PMID- 34798110
OWN - NLM
STAT- MEDLINE
DCOM- 20220126
LR  - 20220126
IS  - 1879-1298 (Electronic)
IS  - 0045-6535 (Linking)
VI  - 291
IP  - Pt 2
DP  - 2022 Mar
TI  - Chemical synthesis and characterization of single-chain C(18)-chloroparaffin 
      materials with defined degrees of chlorination.
PG  - 132938
LID - S0045-6535(21)03410-X [pii]
LID - 10.1016/j.chemosphere.2021.132938 [doi]
AB  - Technical chlorinated paraffins (CPs) are produced via radical chlorination of 
      n-alkane feedstocks with different carbon chain-lengths ( approximately C(10)-C(30)). 
      Short-chain CPs (SCCPs, C(10)-C(13)) are classified as persistent organic 
      pollutants (POPs) under the Stockholm Convention. This regulation has induced a 
      shift to use longer-chain CPs as substitutes. Consequently, medium-chain (MCCPs, 
      C(14)-C(17)) and long-chain (LCCPs, C(>)(17)) CPs have become dominant homologues 
      in recent environmental samples. However, no suitable LCCP-standard materials are 
      available. Herein, we report on the chemical synthesis of single-chain 
      C(18)-CP-materials, starting with a pure n-alkane and sulfuryl chloride 
      (SO(2)Cl(2)). Fractionation of the crude product by normal-phase 
      liquid-chromatography and pooling of suitable fractions yielded in four 
      C(18)-CP-materials with different chlorination degrees (m(Cl,EA) = 39-52%). In 
      addition, polar side-products, tentatively identified as sulfite-, sulfate- and 
      bis-sulfate-diesters, were separated from CPs. The new single-chain materials 
      were characterized by LC-MS, (1)H-NMR and EA. LC-MS provided Relative retention 
      times for different C(18)-CP homologues and side-products. Mathematical 
      deconvolution of full-scan mass spectra revealed the presence of chloroparaffins 
      (57-93%) and chloroolefins (COs, 7-26%) in the four single-chain 
      C(18)-CP-materials. Homologue distributions and chlorination degrees were deduced 
      for CPs and COs. (1)H-NMR revealed chemical shift ranges of mono-chlorinated 
      (delta = 3.2-5.3 ppm) and non-chlorinated (delta = 1.0-3.2 ppm) hydrocarbon moieties. The 
      synthesized C(18)-single-chain standard materials and respective spectroscopic 
      data are useful to identify and quantify LCCPs in various materials and 
      environmental samples. CP- and CO-distributions resemble the ones of existing 
      SCCP and MCCP reference materials and technical mixtures. Furthermore, these 
      materials now allow specific studies on the environmental fate and the 
      transformation of long-chain chloroparaffins and chloroolefins.
CI  - Copyright (c) 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.
FAU - Knobloch, Marco C
AU  - Knobloch MC
AD  - Laboratory for Advanced Analytical Technologies, Swiss Federal Institute for 
      Materials Science and Technology Empa, Uberlandstrasse 129, 8600, Dubendorf, 
      Switzerland; Department of Chemistry, University of Zurich, Winterthurerstrasse 
      190, 8057, Zurich, Switzerland. Electronic address: marco.knobloch@empa.ch.
FAU - Sprengel, Jannik
AU  - Sprengel J
AD  - University of Hohenheim, Institute of Food Chemistry (170b), Garbenstrasse 28, 
      70599, Stuttgart, Germany.
FAU - Mathis, Flurin
AU  - Mathis F
AD  - Laboratory for Advanced Analytical Technologies, Swiss Federal Institute for 
      Materials Science and Technology Empa, Uberlandstrasse 129, 8600, Dubendorf, 
      Switzerland; Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 
      8820, Wadenswil, Switzerland.
FAU - Haag, Regula
AU  - Haag R
AD  - Laboratory for Advanced Analytical Technologies, Swiss Federal Institute for 
      Materials Science and Technology Empa, Uberlandstrasse 129, 8600, Dubendorf, 
      Switzerland.
FAU - Kern, Susanne
AU  - Kern S
AD  - Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, 
      Wadenswil, Switzerland.
FAU - Bleiner, Davide
AU  - Bleiner D
AD  - Laboratory for Advanced Analytical Technologies, Swiss Federal Institute for 
      Materials Science and Technology Empa, Uberlandstrasse 129, 8600, Dubendorf, 
      Switzerland; Department of Chemistry, University of Zurich, Winterthurerstrasse 
      190, 8057, Zurich, Switzerland.
FAU - Vetter, Walter
AU  - Vetter W
AD  - University of Hohenheim, Institute of Food Chemistry (170b), Garbenstrasse 28, 
      70599, Stuttgart, Germany.
FAU - Heeb, Norbert V
AU  - Heeb NV
AD  - Laboratory for Advanced Analytical Technologies, Swiss Federal Institute for 
      Materials Science and Technology Empa, Uberlandstrasse 129, 8600, Dubendorf, 
      Switzerland.
LA  - eng
PT  - Journal Article
DEP - 20211116
PL  - England
TA  - Chemosphere
JT  - Chemosphere
JID - 0320657
RN  - 0 (Hydrocarbons, Chlorinated)
RN  - 8002-74-2 (Paraffin)
SB  - IM
MH  - China
MH  - Environmental Monitoring
MH  - Halogenation
MH  - *Hydrocarbons, Chlorinated/analysis
MH  - Mass Spectrometry
MH  - Paraffin/analysis
OTO - NOTNLM
OT  - Chlorinated olefins (COs)
OT  - Chlorinated paraffins (CPs)
OT  - Long-chain chlorinated paraffins (LCCPs)
OT  - Single-chain CPs
OT  - Standard materials
EDAT- 2021/11/20 06:00
MHDA- 2022/01/27 06:00
CRDT- 2021/11/19 20:15
PHST- 2021/06/25 00:00 [received]
PHST- 2021/11/10 00:00 [revised]
PHST- 2021/11/14 00:00 [accepted]
PHST- 2021/11/20 06:00 [pubmed]
PHST- 2022/01/27 06:00 [medline]
PHST- 2021/11/19 20:15 [entrez]
AID - S0045-6535(21)03410-X [pii]
AID - 10.1016/j.chemosphere.2021.132938 [doi]
PST - ppublish
SO  - Chemosphere. 2022 Mar;291(Pt 2):132938. doi: 10.1016/j.chemosphere.2021.132938. 
      Epub 2021 Nov 16.