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载铁活性炭催化臭氧化降解水中氧乐果的动力学和机理。

Kinetics and mechanism for omethoate degradation by catalytic ozonation with Fe(III)-loaded activated carbon in water.

机构信息

State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing 100085, China.

出版信息

Chemosphere. 2013 Feb;90(6):1966-72. doi: 10.1016/j.chemosphere.2012.10.059. Epub 2012 Nov 21.

Abstract

The kinetics and mechanism for degradation of omethoate (OMT) by catalytic ozonation with Fe(III)-loaded activated carbon (Fe@AC) were investigated in this study with focus on identification of degradation byproducts. The rate constants of OMT reacting with ozone and hydroxyl radical ((·)OH) were determined to be 0.04 and 5.3×10(8) M(-1) s(-1) at pH 7.5 and 20 °C, respectively. OMT was predominantly degraded by ()OH in the catalytic ozonation with Fe@AC. The high-molecular-weight degradation byproducts identified were O,O,O-trimethyl phosphoric ester (TMP), pyrrolidin-2-one, N-methyl-2-sulfanylacetamide, 2-(methylthio)acetamide, O,O,S-trimethylthiophosphate (STMP), and N-methyl-2-(methylthio)acetamide. Besides, low-molecular-weight organic acids and inorganic anions were also detected and quantified, including formic, acetic and oxalic acids as well as nitrate, sulfate and phosphate ions. In the catalytic ozonation, TMP and phosphate were two major P-containing byproducts resulting from OMT degradation. The toxicity of OMT solution gradually decreased during the catalytic ozonation, indicating that Fe@AC is a safe catalyst for OMT removal by ozone in water.

摘要

本研究采用负载三价铁的活性炭(Fe@AC)催化臭氧化降解氧乐果(OMT),重点研究了降解产物的鉴定。在 pH 7.5 和 20°C 下,确定了 OMT 与臭氧和羟基自由基(·OH)的反应速率常数分别为 0.04 和 5.3×10(8) M(-1) s(-1)。在 Fe@AC 催化臭氧化中,OMT 主要通过(·OH)降解。鉴定出的高分子量降解产物有 O,O,O-三甲基磷酸酯(TMP)、吡咯烷-2-酮、N-甲基-2-巯基乙酰胺、2-(甲基硫基)乙酰胺、O,O,S-三甲基硫代磷酸酯(STMP)和 N-甲基-2-(甲基硫基)乙酰胺。此外,还检测并定量了一些低分子量有机酸和无机阴离子,包括甲酸、乙酸和草酸以及硝酸盐、硫酸盐和磷酸盐离子。在催化臭氧化中,TMP 和磷酸盐是 OMT 降解生成的两种主要含磷副产物。在催化臭氧化过程中,OMT 溶液的毒性逐渐降低,表明 Fe@AC 是一种安全的催化剂,可用于水中臭氧去除 OMT。

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