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确定和预测激发态 DOM 与选定 PPCPs 之间的表观反应速率。

The determination and prediction of the apparent reaction rates between excited triplet-state DOM and selected PPCPs.

机构信息

State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control, School of Environment, Tsinghua University, Beijing 100084, China.

Department of Civil, Environmental and Architectural Engineering, University of Colorado, Boulder, CO 80309, United States.

出版信息

Sci Total Environ. 2023 Jul 10;881:163117. doi: 10.1016/j.scitotenv.2023.163117. Epub 2023 Apr 10.

Abstract

To determine and predict the reaction rate between DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient ( [Formula: see text] ) to describe the reaction between DOM* and PPCPs. As the values also included the inhibition effect of DOM's antioxidant moieties, the calculation of [Formula: see text] is inconsistent with that of a bimolecular rate constant via the steady-state kinetic method. The [Formula: see text] values of 12 selected PPCPs were determined in two DOM solutions and ten DOM-containing water samples collected from typical surface water bodies in Beijing. The Pearson coefficients between nine predictors including the absorbance ratio (E2/E3), specific absorption coefficient at 254 nm (SUVA), fluorescence index (FI), biological index (BIX), humification index (HIX), pH, total organic carbon (TOC), total fluorescence intensity (TFI) and TOC normalized TFI (TFI/TOC) and [Formula: see text] were examined. Correlation patterns for sulfonamides, β-blockers and diclofenac supported the electron transfer pathway, and was distinctly different from those appeared for FQs where quenching effect played a main part. TFI and TFI/TOC were recognized as the most useful surrogates in empirically predicting [Formula: see text] . For PPCPs that went through the electron transfer pathway, [Formula: see text] could be well fit to the Rehm-Weller model assuming a proportional relationship between TFI and △G. For FQs, [Formula: see text] was found to linearly correlated with TFI/TOC. The [Formula: see text] values determined in this study enrich the database of PPCPs photolysis parameters, and the correlation analysis provides reference for forecasting PPCPs fate in the aquatic environment.

摘要

为了确定和预测各种水体中 DOM和 PPCPs 之间的反应速率,本研究定义了一个反应速率系数([公式:见文本])来描述 DOM和 PPCPs 之间的反应。由于该值还包含 DOM 的抗氧化部分的抑制效应,因此[公式:见文本]的计算与通过稳态动力学方法计算的双分子速率常数不一致。在两种 DOM 溶液和从北京典型地表水体中采集的十种含有 DOM 的水样中,测定了 12 种选定 PPCPs 的[公式:见文本]值。考察了包括吸光度比(E2/E3)、254nm 处的比吸收系数(SUVA)、荧光指数(FI)、生物指数(BIX)、腐殖化指数(HIX)、pH 值、总有机碳(TOC)、总荧光强度(TFI)和 TOC 归一化 TFI(TFI/TOC)在内的九个预测因子与[公式:见文本]之间的 Pearson 系数。磺胺类、β-受体阻滞剂和双氯芬酸的相关模式支持电子转移途径,与喹诺酮类药物明显不同,后者主要表现为猝灭效应。TFI 和 TFI/TOC 被认为是预测[公式:见文本]的最有用的替代物。对于经历电子转移途径的 PPCPs,[公式:见文本]可以很好地拟合 Rehm-Weller 模型,假设 TFI 和△G 之间存在比例关系。对于 FQs,[公式:见文本]与 TFI/TOC 呈线性相关。本研究中确定的[公式:见文本]值丰富了 PPCPs 光解参数数据库,相关分析为预测 PPCPs 在水环境中的命运提供了参考。

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