title: Matrix effect during the membrane-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry for the determination of a variety of endocrine disrupting compounds in wastewater.
abstract: 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.
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain. Electronic address: arantza.iparragirre@gmail.com.
authors.forename: A
authors.initials: A
authors.lastname: Iparraguirre
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: P
authors.initials: P
authors.lastname: Navarro
authors.affiliation: Department of Analytical Chemistry, University of Santiago de Compostela, Constantino Candeira S/N, 15782 Santiago de Compostela, Spain.
authors.forename: R
authors.initials: R
authors.lastname: Rodil
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Prieto
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: M
authors.initials: M
authors.lastname: Olivares
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: N
authors.initials: N
authors.lastname: Etxebarria
authors.affiliation: Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain.
authors.forename: O
authors.initials: O
authors.lastname: Zuloaga
mesh_terms: D000731:Androstanes / Q000032:analysis; D001559:Benzhydryl Compounds / Q000032:analysis; D002851:Chromatography, High Pressure Liquid; D004054:Diethylstilbestrol / Q000032:analysis; D052244:Endocrine Disruptors / Q000032:analysis*; D004963:Estrenes / Q000032:analysis; D006863:Hydrogen-Ion Concentration; D057230:Limit of Detection; D059625:Liquid-Liquid Extraction; D010636:Phenols / Q000032:analysis; D052616:Solid Phase Extraction; D012997:Solvents / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry; D062065:Wastewater / Q000032:analysis*; D014874:Water Pollutants, Chemical / Q000032:analysis*; D000098826:Bisphenol A Compounds
chemical_list: D000731:Androstanes; D001559:Benzhydryl Compounds; D004054:Diethylstilbestrol; D052244:Endocrine Disruptors; D004963:Estrenes; D010636:Phenols; D012997:Solvents; D062065:Wastewater; D014874:Water Pollutants, Chemical; C006780:bisphenol A; D000098826:Bisphenol A Compounds
keywords: Endocrine disrupting compounds; Liquid chromatography–triple quadrupole mass spectrometry; Membrane assisted solvent extraction; Solid phase extraction; Wastewater