Due to their widespread diffusion, perfluoroalkyl substances (PFASs) have been frequently found in the environment and in several animal species. It has been demonstrated that they can easily reach also humans, mainly through diet. Being lactation a major route of elimination of these contaminants, their occurrence in human milk is of particular interest, especially considering that it generally represents the unique food source for newborns. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the two most important compounds of this family, have been frequently found in human milk at variable concentrations, but still limited data are available. The present study, the first conducted in Italy capable to detect these pollutants at ultra-trace levels by UPLC-MS/MS, confirmed the role of lactation as a relevant source of exposure for breastfed children. The measured concentrations ranged between 15 and 288 ng/L for PFOS and between 24 and 241 ng/L for PFOA. Moreover, mean concentrations and frequencies of both analytes resulted higher in milk samples provided by primiparous women, suggesting that the risk of intake might be higher for first-borns. Finally, comparing these results with previous data, PFOS gradual decrease over time since year 2000 was confirmed.
Organophosphorus pesticides (OPPs), widely used in agriculture, can cause toxic effects to humans and animals. The main purpose of the present work was to determine the contamination in raw milk by the main organophosphorus pesticides used in Italy and to evaluate the opportunity to start specific procedures of risk management along the milk production chain. The samples, collected in 4 Italian dairy plants directly from the tank trucks during the delivering, were representative of 920 tonnes of raw milk. The isolation of the OPPs (acephate, chlorpyriphos, chlorpyriphos-methyl, diazinon, methamidophos, methidathion, phorate, pirimiphos-methyl) was performed by liquid partition followed by clean-up with solid phase extraction. The analyses were carried out by dual column gas chromatography using two nitrogen-phosphorus detectors. Among the 135 samples analysed, 37 were positive in traces and 10 showed an OPP contamination ranging from 5 to 18 μg/kg. The higher results were recorded in the samples collected during the autumn-winter period. The main pollutants detected were acephate and chlorpyriphos. In every positive sample found, the OPP contamination was lower than the maximum residue level (MRL) fixed by the European Commission.