the UV/Cl2 process, especially for decentralized water treatment. To overcome the limitation, an electrochemically driven UV/Cl2 process (E-UV/Cl2) where Cl2 can be electrochemically produced in situ from anodic oxidation of chloride (Cl-) ubiquitously present in various water matrices was evaluated in this study. >5-log inactivation of the ARB (E. coli) was achieved within 5 s of the E-UV/Cl2 process, and no photoreactivation of the ARB was observed after the treatment. In addition to the ARB, intracellular and extracellular ARGs (tetA, sul1, sul2, and ermB) could be effectively degraded (e.g., log(C0/C) > 4 for i-ARGs) within 5 min of the E-UV/Cl2 process. Atomic force microscopy showed that the most of the i-ARGs were interrupted into short fragments (< 30 nm) during the E-UV/Cl2 process, which can thus effectively prevent the self-repair of i-ARGs and the horizontal gene transfer. Modelling results showed that the abatement efficiencies of i-ARG correlated positively with the exposures of •OH, Cl2-•, and ClO• during the E-UV/Cl2 process. Due to the short treatment time (5 min) required for ARB and ARG removal, insignificant concentrations of trihalomethanes (THMs) were generated during of the E-UV/Cl2 process, and the energy consumption (EEO) of ARG removal was ∼0.20‒0.27 kWh/m3-log, which is generally comparable to that of the UV/Cl2 process (0.18-0.23 kWh/m3-log). These results demonstrate that the E-UV/Cl2 process can provide a feasible and attractive alternative to the UV/Cl2 process for ARB and ARG removal in decentralized water treatment system.

Degradation and detoxification of ribavirin by UV/chlorine/Fe(II) process in water treatment system.

Ribavirin (RBV), which is extensively used to treat viral diseases such as COVID-19, is considered one of the major emerging contaminants due to its long-term existence and health risk in the aqueous environmental system. However, research on effective removal of RBV still remains insufficient. In this study, we investigated the RBV degradation kinetics and mechanism in UV/chlorine/Fe(II) process. The degradation rate constant kobs-RBV of RBV was 2.52 × 10-4 s-1 in UV/chlorine/Fe(II) process, which increased by 1.6 times and 1.3 times than that in chlorine alone and UV/chlorine process, respectively. Notably, trace amount Fe(II) promoted RBV degradation in UV/chlorine system through Fe2+/Fe3+ cycles, enhancing the yield of reactive species such as HO· and certain species reactive chlorine radicals (RCS). The contributions of HO· and RCS toward RBV degradation were 53.91% and 16.11%, respectively. Specifically, Cl·, ClO·, and Cl2·- were responsible for 8.59%, 2.69%, and 4.83% of RBV removal. The RBV degradation pathway indicated that the reactive species preferentially attacked the amide moiety of RBV, which cleaved the ether bond and the hydroxyl group. The toxicity evaluation of RBV degradation products elucidated that UV/chlorine/Fe(II) process was beneficial for RBV detoxification.

Viable but non-culturable state formation and resuscitation of different antibiotic-resistant Escherichia coli induced by UV/chlorine.

The presence of "viable but nonculturable" (VBNC) state and bacterial antibiotic resistance (BAR) both pose significant threats to the safety of drinking water. However, limited data was available that explicitly addressed the contribution of bacterial VBNC state in the maintenance and propagation of BAR. Here, the VBNC state induction and resuscitation of two antibiotic-resistant Escherichia coli K12 strains, one carrying multidrug-resistant plasmid (RP4 E. coli) and the other with chromosomal mutation (RIF E. coli) were characterized by subjecting them to different doses of UV/chlorine. The results illustrated that the induction, resuscitation, and associated mechanisms of VBNC ARB exhibit variations based on resistance determinants. RP4 E. coli exhibited a higher susceptibility to enter VBNC state compared to the RIF E. coli., and most VBNC state and resuscitated RP4 E. coli retained original antibiotic resistance. While, reverse mutation in the rpoB gene was observed in VBNC state and recovered RIF E. coli strains induced by high doses of UV/chlorine treatment, leading to the loss of rifampicin resistance. According to RT-qPCR results, ARGs conferring efflux pumps appeared to play a more significant role in the VBNC state formation of RP4 E. coli and the down-regulation of rpoS gene enhanced the speed at which this plasmid-carrying ARB entered into the dormant state. As to RIF E. coli, the induction of VBNC state was supposed to be regulated by the combination of general stress response, SOS response, stringent response, and TA system. Above all, this study highlights that ARB could become VBNC state during UV/chlorine treatments and retain, in some cases, their ability to spread ARGs. Importantly, compared with chromosomal mutation-mediated ARB, both VBNC and resuscitated state ARB that carries multidrug-resistant plasmids poses more serious health risks. Our study provides insights into the relationship between the VBNC state and the propagation of BAR in drinking water 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.

Pseudomonas aeruginosa and related antibiotic resistance genes as indicators for wastewater treatment.

This review aims to examine the existence of Pseudomonas aeruginosa (P. aeruginosa) and their antibiotic resistance genes (ARGs) in aquatic settings and the alternative treatment ways. P. aeruginosa in a various aquatic environment have been identified as contaminants with impacts on human health and the environment. P. aeruginosa resistance to multiple antibiotics, such as sulfamethoxazole, ciprofloxacin, quinolone, trimethoprim, tetracycline, vancomycin, as well as specific antibiotic resistance genes including sul1, qnrs, blaVIM, blaTEM, blaCTX, blaAIM-1, tetA, ampC, blaVIM. The development of resistance can occur naturally, through mutations, or via horizontal gene transfer facilitated by sterilizing agents. In addition, an overview of the current knowledge on inactivation of Pseudomonas aeruginosa and ARG and the mechanisms of action of various disinfection processes in water and wastewater (UV chlorine processes, catalytic oxidation, Fenton reaction, and ozonation) is given. An overview of the effects of nanotechnology and the resulting wetlands is also given.

Kinetics of chlorine and chloramine reactions in reverse osmosis permeate and their impact on radical formation during UV/chlorine advanced oxidation for potable reuse.

Knowledge of the speciation of chlorine and chloramines in reverse osmosis (RO) permeate is needed to estimate the performance (i.e., pollutant log reduction) of subsequent UV/chlorine advanced oxidation processes (AOPs). To accurately predict the speciation, a previously reported breakpoint chlorination kinetic model was experimentally validated for pH 5.5 and reaction times < 3 min and used to predict the kinetics of breakpoint chlorination in RO permeate. The predictions showed that eliminating chloramines by adding chlorine at a dose beyond the chlorine-to-nitrogen (Cl/N) breakpoint ratio is not practical due to the high breakpoint Cl/N ratio for RO permeate (∼3.0 molar ratio) and an estimated > 40 min reaction time. The conversion from monochloramine (NH2Cl) to dichloramine (NHCl2) is the major process involved, and either or both free chlorine and chloramines may be the major species present, depending on the Cl/N ratio. Model simulations showed that increasing the oxidant dose may not always enhance the performance of UV/chlor(am)ine in RO permeate, due to the need for a low free chlorine dose for optimal •OH exposure in RO permeate. Further UV/AOPs modelling showed that it is important to control the NH2Cl concentration to improve the UV/AOP performance in RO permeate, which may be achieved by extending the reaction time after chlorine is added or increasing the applied Cl/N ratio (e.g., increasing chlorine dose). However, these measures only enhance the pollutant percentage removal by about 5 % under the conditions modelled. A simulation tool was developed and is provided to predict the speciation of chlor(am)ine in RO permeate.

Disinfection by-products control in wastewater effluents treated with ozone and biological activated carbon followed by UV/Chlor(am)ine processes.

Sequential utilization of ozone (O3) and biological activated carbon (BAC) followed by UV/chlor(am)ine advanced oxidation process (AOP) has drawn attention in water reuse. However, the formation of disinfection by-products (DBPs) in this process is less evaluated. This study investigated the DBP formation and the relevant toxicity during the O3-BAC-UV/chlor(am)ine treatment of sand-filtered municipal secondary effluent. DBP formation in UV/chlorine and UV/dichloramine (NHCl2) processes were compared, where the impact of key operational parameters (e.g., UV wavelength, pH) on DBP formation were comprehensively evaluated. O3-BAC significantly reduced DBP formation potential (DBPFP) (58.2 %). Compared to UV/chlorine AOP, UV/NHCl2 AOP reduced DBP formation by 29.7 % in short-time treatment, while insignificantly impacting on DBPFP (p > 0.05). UV/NHCl2 AOP also led to lower calculated cytotoxicity (67.7 %) and genotoxicity (55.9 %) of DBPs compared to UV/chlorine AOP. Compared to 254 nm UV light, the utilization of 285 nm UV light decreased the formation of DBPs in wastewater treated with the UV/chlorine AOP and UV/NHCl2 AOP by 31.3 % and 19.2 %, respectively. However, the cytotoxicity and genotoxicity in UV/NHCl2 AOP using 285 nm UV light increased by 83.4 % and 58.5 %, respectively, compared to 254 nm. The concentration of DBPs formed in the UV/NHCl2 AOP at pH 8 was 54.3 % lower than that at pH 7, suggesting a better control of DBPs at alkaline condition. In the presence of bromide, UV/NHCl2 AOP tended to generate more brominated DBPs than UV/chlorine AOP. Overall, UV/NHCl2 AOP resulted in lower concentration and toxicity of DBPs compared to UV/chlorine AOP.

Bromide induced the formation of brominated halonitromethanes from aspartic acid in the UV/chlorine disinfection process.

Brominated halonitromethanes (Br-HNMs) are generated in water disinfection processes and present high toxicity to human health. This work used aspartic acid (ASP) as the precursor to reveal that bromide (Br-) induced the production of Br-HNMs in the UV/chlorine disinfection process. Consequently, six Br-HNMs were identified, and their yields presented an increasing and then declining evolution over the reaction time from 0 to 15 min. Also, the total Br-HNMs yield reached the maximum of 251.1 µg L-1 at 5 min and then declined to 107.1 µg L-1. The total Br-HNMs yield increased from 2.40 to 251.14 µg L-1 with the increase of Cl2:Br- ratios from 0.25 to 3.0 by increasing free chlorine dosage with a fixed Br- concentration, and it increased from 207.59 to 251.14 µg L-1 and then decreased to 93.44 µg L-1 with the increase of Cl2:Br- ratio from 1.0 to 3.6 by increasing Br- concentration with a fixed free chlorine dosage. Besides, the total Br-HNMs yield reached the highest value (251.14 µg L-1) at pH 7.0 and the lowest value (74.20 µg L-1) at pH 8.0. Subsequently, the possible reaction mechanism of Br-HNMs generated from ASP was deduced, and the changes in toxicity of Br-HNMs also followed an increasing and then declining trend, closely relating to Br-HNMs yields and Br- utilization. This work explored and illustrated the yields, influence factors, reaction mechanisms, and toxicity of Br-HNMs formed from Br- containing ASP water during UV/chlorine disinfection, which might help to control Br-HNMs formation.

Optimizing radical yield from free chlorine with tailored UV light emitting diode emission spectra.

Novel UV sources, which do not contain mercury, provide the opportunity for enhancement of current oxidation technologies through spectral optimization, minimizing inefficiencies that currently limit conventional technology. Wastewater reuse is the primary full-scale application of UV advanced oxidation processes (AOPs) in practice but any background absorbance and the low molar absorption by conventional radical promoters (hydrogen peroxide) have historically limited their system efficiency, resulting in the underutilization of photons in a reactor. This bench-scale research evaluated use of longer wavelength UV light emitting diodes (265, 280, and 300 nm) matched with free chlorine to optimize the utilization of photons for advanced oxidation. Free chlorine possesses large absorption bands in the 280 to 300 nm range in basic pH waters which are common in carbon-based reuse and was used to experimentally verify quantum yields of hydroxyl radical generation across the UV LED peak emission wavelengths. pH- and wavelength-dependent fluence-based rate constants were experimentally derived using Nitrobenzene and Benzoic acid as probe compounds and evaluated to determine the contribution of the hydroxyl and chlorine radical. Reclaimed water taken from various advanced treatment steps was treated with this UV LED AOP to investigate how background absorbance affects radical generation and contaminant transformation kinetics. In addition, alternative performance metrics to evaluate hydroxyl radical production at different incident fluence rates and different rates of photon absorption at unique wavelengths across varying background UV absorbance levels were assessed.

Assessment of the UV/DCCNa and UV/NaClO oxidation process for the removal of diethyl phthalate (DEP) in the aqueous system.

In this work, the removal and transformation process of diethyl phthalate (DEP) in UV/dichloroisocyanurate (UV/DCCNa) and UV/sodium hypochlorite (UV/NaClO) systems were compared to evaluate the application potential of UV/DCCNa technology. Compared with UV/NaClO, UV/DCCNa process has the advantage of DEP removal and caused a higher degradation efficiency (93.8%) within 45 min of oxidation in ultrapure water due to the sustained release of hypochloric acid (HOCl). Fourteen intermediate products were found by high-resolution mass spectrometry, and the transformation patterns including hydroxylation, hydrolysis, chlorination, cross-coupling, and nitrosation were proposed. The oxidation processes were also performed under quasi-realistic environmental conditions, and it was found that DEP could be effectively removed in both systems, with yields of disinfection byproduct meeting the drinking water disinfection standard (<60.0 µg/L). Comparing the single system, the removal of DEP decreased in the mixed system containing five kinds of PAEs, which could be attributed to the regeneration of DEP and the competitive effect of •OH occurred among the Dimethyl phthalate (DMP), DEP, Dipropyl phthalate (DPrP), Diallyl phthalate (DAP) and Diisobutyl phthalate (DiBP). However, a greater removal performance presented in UV/DCCNa system compared with UV/NaClO system (69.4% > 62.1%). Further, assessment of mutagenicity and developmental toxicity by Toxicity Estimation Software Tool (T.E.S.T) software indicated that UV/DCCNa process has fewer adverse effects on the environment and is a more environmentally friendly chlorination method. This study may provide some guidance for selecting the suitable disinfection technology for drinking water treatment.

Experimental and theoretical insight into carbamazepine degradation by chlorine-based advanced oxidation processes: Efficiency, energy consumption, mechanism and DBPs formation.

Chlorine has been widely used in different advanced oxidation processes (AOPs) for micropollutants removal. In this study, different chlorine-based AOPs, namely medium pressure (MP) UV/chlorine, low pressure (LP) UV/chlorine, and in-situ chlorination, were compared for carbamazepine (CBZ) removal efficiency, energy consumption, and disinfection by-products (DBPs) formation. All three processes could achieve nearly 100% CBZ removal, while the reaction time needed by in-situ chlorination was double the time required by UV/chlorine processes. The energy consumed per magnitude of CBZ removed (EE/O) of MP UV/chlorine was 13 times higher than that of LP UV/chlorine, and relative to that of in-situ chlorination process. Accordingly, MP and LP UV/chlorine processes generated one to two orders of magnitude more hydroxyl radicals (•OH) and reactive chlorine species (RCS) than in-situ chlorination. Besides, RCS were the dominant reactive species, contributing to 78.3%, 75.6%, and 71.6% of CBZ removal in MP, LP UV/chlorine, and in-situ chlorination, respectively. According to the Gibbs free energy barriers between CBZ and RCS/•OH calculated based on density functional theory (DFT), RCS had more reaction routes with CBZ and showed lower energy barrier in the main CBZ degradation pathways like epoxidation and formation of iminostilbene. When applied to secondary wastewater effluent, UV/chlorine and in-situ chlorination produced overall DBPs ranging from 104.77 to 135.41 µg/L. However, the production of chlorate during UV/chlorine processes was 15 times higher than that during in-situ chlorination.

Effect of ferric salt addition on UV/electro-chlorine advanced oxidation process.

This study discussed the effect of ferric salt addition on UV/electro-chlorine advanced oxidation process using a train of electrolytic and UV flow cells with an ozone-free low-pressure mercury vapour lamp (total irradiance:0.60 W at 254 nm). Ferric salt addition enhanced 1,4-dioxane degradation at an electrolytic current of 0.100 A. By contrast, an inhibitory effect of ferric salt addition was observed at a current of 0.500 A. The enhanced accumulation of free chlorine at a current of 0.500 A directly decreased the 1,4-dioxane degradation rate by scavenging reactive radicals like HO˙ and Cl˙. However, at an electrolytic current of 0.100 A, UV irradiance was relatively excessive for electrochemical chlorine production. The excess UV energy enhanced the photoreduction of FeOH2+, followed by the Fenton-type reaction of Fe2+ and HOCl, which produced HO˙ and consumed free chlorine. As a result, the free chlorine concentration decreased, and the reaction efficiency between the reactive radicals and 1,4-dioxane improved. Thus, the addition of ferric salt to a UV/electro-chlorine system is recommended when the UV irradiance in the system is excessive compared to the electrochemical chlorine supply.

Mn(II) oxidation by the UV/chlorine system under near-neutral pH conditions: The important role of ClO· and ClO2.

The oxidation kinetics of Mn(II) by free chlorine is relatively low under near-neutral pH conditions which limits the Mn removal efficiency in drinking water treatment. Therefore, this study investigated the oxidation efficiency of Mn(II) by the UV-enhanced chlorination (UV/chlorine) system and identified the responsible reactive radical species. The results show that the oxidation kinetic of Mn(II) was greatly enhanced by the UV/chlorine system under near-neutral pH or even acidic conditions. The pseudo-first-order reaction rate of Mn(II) at pH 8.0 (within the first 20 min) increased from 2.60 × 10-5 s-1 to 3.41 × 10-4 s-1. Based on the scavenging experiments and the steady-state kinetic modeling, ClO· and ClO2, whose steady-state concentration (∼10-10 M and ∼10-9 M, respectively at pH 8.0) was at least 4 orders of magnitude higher than that of HO· and Cl·, were recognized as the dominant reactive species contributing to the oxidation of Mn(II). Kinetic model calculations indicate that the contribution of ClO· to the oxidation of Mn(II) was consistently maintained above 70 %, and ClO2 also played an important role in the oxidation of Mn(II) especially under acidic and alkaline conditions. In addition, the background components of HCO3- and Cl- had negligible influence on the oxidation efficiency because they barely changed the concentration of the ClO· and ClO2. This study first demonstrates the important role of ClO2 in the oxidation of Mn(II) in the UV/chlorine system, and the possible role of ClO2 in the degradation of some organic pollutants needs to be carefully evaluated in the future.

Oxidative degradation and possible interactions of coexisting decabromodiphenyl ether (BDE-209) on polystyrene microplastics in UV/chlorine process.

This work was to investigate the transformation of coexisting decabromodiphenyl ether (BDE-209) on microplastics and their possible interactions in UV/chlorine process. Compared with pristine microplastics, the highly aged polystyrene (PS) showed an inhibitory effect on degradation of BDE-209. Increasing initial concentration of BDE-209 on PS inhibited degradation, while the chlorine concentration and pH did not affect the final degradation efficiency. Moreover, the presence of NO3-, SO42-, HCO3- and HA in water was unfavorable for BDE-209 degradation. According to the experimental and calculation results, the contribution to the degradation of BDE-209 was ranked as direct photolysis > HO• > •Cl in the UV/ chlorine system. Chlorination products released by PS during UV/chlorination were detected. Four possible reaction pathways of BDE-209 were proposed, which mainly involved debromination, hydroxylation, chlorine substitution, cleavage of ether bond, and intramolecular elimination of HBr. It was worth noting that PS microplastics not only inhibited the degradation of BDE-209, but also affected the type and abundance of its transformation products. Meanwhile, interaction products of PS and BDE-209 were determined, which was attributed to reactions of PS-derived radicals with •Br/•C6Br5 and •Cl. Results of toxicity evaluation showed that the introduction of carbon-halogen bonds, especially C-Br bond, increased the toxicity of chain scission products of PS. This work provides some new insights into transformation, interaction, and associated ecological risks of coexisting microplastics and surface adsorbed contaminants in the UV/chlorine process of drinking water treatment plants (DWTPs) and wastewater treatment plants (WWTPs).

Analyzing disinfection by-products yield and mechanisms in UV/Cl2 using response surface methodology and quantitative structure-activity relationship models.

The study aimed to investigate the formation of halogenated disinfection byproducts (DBPs) during applying UV/chlorine (UV/Cl2) and unravel the interactive impacts of critical operational parameters and the mechanisms behind DBPs formation. Response surface methodology and quantitative structure-activity relationship models were developed to evaluate the contribution of electrophilic, nucleophilic, and free radical reactions to the formation of DBPs in UV/Cl2. The study found that Cl2 and its interactions dominated the total DBPs and non-Br-DBPs formation, while Br- and the Cl2-Br- interaction played a decisive role in the Br-DBPs formation. The study also observed significant interactions of Br, Cl2, and pH on chloroform, bromodichloromethane, dichloroacetonitrile, 1,1-dichloro-2-propanone, trichloroactic acid, and chlorodibromoacetic acid formations, while no evident interaction on chloral hydrate, dibromochloromethane, trichloroacetone, dibromoacetic acid, and bromodichloroacetic acid formations. The electrophilic substitution of HOBr mainly controlled the formation of trihalomethanes, and the contribution of nucleophilic, electrophilic, and free radical (•OH, Cl•, Cl2•- and ClO•) reactions depended on the molar ratio of Cl2 to Br, and pH-determined hydrolysis rate constants of DBPs and the types of free radicals. Overall, the response surface methodology and quantitative structure-activity relationship models provided a reference for revealing DBPs formation mechanisms in other disinfection processes.

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.

Chlorine oxide radical (ClO) enables the enhanced degradation of antibiotic resistance genes during UV/chlorine treatment by selectively inducing base damage.

Compared to individual UV or chlorine disinfection, the combined UV and chlorine (i.e., UV/chlorine) can substantially promote the degradation of antibiotic resistance genes (ARGs) in the effluent by generating radicals. However, the mechanisms of ARG degradation induced by radicals during UV/chlorine treatment remain largely unknown, limiting further enhancement of ARG degradation by process optimization. Herein, we aimed to uncover the role of different radicals in ARG degradation and the molecular mechanisms of ARG degradation by radicals in UV/chlorine process. The ClO was proven to be responsible for the enhanced ARG degradation during UV/chlorine treatment, while the other radicals (OH, Cl, and Cl2-) played a minor role. This is because ClO possessed both high steady-state concentration and high reactivity toward ARGs (rate constant: 4.29 × 1010 M-1 s-1). The ClO might collaborate with free chlorine to degrade ARG. The ClO degraded ARGs by selectively attacking guanine and thymine but failed to induce strand breakage, while chlorine could break the strand of ARGs. Ultimately, ClO cooperated with chlorine to degrade ARGs quickly by hydroxylation and chlorination of bases and produce many chlorine- and nitrogen-containing products as revealed by high-resolution mass spectrometry. The uncovered degradation mechanisms of ARGs by UV/chlorine provide useful guidelines for process optimization to achieve deep removal of effluent ARGs.

Modeling and optimization of synergistic ozone-ultraviolet-chlorine process for reclaimed water disinfection: From laboratory tests to software simulation.

The ozone-ultraviolet (UV)-chlorine process is a highly effective method of disinfection in water reuse system, but currently still lacks precise quantification and accurate control. It is difficult to determine the dosage of each disinfectant because of the complex interactions that occur between disinfection units and the complicated mathematical calculation required. In this study, we proposed a dosage optimization model for ozone-UV-chlorine synergistic disinfection process. The model was able to identify the cost-effective doses of the disinfectants under the constraints of microbial inactivation, decolorization, and residual chlorine retention requirements. Specifically, the simulation of microbial inactivation rates during synergistic disinfection process was accomplished through quantification of the synergistic effects between disinfection units and the introduction of enhancement coefficients. In order to solve this optimization model rapidly and automatically, a MATLAB-based software program with graphical user interface was developed. This software consisted of calibration unit, prediction unit, assessment unit, and optimization unit, and was able to simulate synergistic ozone-UV-chlorine process and identify the optimal dose of ozone, UV, and chlorine. Validation experiments revealed good agreements between the experimental data and the results calculated by the developed software. The developed software is believed to help the water reclamation plants improve disinfection efficiency and reduce the operational costs of synergistic disinfection processes.

On the increasing competitiveness of UV/Cl to UV/H2O2 advanced oxidation as the organic carbon concentration increases.

UV/Cl and UV/H2O2 are advanced oxidation processes (AOPs) used for drinking water treatment and water reuse. This work explored the hypothesis that UV/Cl becomes more competitive to UV/H2O2 at neutral-to-high pH as the concentration of total organic carbon (TOC) increases. Lab experiments and kinetic modelling were used to compare initial pseudo first-order contaminant decay rate coefficients between the AOPs at various pH and TOC conditions. The relative effect of increasing TOC concentrations on UV/Cl vs. UV/H2O2 depended on the pH, contaminant, and organic matter reactivity towards radicals. For example, while the reaction rate coefficients during both AOPs generally decreased with increasing TOC, the UV/Cl reaction rate coefficients for the solely •OH-reactive sucralose decreased 41-138% less than the UV/H2O2 coefficients as the TOC concentration was increased from 0 to 5 mg-C L-1. However, UV/Cl was more affected than UV/H2O2 when targeting caffeine (a contaminant reactive to chlorine radicals). The data were used to define TOC-pH conditions for which either AOP would be more energy-efficient, under a set of standard conditions. The results suggest that UV/Cl may be competitive to UV/H2O2 under a wider range of treatment scenarios than has been conventionally thought based on tests in pure water.

Roles of Activated Carbon in UV/Chlorine/Activated Carbon-TiO2 Process for Micropollutant Abatement and DBP Control.

The ultraviolet (UV)/chlorine process has attracted increasing attention for micropollutant abatement. However, the limited hydroxyl radical (HO•) generation and the formation of undesired disinfection byproducts (DBPs) are the two major issues in this process. This study investigated the roles of activated carbon (AC) in the UV/chlorine/AC-TiO2 process for micropollutant abatement and DBP control. The degradation rate constant of metronidazole by UV/chlorine/AC-TiO2 was 3.44, 2.45, and 1.58 times higher than those by UV/AC-TiO2, UV/chlorine, and UV/chlorine/TiO2, respectively. AC acted as an electron conductor and dissolved oxygen (DO) adsorbent, resulting in the steady-state concentration of HO• that was ∼2.5 times that of UV/chlorine. Compared with UV/chlorine, the formation of total organic chlorine (TOCl) and known DBPs in UV/chlorine/AC-TiO2 was reduced by 62.3 and 75.7%, respectively. DBP could be controlled via adsorption on AC, and the increased HO• and decreased chlorine radical (Cl•) and chlorine exposure reduced DBP formation. UV/chlorine/AC-TiO2 efficiently abated 16 structurally different micropollutants under environmentally relevant conditions owing to the enhanced generation of HO•. This study provides a new strategy for designing catalysts with photocatalytic and adsorption properties for UV/chlorine to promote micropollutant abatement and DBP control.