title: Determination of estrogenic mycotoxins in environmental water samples by low-toxicity dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.
abstract: A novel, simple, rapid and eco-friendly method based on dispersive liquid-liquid microextraction using a bromosolvent was developed to determine six estrogenic mycotoxins (zearalenone, zearalanone, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) in water samples by liquid chromatography-electrospray ionization tandem mass spectrometry in the negative mode (LC-ESI-MS/MS). The optimal conditions for this method include the use of 100 μL bromocyclohexane as an extraction solvent (using a non-dispersion solvent), 10 mL of aqueous sample (adjusted to pH 4), a vortex extraction time of 2 min, centrifugation for 10 min at 3500 rpm and no ionic strength adjustment. The calibration function was linear and was verified by applying the Mandel fitting test with a 95% confidence level. No matrix effect was observed. According to the relative standard deviations (RSDs), the precision was better than 13% for the repeatability and intermediate precision. The average recoveries of the spiked compounds ranged from 81 to 118%. The method limits of detection (LOD) and quantification (LOQ) considering a 125-fold pre-concentration step were 4-20 and 8-40 ng L(-1), respectively. Next, the method was applied to the analysis of the environmental aqueous samples, demonstrating the presence of β-zearalanol and zearalanone in the river water samples.
authors.affiliation: Analytical Chemistry Department, Chemistry Institute, São Paulo State University-UNESP, Araraquara, SP 14801-970, Brazil.
authors.forename: Elissandro Soares
authors.initials: ES
authors.lastname: Emídio
authors.affiliation: Analytical Chemistry Department, Chemistry Institute, São Paulo State University-UNESP, Araraquara, SP 14801-970, Brazil.
authors.forename: Claudia Pereira
authors.initials: CP
authors.lastname: da Silva
authors.affiliation: Analytical Chemistry Department, Chemistry Institute, São Paulo State University-UNESP, Araraquara, SP 14801-970, Brazil. Electronic address: mssqam@iq.unesp.br.
authors.forename: Mary Rosa Rodrigues
authors.initials: MR
authors.lastname: de Marchi
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D004968:Estrogens, Non-Steroidal / Q000032:analysis*; D005618:Fresh Water / Q000737:chemistry; D057230:Limit of Detection; D059627:Liquid Phase Microextraction; D009183:Mycotoxins / Q000032:analysis*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D053719:Tandem Mass Spectrometry / Q000379:methods; D015025:Zearalenone / Q000032:analysis*; D015029:Zeranol / Q000031:analogs & derivatives* / Q000032:analysis*
chemical_list: D004968:Estrogens, Non-Steroidal; D009183:Mycotoxins; C029659:zearalenol; D015025:Zearalenone; D015029:Zeranol; C028226:taleranol
keywords: Bromosolvents; Dispersive liquid–liquid microextraction; Estrogenic mycotoxins; LC–MS/MS; Water samples