Campos-Mañas Marina Celia, Plaza-Bolaños Patricia, Sánchez-Pérez José Antonio, Malato Sixto, Agüera Ana
Solar Energy Research Centre (CIESOL), Joint Centre University of Almería-CIEMAT, 04120, Almería, Spain.
Solar Energy Research Centre (CIESOL), Joint Centre University of Almería-CIEMAT, 04120, Almería, Spain.
J Chromatogr A. 2017 Jul 21;1507:84-94. doi: 10.1016/j.chroma.2017.05.053. Epub 2017 May 26.
It is well known that wastewater treatment plant (WWTP) effluents usually contain micropollutants such as pharmaceuticals (or their transformation products, TPs) or pesticides, which is a major issue when evaluating their possible reuse (e.g. for irrigation in agriculture). In search for an improved accuracy and simplicity, methods based on the direct injection of the sample (DI) represent a recent trend taking advantage of the increasing sensitivity of new mass spectrometry (MS) instruments. Thus, the present study shows the development and validation of a DI-based method by ultra-high-performance liquid chromatography quadrupole-linear ion trap analyser (UHPLC-QqLIT-MS/MS). The proposed method was applied to the monitoring of 115 organic microcontaminants (including pharmaceuticals, TPs and pesticides) at the ngL/μgL level in wastewater effluents from urban WWTPs. Sample pre-treatment was reduced to acetonitrile addition and filtration of the mixture previous to LC-MS analysis. Total analysis time was <15min. A subsequent validation protocol was carried out in treated WW (TWW), following indications of SANTE and Eurachem Guidelines. Linearity and matrix effect were evaluated in the range of 10-1000ngL. 70% of the analytes showed a moderate matrix effect (≤25%). Trueness (expressed as recovery) and precision (calculated as relative standard deviation, RSD) were evaluated at four concentration levels (20, 50, 500 and 1000ngL) in TWW samples. The LODs ranged from 1 to 357ngL and the LOQs from 10 to 500ngL. 92% of the compounds showed limits of quantification ≤100ngL. In most cases, mean recoveries were in the range 70-120%, and RSD values were ≤20%. The validated method was successfully applied to the analysis of 10 TWW samples, demonstrating the occurrence of 67 target compounds at concentration levels from 26705ngL (4-aminoantipyrine) to 10ngL (tebuconazole and bezafibrate).
众所周知，污水处理厂（WWTP）的出水通常含有微量污染物，如药物（或其转化产物，TPs）或农药，这在评估其可能的再利用（如用于农业灌溉）时是一个主要问题。为了提高准确性和简化操作，基于直接进样（DI）的方法代表了一种利用新型质谱（MS）仪器不断提高的灵敏度的最新趋势。因此，本研究展示了一种基于超高效液相色谱四极杆-线性离子阱分析仪（UHPLC-QqLIT-MS/MS）的直接进样方法的开发与验证。所提出的方法应用于监测城市污水处理厂出水中纳克/升/微克/升水平的115种有机微量污染物（包括药物、TPs和农药）。样品预处理简化为在液相色谱-质谱分析前加入乙腈并过滤混合物。总分析时间<15分钟。按照SANTE和Eurachem指南的指示，在处理后的污水（TWW）中进行了后续验证方案。在10-1000纳克/升范围内评估线性和基质效应。70%的分析物显示出中等基质效应（≤25%）。在TWW样品的四个浓度水平（20、50、500和1000纳克/升）下评估准确性（以回收率表示）和精密度（以相对标准偏差，RSD计算）。检测限范围为1至357纳克/升，定量限范围为10至500纳克/升。92%的化合物显示定量限≤100纳克/升。在大多数情况下，平均回收率在70-120%范围内，RSD值≤20%。经过验证的方法成功应用于10个TWW样品的分析，证明了67种目标化合物的存在，其浓度水平从26705纳克/升（4-氨基安替比林）到10纳克/升（戊唑醇和苯扎贝特）。
