Polycyclic aromatic hydrocarbons (PAHs) were included as priority substances for human biomonitoring (HBM) in the European Human Biomonitoring Initiative (HBM4EU), which intended to harmonise and advance HBM across Europe. For this project, a specific Quality Assurance and Quality Control (QA/QC) programme applying Inter-laboratory Comparison Investigations (ICIs) and External Quality Assurance Schemes (EQUASs) was developed to ensure the comparability and accuracy of participating analytical laboratories. This paper presents the results of four ICI/EQUAS rounds for the determination of 13 PAH metabolites in urine, i.e. 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 2-, 3- and 9-hydroxyfluorene, 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo(a)pyrene. However, 4 PAH metabolites could not be evaluated as the analytical capacity of participating laboratories was too low. Across all rounds and biomarkers, 86% of the participants achieved satisfactory results, although low limits of quantification were required to quantify the urinary metabolites at exposure levels of the general population. Using high-performance liquid or gas chromatography coupled with mass spectrometry (HPLC-MS; GC-MS) and isotope dilution for calibration as well as performing an enzymatic deconjugation step proved to be favourable for the accurate determination of PAHs in urine. Finally, the HBM4EU QA/QC programme identified an international network of laboratories providing comparable results in the analysis of urinary PAH biomarkers, although covering all parameters initially selected was still too challenging.

Aarhus University Department of Environmental Science Frederiksborgvej 399 4000 Roskilde Denmark

ABF Analytisch Biologisches Forschungslabor GmbH Semmelweisstr 5 82152 Planegg Germany

Friedrich Alexander Universität Erlangen Nürnberg Institute and Outpatient Clinic of Occupational Social and Environmental Medicine Henkestraße 9 11 91054 Erlangen Germany

Institute for Prevention and Occupational Medicine of the German Social Accident Insurance Institute of the Ruhr University Bochum Bürkle de la Camp Platz 1 44789 Bochum Germany

National Center for Environmental Health Instituto de Salud Carlos 3 Ctra Majadahonda a Pozuelo Km2 2 28220 Madrid Spain

Norwegian Institute of Public Health Oslo Norway

Oniris INRAE UMR 1329 Laboratoire D'Etude des Résidus et Contaminants Dans les Aliments F 44307 Nantes France

University of Chemistry and Technology Prague Department of Food Analysis and Nutrition Technicka 5 16028 Prague Czech Republic

Wageningen Food Safety Research Part of Wageningen University and Research Akkermaalsbos 2 6708 WB Wageningen the Netherlands

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