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Analytical transport modelling of metabolites formed in dual-porosity media

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Abstract

Contaminants like nitroaromatic compounds can be degraded in the subsurface to similar or even more toxic metabolites. Degradation or transformation rates are dependent on physical, chemical and biological properties which can be different in sedimentological layers or other heterogeneous structures of aquifers. Sediments with low hydraulic conductivity can even consist of immobile water. These regions are only accessible by diffusion. Most modelling approaches accounting for immobile water regions focused on the mathematical description of the transport and decay of the parent compound. The objective of this study was to develop an analytical model to quantify the transport and formation of a metabolite in dual-porosity media describing the exchange between mobile and immobile water regions based on the metabolite’s diffusion coefficient. Column experiments with a well-defined immobile water region were performed under anoxic conditions at three different water flow velocities. The model compound 4-Cl-nitrobenzene was reduced to 4-Cl-aniline (4-Cl-An) by surface-bound Fe (II) species within the immobile water region. Transport and formation of the metabolite were quantified with a modified solution of the single fissure dispersion model assuming additionally for the region with immobile water first-order metabolite production, irreversible sorption and an instantaneous equilibrium sorption. The number of unknown fitting parameters was reduced to two (sorption rate and retardation factor) by stepwise parameter estimation using tracer and parent compound data. Experimental results of the metabolite for each water flow velocity were successfully described with a first-order production term (λ prod = 1.51 ± 0.08 h−1), retardation factor (R im = 2.94 ± 0.45) and first-order irreversible sorption rate (K im = 0.39 ± 0.16 h−1) within the immobile water region. Model results supported that 4-Cl-An was formed within the immobile water region. 4-Cl-An sorbed instantaneously onto the clay matrix while a fraction was irreversibly sorbed. Experimental results and the provided analytical solution help to improve the understanding about reactive transport and the formation of metabolites in dual-porosity media.

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Acknowledgements

This work was funded by the Helmholtz WasserZentrum München which is part of the SolFlux Platform of the Helmholtz Water Network. Partial support of this work through the BMBF project “PERSIST” (02WU1349; JPI Water) is kindly acknowledged.

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Authors and Affiliations

  1. Institute of Groundwater Ecology, Helmholtz Zentrum München, German Research Center for Environmental Health (GmbH), Ingolstaedter Landstr. 1, 85764, Neuherberg, Germany

    Bastian Knorr & Christine Stumpp

  2. Department of Hydrogeology and Engineering Geology, AGH University of Science and Technology Cracow, Al. Mickiewicza 30, 30-059, Cracow, Poland

    Piotr Maloszewski

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  1. Bastian Knorr
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  2. Piotr Maloszewski
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  3. Christine Stumpp
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Correspondence to Christine Stumpp.

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Responsible editor: Marcus Schulz

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Knorr, B., Maloszewski, P. & Stumpp, C. Analytical transport modelling of metabolites formed in dual-porosity media. Environ Sci Pollut Res 24, 4447–4456 (2017). https://doi.org/10.1007/s11356-016-8115-x

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  • DOI: https://doi.org/10.1007/s11356-016-8115-x

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