Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics

Schinkel, Lena; Lehner, Sandro; Knobloch, Marco; Lienemann, Peter; Bogdal, Christian; McNeill, Kristopher; Heeb, Norbert V.

doi:10.1016/j.chemosphere.2017.11.168

Publication type:	Article in scientific journal
Type of review:	Peer review (abstract)
Title:	Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics
Authors:	Schinkel, Lena Lehner, Sandro Knobloch, Marco Lienemann, Peter Bogdal, Christian McNeill, Kristopher Heeb, Norbert V.
et. al:	No
DOI:	10.1016/j.chemosphere.2017.11.168
Published in:	Chemosphere
Volume(Issue):	194
Page(s):	803
Pages to:	811
Issue Date:	2018
Publisher / Ed. Institution:	Elsevier
ISSN:	0045-6535 1879-1298
Language:	English
Subjects:	Chlorinated olefins; Chlorinated paraffins; Deconvolution of mass spectra; First-order kinetics; Thermal transformation product; Alkenes; Environmental monitoring; Hot temperature; Hydrocarbons, Chlorinated; Kinetics; Mass spectrometry; Metallurgy; Paraffin
Subject (DDC):	660: Chemical engineering
Abstract:	Chlorinated paraffins (CPs) are high production volume chemicals widely used as additives in metal working fluids. Thereby, CPs are exposed to hot metal surfaces which may induce degradation processes. We hypothesized that the elimination of hydrochloric acid would transform CPs into chlorinated olefins (COs). Mass spectrometry is widely used to detect CPs, mostly in the selected ion monitoring mode (SIM) evaluating 2-3 ions at mass resolutions R < 20'000. This approach is not suited to detected COs, because their mass spectra strongly overlap with CPs. We applied a mathematical deconvolution method based on full-scan MS data to separate interfered CP/CO spectra. Metal drilling indeed induced HCl-losses. CO proportions in exposed mixtures of chlorotridecanes increased. Thermal exposure of chlorotridecanes at 160, 180, 200 and 220 °C also induced dehydrohalogenation reactions and CO proportions also increased. Deconvolution of respective mass spectra is needed to study the CP transformation kinetics without bias from CO interferences. Apparent first-order rate constants (kapp) increased up to 0.17, 0.29 and 0.46 h-1 for penta-, hexa- and heptachloro-tridecanes exposed at 220 °C. Respective half-life times (τ1/2) decreased from 4.0 to 2.4 and 1.5 h. Thus, higher chlorinated paraffins degrade faster than lower chlorinated ones. In conclusion, exposure of CPs during metal drilling and thermal treatment induced HCl losses and CO formation. It is expected that CPs and COs are co-released from such processes. Full-scan mass spectra and subsequent deconvolution of interfered signals is a promising approach to tackle the CP/CO problem, in case of insufficient mass resolution.
URI:	https://digitalcollection.zhaw.ch/handle/11475/28260
Fulltext version:	Published version
License (according to publishing contract):	Licence according to publishing contract
Departement:	Life Sciences and Facility Management
Organisational Unit:	Institute of Chemistry and Biotechnology (ICBT)
Appears in collections:	Publikationen Life Sciences und Facility Management

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Schinkel, L., Lehner, S., Knobloch, M., Lienemann, P., Bogdal, C., McNeill, K., & Heeb, N. V. (2018). Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics. Chemosphere, 194, 803–811. https://doi.org/10.1016/j.chemosphere.2017.11.168

Schinkel, L. et al. (2018) ‘Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics’, Chemosphere, 194, pp. 803–811. Available at: https://doi.org/10.1016/j.chemosphere.2017.11.168.

L. Schinkel et al., “Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics,” Chemosphere, vol. 194, pp. 803–811, 2018, doi: 10.1016/j.chemosphere.2017.11.168.

SCHINKEL, Lena, Sandro LEHNER, Marco KNOBLOCH, Peter LIENEMANN, Christian BOGDAL, Kristopher MCNEILL und Norbert V. HEEB, 2018. Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics. Chemosphere. 2018. Bd. 194, S. 803–811. DOI 10.1016/j.chemosphere.2017.11.168

Schinkel, Lena, Sandro Lehner, Marco Knobloch, Peter Lienemann, Christian Bogdal, Kristopher McNeill, and Norbert V. Heeb. 2018. “Transformation of Chlorinated Paraffins to Olefins during Metal Work and Thermal Exposure : Deconvolution of Mass Spectra and Kinetics.” Chemosphere 194: 803–11. https://doi.org/10.1016/j.chemosphere.2017.11.168.

Schinkel, Lena, et al. “Transformation of Chlorinated Paraffins to Olefins during Metal Work and Thermal Exposure : Deconvolution of Mass Spectra and Kinetics.” Chemosphere, vol. 194, 2018, pp. 803–11, https://doi.org/10.1016/j.chemosphere.2017.11.168.