4.7 Article

Electrochemical degradation and mechanistic analysis of microcystin-LR at boron-doped diamond electrode

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 243, Issue -, Pages 117-126

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2013.12.091

Keywords

LC-MS/MS; Microcystin-LR; Boron-doped diamond; Quantum chemical calculations

Funding

  1. National Natural Science Foundation of China [51079056/E090301]
  2. Ministry of Science and Technology of China [2010DFA22770]
  3. International Science & Technology Cooperation Program of China [2013DFG50150]

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The electrochemical degradation behavior of microcystin-LR (MC-LR) in aqueous electrolyte at boron-doped diamond (BDD) anode was investigated under neutral pH condition. Hydroxyl radicals ((OH)-O-center dot) formed were detected by photoluminescence (PL) technique using terephthalic acid as a probe molecule, and it was observed to be predominant reactive specie. The intermediates formed in the MC-LR decomposition reaction were identified by LC-MS/MS, among which, two (m/z 1011.8 and 1029.5) were found to have multiple peaks in total ion current (TIC) chromatogram. The degradation of MC-LR was found to be mainly due to (OH)-O-center dot attack that involved hydroxylation of MC-LR via substitution/addition with a simultaneous isomerization, oxidation and oxidative bond cleavage reaction processes. The destruction of conjugated double bond of Adda was achieved by different mechanistic steps involving addition and substitution of (OH)-O-center dot that generated primary by product at m/z 1029.5. The destruction of diene bond of the Mdha, produced an adduct which was observed to be more stable, owing to a very less barrier than its substitution counterpart. (C) 2014 Elsevier B.V. All rights reserved.

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