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.     

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.     

中型污水处理厂中药物和个人护理品的分布与去除

为了解15种药物及个人护理用品(PPCPs)在中小型污水处理厂中的分布及其去除效果,采用液相色谱-串联质谱(LC-MS/MS)技术对3座A2/O工艺的污水处理厂水样进行分析研究。结果显示,除普萘洛尔、吉非罗平和吲哚美辛在3座中小型污水处理厂各个工艺单元中均未被检出外,其余12种目标化合物的检出频率在90%~100%之间。进水水样中PPCPs的平均检出浓度为2 285.4 ng/L,其中咖啡因(CF)的平均检出浓度最高为973.3 ng/L,酮洛芬(KP)的平均检出浓度次之为844.7 ng/L,两者之和占进水水样中PPCPs平均含量的79.5%,表明污水处理厂的主要污染物为CF和KP。3座污水处理厂对CF的去除效果最为显著,平均去除率为95.3%,对15种PPCPs总去除效率在39.3%~82.8%之间。     

高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调p H值至7.0左右,过固相萃取小柱进行富集,用14 m L甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/m L)和58.0%~107.8%(加标水平50 ng/m L),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

Fenton 法降解抗生素磺胺间甲氧嘧啶钠

应用Fenton高级氧化技术降解水溶液中抗生素磺胺间甲氧嘧啶钠(SMMS),系统探讨了起始pH、CSMMS、CFe2+、CH2O2和温度等因素对SMMS降解效果的影响。结果表明:CSMMS=4.53 mg/L,pH=4.0,CH2O2=0.49 mmol/L,CFe2+=19.51μmol/L,T=25℃为最佳反应条件。在最佳条件下,87.4%的SMMS可以在120 min内降解。反应动力学研究表明Fenton氧化降解SMMS分为两个阶段,快速反应阶段和慢速反应阶段,并建立了两阶段动力学模型,模型拟合结果较好。研究结果为含有SMMS的污废水处理提供了基础数据和科学参考。     

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.     

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.     

MBR去除水中新型微污染物PPCPs的效果及影响因素

结合MBR和新型微污染物药品和个人护理用品(PPCPs)的特性,论述了MBR对水中PPCPs的去除效果,并分析其处理过程中的主要影响因素,以期为进一步的研究应用提供理论基础及参考。