氯消毒过程pH变化对典型药物氯化降解动力学的影响

The Influence of pH changes in chlorine disinfection process on the chlorination degradation dynamics of typical drugs

  • 摘要: 药物类污染物在各类水体中普遍被检出,对人体和生态健康造成极大威胁。氯消毒技术是去除水中药物的有效方法,pH是影响氯消毒过程中氧化性物种分布与污染物去除的重要参数。以往研究多采用磷酸盐缓冲液(phosphate buffer solution, PBs)调节体系的初始pH来研究其对污染物降解的影响,但在实际水体氯化消毒过程中,pH是不断变化的,且具有高度非线性和时滞性,进而对污染物降解的影响可能更为复杂。本文选用4种代表性药物来研究加入氯消毒剂后溶液pH的动态变化对其降解动力学变化规律的影响。研究结果表明,未添加PBs时氟喹诺酮类(fluoroquinolones, FQs)总体氯化速率较慢,溶液pH的增长量与游离氯(free available chlorine, FAC)浓度的增长量呈正相关线性趋势,在这种增长趋势下,FQs的表观降解速率常数(kobs)减小,β-阻滞剂类( beta blockers, BBs)的kobs增大。FAC浓度最低(FAC=1 mg/L)时FQs的kobs最大,洛美沙星(lomofloxacin, LOM)、氧氟沙星( ofloxacin, OFL)的kobs分别为0.28 /s和0.22 /s。离子形态对β-受体阻滞剂(beta blockers, BBs)的降解影响较大,高pH下BBs阴离子形态的高占比显著促进了BBs的氯化降解,pH0=9.0时的降解最快,美托洛尔( metoprolol, MTL)、阿替洛尔(atenolol, ATN)的kobs分别为0.028 /s和0.036 /s。进一步研究发现,4种污染物在饮用水中的氯化降解趋势与在纯净水中的一致。

     

    Abstract: Pharmaceutical contaminants have been ubiquitously detected in various water bodies, posing a considerable threat to human and ecological health. Chlorine disinfection technology is an effective approach for eliminating pharmaceuticals from water. pH is a crucial parameter influencing the distribution of oxidizing species and the removal of contaminants during the chlorine disinfection process. Previous studies have predominantly employed phosphate buffer solutions (PBs) to regulate the initial pH of the system for investigating its impact on pollutant degradation. Nevertheless, the pH in actual water chlorination disinfection processes is constantly varying, highly nonlinear, and time-delayed, thereby making the influence on pollutant degradation more intricate. In this paper, four representative pharmaceuticals were selected to study the influence of the dynamic changes in pH of the solution after the addition of chlorine disinfectant on the variation law of their degradation kinetics. The research results indicate that the overall chlorination rate of fluoroquinolones (FQs) slows down when PBs are not added. The increase in pH of the solution is positively correlated with the increase in concentration of free available chlorine (FAC), showing a linear trend. Under this growth trend, the apparent degradation rate constant (kobs) of FQs decreases, while the kobs of β-blockers (BBs) increases. When the FAC concentration is the lowest (FAC=1 mg/L), the kobs of FQs is instead the largest, with lomefloxacin and ofloxacin being 0.28 /s and 0.22 /s, respectively. The ionic form has a considerable impact on the degradation of BBs. The high proportion of the anion form of BBs at a high pH significantly promotes the chlorination degradation of BBs, with the fastest degradation occurring at pH0=9.0. The kobs of metoprolol and atenolol are 0.028 /s and 0.036 /s, respectively. Further studies reveal that the chlorination degradation trend of the four contaminants in drinking water is consistent with that in pure water.

     

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