Bisphenol A and its structural analogues in infant formulas available in the Brazilian market: Optimisation of a UPLC-MS/MS method, occurrence, and dietary exposure assessment.

For the first time, structural analogues to bisphenol A were investigated in infant formulas marketed in Brazil. A fast and high throughput UPLC-MS/MS method was established for simultaneous analysis of bisphenol A, B, E, F, and S in complex infant formula matrices. The influence of mobile phase composition on electrospray ionization response in negative mode was studied to improve the detectability of the method. As also, the main sample preparation variables that could affect the extraction and cleanup were screened by the Plackett-Burman design. The method performance characteristics were adequate, including reliable limits of detection (5-10 µg kg-1) and quantification (10-20 µg kg-1) with suitable recoveries (84.2-108.9 %) and precision (≤18 %). Sixty-one infant formulas were analyzed, and 36 % of total samples contained at least one bisphenol analogue, whose levels ranged between 10.9 and 198.9 µg kg-1. Based on a deterministic approach, the estimated daily intakes for babies up to 6 months old, fed exclusively with infant formula, were below the temporary tolerable daily intake of 4 µg kg-1 body weight set for bisphenol A by the European Food Safety Authority.

Occurrence and risk assessment of endocrine-disrupting compounds in fish muscle: The case study of the Douro River estuary (North East Atlantic Ocean).

This work was focused on evaluating the occurrence of endocrine-disrupting compounds (EDCs) in fish muscles, such as bisphenol analogues, personal care products, including some UV-filters and musk fragrances, and selected pesticides. A total of 238 muscle samples of three fish species (Platichthys flesus, Mugil cephalus, and Dicentrarchus labrax) of an important estuary ending in the North East Atlantic Ocean (Douro River estuary, Portugal), in different seasons of the year, was analysed. M. cephalus was the species with a greater occurrence of contaminants, mainly in fishes collected during the spring. Bisphenol A was the main bisphenol analogue detected with an average content of 23.1 µg/kg wet weight (w.w.). Among chemicals used in personal care products, galaxolide, tonalide, and 2-ethylhexyl salicylate, were the most often found, being present in 15.9% (2.2-538.4 µg/kg w. w.), 4.6% (1.1-57.8 µg/kg w. w.) and 3.4% (3.9-56.1 µg/kg w. w.) of the samples, respectively. About 14% of the samples contained residues of at least one pesticide, being alachlor, aldrin, p,p'-DDT, permethrin, and prochloraz the main chemicals observed, varying from 0.1 µg/kg w. w. (p,p'-DDT) to 37.8 µg/kg w. w. (prochloraz). The daily intake estimates of the most frequent EDCs found in the fish muscles suggested that there are no health concerns, based on the recommended weekly consumption of fish for adults.

Gas chromatography-mass spectrometry determination of polycyclic aromatic hydrocarbons in baby food using QuEChERS combined with low-density solvent dispersive liquid-liquid microextraction.

A sensitive GC-MS method is reported for the determination of twelve polycyclic aromatic hydrocarbons (PAHs) in baby food. The sample preparation involves QuEChERS extraction combined with low-density solvent dispersive liquid-liquid microextraction (LDS-DLLME) and ultra-low temperature (-80 °C). Plackett-Burman screening design was employed to identify the main sample preparation variables that affect the extraction efficiency, such as the volume of toluene used in LDS-DLLME. The suitability of proposed method was verified by analytical selectivity, linearity in solvent and matrix-matched calibration curves and adequate recoveries (72-112%) and precision (RSD values ≤11%), under repeatability and within-laboratory reproducibility conditions. High analytical sensitivity was achieved for the monitoring of PAHs at the strict limit of 1 µg kg-1 fixed by the European Commission for baby foods. The validated method was applied to thirty-two commercial baby food samples, and the investigated PAHs were not detected in any sample.