Analysis of perfluoroalkyl substances in food and evironmental matrices

Abstract

Per- and poly- fluoroalkyl substances (PFASs) are a group of manmade substances synthesised for more than 60 years. Due to their specific properties, PFASs have been widely used for industrial applications including: electronics, textiles, food packaging, flame retardant formulae and laboratory tools, among others. However, it was during the last fifteen years ago that interest for this group of compounds as environmental pollutants was initiated. Due to their high release levels into the environment, stability and accumulation, PFASs have been found ubiquitous in the environment and in biota.

In this context, the main goal of this doctoral PhD thesis was the study of the occurrence, fate and behaviour of a wide range of PFASs in the environment, in food and, finally, in some human matrices. In addition, the physicochemical properties studies and the aerobic biodegradation experiments of 3 perfluoroalkyl phosphonic acids were also evaluated.

Therefore, the first specific objective was the development of different analytical methods to study a wide range of PFASs in selected matrices. The analytical methods have been based on the use of on-line chromatography and off-line extraction, followed by liquid chromatography coupled to tandem mass spectrometry.

These methods have been employed to assess the presence of PFASs in different type of waters from different steps along the water cycle, and also in fish and other food commodities. And finally, the PFAS accumulation in human samples was studied in cord blood and breast milk.

This work is divided into six chapters. The first chapter is the general introduction and the objectives of this PhD Thesis. In the introduction, different aspects are revised, such as synthesis and global production, environmental fate and occurrence, human accumulation, toxicology, regulations and future trends.

Chapters 2, 3, 4 and 5 present the experimental work undertaken during this research. Each chapter has been divided into a specific introduction, results (presented through the corresponding publications) and discussion. Part of the results contained in Chapters 2 and 5 correspond to the experimental work carried out in the laboratory of Prof. Dr. Thomas P. Knepper (Hochschule Fresenius, Idstein, Germany) during a four month research internship, a part of the European Doctoral Programme.

Chapter 6 contains the general conclusions. Finally, a small summary in Catalan is presented.

The cited literature and indexes for tables and figures can be found at the end of this work, as well as the list of publications produced along the duration of the pre-doctoral studies, but which are not presented in this thesis.

The distribution of the publications included in this Thesis is the following:

Chapter 2: Environmental occurrence

Publication 1: “Analysis of perfluoroalkyl substances in waters from Germany and Spain.” Llorca, M., Farré, M., Picó, Y., Müller, J., Knepper, T. P. and Barceló, D. (2012). Science of The Total Environment, 431(0): 139-150.

Publication 2: “Analysis of perfluorinated compounds in sewage sludge by pressurized solvent extraction followed by liquid chromatography–mass spectrometry.” Llorca, M; Farré, M; Picó, Y; Barceló,D; (2011). Journal of Chromatography A, 1218 (30) 4840-4846.

Publication 3: “Fate of a broad spectrum of perfluorinated compounds in soils and biota from Tierra del Fuego and Antarctica.” Llorca, M., Farré, M., Tavano, M. S., Alonso, B., Koremblit, G. and Barceló, D. (2012). Environmental Pollution 163(0): 158-166.

Chapter 3: PFASs in food

Publication 4: “Development and validation of a pressurized liquid extraction liquid chromatography-tandem mass spectrometry method for perfluorinated compounds determination in fish.” Llorca, M., Farré, M., Picó, Y., and Barceló, D. (2009). Journal of Chromatography A 1216(43): 7195-7204.

Publication 5: “Study of the performance of three LC-MS/MS platforms for analysis of perfluorinated compounds.” Llorca, M., Farré, M., Picó, Y., and Barceló, D. (2010) Analytical and Bioanalytical Chemistry 398(3): 1145-1159.

Publication 6: “Infant exposure of perfluorinated compounds: Levels in breast milk and commercial baby food.” Llorca, M., Farré, M., Picó, Y., Teijón, M. L., Álvarez, J. G. and Barceló, D. (2010). Environment International 36(6): 584-592.

Chapter 4: PFASs accumulation in humans

Publication 7: “Analysis of perfluoroalkyl substances in cord blood by turbulent flow chromatography coupled to tandem mass spectrometry.” Llorca, M., Pérez, F., Farré, M., Agramunt, S., Kogevinas, M. and Barceló, D. (2012). Science of The Total Environment 433(0): 151-160.

Les substàncies per- i poli- fluorades (PFASs) són d’origen antropogènic. Aquest ampli grup de compostos s’ha sintetitzat durant més de 60 anys. Degut a les seves propietats específiques s’utilitzen encara en l’actualitat en diferents aplicacions industrials tals com: electrònica, recobriments tèxtils, embolcall d’aliments, escumes ignífugues i material de laboratori entre d’altres. No obstant, no ha estat fins els últims 15 anys quan a aquests compostos se’ls ha començat a considerar contaminants ambientals. Degut als nivells que es troben en el medi ambient, l’estabilitat i l’acumulació que presenten, aquests anàlits tenen una distribució global en el medi i en biota.

En aquest context, el principal objectiu d’aquesta tesi doctoral ha estat l’estudi de la presència, destí i comportament d’un ampli grup de PFASs (13 àcids prfluoroalquílics, 4 perfluorosulfats, 1 perfluorosulfonamida i 3 àcids perfluorofosfònics) en el medi ambient, aliments i, finalment, en algunes matrius humanes. En paral•lel a l’estudi dels esmentats treballs, s’han realitzat en experiments per determinar algunes de les propietats fisicoquímiques i la possible biodegradació aeròbica de 3 àcids perfluorofosfònics.

Per aquest motiu, el primer objectiu específic ha esta el desenvolupament de diferents mètodes analítics per a l’estudi d’aquests anàlits en les matrius seleccionades. Els mètodes analítics desenvolupats han inclòs tant mètodes d’extracció fora de línia com de cromatografia en línia, seguit d’una separació per cromatografia líquida acoblada en tàndem a l’espectrometria de masses.

Aquests mètodes han estat utilitzats per al posterior estudi de la presència de PFASs en diferents mostres d’aigua provinents de tot el cicle de l’aigua així com peix i altres aliments. Finalment, l’acumulació de PFASs en humans s’ha estudiat a partir de l’anàlisi de mostres de sang de cordó umbilical i llet materna.