Accounting for the decreasing reaction potential of heterogeneous aquifers in a stochastic framework of aquifer-scale reactive transport

Many groundwater contaminants react with components of the aquifer matrix, causing a depletion of the aquifer's reactivity with time. We discuss conceptual simplifications of reactive transport that allow the implementation of a decreasing reaction potential in reactive-transport simulations in chemically and hydraulically heterogeneous aquifers without relying on a fully explicit description. We replace spatial coordinates by travel-times and use the concept of relative reactivity, which represents the reaction-partner supply from the matrix relative to a reference. Microorganisms facilitating the reactions are not explicitly modeled. Solute mixing is neglected. Streamlines, obtained by particle tracking, are discretized in travel-time increments with variable content of reaction partners in the matrix. As exemplary reactive system, we consider aerobic respiration and denitrification with simplified reaction equations: Dissolved oxygen undergoes conditional zero-order decay, nitrate follows first-order decay, which is inhibited in the presence of dissolved oxygen. Both reactions deplete the bioavailable organic carbon of the matrix, which in turn determines the relative reactivity. These simplifications reduce the computational effort, facilitating stochastic simulations of reactive transport on the aquifer scale. In a one-dimensional test case with a more detailed description of the reactions, we derive a potential relationship between the bioavailable organic-carbon content and the relative reactivity. In a three-dimensional steady-state test case, we use the simplified model to calculate the decreasing denitrification potential of an artificial aquifer over 200 years in an ensemble of 200 members. We demonstrate that the uncertainty in predicting the nitrate breakthrough in a heterogeneous aquifer decreases with increasing scale of observation

An Electron‐Balance Based Approach to Predict the Decreasing Denitrification Potential of an Aquifer

Numerical models for reactive transport can be used to estimate the breakthrough of a contaminant in a pumping well or at other receptors. However, as natural aquifers are highly heterogeneous with unknown spatial details, reactive transport predictions on the aquifer scale require a stochastic framework for uncertainty analysis. The high computational demand of spatially explicit reactive-transport models hampers such analysis, thus motivating the search for simplified estimation tools. We suggest performing an electron balance between the reactants in the infiltrating solution and in the aquifer matrix to obtain the hypothetical time of dissolved-reactant breakthrough at a receptor if the reaction with the matrix was instantaneous. This time we denote as the advective breakthrough time for instantaneous reaction (τ inst ). It depends on the amount of the reaction partner present in the matrix, the mass flux of the dissolved reactant, and the stoichiometry. While the shape of the reactive-species breakthrough curve depends on various kinetic parameters, the overall timing scales with τ inst . We calculate the latter by particle tracking. The effort of computing τ inst is so low that stochastic calculations become feasible. We apply the concept to a two-dimensional test case of aerobic respiration and denitrification. A detailed spatially explicit reactive-transport model includes microbial dynamics. Scaling the time of local breakthrough curves observed at individual points by τ inst decreased the variability of electron-donor breakthrough curves significantly. We conclude that the advective breakthrough time for instantaneous reaction is efficient in estimating the time over which an aquifer retains its degradation potential

Adsorption as a cause for iron isotope fractionation in reduced groundwater

Iron isotopes were used to investigate iron transformation processes during an in situ field experiment for removal of dissolved Fe from reduced groundwater. This experiment provided a unique setting for exploring Fe isotope fractionation in a natural system. Oxygen-containing water was injected at a test well into an aquifer containing Fe(II)-rich reduced water, leading to oxidation of Fe(II) and precipitation of Fe(III)(hydr)oxides. Subsequently, groundwater was extracted from the same well over a time period much longer than the injection time. Since the surrounding water is rich in Fe(II), the Fe(II) concentration in the extracted water increased over time. The increase was strongly retarded in comparison to a conservative tracer added to the injected solution, indicating that adsorption of Fe(II) onto the newly formed Fe(III)(hydr)oxides occurred. A series of injection-extraction (push-pull) cycles were performed at the same well. The δ57Fe/54Fe of pre-experiment background groundwater (-0.57 ± 0.17 ‰) was lighter than the sediment leach of Fe(III) (-0.24 ± 0.08 ‰), probably due to slight fractionation (only ∼0.3 ‰) during microbial mediated reductive dissolution of Fe(III)(hydr)oxides present in the aquifer. During the experiment, Fe(II) was adsorbed from native groundwater drawn into the oxidized zone and onto Fe(III)(hydr)oxides producing a very light groundwater component with δ57Fe/54Fe as low as -4 ‰, indicating that heavier Fe(II) is preferentially adsorbed to the newly formed Fe(III)(hydr)oxides surfaces. Iron concentrations increased with time of extraction, and δ57Fe/54Fe linearly correlated with Fe concentrations (R2 = 0.95). This pattern was reproducible over five individual cycles, indicating that the same process occurs during repeated injection/extraction cycles. We present a reactive transport model to explain the observed abiotic fractionation due to adsorption of Fe(II) on Fe(III)(hydr)oxides. The fractionation is probably caused by isotopic differences in the equilibrium sorption constants of the various isotopes (Kads) and not by sorption kinetics. A fractionation factor α57/54 of 1.001 fits the observed fractionation. Copyright © 2005 Elsevier Ltd

Efficient calibration of a distributed pde-based hydrological model using grid coarsening

Partial-differential-equation based integrated hydrological models are now regularly used at catchment scale. They rely on the shallow water equations for surface flow and on the Richards' equations for subsurface flow, allowing a spatially explicit representation of properties and states. However, these models usually come at high computational costs, which limit their accessibility to state-of-the-art methods of parameter estimation and uncertainty quantification, because these methods require a large number of model evaluations. In this study, we present an efficient model calibration strategy, based on a hierarchy of grid resolutions, each of them resolving the same zonation of subsurface and land-surface units. We first analyze which model outputs show the highest similarities between the original model and two differently coarsened grids. Then we calibrate the coarser models by comparing these similar outputs to the measurements. We finish the calibration using the fully resolved model, taking the result of the preliminary calibration as starting point. We apply the proposed approach to the well monitored Lerma catchment in North-East Spain, using the model HydroGeoSphere. The original model grid w ith 80,000 finite elements was complemented with two other model variants with approximately 16,000 and 10,000 elements, respectively. Comparing the model results for these different grids, we observe differences in peak discharge, evapotranspiration, and near-surface saturation. Hydraulic heads and low flow, however, are very similar for all tested parameter sets, which allows the use of these variables to calibrate our model. The calibration results are satisfactory and the duration of the calibration has been greatly decreased by using different model grid resolutions