RT Journal Article
T1 Determination of human metabolites of chlorinated phosphorous flame retardants in wastewater by N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide-derivatization and gas chromatography-high resolution mass spectrometry
A1 Castro Bustelo, Verónica
A1 Rodil Rodríguez, María del Rosario
A1 Quintana Álvarez, José Benito
A1 Cela Torrijos, Rafael
A1 Sánchez Fernández, Laura
A1 González Mariño, Iria
K1 Phosphorous flame retardants and plasticizers
K1 Metabolites
K1 Wastewater
K1 Human exposure
K1 Silylation
K1 Gas chromatography-high resolution mass spectrometry
AB The analysis of wastewater for the determination of human biomarkers of exposure (human metabolites) is a non-intrusive, economic and complementary alternative to the analysis of urine in the monitoring of human exposure to chemicals of concern. This study provides the first gas chromatography-based method for the determination of three metabolites of chlorinated organophosphorous flame retardants (OPFRs: bis(2-chloroethyl) phosphate, bis(chloropropyl) phosphate and bis(1,3-dichloro-2-propyl) phosphate) in wastewater. A solid-phase extraction procedure based on the use of mixed-mode reversed-phase weak anion exchange sorbents was optimized including a fractionated elution of OPFRs and their metabolites. Analytes derivatization was investigated by comparing two silylating reagents, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide and N-methyl-N-(trimethylsilyl)trifluoroacetamide, the first one providing better results. Determination was performed by gas chromatography-high resolution mass spectrometry with a quadrupole-time-of-flight system (GC-QTOF) in order to improve selectivity. Furthermore, the use of GC-QTOF combined with the specific ion obtained from silylated metabolites (m/z 154.9924) can be exploited to screen for other phosphate ester metabolites. Under final conditions, the overall method performance was satisfactory, affording method detection limits ranging from 1.1 to 4.6 ng/L, percentages of recovery from 90% to 110%, and relative standard deviations below 13%. The analysis of composite raw wastewater samples collected over 24 h in the NW of Spain allowed to quantify, for the first time in this matrix, the metabolite bis(chloropropyl) phosphate at levels over 60 ng/L
PB Elsevier
SN 0021-9673
YR 2019
FD 2019-09-27
LK http://hdl.handle.net/10347/20586
UL http://hdl.handle.net/10347/20586
LA eng
NO Castro V, Rodil R, Quintana JB, Cela R, Sánchez-Fernández L, González-Mariño I, Determination of human metabolites of chlorinated phosphorous flame retardants in wastewater by N-tert-butyldimethylsilylN-methyltrifluoroacetamide-derivatization and gas chromatography-high resolution mass spectrometry, Journal of Chromatography A (2019), https://doi.org/10.1016/j.chroma.2019.06.015
NO This work was financially supported by the Spanish Agencia Estatal de Investigación (project no. CTM2017-84763-C3-2-R), the Galician Council of Culture, Education and Universities (ED431C2017/36, VC predoctoral contract, ED481A-2017/156, and IGM postdoctoral contract, Plan Galego I2C-Modalidade B, ED481D 2017/003), Gil Dávila Foundation (VC research grant) and FEDER/ERDF
DS Minerva
RD 30 abr 2026