Determination of endocrine disruptors related to the packaging and storage of food in dairy products by UHPLC-ESI-QqQ(MRM)

Trabajo presentado a la XV Reunión científica de la Sociedad Española de Cromatografía y Técnicas Afines - SECyTA 2015. Castellón de la Plana, 27-30 de octubre de 2015.
Endocrine disruptors (ECD, Endocrine Disrupting Chemicals) are chemicals that may interfere with the body’s endocrine system and produce adverse developmental, reproductive, neurological, and immune effects in both humans and wildlife[1]. Due to this, it has been necessary to develop rapid and sensitive method for the determination of ECD. This work presents the results of the analysis of four phthalates[2] (PAEs: dimethyl phthalate, diethyl phthalate, dibutyl phthalate and butyl benzyl phthalate), seven parabens[3] (PBs: methyl paraben, ethyl paraben, n-propyl paraben, iso-propyl paraben, n-butyl paraben, iso-butyl paraben and benzyl paraben) and bisphenol A[4] (BPA) in 42 commercially available milk samples, related to the packaging and storage. Because of contamination problems, a method based on the simultaneous extraction and purification of the sample, was chosen to reduce the manipulation[5]. Briefly, extraction in glass column was carried out by matrix solid phase dispersion (MSPD) put on a layer of Florisil® (purification). The column was eluted with ethyl acetate and concentrated for its final quantification by ultra-high performance liquid chromatography coupled to mass spectrometry (UHPLC-MS). With this method, all the analyte recoveries were higher than 70%. Different brands (11 commercial trademarks) and different types of containers (metallic bag, metal pail, HDPE, PET, Combibloc®, Tetra Brick®, Tetra Gemina® and Tetra Prisma®) have been investigated to study the effect of the container and the possible contamination during the production and processing of the product. The concentration levels and profiles found (expressed as median in pg/g fresh weight) were different for each type of analyte. PBs showed the highest concentration (1564 – 42879 pg/g f.w.), followed by PAEs (2810 – 9094 pg/g f.w.). Finally, BPA showed the lowest concentration (7 – 13 pg /g f.w.). Depending on the type of packaging, the highest PAE concentrations were found for metal pail and carton packages (which incorporate on their inside four layers of polyethylene which protects the content from the exterior moisture). Regarding BPA, the highest concentration was found for HDPE containers (high density polyethylene ). Finally, the highest PB concentrations were obtained for those milk samples packed in PET bottles (polyethylene terephthalate ). However, to the best of our knowledge, this fact seems to be more related with the nature of these samples (fresh milk, not UHT milk) than with the container itself. [1] Commission of the European Communities. Brussels, COM 706 (1999) [2] T. Schettler, Int. J. Androl. 29 (2006) 134-139 [3] A. Ballesteros-Gómez, JCA 1216 (2009) 449-469 [4] L. Brimer, Chemical Food Safety 24 (2011) Cap 24 [5] M. Llompart, JCA 1293 (2013) 10-19 Acknowledgements: Authors thank the Spanish Ministry of Economy and Competitiveness (project AGL2012- 37201), Comunidad Autónoma of Madrid (Spain) and European funding from FEDER programme (project S2013/ ABI-3028, AVANSECAL) for its financial support, Mrs. Sagrario Calvarro for instrumental maintenance and control and Mr. Luis A. Muñoz for his help.
MINECO AGL2012-37201; Fondos FEDER y Comunidad de Madrid (S2013/ABI-3028, AVANSECAL)