Distribution in marine fish and EDI estimation of contaminants of emerging concern by vortex-assisted matrix solid-phase dispersion and HPLC-MS/MS.

Due to their persistence or continuous discharge, toxic substances are present in the aquatic environment, and can bioaccumulate and biomagnify in the food web, generating a significant ecological risk and a threat to human health. The present study assess the occurrence and tissue (muscle, liver, stomach and gills) distribution of 59 anthropogenic contaminants of emerging concern (CECs) in marine fish from Brazil. A simpler and faster analytical methodology based on vortex-assisted matrix solid-phase dispersion (VA-MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated. Limits of quantification ranged from 3.31 to 114 ng g-1 dw with recovery rates between 60 and 140 % and relative standard deviation below 20 %. The ultraviolet filters 4-hydroxybenzophenone (4HB) (benzophenone-3 metabolite) and benzocaine (Et-PABA), and the antibacterial salicylic acid were frequently accumulated in muscle and liver at concentrations between 39.5 and 21.0 ngg-1 dw. The determined concentrations resulted to be lower than the tolerable daily intake recommended by the European Food Safety Authority (EFSA).

Rapid and cost-effective multiresidue analysis of pharmaceuticals, personal care products, and antifouling booster biocides in marine sediments using matrix solid phase dispersion.

Currently, there are many contaminants of concern that need to be accurately determined to help assess their potential environmental hazard. Despite their increasing interest, yet few environmental occurrence data exist, likely because they are present at low levels and in very complex matrices. Therefore, multiresidue analytical methods for their determination need to be highly sensitive, selective, and robust. Particularly, due to the trace levels of these chemicals in the environment, an extensive extraction procedure is required before determination. This work details the development of a fast and cheap vortex-assisted matrix solid-phase dispersion-high performance liquid chromatography tandem-mass spectrometry (VA-MSPD-HPLC-MS/MS) method for multiresidue determination of 59 contaminants of emerging concern (CECs) including pharmaceuticals, personal care products, and booster biocides, in sediment. The validated method provided high sensitivity (0.42-36.8 ngg-1 dw quantification limits), wide and good linearity (r2 > 0.999), satisfactory accuracy (60-140%), and precision below 20% for most target analytes. In comparison with previous methods, relying on traditional techniques, the proposed method demonstrated to be more environmentally friendly, cheaper, simpler, and faster. The method was applied to monitor the occurrence of these compounds in sediments collected in Brazil, using only 2 g dw sediment samples, free-solid support, and 5 mL methanol as extraction solvent. The UV filter avobenzone, the UV stabilizer and antifreeze methylbenzotriazole, the preservative methylparaben, the fluoroquinolone antibiotic ciprofloxacin, and the biocides irgarol and 4,5-dichloro-2-octyl-4-isothiazolin-3-one were determined at concentrations in the range 1.44-69.7 ngg-1 dw.

Evaluation of alternative environmentally friendly matrix solid phase dispersion solid supports for the simultaneous extraction of 15 pesticides of different chemical classes from drinking water treatment sludge.

This study describes the development, optimization and validation of a method for the extraction of 15 pesticides of different chemical classes in drinking water treatment sludge (DWTS) by vortex-assisted Matrix Solid Phase Dispersion (MSPD) with determination by gas chromatography coupled to mass spectrometry. It focused on the application of alternative and different solid supports to the extraction step of the MSPD. The main parameters that influenced the extraction were studied in order to obtain better recovery responses. Recoveries ranged from 70 to 120% with RSD below 20% for all analytes. Limits of quantification (LOQ) of the method ranged from 5 to 500 µg kg-1 whereas the analytical curves showed correlation coefficients above 0.997. The method under investigation used low volume of solvent (5 mL), low sample mass (1.5 g) and low mass of chitin (0.5 g), an environmentally friendly support. It has advantages, such as speed, simplicity and low cost material, over other methods. When the method was applied, 4 out of 15 pesticides were detected in the DWTS samples in concentrations below the LOQ.