药物和个人护理品在生产和使用过程中会以各种方式排放至水环境中，多以微量或痕量、手性形式存在，并且在环境中的赋存具有对映体选择性。由于该类物质在环境中的持久性和生物累积性，会对人体健康和生态系统造成潜在风险。极性有机物整合采样器（POCIS）作为被动采样技术被广泛应用于极性污染物富集采样，但是在应用过程中，采样参数会受到诸多环境因素影响，使得富集采样结果具有一定不确定性。
       本论文选择美托洛尔、普萘洛尔、阿替洛尔、文拉法辛和氟西汀五种常用手性药物对映体为目标污染物，研究其在整合POCIS以及该采样器各组成材料中的多相传质过程，探究POCIS对于手性药物的采样机制，优化采样过程参数，从而提高被动采样器对药物类污染物环境监测的准确性。主要研究结果如下：
（1）采用吸附和渗透实验并结合一阶方程和三室模型计算，获得了表征目标污染物在聚醚砜（PES）和聚四氟乙烯（PTFE）膜中的传质过程的相关参数，结果发现，在PTFE膜中，水流扰动相较于静止条件下所获得的总传质系数（k_o）值约高0.5倍，复合污染物体系中获得的ko值约为单一污染物体系的1.5-2倍，表明水边界层以及污染物之间的相互作用对传质过程影响较大；由于目标污染物受PES膜吸附作用影响，在单一污染物体系中获得的ko值受水流条件影响较小，复合污染物体系中k_o值之间存在3-4个数量级差异，表明污染物在膜材料上的竞争吸附影响其传质过程。
（2）根据目标污染物在Oasis HLB吸附剂上的吸附热力学和吸附动力学特性研究发现，污染物在吸附过程中受多种吸附位点作用，存在吸附剂的表面吸附和粒子内扩散的多步吸附过程，吸附过程受化学吸附或者离子交换控制；温度、盐度和腐殖酸（HA）浓度对污染物吸附浓度具有不同程度影响，各因素之间的交互作用对吸附过程存在一定影响；不同因素影响下，手性药物对映体在吸附剂上的吸附性差异不明显。
（3）通过静态耗损实验并结合一级动力学模型计算获得了不同环境因素影响下POCIS-PES和POCIS-PTFE富集目标污染物的采样速率（R_s）值、采样器分配系数和采样半周期时长，结果表明，两种采样器在水流扰动下对污染物的富集速率要快于静止条件，目标污染物在POCIS-PES中的累计质量比较低；受盐度、HA浓度和生物膜影响，部分手性药物对映体的采样速率分数值（R_s-EF）呈现不同程度的差异性，富集行为存在对映体选择性；路径分析发现膜材料和盐度与Rs值呈负向效应，污染物特性、HA和水流扰动对Rs值影响呈正向效应，污染物自身性质对于R_s值的影响较大。
（4）静态更新实验与静态耗损实验结果比较发现，静态更新实验所得的污染物R_s值不易受环境因素影响，两种校准实验在盐度和HA与水流协同作用下获得的R_s值具有较高的一致性（线性相关系数R²=0.90-0.99），而实际水样会对静态耗损实验产生较大的影响。随着盐度的升高和生物膜层的存在，两个校准实验中手性药物对映体的富集行为存在较大差异。而随HA浓度递增，两种校准实验中各手性药物对映体R_s-EF值差异不明显；两种校准方法所获得的采样参数均能准确地反映POCIS的富集过程，其中静态更新实验所获得时间加权平均（TWA）浓度差值范围小于静态耗损实验所获得的TWA浓度差值范围。
 

Pharmaceuticals and personal care products are discharged to the aqueous environment in various ways during production and use, mostly in trace, chiral forms, and are enantioselective in their environmental fate. Due to their persistence and bioaccumulation in the environment, these substances pose potential risks to human health and ecosystems. Polar organic compound integrated sampler (POCIS) as a passive sampler for polar compounds is widely used for enrichment sampling of such pollutants, but in the application process, the sampling parameters can be affected by many environmental factors, making the enrichment sampling results have some errors.
In this thesis, five commonly used chiral pharmaceuticals, metoprolol, propranolol, atenolol, venlafaxine and fluoxetine, were selected as target pollutants to investigate the multi-phase mass transfer process of their enantiomers in the integrated POCIS and each component, to explore the sampling mechanism of POCIS for chiral pharmaceuticals, to optimize the sampling process parameters, to reduce the monitoring errors caused by sampling uncertainties, and thus to improve the accuracy of passive sampling devices for environmental monitoring of pharmaceuticals pollutants. The main results of the study are as follows.
(1) The relevant parameters characterizing the mass transfer process of the selected contaminants in polyethersulfone (PES) and polytetrafluoroethylene (PTFE) membranes were obtained by using adsorption and permeation experiments combined with first-order equations and three-compartment model calculations, and it was found that the overall mass transfer coefficient (k_o) values obtained in PTFE membranes were about 0.5 times higher for turbulence compared to static conditions, and the k_o values obtained in the composited pollutant system were about 1.5-2 times higher than those in the single pollutant system, indicating that the water boundary layer and the interaction between the contaminants had a greater influence on the mass transfer process; the ko values obtained in the single pollutant system were less affected by the water flow conditions because the selected contaminants were affected by the adsorption on the PES membrane, and there were 3-4 orders of magnitude differences between the k_o values in the composite pollutant system, indicating that the competing adsorption of the contaminants on the membrane material affected its mass transfer process.
(2) According to the study on the adsorption thermodynamics and adsorption kinetics of the selected pollutants on Oasis HLB adsorbent, it was found that the pollutants were subject to multiple adsorption sites in the adsorption process, and there was a multi-step adsorption process of surface adsorption and intraparticle diffusion of the adsorbent, and the adsorption process was controlled by chemisorption or ion exchange; temperature, salinity and humic acid (HA) concentration had different degrees of influence on the adsorption concentration of the pollutants, and the interaction between the factors had some influence on the adsorption process; the adsorption of chiral drug enantiomers on the adsorbent was not significantly different under the influence of different factors. 
(3) The sampling rate (R_s) values, sampler partition coefficients and sampling half-cycle durations of POCIS-PES and POCIS-PTFE enrichment of selected contaminants under the influence of different environmental factors were obtained by static depletion experiments and combined with first-order kinetic model calculations, and the results showed that the enrichment rates of both samplers for contaminants under turbulence were faster than under static conditions, The cumulative mass of the selected contaminants in POCIS-PES was relatively low, and the sampling rate fraction (R_s-EF) values of some chiral pharmaceutical enantiomers showed different degrees of variability by salinity, HA concentration and biofilm, and there was enantioselectivity in enrichment behavior; path analysis revealed that membrane material and salinity had a negative effect with R_s values, and contaminant characteristics, HA and turbulence had a positive effect on R_s values, and the nature of the contaminants themselves had a greater effect on Rs values. 
(4) Comparison of the results of the static renewal experiment with those of the static depletion experiment revealed that the R_s values of contaminants obtained from the static renewal experiment were less susceptible to environmental factors, and the Rs values obtained from the two calibration experiments were in high agreement (linear correlation coefficient R² = 0.90-0.99) for salinity and HA in concert with water flow, while the actual water samples would have a greater effect on the static depletion experiment. The enrichment behavior of the chiral pharmaceutical enantiomers in the two calibration experiments differed significantly with increasing salinity and the presence of biofilm layer. In contrast, the differences in R_s-EF of each chiral pharmaceutical enantiomer in the two calibration experiments were not significant with increasing HA concentration. The sampling parameters obtained by both calibration methods accurately reflected the enrichment process of POCIS, where the range of time weighted average (TWA) concentration differences obtained from the static renewal experiment was smaller than the range of TWA concentration differences obtained from the static depletion experiment.