Rodil Rosario, Quintana José Benito, López-Mahía Purificación, Muniategui-Lorenzo Soledad, Prada-Rodríguez Darío
Department of Analytical Chemistry, Faculty of Sciences, University of A Coruña, Campus A Zapateira S.N., 15071 A Coruña, Spain.
J Chromatogr A. 2009 Apr 3;1216(14):2958-69. doi: 10.1016/j.chroma.2008.09.041. Epub 2008 Sep 17.
This paper describes the development and validation of a method for the simultaneous determination of 53 multi-class emerging organic pollutants in water samples using solid-phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using electrospray ionisation (ESI) in both positive and negative modes. Target compounds include acidic herbicides, UV filters, insect repellents, organophosphorous flame retardants, a bactericide, pharmaceuticals and metabolites. A single SPE consisting on the loading of 200-500 mL of sample adjusted to pH 7 on Oasis HLB 200mg cartridges and elution with methanol, permitted obtaining good recoveries: higher than 60% for tap, surface and wastewater in most cases. The 7 isotopically labelled internal standards effectively compensated losses during sample preparation and matrix effects at LC-MS/MS determination. The precision of the method, calculated as relative standard deviation (RSD) was below 15% for all compounds and all tested matrices. Detection limits (LODs) based on the confirmation, less intense, MRM (multiple reaction monitoring) transition and considering blanks varied between 0.3 and 30 ngL(-1). Finally, the developed method was applied to the determination of target analytes in various samples, including tap, surface and waste water. Among the tested emerging pollutants, 31 were found in wastewater in concentrations reaching up to 10 microgL(-1) in the case of ibuprofen. Also, 13 species were detected in tap water with concentrations up to 0.13 microgL(-1) for tri(chloropropyl) phosphate (TCPP).
本文描述了一种用于同时测定水样中53种多类新兴有机污染物的方法的开发与验证。该方法采用固相萃取（SPE），随后进行液相色谱-串联质谱（LC-MS/MS）分析，在正、负模式下均使用电喷雾电离（ESI）。目标化合物包括酸性除草剂、紫外线过滤剂、驱虫剂、有机磷阻燃剂、一种杀菌剂、药物及其代谢物。采用单个SPE，即向200mg的Oasis HLB柱上加载200 - 500mL pH调至7的样品，并用甲醇洗脱，可获得良好的回收率：在大多数情况下，自来水、地表水和废水的回收率均高于60%。7种同位素标记的内标有效补偿了样品制备过程中的损失以及LC-MS/MS测定时的基质效应。该方法的精密度以相对标准偏差（RSD）计算，所有化合物和所有测试基质的RSD均低于15%。基于确认的、强度较低的多反应监测（MRM）转换并考虑空白样计算的检测限（LOD）在0.3至30 ngL⁻¹之间。最后，将所开发的方法应用于各种样品中目标分析物的测定，包括自来水、地表水和废水。在测试的新兴污染物中，废水中发现了31种，其中布洛芬的浓度高达10 μg L⁻¹。此外，自来水中检测到13种，其中磷酸三（氯丙基）酯（TCPP）的浓度高达0.13 μg L⁻¹。
