title: Analytical transport modelling of metabolites formed in dual-porosity media.
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 (λprod= 1.51 ± 0.08 h-1), retardation factor (Rim= 2.94 ± 0.45) and first-order irreversible sorption rate (Kim= 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.
authors.affiliation: Institute of Groundwater Ecology, Helmholtz Zentrum München, German Research Center for Environmental Health (GmbH), Ingolstaedter Landstr. 1, 85764, Neuherberg, Germany.
authors.forename: Bastian
authors.initials: B
authors.lastname: Knorr
authors.affiliation: Department of Hydrogeology and Engineering Geology, AGH University of Science and Technology Cracow, Al. Mickiewicza 30, 30-059, Cracow, Poland.
authors.forename: Piotr
authors.initials: P
authors.lastname: Maloszewski
authors.affiliation: Institute of Groundwater Ecology, Helmholtz Zentrum München, German Research Center for Environmental Health (GmbH), Ingolstaedter Landstr. 1, 85764, Neuherberg, Germany. christine.stumpp@helmholtz-muenchen.de.
authors.forename: Christine
authors.initials: C
authors.lastname: Stumpp
mesh_terms: D004058:Diffusion; D008956:Models, Chemical; D016062:Porosity
keywords: Analytical modelling; Dual-porosity column experiment; Immobile water; Matrix diffusion; Metabolite; Nitroaromatic compounds; Reactive solute transport; Transformation