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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (2) : 25    https://doi.org/10.1007/s11783-019-1204-6
RESEARCH ARTICLE
Identification of important precursors and theoretical toxicity evaluation of byproducts driving cytotoxicity and genotoxicity in chlorination
Qian-Yuan Wu1, Yi-Jun Yan1, Yao Lu2, Ye Du2(), Zi-Fan Liang1, Hong-Ying Hu2,3
1. Key Laboratory of Microorganism Application and Risk Control of Shenzhen, Guangdong Provincial Engineering Research Center for Urban Water Recycling and Environmental Safety, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China
2. Shenzhen Environmental Science and New Energy Technology Engineering Laboratory, Tsinghua-Berkeley Shenzhen Institute, Shenzhen 518055, China
3. Environmental Simulation and Pollution Control State Key Joint Laboratory, State Environmental Protection Key Laboratory of Microorganism Application and Risk Control (SMARC), School of Environment, Tsinghua University, Beijing 100084, China
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Abstract

• NOM formed more C-DBPs while amino acids formed more N-DBPs during chlorination

• Aspartic acid and asparagine showed the highest toxicity index during chlorination

• Dichloroacetonitrile might be a driving DBP for cytotoxicity and genotoxicity

• Dichloroacetonitrile dominated the toxicity under different chlorination conditions

Chlorination, the most widely used disinfection process for water treatment, is unfortunately always accompanied with the formation of hazardous disinfection byproducts (DBPs). Various organic matter species, like natural organic matter (NOM) and amino acids, can serve as precursors of DBPs during chlorination but it is not clear what types of organic matter have higher potential risks. Although regulation of DBPs such as trihalomethanes has received much attention, further investigation of the DBPs driving toxicity is required. This study aimed to identify the important precursors of chlorination by measuring DBP formation from NOM and amino acids, and to determine the main DBPs driving toxicity using a theoretical toxicity evaluation of contributions to the cytotoxicity index (CTI) and genotoxicity index (GTI). The results showed that NOM mainly formed carbonaceous DBPs (C-DBPs), such as trichloromethane, while amino acids mainly formed nitrogenous DBPs (N-DBPs), such as dichloroacetonitrile (DCAN). Among the DBPs, DCAN had the largest contribution to the toxicity index and might be the main driver of toxicity. Among the precursors, aspartic acid and asparagine gave the highest DCAN concentration (200 g/L) and the highest CTI and GTI. Therefore, aspartic acid and asparagine are important precursors for toxicity and their concentrations should be reduced as much as possible before chlorination to minimize the formation of DBPs. During chlorination of NOM, tryptophan, and asparagine solutions with different chlorine doses and reaction times, changes in the CTI and GTI were consistent with changes in the DCAN concentration.

Keywords Chlorination      Dichloroacetonitrile      Aspartic acid      Asparagine      Toxicity index     
Corresponding Author(s): Ye Du   
Issue Date: 27 December 2019
 Cite this article:   
Qian-Yuan Wu,Yi-Jun Yan,Yao Lu, et al. Identification of important precursors and theoretical toxicity evaluation of byproducts driving cytotoxicity and genotoxicity in chlorination[J]. Front. Environ. Sci. Eng., 2020, 14(2): 25.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1204-6
https://academic.hep.com.cn/fese/EN/Y2020/V14/I2/25
Amino acids CAS Formula Structure
L-tryptophan 73-22-3 C11H12N2O2
L-tyrosine 60-18-4 C9H11NO3
L-phenylalanine 63-91-2 C9H11NO2
L-aspartic acid 56-84-8 C4H7NO4
L-asparagine 70-47-3 C4H8N2O3
L-arginine 74-79-3 C6H14N4O2
L-histidine 71-00-1 C6H9N3O2
Tab.1  Information of amino acids used in this study
DBPs LC50 (M) 50% TDNA or midpoint of Tail moment (M) Reference
TCM 9.62 × 10?3 NA a) Wagner and Plewa (2009)
CH 1.16 × 10?3 NA a) Jeong et al. (2015)
DCAN 5.73 × 10?5 2.75 × 10?3 Muellner et al. (2007)
TCAM 2.05 × 10?3 6.54 × 10?3 Plewa et al. (2007)
TCA NA a) NA a Wagner and Plewa (2017)
Tab.2  LC 50 (M) and 50% TDNA or midpoint of Tail moment (M) of DBPs reported in the literature
Fig.1  Levels of DBPs formed during chlorination of different precursors: (a) TCM, (b) TCAL, (c) DCAN, (d) TCAM, and (e) TCA (chlorine dose 9 mg/L, 12.7 μM; and contact time 24 h).
Fig.2  (a) Chlorine byproduct (ClBP) and (b) nitrogen byproduct (NBP) concentrations produced by different precursors during chlorination (chlorine dose 9 mg/L, 12.7 μM; and contact time 24 h).
Fig.3  (a) Cytotoxicity index and (b) genotoxicity index results for the chlorination of different precursors (chlorine dose 9 mg/L, 12.7 μM; and contact time 24 h).
Fig.4  Effects of chlorine dose (chlorine dose 0, 3, 6, 9 mg/L (or 0, 4.2, 8.5, 12.7 μM); and reaction time 1 h) on DBP formation and the toxicity index: (a) NOM as the precursor, (b) tryptophan as the precursor, (c) asparagine as the precursor, (d) cytotoxicity index (CTI), and (e) genotoxicity index (GTI).
Fig.5  Effects of reaction time (chlorine dose 9 mg/L (12.7 μM); and reaction time 0.5, 1, 12, or 24 h) on DBP formation and toxicity index: (a) NOM as the precursor, (b) tryptophan as the precursor, (c) asparagine as the precursor, (d) cytotoxicity index (CTI), and (e) genotoxicity index (GTI).
Precursors N-DBPs (μg/L) C-DBPs (μg/L) Total DBPs (μg/L)
NOM 8.13 121.46 129.59
Tryptophan 16.90 75.90 92.81
Tyrosine 6.39 14.04 20.43
Phenylalanine 0.28 2.77 3.05
Aspartic acid 197.49 34.87 232.36
Asparagine 198.67 36.10 234.77
Arginine ND a) 2.76 2.76
Histidine 19.26 10.40 29.65
Tab.3  DBP formation from the chlorination of different precursors
Fig.6  Correlation between DCAN and NBP concentrations and the toxicity index: (a) DCAN–CTI, (b) DCAN–GTI, (c) NBPs–CTI, and (d) NBPs–GTI. Data are the concentrations of DCAN and NBPs, CTI, and GTI for different precursors (chlorine dose 9 mg/L (12.7 μM); and reaction time 24 h).
DBP index Toxicity index Pearson correlation coefficient Significance (p)
DCAN CTI 1.000 <0.01
GTI 1.000 <0.01
NBP CTI 1.000 <0.01
GTI 1.000 <0.01
Tab.4  Correlation analysis between DCAN, NBP and toxicity index
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