Kinetics and mechanism of sulfate radical- and hydroxyl radical-induced degradation of highly chlorinated pesticide lindane in UV/peroxymonosulfate system

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2017-06, Vol.318, p.135-142
• Main Authors: Khan, Sanaullah, He, Xuexiang, Khan, Javed Ali, Khan, Hasan M., Boccelli, Dominic L., Dionysiou, Dionysios D.
• Format: Article
• Language: English
• Subjects: Degradation mechanism; Lindane; Second-order rate constant; UV/peroxymonosulfate; Water quality parameters
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2016.05.150

[Display omitted] •Removal of lindane by UV-C/peroxymonosulfate based AOPs was investigated.•Lindane showed a comparable or slightly higher reactivity towards SO4- than HO.•Degradation efficiency was significantly affected in presence of NOM or alkalinity.•A reasonable mineralization of lindane was achieved by UV/PMS.•Transformation mechanism was proposed based on by-products identified via GC–MS. Lindane is a highly persistent chlorinated pesticide and a potent endocrine disruptor. The strong electron withdrawing property of the chlorine atoms results in a relatively low reactivity of lindane with OH in conventional advanced oxidation processes (AOPs). In this study, the degradation of lindane by UV (254nm)/peroxymonosulfate (UV/PMS), which can generate both OH and SO4-, was investigated. A second-order rate constant of 1.3×109M−1s−1 between lindane and SO4- was determined using competition kinetics, suggesting a strong role of SO4-. The degree of degradation changed with different initial solution pH, achieving 86, 92 and 55% removal of lindane at pH 4.0, 5.8 and 8.0, respectively, in 180min, attributable to the varying concentrations of OH and SO4-. The addition of common water quality constituents, e.g., humic acid or inorganic anions, at pH 5.8 showed a varied inhibition effect with 61% degradation in the presence of 1.0mgL−1 humic acid, and 45, 60, 88 and 91% degradation in the presence of 1mM CO32−, HCO3−, Cl− and SO42−, respectively, in 180min. With the kinetics being demonstrated to be feasible, the degradation mechanism of lindane by UV/PMS was also assessed. Based on the detected by-products through GC–MS analysis, plausible reaction pathways were proposed, suggesting dechlorination, chlorination, dehydrogenation and hydroxylation via OH and/or SO4- attack. Meanwhile, reasonable mineralization efficiency was observed, with a 56% total organic carbon removal in 360min, at an initial PMS concentration of 500μM. Results from both degradation kinetics and transformation mechanism indicate that UV/PMS is a potential method for the treatment of water contaminated with lindane.