Abstract：
Ketoprofen (KET), as a non-steroidal anti-inflammatory drug frequently detected in aqueous environments, is a threat to human health due to its accumulation and low biodegradability, which requires the transformation and degradation of KET in aqueous environments. In this paper, the reaction process of ozone-initiated KET degradation in water was investigated using density functional theory (DFT) method at the M06-2X/6-311++g(3df,2p)//M06-2X/6-31+g(d,p) level. The detailed reaction path of KET ozonation is proposed. The thermodynamic results show that ozone-initiated KET degradation is feasible. Under ultraviolet irradiation, the reaction of ozone with water can also produce OH radicals (HO·) that can react with KET. The degradation reaction of KET caused by HO· was further studied. The kinetic calculation illustrates that the reaction rate (1.99 × 10-1 (mol/L)-1 sec-1) of KET ozonation is relatively slow, but the reaction rate of HO· reaction is relatively high, which can further improve the degradation efficiency. On this basis, the effects of pollutant concentration, ozone concentration, natural organic matter, and pH value on degradation efficiency under UV/O3 process were analyzed. The ozonolysis reaction of KET is not sensitive to pH and is basically unaffected. Finally, the toxicity prediction of oxidation compounds produced by degradation reaction indicates that most of the degradation products are harmless, and a few products containing benzene rings are still toxic and have to be concerned. This study serves as a theoretical basis for analyzing the migration and transformation process of anti-inflammatory compounds in the water environment.
摘要：
酮洛芬（KET），作为一种经常在水性环境中检测到的非甾体抗炎药，由于其积累和低生物降解性，对人类健康构成威胁，这需要KET在水环境中的转化和降解。在本文中,使用密度泛函理论（DFT）方法在M06-2X/6-311g（3df，2p)//M06-2X/6-31+g(d,P）水平。提出了KET臭氧化的详细反应途径。热力学结果表明，臭氧引发的KET降解是可行的。在紫外线照射下，臭氧与水的反应还可以产生可以与KET反应的OH自由基（HO·）。进一步研究了HO·引起的KET的降解反应。动力学计算表明，KET臭氧化的反应速率（1.99×10-1（mol/L）-1sec-1）相对较慢，但是HO·反应的反应速率相对较高，可以进一步提高降解效率。在此基础上,污染物浓度的影响，臭氧浓度,天然有机物,和pH值对UV/O3工艺降解效率的影响进行了分析。KET的臭氧分解反应对pH不敏感，基本不受影响。最后,降解反应产生的氧化化合物的毒性预测表明，大多数降解产物是无害的，一些含有苯环的产品仍然有毒，必须引起关注。本研究为分析抗炎化合物在水环境中的迁移转化过程提供了理论基础。
