水中常见药物和个人护理品的分析方法改进研究

发布时间：2018-07-17 17:28

【摘要】：近年来,药物和个人护理品(PPCPs)在水中频繁检出,成为一类受到广泛关注的新兴污染物。准确把握PPCPs的环境存在水平,是阐明其迁移转化规律和评价其环境风险的重要基础。由于PPCPs种类繁多,各个国家/地区的生产和使用情况不同,因而其水环境中常见的主要PPCPs也会有很大差异。为此,必须开发针对性强、准确灵敏而方便快捷的分析方法。本研究根据我国PPCPs的生产消费特点,建立了水中常见38种PPCPs的分析方法并开展了案例应用;在此基础上引入同位素内标,进一步开发了定量更准确、稳定性更好的PPCPs精准测定方法。首先,以国际上主流的固相萃取液相色谱串联质谱分析方法为基础,通过对采水瓶材质、固相萃取柱、液相色谱质谱参数等的系统优化,建立了针对我国水体中常见的38种PPCPs(包括16种人用和22种兽用PPCPs)的分析方法。筛选采用国产固相萃取柱Cleanert PEP-2来等效替代进口柱Oasis HLB,大大降低了分析成本。将方法用于饮用水、河水、污水等实际水样考察其适用性,结果表明:平行实验的相对标准偏差小于30%,空白实验中无高于方法定量限的本底存在,表明所建立的分析方法能够很好的应用于多种类型水体的监测。接着,以清华大学校园内的两座中水站为对象,利用所建立的方法进行了长达一个学期的跟踪监测。结果发现:方法能够很好地用于本案例的实际监测;PPCPs在进水中的浓度与学生学习、生活的活动规律具有较强的关联性;两座中水站对PPCPs的去除率均优于普通市政污水处理厂,这得益于所采用的膜生物反应器(MBR)工艺和全年保持室温的稳定运行条件。最后,针对现有方法中内标物数量较少且与目标物结构和性质差异较大,从而导致方法系统误差较大的问题,开展了同位素内标方法的探索。结合最新的可获得性情况,将方法中的提取内标从4种扩展至31种,使绝大多数的目标物可以按照同位素稀释法原理进行定量。结果表明:改进方法的方法检出限(MDL)总体上比常规内标法更低了一个数量级;同时在精密度和准确度上也要优于内标法。该方法为水中PPCPs的监测提供了更为精准的选择,尤其适用于目标物浓度极低或基质复杂的监测场合,以及对数据准确度要求更高的科研目的。
[Abstract]:In recent years, drugs and personal care products (PPCPs) have been frequently detected in water, and have become a kind of emerging pollutants. Accurately grasping the environmental level of PPCPs is an important basis for clarifying the laws of their migration and transformation and evaluating their environmental risks. Due to the variety of PPCPs and the different production and use of PPCPs in different countries and regions, the main PPCPs in their water environment are also very different. Therefore, it is necessary to develop analytical methods with strong pertinence, accuracy, sensitivity and convenience. According to the characteristics of production and consumption of PPCPs in China, the analytical methods of 38 common PPCPs in water were established and the case application was carried out in this study, based on which the isotopic internal standard was introduced to further develop a more accurate quantitative method. A more stable and accurate method for the determination of PPCPs. First of all, based on the international mainstream solid-phase extraction liquid chromatography-tandem mass spectrometry (SPEC-MS) method, the material of the water bottle, the solid phase extraction column, the parameters of the liquid-phase chromatography-mass spectrometry were optimized. A method for the analysis of 38 species of PPCPs (including 16 human and 22 animal PPCPs) was established. The domestic solid phase extraction column (Cleanert PEP-2) was used to replace the imported column Oasis HLB.The analysis cost was greatly reduced. The method was used to investigate the applicability of the method in drinking water, river water, sewage and other real water samples. The results showed that the relative standard deviation of parallel experiments was less than 30, and there was no background above the quantitative limit of the method in the blank experiment. The results show that the proposed analytical method can be applied to the monitoring of many kinds of water bodies. Then, two middle water stations on the campus of Tsinghua University were used to track and monitor for a semester. The results show that the method can be used to monitor the concentration of PPCPs in the influent and the students' learning and living rules, and the removal rate of PPCPs by the two intermediate water stations is better than that of ordinary municipal wastewater treatment plants. This is due to the membrane bioreactor (MBR) process and stable operating conditions at room temperature throughout the year. Finally, aiming at the problem that the quantity of internal standard is small and the structure and property of the method are different from the target, which leads to the large systematic error of the method, the research of the isotope internal standard method is carried out. According to the latest available conditions, the extraction internal standard of the method is extended from 4 to 31, so that most of the target materials can be quantified according to the principle of isotope dilution method. The results show that the detection limit (MDL) of the improved method is lower by an order of magnitude than that of the conventional internal standard method, and the precision and accuracy of the improved method are also better than that of the internal standard method. This method provides a more accurate choice for the monitoring of PPCPs in water, especially for the monitoring situations where the concentration of the target material is very low or the matrix is complex, and for scientific research purposes which require higher accuracy of the data.
【学位授予单位】：清华大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X832

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