Multiresidue Methods for the Determination of Organic Micropollutants and Their Metabolites in Fish Matrices

Abstract

Two analytical methods were developed for the determination of 48 organic compounds and 20 of their main by‐products in fish matrices. The targeted compounds belong to various chemical classes of metabolizable (phthalates, polycyclic aromatic hydrocarbons, insecticides [pyrethroids and N,N‐diethyl‐meta‐toluamide]) and legacy (organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers) pollutants. Analyses were performed by gas and liquid chromatography–tandem mass spectrometry in multiple reaction monitoring (MRM) and dynamic MRM, respectively. Method performances were satisfactory, with results meeting the validation criteria because they achieved good linearity responses, recovery, precision, and accuracy for most of the 68 investigated compounds. The methods were then applied on 3 feral chub (Squalius cephalus) collected from the Marne hydrographic network (France). Twenty‐six parent compounds and 5 metabolites were systematically detected in fish matrices, with substantial concentration variability within and among individuals. Phthalates and pyrethroids accounted for most of the pollutant load. Metabolite concentrations in liver samples exceeded those of parent molecules in fish muscle. The present study presents 2 reliable methods for the determination of a wide range of contaminants and underlines the importance of metabolite analysis for a more comprehensive understanding of pollutant bioaccumulation and fate in aquatic organisms. Environ Toxicol Chem 2019;38:1866–1878. © 2019 SETAC.

Trophic Transfer of Micropollutants and Their Metabolites in an Urban Riverine Food Web

“…At last, PAH, phthalate, and pyrethroid metabolite analyses were conducted according to recently validated methods . Samples (500 mg) were homogenized in ammonium acetate (2 mL, 1 M, pH 6.5), using a vortex (15 s) and ultrasound (10 min).…”

“…First, 500 mg of samples were spiked with a mixture of internal standards for analyses of PAHs, phthalates, pyrethroids, and OCPs (phenanthrene-d 10 , pyrened 10 , benzo[a]anthracene-d 12 (Cluzeau Info Labo, Sainte-Foyla-Grande, France), DEP-d 4 , and DEHP-d 4 (LGC Standards, Molsheim, France), 13 C cis-permethrin, and lindane-d 6 (BCP Instruments, Oullins, France)). Samples were processed according to validated methods, 30 through accelerated solvent extraction (ASE 350, Thermo Fisher Scientific), using different solvents (hexane/[DCM, 1:1, and hexane/acetone, 1:1), and purification using Florisil cartridges (Supelco 1 g/6 mL, Sigma-Aldrich, St Quentin Fallavier, France), and PAHs, phthalate diesters, pyrethroid pesticides, and OCPs were analyzed using an Agilent 7890 A gas chromatograph (GC) coupled to a 7000 B triple quadrupole mass spectrometer system (MS/MS) (Agilent Technologies, Les Ulis, France).…”

“…At last, PAH, phthalate, and pyrethroid metabolite analyses were conducted according to recently validated methods. 30 Samples (500 mg) were homogenized in ammonium acetate (2 mL, 1 M, pH 6.5), using a vortex (15 s) and ultrasound (10 min). β-Glucuronidase (10 μL, from Escherichia coli K12, Sigma-Aldrich, Germany) was added to deconjugate metabolites (90 min, 37 °C, 170 rpm).…”

Fish from urban rivers and with high pollutant levels have shorter telomeres

“…Metabolites were quantified in fewer individuals (n = 66; electronic supplementary material, appendix B, table S3) since some of them did not yield sufficient biological material to carry out chemical analyses. Analyses of organic pollutants (16 polycyclic aromatic hydrocarbons (PAHs); 7 phthalate esters; 7 pyrethroids; 4 organochlorine pesticides (OCPs); 7 polychlorinated biphenyls (PCBs); 6 polybrominated diphenyl ethers (PBDEs) and their metabolites (11 hydroxylated PAHs; 9 phthalate monoesters; 4 metabolites of pyrethroids) were performed in muscle and liver respectively, following previously published protocols [32].…”

Potential Benefits of Acanthocephalan Parasites for Chub Hosts in Polluted Environments

“…The analytical methods used are described in the work of Molbert et al A total of 48 parent compounds (16 polycyclic aromatic hydrocarbons (PAHs); 7 phthalate esters; 7 pyrethroids; DEET; 4 organochlorine pesticides (OCPs); 7 polychlorinated biphenyls (PCBs); 6 polybrominated diphenyl ethers (PBDEs)) and some of their metabolites (11 hydroxylated PAHs (OH-PAHs), 9 phthalate monoesters; 4 byproducts of pyrethroids) were analyzed in four matrices: fish muscle ( n = 118), liver ( n = 26 and 93 for parent compounds and metabolites, respectively), stomach content ( n = 35), and parasite tissues ( n = 19 and 9 for parent compounds and metabolites, respectively). Due to a lack of biological material, chemical analyses were run on a reduced data set depending on the matrix.…”