Molecular characterization of transformation and halogenation of natural organic matter during the UV/chlorine AOP using FT-ICR mass spectrometry

UV/chlorine process,as an emerging advanced oxidation process(AOP),was effective for removing micro-pollutants via various reactive radicals,but it also led to the changes of natural organic matter(NOM)and formation of disinfection byproducts(DBPs).By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS),the transformation of Suwannee River NOM(SRNOM)and the formation of chlorinated DBPs(Cl-DBPs)in the UV/chlorine AOP and subsequent post-chlorination were tracked and compared with dark chlorination.In comparison to dark chlorination,the involvement of Cl O·,Cl·,and HO·in the UV/chlorine AOP promoted the transformation of NOM by removing the compounds owning higher aromaticity(AI mod)value and DBE(double-bond equivalence)/C ratio and causing the decrease in the proportion of aromatic compounds.Meanwhile,more compounds which contained only C,H,O,N atoms(CHON)were observed after the UV/chlorine AOP compared with dark chlorination via photolysis of organic chloramines or radical reactions.A total of 833 compounds contained C,H,O,Cl atoms(CHOCl)were observed after the UV/chlorine AOP,higher than 789 CHOCl compounds in dark chlorination,and one-chlorine-containing components were the dominant species.The different products from chlorine substitution reactions(SR)and addition reactions(AR)suggested that SR often occurred in the precursors owning higher H/C ratio and AR often occurred in the precursors owning higher aromaticity.Post-chlorination further caused the cleavages of NOM structures into small molecular weight compounds,removed CHON compounds and enhanced the formation of Cl-DBPs.The results provide information about NOM transformation and Cl-DBPs formation at molecular levels in the UV/chlorine AOP.

E. coli and bacteriophage MS2 disinfection by UV, ozone and the combined UV and ozone processes

The combination of low-dose ozone with ultraviolet （UV） irradiation should be an option to give benefit to disinfection and reduce drawbacks of UV and ozone disinfection. However, less is known about the disinfection performance of UV and ozone （UV/ozone） coexposure and sequential UV-followed-by-ozone （UV- ozone） and ozone-followed-by-UV （ozone-UV） expo- sures. In this study, inactivation of E. coli and bacterioph- age MS2 by UV, ozone, UV/ozone coexposure, and sequential UV-ozone and ozone-UV exposures was investigated and compared. Synergistic effects of 0.5-0.9 log kill on E. coli inactivation, including increases in the rate and efficiency, were observed after the UV/ozone coexposure at ozone concentrations as low as 0.05 mg-L-1 in ultrapure water. The coexposure with 0.02-mg.L-1 ozone did not enhance the inactivation but repressed E. coli photoreactivation. Little enhancement on E. coli inactivation was found after the sequential UV-ozone or ozone-UV exposures. The synergistic effect on MS2 inactivation was less significant after the UV/ozone coexposure, and more significant after the sequential ozone-UV and UV-ozone exposures, which was 0.2 log kill for the former and 0.8 log kill for the latter two processes, at ozone dose of 0.1 mg. t-1 and UV dose of 8.55 mJ. cm 2 in ultrapure water. The synergistic effects on disinfection were also observed in tap water. These results show that the combination of UV and low-dose ozone is a promising technology for securing microbiological quality of water.

Dosing low-level ferrous iron in coagulation enhances the removal of micropollutants, chlorite and chlorate during advanced water treatment

Drinking water utilities are interested in upgrading their treatment facilities to enhance micropollutant removal and byproduct control.Pre-oxidation by chlorine dioxide(ClO_(2))followed by coagulation-flocculation-sedimentation and advanced oxidation processes(AOPs)is one of the promising solutions.However,the chlorite(ClO_(2)^(-))formed from the ClO_(2) preoxidation stage cannot be removed by the conventional coagulation process using aluminum sulfate.ClO_(2)^(–)negatively affects the post-UV/chlorine process due to its strong radical scavenging effect,and it also enhances the formation of chlorate(ClO_(3)^(–)).In this study,dosing micromolar-level ferrous iron(Fe(II))into aluminum-based coagulants was proposed to eliminate the ClO_(2)^(–)generated from ClO_(2) pre-oxidation and benefit the post-UV/chlorine process in radical production and ClO_(3)^(–)reduction.Results showed that the addition of 52.1-μmol/L FeSO_(4) effectively eliminated the ClO_(2)^(-)generated from the pre-oxidation using 1.0 mg/L(14.8μmol/L)of ClO 2.Reduction of ClO_(2)^(-)increased the degradation rate constant of a model micropollutant(carbamazepine)by 55.0%in the post-UV/chlorine process.The enhanced degradation was verified to be attributed to the increased steady-state concentrations of HO^(-)·and ClO_(2)·by Fe(II)addition.Moreover,Fe(II)addition also decreased the ClO_(3)^(–)formation by 53.8%in the UV/chlorine process and its impact on the formation of chloroorganic byproducts was rather minor.The findings demonstrated a promising strategy to improve the drinking water quality and safety by adding low-level Fe(II)in coagulation in an advanced drinking water treatment train.

DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination

The formation of disinfection by-products（DBPs） from the degradation of N,N-diethyl-3-methyl benzoyl amide（DEET） and ibuprofen（IBP） by the ultraviolet irradiation（UV）/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H_2O_2 process.The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H_2O_2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species U（RCS） and hydroxyl radicals（HO） in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50%after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine（TOCl）, respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H_2O_2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%–63% higher,Ulikely due to the generation of more DBP precursors from the attack of RCS, in addition to HO.