New method for the determination of parabens and bisphenol A in human milk samples using ultrasound-assisted extraction and clean-up with dispersive sorbents prior to UHPLC-MS/MS analysis.
A sensitive and accurate analytical method for the determination of methyl-, ethyl-, propyl- and butylparaben and bisphenol A in human milk samples has been developed and validated. The combination of ultrasound-assisted extraction (UAE) and a simplified and rapid clean-up technique that uses sorbent materials has been successfully applied for the preparation of samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. The analytes were extracted from freeze-dried human milk samples using acetonitrile and ultrasonic radiation (three 15-min cycles at 70% amplitude), and further cleaned-up with C18 sorbents. The most influential parameters affecting the UAE method and the clean-up steps were optimized using design of experiments. Negative electrospray ionization (ESI) in the selected reaction monitoring (SRM) mode was used for MS detection. The use of two reactions for each compound allowed simultaneous quantification and identification in one run. The analytes were separated in less than 10min. Deuterium-labeled ethylparaben-d5 (EPB-d5) and deuterium-labeled bisphenol A-d16 (BPA-d16) were used as surrogates. The limits of quantification ranged from 0.4 to 0.7ngmL(-1), while inter- and intra-day variability was under 11.1% in all cases. In the absence of certified reference materials, recovery assays with spiked samples using matrix-matched calibration were used to validate the method. Recovery rates ranged from 93.8% to 112.2%. The proposed method was satisfactorily applied for the determination of four selected parabens and bisphenol A in human milk samples obtained from nursing mothers living in the province of Granada (Spain).
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain.
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Rodríguez-Gómez
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain.
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Dorival-García
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain. Electronic address: azafra@ugr.es.
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Zafra-Gómez
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain.
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Camino-Sánchez
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain.
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Ballesteros
Research Group of Analytical Chemistry and Life Sciences, Department of Analytical Chemistry, Campus of Fuentenueva, University of Granada, E-18071 Granada, Spain.
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Navalón
D001559:Benzhydryl Compounds / Q000032:analysis* / Q000737:chemistry; D005591:Chemical Fractionation; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D006801:Humans; D057230:Limit of Detection; D016014:Linear Models; D008895:Milk, Human / Q000737:chemistry*; D010226:Parabens / Q000032:analysis* / Q000737:chemistry; D010636:Phenols / Q000032:analysis* / Q000737:chemistry; D015203:Reproducibility of Results; D013010:Sonication / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D000098826:Bisphenol A Compounds
D001559:Benzhydryl Compounds; D010226:Parabens; D010636:Phenols; C006780:bisphenol A; D000098826:Bisphenol A Compounds
Endocrine disrupting chemicals; Human milk; Sorbent materials; UHPLC–MS/MS; Ultrasound-assisted extraction