title: Microextraction with polyethersulfone for bisphenol-A, alkylphenols and hormones determination in water samples by means of gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry analysis.
abstract: In the present work, the suitability of polyethersulfone (PES) tube was assessed for the simultaneous sorptive microextraction of commonly found endocrine disrupting compounds in natural waters such as bisphenol-A (BPA), nonylphenol technical mixture (NP mix), 4-tert-octylphenol (4tOP), 4-n-octylphenol (4-nOP), 17β-estradiol (E2) and 17α-ethynilestradiol (EE2). After the concentration of target compounds in the PES polymer, the analytes were recovered soaking the polymer with a suitable solvent (ethyl acetate or methanol), derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) and determined by gas chromatography-mass spectrometry (GC-MS). The analysis was also performed without derivatization step by means of liquid chromatography-tandem mass spectrometry (LC-MS/MS). Extraction parameters (addition of MeOH, ionic strength, extraction speed and time and desorption time) were evaluated and the optimum conditions were fixed as follows: 150 mL water samples containing a 10% (w/v) of sodium chloride and using 5 tubular PES sorbent fibers (1.5 cm length×0.7 mm o.d.). Equilibrium conditions were achieved after 9 h, with absolute extraction efficiencies ranging from 27 to 56%. On the whole, good apparent recoveries were achieved (68-103% and 81-122% for GC-MS and LC-MS/MS, respectively) using deuterated analogues as surrogates. Achieved quantification limits (LOQs) varied between 2-154 ng/L and 2-63 ng/L for all the compounds using GC-MS and LC-MS/MS, respectively. The effect of organic matter was evaluated previous to apply the final method to the analysis of estuarine and wastewater real samples. The comparison of both methods showed that overall, PES-LC-MS/MS provided shorter sample preparation time and better LODs, but PES-silylation-GC-MS allowed the simultaneous determination of all the studied compounds with adequate repeatability and accuracy.
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: Ros
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: Vallejo
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: L
authors.initials: L
authors.lastname: Blanco-Zubiaguirre
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: A
authors.initials: A
authors.lastname: Delgado
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. Electronic address: ailette.prieto@ehu.es.
authors.forename: A
authors.initials: A
authors.lastname: Prieto
mesh_terms: D001559:Benzhydryl Compounds / Q000302:isolation & purification*; D002853:Chromatography, Liquid; D052244:Endocrine Disruptors / Q000302:isolation & purification*; D004958:Estradiol / Q000302:isolation & purification; D004997:Ethinyl Estradiol / Q000302:isolation & purification; D005618:Fresh Water / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D006801:Humans; D057230:Limit of Detection; D010636:Phenols / Q000302:isolation & purification*; D011108:Polymers / Q000737:chemistry*; D015203:Reproducibility of Results; D052617:Solid Phase Microextraction / Q000379:methods; D012997:Solvents / Q000737:chemistry; D013450:Sulfones / Q000737:chemistry*; D053719:Tandem Mass Spectrometry; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000302:isolation & purification*; D000098826:Bisphenol A Compounds
chemical_list: D001559:Benzhydryl Compounds; D052244:Endocrine Disruptors; D004958:Estradiol; D004997:Ethinyl Estradiol; D010636:Phenols; D011108:Polymers; D012997:Solvents; D013450:Sulfones; D062065:Wastewater; D014874:Water Pollutants, Chemical; C022840:polyether sulfone; C025256:nonylphenol; C080417:4-octylphenol; C105260:4-tert-octylphenol; C006780:bisphenol A; D000098826:Bisphenol A Compounds
keywords: Endocrine disrupting compounds; Gas chromatography–mass spectrometry; Liquid chromatography–tandem mass spectrometry; Polyethersulfone tubes; Water samples