S1 SUPPORTING INFORMATION Biomarkers, matrices and analytical methods targeting human exposure to chemicals selected for a European human biomonitoring initiative Katrin Vorkampa, Argelia Castañob, Jean-Philippe Antignacc, Luis D. Boadad, Enrique Cequiere, Adrian Covacif, Marta Esteban Lópezb, Line S. Hauge, Monika Kasper-Sonnenbergg, Holger M. Kochg, Octavio Pérez Luzardod, Agnese Osīteh, Loïc Rambaudi, Maria-Teresa Pinorinij¤, Gabriele Sabbionij¤, Cathrine Thomsene aAarhus University, Department of Environmental Science, Denmark; bInstituto de Salud Carlos III, National Centre for Environmental Health, Spain; cOniris, INRAE, LABERCA, Nantes, France; dUniversity of Las Palmas de Gran Canaria, Institute for Biomedical and Health Research, Spain; eNorwegian Institute of Public Health, Norway; fUniversity of Antwerp, Toxicological Centre, Belgium; gRuhr University Bochum, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Germany; hUniversity of Latvia, Department of Analytical Chemistry, Latvia; iSanté Publique France, Department of Environmental Health, France; jAlpine Institute of Chemistry and Toxicology, Olivone, Switzerland  Corresponding author. E-mail: kvo@envs.au.dk. Phone: +45-87158483. Postal address: Aarhus University, Department of Environmental Science, Frederiksborgvej 399, 4000 Roskilde, Denmark  Present address: University of Lleida, Alcalde Rovira Roure 191, 25198 Lleida, Spain ¤ Present address: Università della Svizzera italiana, Research and Transfer Service, 6900 Lugano, Switzerland S2 Table S1: List of acronyms used in this article Acronym Full name AAS Atomic absorption spectrometry ABP Aminobiphenyl ADONA Ammonium 4,8-dioxa-3H-perfluorononanoate BBOEP Bis(2-butoxyethyl) phosphate BzBP Benzyl butyl phthalate BCIPHIPP 1-Hydroxy-2-propyl-bis(1-chloro-2-propyl)phosphate BCIPP Bis(chloroisopropyl) phosphate; bis(1-chloro-2-propyl) phosphate BDCIPP Bis(1,3-dichloroisopropyl) phosphate BCEP Bis(2-chloroethyl) phosphate BDE Bromodiphenyl ether BEHP Bis(2-ethylhexyl) phosphate BEH-TEBP Bis(2-ethylhexyl) tetrabromophthalate BMPP Biscresyl phosphate (Bis(methylphenyl) phosphate) BPA Bisphenol A BPF Bisphenol F BPS Bisphenol S BTBPE 1,2-Bis(2,4,6- tribromophenoxy)ethane CA Chloroaniline CAS Chemical Abstracts Service 5cx-MEPP Mono-(5-carboxy-2-ethylpentyl) phthalate cx-MIDP Carboxy-(mono-isodecyl) phthalate (carboxylated DIDP metabolite) cx-MINCH Cyclohexane-1,2-dicarboxylate-mono-carboxyisononyl ester cx-MINP Carboxy-(mono-isononyl) phthalate (carboxylated DINP metabolite) cx-MPrHpP Carboxy-(mono-2-propyl-heptyl) phthalate DBDPE Decabromodiphenyl ethane DBE-DBCH Tetrabromoethylcyclohexane DBP Dibutyl phthalate DCA Dichloroaniline DCHP Dicyclohexyl phthalate DDC-CO Dechlorane plus DEHP Bis(2-ethylhexyl) phthalate DEP Diethyl phthalate / Diethyl phosphate DIBP Diisobutyl phthalate DIDP Diisodecyl phthalate DINCH 1,2-cyclohexane dicarboxylic acid diisononyl ester DINP Diisononyl phthalate diPAP Polyfluoroalkyl phosophoric acid diester DIPeP Diisopentyl phthalate DMA Dimethylaniline DMP Dimethyl phthalate DNBP Di-n-butyl phosphate DNHxP Di-n-hexyl phthalate DNOP Di-n-octyl phthalate DNPeP Di-n-pentyl phthalate DP Dechlorane plus DPHP Diphenyl phosphate DPrHpP Di(2-propyl-heptyl) phthalate DRC Dynamic reaction cell EA Ethylaniline S3 EB Exposure biomarker ECNI Electron capture negative ionization EHDPHP 2-Ethylhexyl diphenyl phosphate EH-TBB 2-Ethylhexyl-2,3,4,5-tetrabromobenzoate EI Electron ionization EtFOSAA N-ethyl-perfluorooctane sulfonamidoacetate EtFOSE N-ethyl-perfluorooctane sulfonamidoethanol FOSA Perfluoroalkyl sulfonamide FOSE Perfluoroalkyl sulfonamidoethanol FR Flame retardant FTCA Fluorotelomer carboxylic acid FTOH Fluorotelomer alcohol FTSA Fluorotelomer sulfonic acid FTUCA Fluorotelomer unsaturated carboxylic acid GC Gas chromatography GC-MS Gas chromatography-mass spectrometry GC-MS/MS Gas chromatography-tandem mass spectrometry GPC Gel permeation chromatography Hb Haemoglobin HBB Hexabromobenzene HBCDD Hexabromocyclododecane HBM4EU Human Biomonitoring for Europe HFR Halogenated flame retardant HPLC High performance liquid chromatography HRMS High resolution mass spectrometry ICP-MS Inductively coupled plasma-mass spectrometry i,p-PHPHP Isopropylphenyl phenyl phosphate i,p-TPHP Isopropyl triphenyl phosphate LC Liquid chromatography LC-MS/MS High performance liquid chromatography-tandem mass spectrometry LLE Liquid-liquid extraction LOD Limit of detection LRMS Low resolution mass spectrometry M Matrix MA Methylaniline MBzP Monobenzyl phthalate MCHP Monocyclohexyl phthalate MDA 4,4-Methylenedianiline MDL Method detection limit MECPP Mono(2-ethyl-5-carboxypentyl) phthalate MeFOSAA N-methyl-perfluorooctane sulfonamidoacetate MeFOSE N-methyl-perfluorooctane sulfonamidoethanol MEHHP Mono(2-ethyl-5-hydroxyhexyl) phthalate MEP Monoethyl phthalate MeOA Methoxyaniline MEOHP Mono(2-ethyl-5-oxo-hexyl) phthalate MIBP Monoisobutyl phthalate MIPeP Monoisopentyl phthalate MMP Monomethyl phthalate MNBP Mono-n-butyl phthalate MNHxP Mono-n-hexyl phthalate S4 MNOP Mono-n-octyl phthalate MNPeP Mono-n-pentyl phthalate MOCA 4,4-Methylenebis(2-chloroaniline) monoPAP Polyfluoroalkyl phosophoric acid monoester NA Naphthylamine N-EtFOSA N-ethyl-perfluoro-1-octanesulfonamide NHANES National Health and Nutrition Examination Survey N-MeFOSA N-methyl-perfluoro-1-octane sulfonamide 5OH-MEHP Mono(2-ethyl-5-hydroxyhexyl) phthalate OH-MIDP OH-mono-isodecyl phthalate OH-MINCH Cyclohexane-1,2-dicarboxylate-mono-hydroxyisononyl ester OH-MINP OH-mono-isononyl phthalate OH-MPrHpP OH-mono-2-propyl-heptyl phthalate OPFR Organophosphorous flame retardant 5oxo-MEHP Mono(2-ethyl-5-oxo-hexyl) phthalate Oxo-MIDP Oxo-mono-isodecyl phthalate Oxo-MINCH Cyclohexane-1,2-dicarboxylate-mono-oxoisononyl ester Oxo-MINP Oxo-mono-isononyl phthalate Oxo-MPrHpP Oxo-mono-2-propyl-heptyl phthalate PAH Polycyclic aromatic hydrocarbon PBDE Polybrominated diphenyl ether PBEB Pentabromoethylbenzene PBT Pentabromotoluene PDA Phenylenediamine PFAS Per- and polyfluoroalkyl substance PFBA Perfluorobutanoic acid PFBS Perfluorobutane sulfonate PFCA Perfluoralkyl carboxylic acids PFDA Perfluorodecanoic acid PFDoDA Perfluorododecanoic acid PFDPA Perfluorodecyl phosphonic acid PFDS Perfluorodecane sulfonate PFHpA Perfluoroheptanoic acid PFHpS Perfluoroheptane sulfonate PFHxA Perfluorohexanoic acid PFHxDA Perfluorohexadecanoic acid PFHxPA Perfluorohexyl phosphonic acid PFHxS Perfluorohexane sulfonate PFNA Perfluorononaoic acid PFOA Perfluorooctanoic acid PFODA Perfluorooctadecanoic acid PFOPA Perfluorooctyl phosphonic acid PFOS Perfluorooctane sulfonate PFPeA Perfluoropentanoic acid PFPiA Perfluorophosphinic acid PFSA Perfluoroalkane sulfonic acid PFTeDA Perfluorotetradecanoic acid PFTrDA Perfluorotridecanoic acid PFUnDA Perfluoroundecanoic acid POP Persistent organic pollutant PTFE Polytetrafluoroethylene S5 QA/QC Quality assurance/quality control REACH European Regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals RoHS Restriction of Hazardous Substances Directive SPE Solid phase extraction SVHC Substances of Very High Concern TBBPA Tetrabromobisphenol A TBOEP Tris(2-butoxyethyl) phosphate TBX 2,3,5,6-Tetrabromoxylene TCEP Tri(2-chloroethyl) phosphate TCIPP Tri(chloroisopropyl) phosphate TDA Toluenediamine TDCIPP Tri(1,3-dichloroisopropyl) phosphate TEP Triethyl phosphate TEHP Tris(2-ethylhexyl) phosphate TMPP Tricresyl phosphate (Tris(methylphenyl) phosphate) TNBP Tri-n-butyl phosphate TOPA Total oxidizable precursor analysis TPHP Triphenyl phosphate S6 Table S2: Chemical structures of some phthalates and DINCH Compound name Acronym CAS no. Structure Dibutyl phthalate DBP 84-74-2 Diisobutyl phthalate DIBP 84-69-5 Benzyl butyl phthalate BzBP 85-68-7 Bis(2- ethylhexyl)phthalate DEHP 117-81-7 Di-n-octyl phthalate DNOP 117-84-0 Diisononyl phthalate DINP* 28553-12-0 and 68515-48-0 1,2-cyclohexane dicarboxylic acid diisononyl ester DINCH* 166412-78-8 * One of many alkyl chain isomers shown. O O O O CH3 CH3 O O O O CH3CH3 CH3 CH3 O O O O CH3 O O CH3 CH3 O O CH3 CH3 O O O O CH3 CH3 O O O O CH3 CH3 CH3 CH3 O O O O CH3 CH3 CH3 CH3 S7 Table S3: Chemical structures of bisphenols A, S and F Compound name Acronym CAS no. Structure Bisphenol A BPA 80-05-7 Bisphenol S BPS 80-09-1 Bisphenol F (4,4-Bisphenol F) BPF 620-92-8 Table S4: Chemical structures of some per- and polyfluoroalkyl substances (PFASs) mentioned in the article Compound name Acronym CAS no. Structure Perfluorohexane sulfonate PFHxS 355-46-4 Perfluorooctane sulfonate PFOS 1763-23-1 Perfluorooctanoic acid PFOA 335-67-1 Perfluorononanoic acid PFNA 375-95-1 Perfluoro-1- octaperfluoro-1-octane sulfonamide FOSA 754-91-6 N-ethylperfluoro-1- octane sulfonamide N-EtFOSA 4151-50-2 CH3 CH3 OHOH S O OHOH O OHOH F F F F F F F F F F S O O O – F F F F F F F F F F F F F F F F F F S O O O – F F O OH F F F F F F F F F F F F F F F O OH F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F S O O F F NH2 F F F F F F F F F F F F F F F S O O F F NH CH3 S8 Table S5: Chemical structures of some halogenated flame retardants (HFRs) mentioned in the article Compound name Acronym CAS no. Structure 2,2’,4,4’-Tetrabromodiphenyl ether BDE-47 5436-43-1 2,2’,4,4’,5,5’- Hexabromodiphenyl ether BDE-153 68631-49-2 Decabromodiphenyl ether BDE-209 1163-19-5 Hexabromocylododecane HBCDD α-HBCDD: 134237-50-6; γ-HBCDD: 134-237-52-8 Tetrabromobisphenol A TBBPA 79-94-7 Bis(2- ethylhexyl)tetrabromophthalate BEH- TEBP 26040-51-7 2-Ethylhexyl-2,3,4,5- tetrabromobenzoate EH-TBB 183658-27-7 Decabromodiphenyl ethane DBDPE 84852-53-9 Dechlorane plus DP; DDC-CO 13560-89-9 O Br BrBr Br O Br BrBr Br Br Br O Br BrBr Br Br Br Br Br Br Br CH3 CH3 OHOH Br BrBr Br O O CH3 CH3 O O CH3 CH3 Br Br Br Br O O CH3 CH3 Br Br Br Br BrBr Br Br Br Br Br Br Br Br S9 Table S6: Chemical structures of some organophosphorous flame retardants (OPFRs) mentioned in the article. The side chains R can differ (R1-R3) for other compounds. General structure Compound name Acronym CAS no. R Tri(2-chloroethyl) phosphate TCEP 115-96-8 CH3 Cl Tri(1-chloroisopropyl) phosphate TCIPP 13674-84-5 CH3 Cl CH3 Tri(1,3-dichloro- isopropyl) phosphate TDCIPP 13674-87-8 CH3 Cl Cl Triphenyl phosphate TPHP 115-86-6 CH3 Tris-n-butyl phosphate TNBP 126-73-8 CH3 CH3 Tris(2-butoxyethyl) phosphate TBOEP 78-51-3 CH3 O CH3 Triscresylphosphate TMPP 1330-78-5 CH3 CH 3 P O O O OR R R S10 Table S7: Chemical structures of some polycyclic aromatic hydrocarbons (PAHs) mentioned in the article Compound name CAS no. Structure Naphthalene 91-20-3 Fluorene 86-73-7 Phenanthrene 85-01-8 Pyrene 129-00-0 Chrysene 218-01-9 Benzo[a]pyrene 50-32-8 Benzo[e]pyrene 192-97-2 Benz[a]anthracene 56-55-3 Benzo[b]fluoranthene 205-99-2 Benzo[j]fluoranthene 205-82-3 Benzo[k]fluoranthene 207-08-9 S11 Dibenzo[a,h]anthracene 53-70-3 S12 Table S8: Chemical structures of some arylamines mentioned in the article Compound name Acronym CAS no. Structure 4,4- Methylenedianiline MDA 101-77-9 4,4-Methylenebis(2- chloroaniline) MOCA 101-14-4 2,4-Toluenediamine 2,4-TDA 95-80-7 CH3 NH2 NH2 2,6-Toluenediamine 2,6-TDA 823-40-5 CH3 NH2NH2 2,5-Toluenediamine 2,5-TDA 95-70-5 CH3 NH2 NH2 1,4-Phenylenediamine 1,4-PDA 106-50-3 NH2 NH2 Aniline - 62-53-3 2-Methylaniline 2-MA 95-53-4 NH2 CH3 4-Methylaniline 4-MA 106-49-0 NH2 CH3 2-Methoxyaniline 2-MeOA 90-04-0 NH2 OCH3 4-Chloroaniline 4-CA 106-47-8 NH2 Cl 3,4-Dichloroaniline 3,4-DCA 95-76-1 NH2 Cl Cl NH2NH2 NH2NH2 ClCl NH2