TY - JOUR
T1 - A large scale multi-laboratory suspect screening of pesticide metabolites in human biomonitoring
T2 - From tentative annotations to verified occurrences
AU - Huber, Carolin
AU - Nijssen, Rosalie
AU - Mol, Hans
AU - Philippe Antignac, Jean
AU - Krauss, Martin
AU - Brack, Werner
AU - Wagner, Kevin
AU - Debrauwer, Laurent
AU - Maria Vitale, Chiara
AU - James Price, Elliott
AU - Klanova, Jana
AU - Garlito Molina, Borja
AU - Leon, Nuria
AU - Pardo, Olga
AU - Fernández, Sandra F.
AU - Szigeti, Tamás
AU - Középesy, Szilvia
AU - Šulc, Libor
AU - Čupr, Pavel
AU - Mārtiņsone, Inese
AU - Akülova, Läsma
AU - Ottenbros, Ilse
AU - Vermeulen, Roel
AU - Vlaanderen, Jelle
AU - Luijten, Mirjam
AU - Lommen, Arjen
N1 - Funding Information:
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 733032 HBM4EU. C.M.V., E.J.P, L.Š., P.Č. & J.K. acknowledge the RECETOX research infrastructure supported by the Ministry of Education, Youth and Sports of the Czech Republic (LM2018121) and the Ministry of Education, Youth and Sports of the Czech Republic (CZ.02.1.01/0.0/0.0/17_043/0009632). This work was supported from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 857560 and No 857340. E.J.P. acknowledges support from Czech Operational Programme Research, Development and Education - Project MSCAfellow4@MUNI (No. CZ.02.2.69/0.0/0.0/20_079/0017045). L.D. and K.W. would like to thank the MetaboHUB French National Infrastructure (MetaboHUB-ANR-11-INBS-0010, 2011). The QExactive Plus LC-HRMS used at UFZ is part of the major infrastructure initiative CITEPro (Chemicals in the Terrestrial Environment Profiler) funded by the Helmholtz Association. The Dutch Ministry of Agriculture, Nature and Food Quality are acknowledged for co-funding through projects 1277354201 and 1267333701. The European Union is acknowledged for co-funding through the European Regional Development Fund Operational Programme (ERDF) of the Valencia Region (2014-2020). This publication reflects only the author's view and the European Commission is not responsible for any use that may be made of the information it contains.
Funding Information:
This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 733032 HBM4EU. C.M.V. E.J.P, L.Š. P.Č. & J.K. acknowledge the RECETOX research infrastructure supported by the Ministry of Education, Youth and Sports of the Czech Republic (LM2018121) and the Ministry of Education, Youth and Sports of the Czech Republic (CZ.02.1.01/0.0/0.0/17_043/0009632). This work was supported from the European Union's Horizon 2020 research and innovation programme under grant agreement No 857560 and No 857340. E.J.P. acknowledges support from Czech Operational Programme Research, Development and Education - Project MSCAfellow4@MUNI (No. CZ.02.2.69/0.0/0.0/20_079/0017045). L.D. and K.W. would like to thank the MetaboHUB French National Infrastructure (MetaboHUB-ANR-11-INBS-0010, 2011). The QExactive Plus LC-HRMS used at UFZ is part of the major infrastructure initiative CITEPro (Chemicals in the Terrestrial Environment Profiler) funded by the Helmholtz Association. The Dutch Ministry of Agriculture, Nature and Food Quality are acknowledged for co-funding through projects 1277354201 and 1267333701. The European Union is acknowledged for co-funding through the European Regional Development Fund Operational Programme (ERDF) of the Valencia Region (2014-2020). This publication reflects only the author's view and the European Commission is not responsible for any use that may be made of the information it contains.
Publisher Copyright:
© 2022
PY - 2022/10
Y1 - 2022/10
N2 - Within the Human Biomonitoring for Europe initiative (HBM4EU), a study to determine new biomarkers of exposure to pesticides and to assess exposure patterns was conducted. Human urine samples (N = 2,088) were collected from five European regions in two different seasons. The objective of the study was to identify pesticides and their metabolites in collected urine samples with a harmonized suspect screening approach based on liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) applied in five laboratories. A combined data processing workflow included comprehensive data reduction, correction of mass error and retention time (RT) drifts, isotopic pattern analysis, adduct and elemental composition annotation, finalized by a mining of the elemental compositions for possible annotations of pesticide metabolites. The obtained tentative annotations (n = 498) were used for acquiring representative data-dependent tandem mass spectra (MS2) and verified by spectral comparison to reference spectra generated from commercially available reference standards or produced through human liver S9 in vitro incubation experiments. 14 parent pesticides and 71 metabolites (including 16 glucuronide and 11 sulfate conjugates) were detected. Collectively these related to 46 unique pesticides. For the remaining tentative annotations either (i) no data-dependent MS2 spectra could be acquired, (ii) the spectral purity was too low for sufficient matching, or (iii) RTs indicated a wrong annotation, leaving potential for more pesticides and/or their metabolites being confirmed in further studies. Thus, the reported results are reflecting only a part of the possible pesticide exposure.
AB - Within the Human Biomonitoring for Europe initiative (HBM4EU), a study to determine new biomarkers of exposure to pesticides and to assess exposure patterns was conducted. Human urine samples (N = 2,088) were collected from five European regions in two different seasons. The objective of the study was to identify pesticides and their metabolites in collected urine samples with a harmonized suspect screening approach based on liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) applied in five laboratories. A combined data processing workflow included comprehensive data reduction, correction of mass error and retention time (RT) drifts, isotopic pattern analysis, adduct and elemental composition annotation, finalized by a mining of the elemental compositions for possible annotations of pesticide metabolites. The obtained tentative annotations (n = 498) were used for acquiring representative data-dependent tandem mass spectra (MS2) and verified by spectral comparison to reference spectra generated from commercially available reference standards or produced through human liver S9 in vitro incubation experiments. 14 parent pesticides and 71 metabolites (including 16 glucuronide and 11 sulfate conjugates) were detected. Collectively these related to 46 unique pesticides. For the remaining tentative annotations either (i) no data-dependent MS2 spectra could be acquired, (ii) the spectral purity was too low for sufficient matching, or (iii) RTs indicated a wrong annotation, leaving potential for more pesticides and/or their metabolites being confirmed in further studies. Thus, the reported results are reflecting only a part of the possible pesticide exposure.
KW - Exposomics
KW - HBM4EU
KW - Human biomonitoring
KW - LC-HRMS
KW - Pesticide metabolites
KW - Pesticides
KW - Suspect screening
UR - http://www.scopus.com/inward/record.url?scp=85136718211&partnerID=8YFLogxK
U2 - 10.1016/j.envint.2022.107452
DO - 10.1016/j.envint.2022.107452
M3 - Article
C2 - 35994799
AN - SCOPUS:85136718211
SN - 0160-4120
VL - 168
JO - Environment International
JF - Environment International
M1 - 107452
ER -