Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene

Boris M Van Breukelen*, Héloïse A.A. Thouement, Philip E Stack, Mindy Vanderford, Paul Philp, Tomasz Kuder

*Corresponding author for this work

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular C–Cl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.

Original languageEnglish
Pages (from-to)79-89
Number of pages11
JournalJournal of Contaminant Hydrology
Volume204
Early online date17 Jul 2017
DOIs
Publication statusPrint publication - Sep 2017

Fingerprint

chlorine isotope
Dechlorination
hydrogen isotope
Chlorine
dechlorination
Fractionation
trichloroethylene
Isotopes
ethylene
carbon isotope
Hydrogen
Carbon
fractionation
isotope
modeling
kinetics
Kinetics
Vinyl Chloride
data analysis
reactive transport

Keywords

  • Chlorinated ethenes
  • Contaminated sites
  • Natural attenuation
  • Reactive transport modeling
  • Reductive dechlorination
  • Stable isotopes

Cite this

Van Breukelen, Boris M ; Thouement, Héloïse A.A. ; Stack, Philip E ; Vanderford, Mindy ; Philp, Paul ; Kuder, Tomasz. / Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene. In: Journal of Contaminant Hydrology. 2017 ; Vol. 204. pp. 79-89.
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Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene. / Van Breukelen, Boris M; Thouement, Héloïse A.A.; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz.

In: Journal of Contaminant Hydrology, Vol. 204, 09.2017, p. 79-89.

Research output: Contribution to journalArticle

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T1 - Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene

AU - Van Breukelen, Boris M

AU - Thouement, Héloïse A.A.

AU - Stack, Philip E

AU - Vanderford, Mindy

AU - Philp, Paul

AU - Kuder, Tomasz

PY - 2017/9

Y1 - 2017/9

N2 - Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular C–Cl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.

AB - Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular C–Cl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.

KW - Chlorinated ethenes

KW - Contaminated sites

KW - Natural attenuation

KW - Reactive transport modeling

KW - Reductive dechlorination

KW - Stable isotopes

U2 - 10.1016/j.jconhyd.2017.07.003

DO - 10.1016/j.jconhyd.2017.07.003

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VL - 204

SP - 79

EP - 89

JO - Journal of Contaminant Hydrology

JF - Journal of Contaminant Hydrology

SN - 0169-7722

ER -