| Publikationstyp: | Beitrag in wissenschaftlicher Zeitschrift |
| Art der Begutachtung: | Peer review (Abstract) |
| Titel: | Transformation of chlorinated paraffins to olefins during metal work and thermal exposure : deconvolution of mass spectra and kinetics |
| Autor/-in: | 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 |
| Erschienen in: | Chemosphere |
| Band(Heft): | 194 |
| Seite(n): | 803 |
| Seiten bis: | 811 |
| Erscheinungsdatum: | 2018 |
| Verlag / Hrsg. Institution: | Elsevier |
| ISSN: | 0045-6535 1879-1298 |
| Sprache: | Englisch |
| Schlagwörter: | 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 |
| Fachgebiet (DDC): | 660: Technische Chemie |
| Zusammenfassung: | 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 |
| Volltext Version: | Publizierte Version |
| Lizenz (gemäss Verlagsvertrag): | Lizenz gemäss Verlagsvertrag |
| Departement: | Life Sciences und Facility Management |
| Organisationseinheit: | Institut für Chemie und Biotechnologie (ICBT) |
| Enthalten in den Sammlungen: | 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.
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