Modeling 3D-CSIA data

Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene

Journal Article (2017)
Author(s)

Boris Van Breukelen (TU Delft - Sanitary Engineering)

H.A.A. Thouement (TU Delft - Sanitary Engineering)

Philip E. Stack (Scotland's Rural College)

Mindy Vanderford (HydroGeoLogic)

Paul Philp (University of Oklahoma)

Tomasz Kuder (University of Oklahoma)

Research Group
Sanitary Engineering
Copyright
© 2017 B.M. van Breukelen, H.A.A. Thouement, Philip E. Stack, Mindy Vanderford, Paul Philp, Tomasz Kuder
DOI related publication
https://doi.org/10.1016/j.jconhyd.2017.07.003
More Info
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Publication Year
2017
Language
English
Copyright
© 2017 B.M. van Breukelen, H.A.A. Thouement, Philip E. Stack, Mindy Vanderford, Paul Philp, Tomasz Kuder
Research Group
Sanitary Engineering
Volume number
204
Pages (from-to)
79-89
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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 CCl 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.