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水杨酸在水中臭氧氧化的动力学及转化产物研究

Study on the kinetics and transformation products of salicylic acid in water via ozonation.

作者信息

Hu Ruikang, Zhang Lifeng, Hu Jiangyong

机构信息

Department of Civil & Environmental Engineering, The National University of Singapore, Block E1A, #07-03, No.1 Engineering Drive 2, Singapore 117576, Republic of Singapore; PUB Water Quality Laboratory, Water Quality Office, PUB, 82 Toh Guan Road East, #04-03, Singapore 608576, Republic of Singapore.

PUB Water Quality Laboratory, Water Quality Office, PUB, 82 Toh Guan Road East, #04-03, Singapore 608576, Republic of Singapore.

出版信息

Chemosphere. 2016 Jun;153:394-404. doi: 10.1016/j.chemosphere.2016.03.074. Epub 2016 Mar 28.

Abstract

As salicylic acid is one of widely used pharmaceuticals, its residue has been found in various environmental water systems e.g. wastewater, surface water, treated water and drinking water. It has been reported that salicylic acid can be efficiently removed by advanced oxidation processes, but there are few studies on its transformation products and ozonation mechanisms during ozonation process. The objective of this study is to characterize the transformation products, investigate the degradation mechanisms at different pH, and propose the ozonation pathways of salicylic acid. The results showed that the rate of degradation was about 10 times higher at acidic condition than that at alkaline condition in the first 1 min when 1 mg L(-1) of ozone solution was added into 1 mg L(-1) of salicylic acid solution. It was proposed that ozone direct oxidation mechanism dominates at acidic condition, while indirect OH radical mechanism dominates at alkaline condition. A two stages pseudo-first order reaction was proposed at different pH conditions. Various hydroxylation products, carbonyl compounds and carboxylic acids, such as 2,5-dihydroxylbenzoic acid, 2,3-dihydroxylbenzoic acid, catechol, formaldehyde, glyoxal, acetaldehyde, maleic acid, acetic acid and oxalic acid etc. were identified as ozonation transformation products. In addition, acrylic acid was identified, for the first time, as ozonation transformation products through high resolution liquid chromatography-time of flight mass spectrometer. The information demonstrated in this study will help us to better understand the possible effects of ozonation products on the water quality. The degradation pathways of salicylic acid by ozonation in water sample were proposed. As both O3 and OH radical were important in the reactions, the degradation pathways of salicylic acid by ozonation in water sample were proposed at acidic and basic conditions. To our knowledge, there was no integrated study reported on the ozonation of salicylic acid in water, in terms of transformation products, kinetic, mechanism, as well as degradation pathways.

摘要

由于水杨酸是一种广泛使用的药物,其残留物已在各种环境水系统中被发现,例如废水、地表水、处理水和饮用水。据报道,高级氧化工艺可以有效地去除水杨酸,但关于其在臭氧化过程中的转化产物和臭氧化机制的研究较少。本研究的目的是表征转化产物,研究不同pH值下的降解机制,并提出水杨酸的臭氧化途径。结果表明,当向1mg/L的水杨酸溶液中加入1mg/L的臭氧溶液时,在酸性条件下前1分钟的降解速率比碱性条件下高约10倍。有人提出,在酸性条件下臭氧直接氧化机制占主导,而在碱性条件下间接羟基自由基机制占主导。在不同pH条件下提出了两阶段准一级反应。各种羟基化产物、羰基化合物和羧酸,如2,5-二羟基苯甲酸、2,3-二羟基苯甲酸、儿茶酚、甲醛、乙二醛、乙醛、马来酸、乙酸和草酸等被鉴定为臭氧化转化产物。此外,通过高分辨率液相色谱-飞行时间质谱仪首次鉴定出丙烯酸为臭氧化转化产物。本研究中展示的信息将有助于我们更好地理解臭氧化产物对水质的可能影响。提出了水样中水杨酸的臭氧化降解途径。由于O3和羟基自由基在反应中都很重要,因此提出了水样中水杨酸在酸性和碱性条件下的臭氧化降解途径。据我们所知,关于水中水杨酸臭氧化的转化产物、动力学、机制以及降解途径,尚无综合研究报道。

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