Determination of pesticide residues in soybeans using QuEChERS followed by deep eutectic solvent-based DLLME preconcentration prior to gas chromatography-mass spectrometry analysis.

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis.

Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil.

Accumulation of pesticides has a harmful impact on the environment and human health. The main goal of this work was to develop a method to determine and quantify the residues of thirteen pesticides in edible fish and bivalves such as parati (Mugil curema), seabass (Centropomus ssp.), mullet (Mugil brasiliensis), clams (Anomalocardia brasiliana) and mussel (Mytilus galloprovincialis) collected from Sepetiba Bay and Parnaiba River Delta (Brazil) between 2019 and 2020. Matrix solid-phase dispersion (MSPD) was used for extraction and quantification through gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The method was validated (linearity, accuracy and precision) for fatty fish (Salmo salar), lean fish (Mugil curema) and bivalves (Mytilus edulis). The survey found linear correlation coefficients (r) equal to or greater than 0.9 for almost all analytes. The relative standard deviations (RSD) of five replicates were less than 20% for almost all analytes at different concentrations in lean fish, fatty fish and bivalves. Most analytes showed satisfactory accuracy. Alachlor herbicide was found in samples of seabass, mussels, clams and parati with levels ranging between 0.55 to 420.39 µg kg-1 dw. Ethion was found in parati (maximum 211.22 µg kg-1 dw), mussels (15.1 µg kg-1 dw) and clams (maximum 44.50 µg kg-1 dw). Alachlor was found in clams (maximum 93.1 µg kg-1 dw), and bifenthrin was found in parati (maximum 43.4 µg kg-1 dw) and clams (maximum 42.21 µg kg-1 dw). The validated method was satisfactory for the determination of eleven pesticides in the fatty fish matrix, and thirteen pesticides in the samples of lean fish and bivalves. The presence of alachlor, ethion and bifenthrin stands out.

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.

Bisphenols A, F, S and AF trigger apoptosis and/or endoplasmic reticulum stress in human endometrial stromal cells.

Disruption of non-differentiated endometrial stromal cells could have noxious consequences in female reproduction, impairing endometrial remodelling and implantation. Following the classification of bisphenol A (BPA) as an endocrine disrupting chemical, it started to be gradually withdrawn from the market, being substituted by structural analogues, whose effects in human health are not fully understood. This work used a telomerase-immortalized human endometrial stromal cell line (St-T1b) to study the effects of BPA and its three most commercialized structural analogues (ranked: bisphenols S, F and AF) on endometrial stromal cells to understand their effects on female reproductive function. Bisphenols showed dissimilar effects. All four compounds generated endoplasmic reticulum (ER) stress. In addition, bisphenols A, F and AF induced apoptosis through different mechanisms, with bisphenol AF causing cell cycle arrest at G2/M phase. Bisphenol AF decreased mitochondrial transmembrane potential and bisphenols A, F and AF produced oxidative stress.

Mixture of environmental pollutants in breast milk from a Spanish cohort of nursing mothers.

Breastfeeding is one of the most effective ways to ensure child health and survival, with several benefits for both the infants and their mothers. However, breast milk can contain environmental pollutants with endocrine disruption capacity, neurotoxicity and/or potential to alter microbiota. Monitoring breast milk provides information on the current chemical exposure of breastfed infants and, in addition, on the current and historical exposure of nursing mothers. In this study, the levels of a wide range of pollutants were measured in breast milk of Spanish nursing mothers. Target chemicals were dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene (DDE), hexachlorobenzene (HCB), oxy-chlordane, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), per- and poly-fluoroalkyl substances (PFASs) (including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)), chlorpyrifos, bisphenol A (BPA), tetrabromobisphenol A (TBBPA), and a number of toxic and essential elements. Traces of most chemicals were found. A correlation between the levels of some persistent organic pollutants (POPs) and maternal characteristics (age and body mass index) was observed, while smoking was associated to higher concentrations of some toxic elements. Higher levels of PCBs were detected in samples from Spanish primiparous mothers compared to non-Spanish multiparous women. Breast milk from low-income mothers showed higher content of DDT and DDE than high-income mothers. Although breastfeeding is clearly beneficial for babies, the exposure to this mixture of hazardous substances, as well as their interaction and combined effects must not be disregarded.

Early-life intake of major trace elements, bisphenol A, tetrabromobisphenol A and fatty acids: Comparing human milk and commercial infant formulas.

In the present study, the presence of a wide spectrum of major and trace elements (As, Ag, Al, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni, Sr, Sb, Se, Sn, Pb, V, and Zn), fatty acids, as well as some pollutants like free and total BPA and tetrabromobisphenol A (TBBPA), was analysed in human milk (n = 53) and infant formula (n = 50) samples. In addition, the infant exposure to these chemicals was assessed. The content of free BPA and several elements (Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Sn, Sr, and Zn) was higher (p < 0.01) in infant formula samples. Furthermore, human milk contained levels of BPA and elements that, in almost all cases, were well below their respective EFSA and/or WHO thresholds, being also independent of the maternal characteristics (e.g., age, BMI or breastfeeding period). The fatty acid profiling also revealed major differences between human milk and infant formulas, which should be taken in account in the development of new formulas as well as in specific recommendations for the diet of breastfeeding mothers. Anyway, the results of this study reinforce that breastfeeding should be always the first feeding option in early life.

Environmental contaminants of emerging concern in seafood--European database on contaminant levels.

Marine pollution gives rise to concern not only about the environment itself but also about the impact on food safety and consequently on public health. European authorities and consumers have therefore become increasingly worried about the transfer of contaminants from the marine environment to seafood. So-called "contaminants of emerging concern" are chemical substances for which no maximum levels have been laid down in EU legislation, or substances for which maximum levels have been provided but which require revision. Adequate information on their presence in seafood is often lacking and thus potential risks cannot be excluded. Assessment of food safety issues related to these contaminants has thus become urgent and imperative. A database (www.ecsafeseafooddbase.eu), containing available information on the levels of contaminants of emerging concern in seafood and providing the most recent data to scientists and regulatory authorities, was developed. The present paper reviews a selection of contaminants of emerging concern in seafood including toxic elements, endocrine disruptors, brominated flame retardants, pharmaceuticals and personal care products, polycyclic aromatic hydrocarbons and derivatives, microplastics and marine toxins. Current status on the knowledge of human exposure, toxicity and legislation are briefly presented and the outcome from scientific publications reporting on the levels of these compounds in seafood is presented and discussed.

Development and validation of a matrix solid-phase dispersion method to determine acrylamide in coffee and coffee substitutes.

The present study describes the development and validation of a new method based on a matrix solid-phase dispersion (MSPD) sample preparation procedure followed by GC-MS for determination of acrylamide levels in coffee (ground coffee and brewed coffee) and coffee substitute samples. Samples were dispersed in C(18) sorbent and the mixture was further packed into a preconditioned custom-made ISOLUTE bilayered SPE column (C(18)/Multimode; 1 g + 1 g). Acrylamide was subsequently eluted with water, and then derivatized with bromine and quantified by GC-MS in SIM mode. The MSPD/GC-MS method presented a LOD of 5 microg/kg and a LOQ of 10 microg/kg. Intra and interday precisions ranged from 2% to 4% and 4% to 10%, respectively. To evaluate the performance of the method, 11 samples of ground and brewed coffee and coffee substitutes were simultaneously analyzed by the developed method and also by a previously validated method based in a liquid-extraction (LE) procedure, and the results were compared showing a high correlation between them.