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Environ Sci Technol. 2015 Sep 1;49(17):10373-9. doi: 10.1021/acs.est.5b00483. Epub 2015 Aug 21.

Production of Hydroxyl Radical via the Activation of Hydrogen Peroxide by Hydroxylamine.

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College of Biology and the Environment, Nanjing Forestry University , Nanjing 210037, China.
School of Environmental Science and Engineering, Zhejiang Gongshang University , Hangzhou 310018, China.
College of Architecture and Environment, Sichuan University , Chengdu 610065, China.
School of Environmental Science and Engineering, Sun Yat-sen University , Guangzhou 510275, China.
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology , Harbin 150090, China.


The production of the hydroxyl radical (HO·) is important in environmental chemistry. This study reports a new source of HO· generated solely from hydrogen peroxide (H2O2) activated by hydroxylamine (HA). Electron paramagnetic resonance analysis and the oxidation of a HO· probe, benzoic acid, were used to confirm the production of HO·. The production of HO· increased with increasing concentrations of either HA or H2O2 as well as decreasing pH. The second-order rate constant for the reaction was (2.2 ± 0.2) × 10(-4) M(-1) s(-1). HO· was probably produced in two steps: the activation of H2O2 by protonated HA and then reaction between the H2O2 and the intermediate protonated aminoxyl radical generated in the first step. Such a two-step oxidation can possibly be ascribed to the ionizable hydroxyl moiety in the molecular structure of HA, as is suggested by comparing the reactivity of a series of HA derivatives in HO· production. The results shed light on a previously unknown source of HO· formation, which broadens the understanding of its role in environmental processes.

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