Electronic Supplementary Information for. Occurrence, Profiling and Prioritization of Halogenated Disinfection By-Products in Drinking Water of China
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1 Electronic Supplementary Information for Occurrence, Profiling and Prioritization of Halogenated Disinfection By-Products in Drinking Water of China Huanhuan Ding, a Liping Meng, b Haifeng Zhang, a a Jianwei Yu, a Wei An, a Jianying Hu b and Min Yang a * a State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing , China b College of Urban and Environmental Sciences, Peking University, Beijing , China Figure 1 Tables 8
2 TCM DCBM DBCM TBM DCIM DBIM BCIM TIM CNM TCNM BCNM TBNM CAN BAN IAN DCAN DBAN BCAN TCAN
3 CAA DCAA TCAA BAA DBAA TBAA BCAA DCBAA DBCAA Figure S1. The structures and acronyms of target analytes.
4 Table S1. Limit of quantization (LOQs, μg L -1 ) and recoveries (n=3) of DBPs in drinking waters. Cmpound Acronym LOQs (μg L -1 ) Recoveries (mean ± RSD) THM4 Chloroform TCM ± 17.4 Bromodichoromethane BDCM ± 8.0 Dibromochloromethane DBCM ±13.2 Bromofrom TBM ± 12.7 Iodinated THMs Dichloroiodomethane DCIM ± 10.7 Bromochloroiodomethane BCIM ± 8.6 Dibromoiodomethane DBIM ± 11 Iodoform TIM ± 7.0 HAAs Monochloroacetic acid CAA ± 1.5 Dichloroacetic acid DCAA ± 6.4 Trichloroacetic acid TCAA ± 0.5 Monobromoacetic acid BAA ± 1.1 Dibromoacetic acid DBAA ± 3.9 Tribromoacetic acid TBAA ± 0.6 Bromochloroacetic acid BCAA ± 2.7 Bromodichloroacetic acid BDCAA ± 4.4 Chlorodibromoacetic acid CDBAA ± 13 HANs Chloroacetonitrile CAN ± 6.7 Dichloroacetonitrile DCAN ±7.5 Trichloroacetonitrile TCAN ± 4.4 Bromoacetonitrile BAN ± 12.8
5 Dibromoacetonitrile DBAN ± 15 Bromochloroacetonitrile BCAN ± 7.5 Iodoacetonitrile IAN ± 7.8 HNMs Chloronitromethane CNM ± 4.9 Trichloronitromethane TCNM ± 3.5 Bromochloronitromethane BCNM ± 6.3 Tribromonitromethane TBNM ± 6.2 Internal standars Bromofluorobenzene 99 ± dibromopropane 105 ± 2.2 decafluorobyphenyl 113 ± 11.6 Table S2 Optimized instrumental and SRM conditions of HAAs. Retention compound Dwell Precursor ion Product ion Cone Collsion time (min) time (s) Voltage (V) energy (ev) 1.42 CAA BAA DCAA BCAA DBAA TCAA BDCAA CDBAA TBAA
6 Table S3. DBPs measured in drinking water samples collected from 70 water treatment plants (μg L -1 ) and major water quality parameters. DBP 1 a TCM BDCM DBCM ND b TBM ND ND ND ND ND ND ND ND ND 0.16 ND ND ND ND 0.12 ND ND ND THM DCIM ND ND ND ND ND ND ND ND 0.46 ND ND ND ND ND 0.71 BCIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DBIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND I-THMs ND ND ND ND ND ND ND ND 0.46 ND ND ND ND ND 0.71 CAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCAA 6.69 ND ND
7 TCAA ND ND ND ND BAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCAA ND ND 2.33 ND ND ND ND ND ND ND ND ND ND ND ND 2.32 ND 1.14 DBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 2.21 DBCAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HAAs CAN ND ND ND ND 0.16 ND ND ND ND ND ND 0.07 DCAN ND ND ND ND 0.61 ND ND ND TCAN BAN ND ND ND ND ND 0.03 ND ND ND 0.03 BCAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DBAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
8 IAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HANs CNM ND ND 0.07 TCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HNMs ND ND 0.07 TOC (mg L -1 ) c Br - (μg L -1 ) I - (μg L -1 ) ND ND ND ND ND ND ND ND ND ND NH + 4 (mg L -1 ) < < disinfectant Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 NH 2 Cl Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 NH 2 Cl NH 2 Cl Cl 2 ClO 2 Cl 2 NH 2 Cl SW f type river river river river river river river river LR d GW e LR LR LR LR river river river river
9 DBP TCM BDCM DBCM TBM ND ND ND ND ND ND ND ND THM DCIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DBIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND I-THMs ND ND ND ND ND ND ND ND ND ND ND ND ND ND CAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCAA TCAA 2.55 ND
10 BAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCAA ND ND ND ND ND ND ND ND 3.38 ND ND ND ND DBAA ND 2.19 ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DBCAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HAAs CAN ND ND 0.03 ND ND ND 0.11 DCAN ND ND 2.10 TCAN ND ND ND BAN ND 0.01 ND ND ND ND BCAN ND ND ND ND ND ND ND 0.40 ND ND ND ND ND 2.40 DBAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND IAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
11 HANs ND 4.60 CNM ND ND ND 0.07 ND TCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HNMs ND ND ND 0.07 ND TOC (mg L -1 ) Br - (μg L -1 ) ND I - (μg L -1 ) ND ND ND - ND ND ND ND - ND ND - ND ND ND ND ND ND NH + 4 (mg L -1 ) <0.04 <0.04 < disinfectant Cl 2 ClO 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 NH 2 Cl Cl 2 Cl 2 SW type river LR LR LR LR LR river river river LR river river river river river LR river river
12 DBP TCM BDCM DBCM ND ND TBM ND ND ND ND THM DCIM ND ND ND ND ND ND ND 1.94 ND 3.67 ND ND BCIM ND ND ND ND ND 0.68 ND 1.75 ND ND ND ND ND ND ND 1.91 ND ND DBIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND I-THMs ND ND ND ND ND ND ND 1.94 ND 5.58 ND ND CAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCAA 2.01 ND ND TCAA ND ND ND ND ND
13 BAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCAA ND ND ND ND 2.57 ND ND ND ND DBAA ND ND ND ND ND ND ND ND ND ND DCBAA ND ND ND ND ND ND ND ND ND ND ND 3.13 ND ND ND 3.38 ND ND DBCAA ND ND ND ND ND ND ND ND ND ND ND 4.83 ND ND ND 4.09 ND ND TBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HAAs CAN 0.13 ND 0.05 ND ND ND ND ND ND ND ND ND ND ND DCAN ND 0.06 TCAN ND ND ND ND ND 0.17 ND ND ND ND ND 0.97 BAN ND ND ND ND ND 0.06 ND ND ND ND ND ND 0.07 BCAN ND ND ND ND 3.61 ND 4.43 ND ND DBAN ND ND ND ND ND ND ND ND 2.63 ND ND ND ND ND ND 4.08 ND ND IAN ND ND ND ND ND ND ND 0.2 ND ND ND ND ND ND ND 0.86 ND ND
14 HANs CNM ND 0.06 ND ND ND TCNM ND ND ND ND ND ND ND ND ND ND ND ND ND 0.11 ND ND BCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HNMs ND 0.06 ND ND ND TOC (mg L -1 ) Br - (μg L -1 ) ND ND ND - ND ND - ND I - (μg L -1 ) - ND - ND ND ND ND - ND ND ND - ND ND - ND - ND NH + 4 (mg L -1 ) < disinfectant Cl 2 Cl 2 Cl 2 Cl 2 NH 2 Cl Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 NH 2 Cl Cl 2 Cl 2 ClO 2 Cl 2 Cl 2 Cl 2 SW type river LR LR LR river river river river river LR LR LR LR LR LR river river LR
15 DBP TCM BDCM DBCM ND TBM ND 0.30 ND ND ND THM DCIM ND ND 1.21 ND ND ND 2.00 ND ND ND ND ND ND 0.60 BCIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DBIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TIM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND I-THMs ND ND 1.21 ND ND ND 2.00 ND ND ND ND ND ND 0.60 CAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND DCAA ND TCAA 1.29 ND ND
16 BAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND BCAA ND ND ND ND ND ND ND ND ND ND ND DBAA ND ND ND ND ND ND ND ND ND ND ND DCBAA ND ND ND ND ND ND ND ND ND ND 4.82 ND ND ND ND ND DBCAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBAA ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HAAs CAN ND ND ND DCAN TCAN ND 0.50 ND BAN ND ND 0.50 ND ND ND ND ND BCAN ND ND 1.84 ND ND ND DBAN ND ND 1.22 ND ND ND ND ND ND ND ND ND 0.85 ND IAN ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
17 HANs CNM ND ND 0.02 ND ND TCNM ND ND ND ND ND 0.07 ND ND ND ND ND ND ND ND 0.02 ND BCNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND TBNM ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND HNMs ND ND 0.02 ND ND TOC (mg L -1 ) Br - (μg L -1 ) I - (μg L -1 ) ND - - ND - - ND ND - ND ND ND NH + 4 (mg L -1 ) <0.02 <0.02 < disinfectant Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 SW type LR LR LR LR LR LR LR LR LR LR GW GW GW LR LR LR a the number of the water treatment plant. b not detected. c not measured. d Lake and Reservoir. e Groundwater. f source water TOC, Br -, I -, and NH 4 + were all detected in source water of the drinking water treatments.
18 Table S4. Concentrations of selected DBPs and their abundant species in drinking water samples of China (μg L -1 ). parameter minimun median 75th percentile maximum THM I-THMs ND ND HAAs DCAA ND TCAA ND HANs ND DCAN ND HNMs ND CNM ND TCNM ND ND ND 0.28
19 Table S5. The CHO toxic data of THMs from pervious study. 1-3 Chemical CHO genotoxic potency (M) CHO cytotoxicity %C 1/2 value (M) TIM NS DBIM NS DCIM NS BCIM NS TCM NS BDCM NS DBCM NS TBM NS THM4: The unit of genetoxicity index value =NS The unit of cytotoxicity index value = I-THMs: The unit of genetoxicity index value = NS The unit of cytotoxicity index value =
20 Table S6. The CHO toxic data of HAAs from previous study. 1, 4 Chemical CHO genotoxic potency (M) CHO cyctotoxicity %C 1/2 value (M) BAA DBAA TBAA CAA DCAA NS TCAA NS HAAs: The unit of genetoxicity index value = The unit of cytotoxicity index value =
21 Table S7. The CHO toxic data of HANs from previous study. 5 Chemical CHO genotoxic potency (M) CHO cytotoxicity % C½ value (M) IAN BAN DBAN BCAN CAN DCAN TCAN HANs: The unit of genetoxicity index value = The unit of cytotoxicity index value =
22 Table S8. The CHO toxic data of HNMs from previous study. 6 Chemical CHO genotoxic potency (M) CHO cytotoxicity %C ½ value (M) TBNM CNM TCNM BCNM HANs: The unit of genetoxicity index value = The unit of cytotoxicity index value =
23 Reference: 1. M. J. Plewa, Y. Kargalioglu, D. Vankerk, R. A. Minear and E. D. Wagner, Environmental and Molecular Mutagenesis, 2002, 40, S. D. Richardson, Trac-Trends in Analytical Chemistry, 2003, 22, M. J. Plewa, E. D. Wagner, M. G. Muellner, K.-M. Hsu and S. D. Richardson, in Disinfection by-products in Drinking Water: Occurrence, Formation, Health Effects, and Control, eds. T. Karanfil, S. W. Krasner and Y. Xie, Editon edn., 2008, vol. 995, pp M. J. Plewa, J. E. Simmons, S. D. Richardson and E. D. Wagner, Environmental and Molecular Mutagenesis, 2010, 51, M. G. Muellner, E. D. Wagner, K. McCalla, S. D. Richardson, Y. T. Woo and M. J. Plewa, Environmental Science & Technology, 2007, 41, M. J. Plewa, E. D. Wagner, P. Jazwierska, S. D. Richardson, P. H. Chen and A. B. McKague, Environmental Science & Technology, 2004, 38,
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