Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

城市污水处理厂及其受纳水体中5种典型PPCPs的赋存特征和生态风险

以5种药品及个人护理用品(pharmaceuticals and personal care products,PPCPs)包括氯贝酸、酮洛芬、萘普生、双氯芬酸和布洛芬为目标物,初步研究了它们在上海某生活污水处理厂不同污水处理单元中的赋存特征和去除特性,探讨了污水处理厂受纳河流中5种PPCPs的分布情况,并对其在受纳水体中的生态风险进行了初步评估.结果表明,5种PPCPs在污水处理厂进水中均被检出,表明生活污水是污水处理厂中PPCPs的来源之一.5种PPCPs在整个污水处理工艺中不能全部去除,微生物转化/降解是主要降解机制.受纳污水河流中5种PPCPs的分布特征与污水处理厂出水中的相似,且排污口下游水体中目标物浓度普遍高于上游,反映出污水处理厂排放可能是其受纳水体中PPCPs的主要来源之一.初步风险评估结果表明,受纳水体中双氯芬酸存在高生态风险,而酮洛芬、萘普生、氯贝酸和布洛芬的生态风险相对较低.     

TiO2/粉煤灰光催化降解双氯芬酸钠研究

以燃煤电厂外排的废弃物粉煤灰(CFA)为载体,采用混合泥浆法将TiO2负载在CFA的表面,得到一种新型的复合光催化剂TiO2/CFA.对TiO2/CFA进行了扫描电镜分析、X射线衍射分析和氮吸附测试,并以双氯芬酸钠的光催化降解为评价手段,研究了TiO2负载量对TiO2/CFA光催化性能及重复使用性能的影响.结果表明,TiO2负载量的增加有助于提高TiO2/CFA的光催化性能,但当TiO2负载量过高时,CFA上的TiO2在水处理过程中容易脱落,对TiO2/CFA光催化剂的重复使用性能不利.本研究中,最佳的TiO2负载量约为50%,循环使用6次,其光催化降解效率没有明显降低,双氯芬酸钠的降解率均可达70%以上.     

污水处理厂中红霉素抗药性基因的污染特征及选择性因子

采用固相萃取-高效液相色谱串联质谱(SPE-HPLC-MS/MS)检测分析了上海某污水处理厂中12种不同药品和个人护理品(pharmaceutical and personal care products,PPCPs)的含量水平和分布特征,采用实时荧光定量PCR方法定量检测分析了7种红霉素抗药性基因(ERY-ARGs)在污水处理厂中的分布和丰度变化.结果表明,在污水处理厂中共检出5种PPCPs(包括磺胺甲唑、红霉素、四环素、卡马西平和三氯生),浓度范围分别为24.5~38.7、47.5~49.2、43.1~85.4、2.5~3.9和423.2~8 973.3ng·L-1.两段A/O生物处理工艺对三氯生具有较好的去除效果,但对其余4种PPCPs的去除效果较差.与此同时,目标ERY-ARGs在污水处理厂中均被检出,在原水中的丰度达9.28×103(erm A)~1.83×108(ere A)copies·L-1,虽然两段A/O工艺能够显著降低污水中的ERY-ARGs(1.19 log~3.97 log),但其在最终处理出水中的浓度仍然较高.通过相关性分析可知,ERY-ARGs与红霉素和三氯生之间均具有显著相关性(P<0.05),表明污水处理厂中红霉素对ERY-ARGs的产生和传播具有重要影响,而三氯生对ERY-ARGs可能存在交叉选择性作用.     

骆马湖表层水体中32种PPCPs类物质的污染水平、分布特征及风险评估

为评价骆马湖水体中药品和个人护理品(PPCPs)的污染水平、空间分布特征及生态风险,利用高效液相色谱-串联质谱测定了骆马湖水体中22个采样点的32种PPCPs.结果表明,骆马湖表层水体中共检出了23种PPCPs,总浓度范围为892~1 536 ng·L~(-1),其中浓度最高的为诺氟沙星(256~707 ng·L~(-1)),其次是酮洛芬(85~438 ng·L~(-1))、安赛蜜(101~290 ng·L~(-1))及萘普生(1.9~112 ng·L~(-1)).不同采样位点的PPCPs浓度存在一定的空间差异,呈现湖东北部地区较高,西南部地区较低的趋势.房亭河入湖口处PPCPs浓度较高,嶂山闸出湖口处浓度较低.对13种药物类PPCPs生态风险评价结果表明,诺氟沙星RQs为0.26~0.72,对于骆马湖水生生态系统表现为中风险,吉非罗齐在大部分采样点RQs0.01,表现为低风险,其余的化合物RQs0.01未表现出生态环境风险.采用简单叠加模型计算PPCPs的联合毒性风险熵范围为0.29~0.75,整体上看,骆马湖PPCPs对于水生生物表现出中风险.对6种PPCPs的人体健康风险结果表明,RQs均小于1,表明骆马湖PPCPs对人体健康无直接风险.     

药品和个人护理用品在固体基底中的检测方法和分布现状

药品和个人护理用品(Pharmaceuticals and personal care products,PPCPs)在环境中广泛存在,威胁生态环境和人类健康,受到越来越多的关注.本文综述了固体基底中PPCPs的检测方法,总结了国内外污泥、土壤、沉积物等基底中PPCPs的污染现状,并对PPCPs的进一步研究进行了展望.结果表明,PPCPs的检测方法朝多样化和趋优化的方向发展.污泥样品中PPCPs种类多、浓度高(μg·kg-1—mg·kg-1),土壤和沉积物中虽然浓度不高,但是总量不可小觑.目前,固体基底中的PPCPs还需要更全面和更广泛的研究.     

不同特征污染源中指示性药物和个人护理品识别与筛选

通过分析我国地表水中药物和个人护理品（PPCPs）主要污染源排放特征,识别和筛选出咖啡因、卡马西平和磺胺嘧啶为我国地表水环境中的指示性PPCPs（i-PPCPs）,分别指征城镇生活污水、城镇污水处理厂出水和养殖废水三类特征污染排放源.同时,基于筛选的i-PPCPs开展了初步应用研究,结果表明,生活污水是北运河和黄浦江流域地表水中PPCPs的主要来源.研究结果为构建更综合和有效的PPCPs的溯源体系,识别我国城市地表水环境中PPCPs的主要排放源提供了理论依据.     

药品和个人护理用品(PPCPs)对环境的污染现状与研究进展

在过去的30多年中，有关有毒污染物的研究主要集中在工业化学物质和农药上。近5年多来，国外已经开始关注药品和个人护理用品（PPCPs）对环境的污染，但在我国还没有引起重视。国外的研究表明，合成麝香物质、显影剂、抗生素、雌激素、消炎止痛药、杀菌消毒剂等与人类生活密切相关的药品和个人护理用品在环境中普遍存在，但是其质量浓度通常非常低，多数情况下在ng/L～μg/L水平。粪便施肥和污水排放是PPCPs进入环境的主要途径。在常见的PPCPs中，抗生素和消炎止痛药在环境中检测出的频率最高，在地表水、地下水、饮用水、污泥、土壤等环境介质中，PPCPs在地表水中检测出的频率最高。目前关于PPCPs的研究主要集中在分析方法以及环境污染水平的调查，有关PPCPs在环境中的迁移转化规律，生态与健康风险以及PPCPs污染控制技术等方面的研究有待加强。     

Screening of indicator pharmaceuticals and personal care products in landfill leachates: a case study in Shanghai,China

● A systematic framework was developed to identify i-PPCPs for landfill leachate. ● The wide-scope target analysis offered a basis for comprehensive i-PPCP screening. ● Source-specificity and representativeness analysis helped to refine i-PPCPs. ● Erythromycin, gemfibrozil and albendazole were identified as i-PPCPs for leachate. Identifying potential sources of pharmaceuticals and personal care products (PPCPs) in the environment is critical for the effective control of PPCP contamination. Landfill leachate is an important source of PPCPs in water; however, it has barely been involved in source apportionment due to the lack of indicator-PPCPs (i-PPCPs) in landfill leachates. This study provides the first systematic framework for identifying i-PPCPs for landfill leachates based on the wide-scope target monitoring of PPCPs. The number of target PPCPs increased from < 20 in previous studies to 68 in the present study. Fifty-nine PPCPs were detected, with median concentrations in leachate samples ranging from below the method quantification limit (MQL) to 41 μg/L, and 19 of them were rarely reported previously. A total of 29 target compounds were determined to be PPCPs of high concern by principal component analysis according to multiple criteria, including occurrence, exposure potential, and ecological effect. Coupled with source-specificity and representativeness analysis, erythromycin, gemfibrozil, and albendazole showed a significant difference in their occurrence in leachate compared to other potential sources (untreated and treated municipal wastewater and livestock wastewater) and correlated with total PPCP concentrations; these were recommended as i-PPCPs for leachates. Indicator screening procedure can be used to develop a sophisticated source apportionment method to identify sources of PPCPs from adjacent landfills.     

高级氧化联合生物活性炭工艺深度净化污水中PPCPs研究进展

污水处理厂传统的二级生化处理对药品及个人护理用品(Pharmaceutical and Personal Care Products, PPCPs)等新兴污染物的去除率较低, PPCPs随出水排放会给生态环境带来较大的风险,并会经过生物富集最终危害到人体健康,因此需要通过进一步的深度净化以削减其风险.本文综述了常见PPCPs在污水处理系统的分布特征及生态风险,阐述了高级氧化工艺(Advanced oxidation processes, AOPs)、生物活性炭工艺(Biological activated carbon, BAC)以及高级氧化联合生物活性炭工艺(AOPs-BAC)深度净化PPCPs的净化原理,在此基础上,综述了AOPs-BAC工艺对污水中PPCPs的深度净化效果及主要影响因素,并探讨了AOPs-BAC工艺对污水中PPCPs的风险削减能力,为污水中PPCPs深度净化工艺的研发及PPCPs的生态风险控制提供了参考.