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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng    2012, Vol. 6 Issue (1) : 75-81     https://doi.org/10.1007/s11783-011-0331-5
RESEARCH ARTICLE
Characterization of chlorine dioxide as disinfectant for the removal of low concentration microcystins
Mingsong WU1, Junli HUANG1(), Yuling ZHANG2, Shijie YOU1, Shaofeng LI3, Zhilin RAN1,3, Yu TIAN1
1. Key Laboratory of Water Resource Utilization and Environmental Pollution Control, Harbin Institute of Technology, Harbin 150090, China; 2. College of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China; 3. Department of Architecture Engineering, Shenzhen Polytechnic Institute, Shenzhen 518055, China
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Abstract

Microcystins, which represents one kind of cancerogenic organic compounds, is abundant in eutrophication water. The effects of reaction factors on chlorine dioxide (ClO2) for removal of low-concentration Microcystin-LR, Microcystin-RR, and Microcystin-YR in water as well as the reaction mechanisms was investigated by using enzyme-linked immunosorbent assay (ELISA) kit and gas chromatography–mass spectrometry (GC-MS). The results showed that MC-LR, MC-RR, and MC-YR could be efficiently decomposed by ClO2. The degradation efficiency was shown positively correlated to the concentration of ClO2 and reaction time; while the effect of reaction temperature and pH is slight. The kinetic constants and activation energies of the reaction of MC-LR, MC-RR, and MC-YR with ClO2 are determined as 459.89, 583.15, 488.43 L·(mol·min)-1 and 64.78, 53.01, 59.15 kJ·mol-1, respectively. As indicated by high performance liquid chromatography mass spectrometer (HPLC-MS) analysis, degradation should be accomplished via destruction of Adda group by oxidation, with the formation of dihydroxy substituendums as end products. This study has provided a fundamental demonstration of ClO2 serving as oxidizing disinfectant to eliminate microcystins from raw water source.

Keywords disinfection      chlorine dioxide      microcystins      reaction mechanism     
Corresponding Author(s): HUANG Junli,Email:junli_hit@126.com   
Issue Date: 01 February 2012
 Cite this article:   
Mingsong WU,Junli HUANG,Yuling ZHANG, et al. Characterization of chlorine dioxide as disinfectant for the removal of low concentration microcystins[J]. Front Envir Sci Eng, 2012, 6(1): 75-81.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-011-0331-5
http://journal.hep.com.cn/fese/EN/Y2012/V6/I1/75
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Mingsong WU
Junli HUANG
Yuling ZHANG
Shijie YOU
Shaofeng LI
Zhilin RAN
Yu TIAN
Fig.1  Removal of MCs as function of ClO dosage at pH of 6.8, temperature of 22 °C, reaction time of 30 min, and initial MC concentration of 6 μg·L
Fig.2  Removal of MCs as function of reaction time at pH of 6.8, temperature of 22 °C, initial MC concentration of 6 μg·L, and ClO dosage of 0.6 mg·L
Fig.3  Removal of MCs as function of pH value at temperature of 22 °C, reaction time of 30 min, initial MC concentration of 6 μg·L, and ClO dosage of 0.6 mg·L
Fig.4  Removal of MCs as function of temperature at pH of 6.8, reaction time of 30 min, initial MC concentration of 6 μg·L, and ClO dosage of 0.6 mg·L
Fig.5  Dependence of MCs removal on initial concentrations of MCs at temperature of 22°C, pH of 6.8, reaction time of 30 min, initial MC concentration of 6 μg·L, and ClO dosage of 0.6 mg·L
pHreaction of MC with ClO2
MC-LRMC-RRMC-YR
second order rate, K/(L·(mol·min) -1)3.44518611524
6.48460583488
10.41401528422
active energy, Ea/(kJ·mol-1)6.4864.7853.0159.15
Tab.1  Second order rate constants and active energies for the reaction of MCs and ClO
Fig.6  Daughter ion recordings of the 1029.54 (a), 1072.58 (b), and 1079.50 (c) in the oxidation products of MC-LR, MC-RR, and MC-YR
MC-LRMC-RRMC-YR
m/zfragmentm/zfragmentm/zfragment
1029[MC-LR+ 2OH+ H] +1072[MC-RR+ 2OH+ H]+1079[M+ 2OH+ H]+
1011[MC-LR+ 2OH+ H-H2O] +1054[MC-RR+ 2OH+ H-H2O]+1061[M+ 2OH-H2O+ H]+
993[MC-LR+ 2OH-H2O+ H] +1036[MC-RR+ 2OH-H2O+ H]+1043[M+ 2OH-2H2O+ H]+
882[MC-LR+ 2OH-2H2O+ H] +633[Arg-Adda-Glu+ 2OH+ H]+1007[M+ 2OH-4H2O+ H]+
765[Mdha-Ala-Leu-MeAsp-Arg-adda+ 2OH+ H] +504[Arg-Adda+ 2OH+ H]+633[Arg-Adda-Glu+2OH+ H]+
633[Arg-Adda-Glu+ 2OH+ H] +453[Glu-Adda+ 2OH-2H2O+ H]+
597[Arg-Adda-Glu+ 2OH-2H2O+ H] +
Tab.2  Suggested formulas for the major daughter ions of the oxidation products of MCs
Fig.7  General molecular formula of MC-LR, MC-RR, and MC-YR
Fig.8  Schematic representation of two reaction modes of ClO and MCs
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