PMID- 37480948 OWN - NLM STAT- MEDLINE DCOM- 20230809 LR - 20230809 IS - 1879-1298 (Electronic) IS - 0045-6535 (Linking) VI - 338 DP - 2023 Oct TI - Fingerprinting of chlorinated paraffins and their transformation products in plastic consumer products. PG - 139552 LID - S0045-6535(23)01819-2 [pii] LID - 10.1016/j.chemosphere.2023.139552 [doi] AB - Chlorinated paraffins (CPs) can be classified according to their length as short-chain (SC, C(10)-C(13)), medium-chain (MC, C(14)-C(17)) and long-chain (LC, C (>/= 18)) CPs. Technical CP-mixtures can contain a wide range of carbon- (C-, n(C) = 10-30) and chlorine- (Cl-, n(Cl) = 3-19) homologues. CPs are high-production volume chemicals (>10(6) t/y). They are used as flame-retardants, plasticizers and coolant fluids. Due to the persistence, bioaccumulation, long-range environmental transport potential and adverse effects, SCCPs are regulated as persistent organic pollutants (POPs) by the Stockholm Convention. Transformation of CPs can lead to the formation of unsaturated compounds such as chlorinated mono- (CO), di- (CdiO) and tri-olefins (CtriO). Such transformation reactions can occur at different stages of CP manipulation providing characteristic C-/Cl-homologue distributions. All this results in unique patterns that collectively create a fingerprint, which can be distinguished from CP-containing samples. Therefore, CP-fingerprinting can develop into a promising tool for future source apportionment studies and with it, the reduction of environmental burden of CPs and hazards to humans. Herein, CP-containing plastics were studied to establish fingerprints and develop this method. We analyzed four household items by reverse-phase liquid-chromatography coupled with a mass spectrometer with an atmospheric pressure chemical ionization source and an Orbitrap mass analyzer (RP-LC-APCI-Orbitrap-MS) operated at a resolution of 120000 (FWHM at m/z 200). MS-data of different CP-, CO-, CdiO- and CtriO-homologues were efficiently processed with an R-based automatic mass spectra evaluation routine (RASER). From the 16720 ions searched for, up to 4300 ions per sample were assigned to 340 C-/Cl-homologues of CPs and their transformation products. Specific fingerprints were deduced from the C-/Cl-homologues distributions, the carbon- (n(C)) and chlorine- (n(Cl)) numbers and saturation degree. These fingerprints were compared with the ones obtained by a GC-ECNI-Orbitrap-MS method. CI - Copyright (c) 2023 The Authors. Published by Elsevier Ltd.. All rights reserved. FAU - Mendo Diaz, O AU - Mendo Diaz O AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland; Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland. Electronic address: Oscar.mendodiaz@empa.ch. FAU - Tell, A AU - Tell A AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland; Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, Wadenswil, Switzerland. FAU - Knobloch, M AU - Knobloch M AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland; Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Canonica, E AU - Canonica E AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland; Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, Wadenswil, Switzerland. FAU - Walder, C AU - Walder C AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland. FAU - Buser, A M AU - Buser AM AD - Swiss Federal Office for the Environment, Monbijoustrasse 40, 3003, Bern, Switzerland. FAU - Stalder, U AU - Stalder U AD - Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Bigler, L AU - Bigler L AD - Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Kern, S AU - Kern S AD - Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, Wadenswil, Switzerland. FAU - Bleiner, D AU - Bleiner D AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland; Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Heeb, N V AU - Heeb NV AD - Swiss Federal Laboratories for Materials Science and Technology Empa, Uberlandstrasse 129, 8600 Dubendorf, Switzerland. LA - eng PT - Journal Article DEP - 20230720 PL - England TA - Chemosphere JT - Chemosphere JID - 0320657 RN - 0 (Hydrocarbons, Chlorinated) RN - 4R7X1O2820 (Chlorine) RN - 8002-74-2 (Paraffin) RN - 0 (Plastics) SB - IM MH - Humans MH - *Hydrocarbons, Chlorinated/analysis MH - Chlorine/analysis MH - Paraffin/analysis MH - Plastics MH - Environmental Monitoring/methods MH - China OTO - NOTNLM OT - Fingerprinting of plastic materials OT - Homologue pattern OT - Persistent organic pollutants (POPs) OT - R-based automatic spectra evaluation routine (RASER) OT - Short-chained chlorinated paraffins (SCCPs) COIS- Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2023/07/23 01:11 MHDA- 2023/08/09 06:43 CRDT- 2023/07/22 19:21 PHST- 2023/01/18 00:00 [received] PHST- 2023/07/14 00:00 [revised] PHST- 2023/07/16 00:00 [accepted] PHST- 2023/08/09 06:43 [medline] PHST- 2023/07/23 01:11 [pubmed] PHST- 2023/07/22 19:21 [entrez] AID - S0045-6535(23)01819-2 [pii] AID - 10.1016/j.chemosphere.2023.139552 [doi] PST - ppublish SO - Chemosphere. 2023 Oct;338:139552. doi: 10.1016/j.chemosphere.2023.139552. Epub 2023 Jul 20.