| 引用本文: | 卢红选，刘卫国.2016.HPLC-MS/MS测定城市废水中的10种药物与个人护理用品[J].地球环境学报,(4):425-430 |
| LU Hongxuan, LIU Weiguo.2016.Determination of 10 pharmaceuticals and personal care products in waste water by HPLC-MS/MS[J].Journal of Earth Environment,(4):425-430 |
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| HPLC-MS/MS测定城市废水中的10种药物与个人护理用品 |
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卢红选，刘卫国1,2
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1.中国科学院地球环境研究所 黄土与第四纪地质国家重点实验室，西安710061;2. 西安交通大学 人居环境与建筑工程学院，西安 710049
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| 摘要: |
| 采用固相萃取技术对水样进行预处理，结合液相色谱-串联质谱分析方法（HPLC-MS/MS），建立了同时检测城市废水中包括扑热息痛、萘普生、磺胺甲恶唑、磺胺二甲嘧啶、三氯生、双氯芬酸钠、三氯卡班、盐酸四环素、盐酸土霉素、吉非罗平在内共计10种药物与个人护理用品（PPCPs）的分析检测方法。采用中性条件萃取水样，控制上样流速为3—5 mL∙min–1，用甲醇溶液洗脱。纯水的平均加标回收率为40.8%—104.5%，相对标准偏差为5.0%—25.5%（n=3）。应用所建立的分析方法，对西安浐河表层水进行了分析。结果表明：该方法可用于城市废水PPCPs的检测。10种目标物质中，共检测到4种，其含量为1.4—15.0 ng∙L–1。 |
| 关键词: 固相萃取 高效液相色谱-串联质谱 药物与个人护理品 城市废水 |
| DOI：10.7515/JEE201604010 |
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| 基金项目:国家自然科学基金项目（41572157） |
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| Determination of 10 pharmaceuticals and personal care products in waste water by HPLC-MS/MS |
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LU Hongxuan, LIU Weiguo1,2
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1. State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment,
Chinese Academy of Sciences, Xi’an 710061, China;2. School of Human Settlements and Civil Engineering, Xi’an Jiaotong University, Xi’an 710049, China
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| Abstract: |
| Background, aim, and scope Pharmaceuticals and personal care products (PPCPs) represent a variety of chemical, widely used by consumers on a daily basis which include prescription and non-prescription drugs, cosmetics, cleansers, detergents and fragrance produces. PPCPs are considered potentially hazardous compounds because some are ubiquitous, persistent, and biologically active compounds with recognized endocrine disrupting functions (Daughton and Ternes, 1999). These compounds have been widely detected in various environmental matrices throughout the world including rivers (Glen et al, 2003; Tixier et al, 2003; Yu and Chu, 2009; Zhang et al, 2011; Wu et al, 2014), lakes (Buser and Theobald, 1998; Glen et al, 2003; Tixier et al, 2003; Blair et al, 2013; Ferguson et al, 2013; Zhu et al, 2013), oceans (Weigel et al, 2002; Del Rosario et al, 2014), groundwater (Barnes et al, 2008), waste and drinking water (Carmona et al, 2014) and food (Wu et al, 2012; Baron et al, 2014). Detection methods of PPCP include spectrophotometry, gas chromatography, liquid chromatography and electrophoresis. The recent advances in analytical instrumentation have allowed the unequivocal identification and confirmation of the presence of any compound at very low levels using LC-MS2. The multiple reaction monitoring (MRM) allows monitoring two transitions between precursor and product ions. It is possible to quantify and confirm the presence of PPCPs at very low concentration levels. However, due to the absence of official monitoring protocols, there is an increasing demand of analytical methods that allow the determination of those compounds in order to obtain more information regarding their behavior and fate in the environments. Therefore, we proposed here a method for the determination of ten pharmaceuticals and personal care products, including acetaminophen, naproxen, diclofenac, sulfamethoxazole, sulfadimidine, triclosan, triclocarban, tetracycline hydrochloride, oxytetracycline and gemfibrozile, in waste water using high performance liquid chromatography-tandem mass spectrometry. The aim of this work is to develop an efficient method for determination of various PPCPs in water. Materials and methods Filtered water samples were extracted using solid-phase extraction cartridges (SPEs) extraction. HLB SPEs (Poly-sery HLB, 6 mL / 500 mg, CNW) were conditioned with 3×5 mL of water. Water samples were allowed to pass through the cartridges at a flow rate of approximately 5 — 10 mL ∙ min–1. After sample loading, the cartridges were then subsequently dried for 30 min under full vacuum, and subsequently the ten pharmaceutical compounds were eluted with 10 mL of methanol. The residue was dissolved in 0.5 mL of methanol and transferred into vials for analysis. The PPCPs were analyzed using liquid chromatography-mass spectrometry (LC-MS) with a Shimadzu 8030 system equipped with an autosampler and Labsolutions manager software. Results Electrospray ionization (ESI) was used as LC-MS interfaces since it is the most frequently used ionization mode which is a soft ionization technique, suitable for polar and moderately non˗polar compounds. Fragmentor, collision energy, and other source parameters were optimized by injecting individual standard solutions into mass spectrometer by flow injection analysis (FIA). After that, two different MRM transitions were selected for each compound: one for quantification and one for qualification. These ions were monitored under time scheduled MRM conditions. The analysis was done with electrospray ionization in negative mode (ESI–) for TCC, NPX, TCS, DF, GF and in positive mode (ESI+) for the ACT, SMX, SMT, TC, OTC. The initial mobile phase proportion was 20% A and 80% B where A=methanol and B = formic acid:water 1:9999, held for 10 min. A was then increased linearly to 90% in 25 min. The MRM transitions for different PPCPs are as follows: ACT m/z 151/110; NPX m/z 229/185; SMX m/z 254/156; SMT m/z 279/186; TCS m/z 287/35; DF m/z 294/250; TCC m/z 313/60; TC m/z 445/410; OTC m/z 461/426; GF m/z 249/121. Discussion The linearity of the MS-MS detector was tested with matrix extracts containing PPCPs at concentration between 1 μg ∙ L–1 and 250 μg ∙ L–1 for ACT, NPX and DF, between 1 μg ∙ L–1 and 100 μg ∙ L–1 for SMX and SMT, between 2.5 μg ∙ L–1 and 100 μg ∙ L–1 for TCS and TCC, between 2.5 μg ∙ L–1 and 250 μg ∙ L–1 for TC, OTC and GF. The average recoveries of the target compounds in the spiked pure water samples ranged from 40.8% — 104.5% with the relative standard deviations ranged from 5.0% — 25.5% (n = 3). The waste water sample collected from Chanhe River in Xi’an was investigated as a case study. Among the 10 PPCPs, 4 PPCPs were detected and the concentrations ranged from 1.4 ng ∙ L–1 to 15.0 ng ∙ L–1. Conclusions A method using HPLC-MS/MS has been developed and validated for determination of 10 PPCPs (TCC, NPX, TCS, DF, GF, ACT, SMX, SMT, TC and OTC) in water. Subsequently, the method was successfully applied to analysis of the investigated chemicals in water samples collected from Chanhe River in Xi’an. Recommendations and perspectives The complexity of the biological matrices and the low concentration levels of these compounds make necessary the use of advanced sample treatment procedures, sample clean-up, to remove potentially interfering matrix components, as well as the concentration of analytes. Increased attention would have to be paid to metabolites generated in the organisms and released into the environment as well as to metabolites generated in the environment itself by biodegradation, photolytic or oxidation reactions. |
| Key words: solid phase extraction HPLC-MS/MS pharmaceuticals and personal care products (PPCPs) waste water |
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