Development of multi-residue extraction procedures using QuEChERS and liquid chromatography tandem mass spectrometry for the determination of different types of organic pollutants in mussel

Abstract

This study aimed to develop multi-residue methods for the extraction of organic pollutants in mussels (Mytilus galloprovincialis), including 11 pharmaceuticals, 5 pesticides, 5 perfluoroalkyl substances (PFASs) and 2 illicit drugs. The combination of 4 different QuEChERS methods and 12 clean-ups (a total of 44 combinations) were tested. QuEChERS included acidified (AQ), non-acidified (SQ) and their miniaturized versions. The clean-ups included 6 different conventional dispersive solid phase extraction (dSPE) plus 2 enhanced matrix removal (EMR-Lipid) and 4 SPE procedures (including sorbents focused on phospholipid removal and polymer-based). After sample analysis via HPLC-MS/MS, the three methods that provided the best results were validated in terms of linearity, accuracy, precision, sensitivity and matrix effect. The methods selected were the combination of (i) SQ and EMR-Lipid, (ii) AQ and Z-sep+ bulk based dSPE and (iii) AQ and graphitized carbon black (GCB) based dSPE. Recoveries at two concentration levels (50 and 500 ng/g) ranged 53.9-124.0%, 58.5-124.0% and 60.3-127.0%, respectively and limits of detection (LODs) were <10 ng/g for most analytes using any of the methods. The three methods were tested in non-spiked mussel samples purchased in local markets, but organic pollutants were not detected in any sample.However, the methods probed to successfully extract a wide range of organic pollutants in mussel samples from the market and from bioaccumulation trials.

Bioaccumulation of emerging contaminants in mussel (Mytilus galloprovincialis): Influence of microplastics

“…Water extraction was performed employing solid phase extraction (SPE) following the method by Carmona et al (2017). For mussel visceral mass extraction, the method developed by Álvarez-Ruiz et al (2021b) combining QuEChERS extraction and EMR-Lipid clean-up was employed and for haemolymph, SPE was used as described by Álvarez-Ruiz et al (2021a). Additional information can be found in Text S-2 of the supplementary material.…”

“…presented inconsistent concentrations (Tables S-7 and S-8), likely due to interfering compounds naturally present in the mussel (Álvarez-Ruiz et al, 2021b), and hence the results were considered not representative and not modelled. Although chlorfenvinphos and chlorpyrifos were added to the food, Cw was set as the mean concentration for modelling purposes during exposure stage; so their results should be interpreted with caution.…”

Evaluation of uptake of the cytostatic methotrexate in Elliptio complanata mussels by LC–MS/MS

“…In comparison, some method developments and validations have been reported for the analysis of other pharmaceuticals in many kinds of mussel species (Álvarez-Ruiz et al 2021 ; Bayen et al 2015 ; Daniele et al 2016 ; Mijangos et al 2019 ; Núñez et al 2016 , 2015 ). The limit of quantification (LOQ) was typically in the range 5–125 ng g −1 , with some exceptions lower than 1 ng g −1 .…”

“…Another team (Núñez et al 2016 , 2015 ) developed a QuEChERS extraction, LC–MS/MS analytical method for the analysis of seven pharmaceuticals in bivalves resulting in apparent recoveries ranging from 35 to 77% with limit of quantification from 5 to 100 ng g −1 . Alvarez-Muñoz et al ( 2021 ) also developed a QuEChERS extraction, LC–MS/MS analytical method resulting in limit of quantification from 0.78 to 68 ng g −1 and apparent recovery from 16 to 134%. Mijangos et al’s ( 2019 ) team developed a 41 multiclass organic pollutants with multistep extraction method with focused ultrasound liquid extraction (FUSLE) followed by solid phase extraction (SPE), analyzed by LC–MS/MS, resulting in apparent recovery values ranging from 71 to 126% and method detection limits ranging from 4 to 48 ng g −1 .…”

Development and validation according to the SANTE guidelines of a QuEChERS-UHPLC-QTOF-MS method for the screening of 204 pesticides in bivalves

“…This mixture reduces fat and pigment levels in matrices and it is recommended for matrices with >18% of lipid (Álvarez-Ruiz et al, 2021), which is not the case for bivalve samples, whose lipid content is usually below 10%. EMR-Lipid, whose structure is a proprietary secret, removes lipids from sample matrices (Álvarez-Ruiz et al, 2021;Pang et al, 2021) but its ability to remove other interferents such as proteins has not yet been described in literature.…”