Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
J Chromatogr A. 2014 Aug 22;1356:163-70. doi: 10.1016/j.chroma.2014.06.051. Epub 2014 Jun 21.
Membrane-assisted solvent extraction (MASE) coupled to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) was studied for the determination of a variety of emerging and priority compounds in wastewater. Among the target analytes studied certain hormones (estrone (E1), 17β-estradiol (E2), androsterone (ADT), 17α-ethynyl estradiol (EE2), diethylstilbestrol (DES), equilin (EQ), testosterone (TT), mestranol (MeEE2), 19-norethisterone (NT), progesterone (PG) and equilenin (EQN)), alkylphenols (APs) (4-tert-octylphenol (4tOP), nonylphenol technical mixture (NPs) and 4n-octylphenol (4nOP)) and BPA were included. The work was primarily focused in the LC-MS/MS detection step, both in terms of variable optimization and with respect to the matrix effect study. Both, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were assessed both in the negative and positive mode, including the optimization of MS/MS operating conditions. The best results were obtained, in most of the cases, for ESI using 0.05% ammonium hydroxide as buffer solution in the mobile phase, composed with methanol and water. Under optimum detection conditions, matrix effect during the detection step was thoroughly studied. Dilution, correction with deuterated analogues and clean-up of the extracts were evaluated for matrix effect correction. Clean-up with Florisil together with correction with deuterated analogues provided the most satisfactory results, with apparent recoveries in the 57-136% range and method detection limits in the low ngL(-1) level for most of the analytes. For further validation of the method, two separated extraction procedures, the above mentioned MASE, and conventional solid phase extraction (SPE) were compared during the analysis of real samples and comparable results were successfully obtained for E1, E2, EE2, DES, NT, TT, EQ, PG, BPA, ADT, 4nOP, 4tOP, NPs and EQN.
膜辅助溶剂萃取 (MASE) 与液相色谱-三重四极杆质谱联用 (LC-MS/MS) 结合，用于测定废水中的多种新兴和优先化合物。在所研究的目标分析物中，某些激素（雌酮 (E1)、17β-雌二醇 (E2)、雄甾酮 (ADT)、17α-乙炔基雌二醇 (EE2)、己烯雌酚 (DES)、马烯雌酮 (EQ)、睾丸激素 (TT)、美雌醇 (MeEE2)、19-去甲睾酮 (NT)、孕酮 (PG) 和表马烯雌酮 (EQN)）、烷基酚 (APs)（4-叔辛基酚 (4tOP)、壬基酚混合物 (NPs) 和 4-正辛基酚 (4nOP)) 和双酚 A 都包括在内。这项工作主要集中在 LC-MS/MS 检测步骤，包括变量优化和基质效应研究。评估了电喷雾电离 (ESI) 和大气压化学电离 (APCI) 在正、负模式下的效果，包括优化 MS/MS 操作条件。在大多数情况下，使用 0.05% 氨作为流动相中的缓冲溶液，甲醇和水的混合物，ESI 获得了最佳结果。在最佳检测条件下，彻底研究了检测步骤中的基质效应。评估了稀释、用氘代类似物校正和提取物净化对基质效应校正的影响。用 Florisil 净化并与氘代类似物校正相结合，为大多数分析物提供了最令人满意的结果，表观回收率在 57-136%范围内，方法检测限在低 ngL(-1) 水平。为了进一步验证该方法，在分析实际样品时比较了上述 MASE 和常规固相萃取 (SPE) 两种分离提取程序，成功获得了 E1、E2、EE2、DES、NT、TT、EQ、PG、BPA、ADT、4nOP、4tOP、NPs 和 EQN 的可比结果。
