Kinetics of the Chemical Oxidation of the Pharmaceuticals Primidone, Ketoprofen, and Diatrizoate in Ultrapure and Natural Waters
Kinetics of the Chemical Oxidation of the Pharmaceuticals Primidone, Ketoprofen, and Diatrizoate in Ultrapure and Natural Waters
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DOI：
10.1021/ie801762p
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发表时间：
2009-04-01
影响因子：
4.2
通讯作者：
Casas, Francisco
中科院分区：
文献类型：
--
作者：
Real, Francisco J.;Benitez, F. Javier;Casas, Francisco
研究了臭氧氧化、紫外光照射和芬顿试剂等高级氧化技术对扑米酮、酮洛芬和泛影酸钠的氧化反应。建立了操作变量的影响，并确定在大多数氧化系统的一阶速率常数。具体而言，对于与臭氧的反应，通过竞争动力学模型获得了以下速率常数：扑米酮、酮洛芬和泛影葡胺分别为1.0 +/- 0.1、0.40 +/- 0.07和0.05 +/- 0.01 M（-1）·s（-1）。结果表明，与OH自由基的反应是这些化合物氧化转化的主要途径。在254 nm的光降解实验中，还测定了不同pH和温度下每种化合物的量子产率。此外，竞争动力学模型也用于芬顿试剂实验，其允许评估与羟基自由基反应的速率常数，其值如下：扑米酮为（6.7 +/- 0.2）x 10（9）M（-1）.s（-1），酮洛芬为（8.4 +/- 0.3）x 10（9）M（-1）.s（-1），泛影葡胺为（5.4 +/- 0.3）x 10（8）M（-1）.s（-1）。此外，同时氧化这些选定的药物在一些天然水系统（商业矿泉水，地下水，地表水从水库）进行了研究。建立了操作条件对去除效率的影响。最后，提出了一个动力学模型，预测臭氧在这些天然沃茨中消除选定的药物，理论结果与实验结果吻合良好。
Oxidation of three pharmaceuticals (primidone, ketoprofen, and diatrizoate sodium) by means of several advanced oxidation processes including such as ozonation, UV radiation, and Fenton's reagent has been studied. The influence of operating variables was established, and first-order rate constants were determined in most of the oxidation systems. Specifically, for the reactions with ozone, the following rate constants were obtained by means of a competition kinetic model: 1.0 +/- 0.1, 0.40 +/- 0.07, and 0.05 +/- 0.01 M(-1).s(-1), for primidone, ketoprofen, and diatrizoate, respectively. The results showed that reaction with OH radicals was the major pathway for the oxidative transformation of these compounds. In the photodegradation experiments by 254 nm radiation, the quantum yields were also determined for every compound at different pH and temperatures. Additionally, the competition kinetic model, which was also used in Fenton's reagent experiments, allowed to evaluate the rate constants for the reaction with hydroxyl radicals whose values were the following: (6.7 +/- 0.2) x 10(9) M(-1).s(-1) for primidone, (8.4 +/- 0.3) x 10(9) M(-1).s(-1) for ketoprofen, and (5.4 +/- 0.3) x 10(8) M(-1).s(-1) for diatrizoate. Furthermore, the simultaneous oxidation of these selected pharmaceuticals in some natural water systems (a commercial mineral water, a groundwater, and surface water from a reservoir) was studied. The influence of the operating conditions on the removal efficiency was established. Finally, a kinetic model was proposed for the prediction of the elimination of the selected pharmaceuticals by ozone in these natural waters, with theoretical results that agreed well with the experimental ones.