Nucleophilic hydrolysis of dichloroacetonitrile and trichloroacetonitrile disinfection byproducts by peroxymonosulfate: Kinetics and mechanisms

In this work, it was found that peroxymonosulfate (PMS) could appreciably accelerate the transformation rates of dichloroacetonitrile (DCAN) and trichloracetonitrile (TCAN) in aqueous solutions, especially under alkaline pHs. The impact of reactive oxygen species scavengers (methyl alcohol for sulfate radical, tert-butyl alcohol for hydroxyl radical, and azide for singlet oxygen) and water matrices (chloride (Cl−), bicarbonate (HCO3−), and natural organic matter (NOM)) on DCAN and TCAN transformation by PMS is evaluated, revealing negligible effects. A nucleophilic hydrolysis pathway, as opposed to an oxidation process, was proposed for the transformation of DCAN and TCAN by PMS, supported by the hydrolyzable characteristics of these compounds and validated through density functional theory calculations. Kinetic analysis indicated that the transformation of DCAN and TCAN by PMS adhered to a second-order kinetic law, with higher reaction rates observed at elevated pH levels within the range of 7.0–10.0. Kinetic modeling incorporating the hydrolytic contributions of water, hydroxyl ion, and protonated and deprotonated PMS (i.e., HSO5− and SO52−) effectively fitted the experimental data. Species-specific second-order rate constants reveal that SO52− exhibited significantly higher reactivity towards DCAN ((1.69 ± 0.22) × 104 M−1h−1) and TCAN ((6.06 ± 0.18) × 104 M−1h−1) compared to HSO5− ((2.14 ± 0.12) × 102 M−1h−1) for DCAN; and (1.378 ± 0.11) × 103 M−1h−1 for TCAN). Comparative analysis of DCAN and TCAN transformation efficiencies by four different oxidants indicated that PMS rivaled chlorine but falls short of hydrogen peroxide, with peroxydisulfate displaying negligible reactivity. Overall, this study uncovers the nucleophilic hydrolysis characteristics of PMS, supplementing its recognized role as an oxidant precursor or mild oxidant, and underscores its significant implications for environmental remediation. [Display omitted] •PMS without any activation obviously accelerated HANs hydrolysis rates at alkaline pH.•HANs were transformed by PMS via a non-oxidative nucleophilic hydrolysis pathway.•PMS was as effective as HOCl but less effective than H2O2 in hydrolysis of HANs.•Kinetics of HANs hydrolysis by PMS at different pHs was investigated.