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饮用水处理中二甲基氧膦氯化反应的动力学和机制。

Kinetics and mechanism of dimethoate chlorination during drinking water treatment.

机构信息

School of Environment, Tsinghua University, Beijing 100084, China; School of Environmental Engineering, Nanjing Institute of Technology, Nanjing 211167, China.

School of Environment, Tsinghua University, Beijing 100084, China.

出版信息

Chemosphere. 2014 May;103:181-7. doi: 10.1016/j.chemosphere.2013.11.061. Epub 2013 Dec 28.

Abstract

Dimethoate (DMT), a commonly used organophosphorus pesticide, is of great concern because of its toxicity and potentially harmful effects on water sources. The elimination of DMT as well as the toxicity and persistence of the byproducts formed during DMT degradation is most important for the safety of drinking water. This study first determined the reaction kinetics of DMT with free chlorine (FC) under typical water treatment conditions. The reaction between DMT and FC proceeded rapidly, exhibiting first-order with respect to each reactant. The degradation of DMT by FC was highly pH dependent, and the pseudo-first-order rate constant decreased obviously from 0.13 to 0.02 s(-1) with an increase in pH from 7.0 to 8.3. Bromide ion accelerated the reaction by acting as a catalyst, and the accelerated reaction rate was linearly proportional to the bromide concentration. As a ubiquitous component in natural waters, humic acid also increased the reaction rate. However, the presence of ammonium inhibited the degradation of DMT due to its rapid converting FC to chloramines. Omethoate (OMT) was identified as an important byproduct of DMT chlorination, but only accounted for ca. 28% of the DMT degraded; and other two organic byproducts were also identified. The acute toxicity of DMT solution increased after treatment with FC due to the formation of more toxic byproducts (e.g. OMT).

摘要

乐果(DMT)是一种常用的有机磷农药,由于其毒性以及对水源可能产生的有害影响而受到广泛关注。消除 DMT 以及 DMT 降解过程中形成的副产物的毒性和持久性,对于饮用水的安全至关重要。本研究首先确定了 DMT 在典型水处理条件下与自由氯(FC)的反应动力学。DMT 与 FC 之间的反应迅速进行,对每种反应物均表现为一级反应。FC 对 DMT 的降解高度依赖 pH 值,当 pH 值从 7.0 增加到 8.3 时,假一级速率常数从 0.13 明显降低到 0.02 s(-1)。溴离子作为催化剂加速了反应,加速反应速率与溴离子浓度呈线性关系。作为天然水中普遍存在的成分,腐殖酸也提高了反应速率。然而,由于铵迅速将 FC 转化为氯胺,抑制了 DMT 的降解。氧乐果(OMT)被鉴定为 DMT 氯化的重要副产物,但仅占 DMT 降解量的约 28%;还鉴定出另外两种有机副产物。由于形成了更多的有毒副产物(例如 OMT),FC 处理后的 DMT 溶液的急性毒性增加。

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