The Influence of Cu(II) on the Formation and Distribution of Disinfection By-Products during the Chlorination of Drinking Water

  • Shao-gang LiuEmail author
  • Zhi-liang Zhu
  • Xue-cai Tan
  • Xin-hui Feng
  • Zai-yin Huang
  • Yan-ling Qiu
  • Jian-fu Zhao


The catalytic effect of Cu(II) on the formation of disinfection by-products (DBPs) and chlorine degradation during chlorination of humic acid (HA) solutions was comparatively investigated under different experimental conditions. The experimental results showed that the total organic halogen (TOX) and trihalomethane (THM) formation increased with increasing Cu(II) concentration during chlorination, while haloacetic acids (HAAs) increased insignificantly. Accelerated chlorine decay and increased TOX and HAA formation were observed at high pH in the presence of 1.0 mg/L Cu(II) compared with that observed at low pH but THM formation decrease. Furthermore, the Cu(II) effect catalyzed the formation of brominated DBPs as it did for chlorine analogues in the presence of bromide ion. The microcalorimetry analysis demonstrated that more DBPs were formed in the Cu(II)-catalyzed chlorination, in which second-order rate constants obtained from reaction of HA with chlorine under given experimental conditions were 0.00256 M−1 s−1 (without Cu(II)) and 0.00865 M−1 s−1 (with Cu(II)), respectively. To discriminately examine the role of Cu(II) in greater detail, nine model compounds, which approximately represent the chemical structural units of HA, were individually oxidized by chlorine. It was demonstrated that carboxylic acids significantly enhanced the formation of TOX, THMs, and HAAs in the presence of Cu(II). Based on the previously published information and our experimental results, the possible pathway for Cu(II)-catalyzed TOX, THM, and HAA formation from chlorination of carboxylic acids were tentatively proposed.


Cu(II) Chlorination Total organic halogen Disinfection by-products Microcalorimetry Catalysis pathway 



This work was financially supported by National Mega-Project of Science and Technology of China (No. 2008ZX07421-002), the National Eleventh Five-Year Pillar Program of Science and Technology of China (No. 2006BAJ04A07), and Guangxi Natural Science Foundation (No. 2011GXNSFB018021, 0991001z). We thank Mrs. Chen Jie and Gao-chao Fan for many helpful discussions and assistance.

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Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • Shao-gang Liu
    • 1
    • 2
    • 4
    Email author
  • Zhi-liang Zhu
    • 3
  • Xue-cai Tan
    • 1
    • 2
  • Xin-hui Feng
    • 1
    • 2
  • Zai-yin Huang
    • 1
    • 2
  • Yan-ling Qiu
    • 3
  • Jian-fu Zhao
    • 3
  1. 1.College of Chemistry and Chemical Engineering of Guangxi University for Nationalities, Key Laboratory of Chemical and Biological Transforming ProcessUniversity of GuangxiNanningChina
  2. 2.Guangxi Key Laboratory of Chemistry and Engineering of Forest ProductsNanningChina
  3. 3.State Key Laboratory of Pollution Control and Resource Reuse, Key Laboratory of Yangtze Aquatic Environment of Ministry of EducationTongji UniversityShanghaiChina
  4. 4.College of Chemistry and Chemical EngineeringGuangxi University for NationalitiesNanningPeople’s Republic of China

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