A general description of the mathematical and numerical formulations used in modern numerical reactive transport codes relevant for subsurface environmental simulations is presented. The formulations are followed by short descriptions of commonly used and available subsurface simulators that consider continuum representations of flow, transport, and reactions in porous media. These formulations are applicable to most of the subsurface environmental benchmark problems included in this special issue. The list of codes described briefly here includes PHREEQC, HPx, PHT3D, OpenGeoSys (OGS), HYTEC, ORCHESTRA, TOUGHREACT, eSTOMP, HYDROGEOCHEM, CrunchFlow, MIN3P, and PFLOTRAN. The descriptions include a C. I. Steefel ( ) · B. Arora · S. Molins · N. Spycher

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Model simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO 2 partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe ?2 and S-2 oxidation) to match locally-observed high CO 2 concentrations above reduced zones. Observed seasonal variations in CO 2 concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m-2 d-1 , while including water table variations resulted in an overall decrease in the simulated fluxes. We conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations. Keywords Flood plain Á Reduced zones Á Subsurface carbon dynamics Á Temporal variability Á Biogeochemical processes

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplain aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.

To understand how redox processes influence carbon, nitrogen, and iron cycling within the intrameander hyporheic zone, we developed a biotic and abiotic reaction network and incorporated it into the reactive transport simulator PFLOTRAN. Two‐dimensional reactive flow and transport simulations were performed (1) to evaluate how transient hydrological conditions control the lateral redox zonation within an intrameander region of the East River in Colorado and (2) to quantify the impact of a single meander on subsurface exports of carbon and other geochemical species to the river. The meander's overall contribution to the river was quantified by integrating geochemical outfluxes along the outside of the meander bend. The model was able to capture the field‐observed trends of dissolved oxygen, nitrate, iron, pH, and total inorganic carbon along a 2‐D transect. Consistent with field observations, simulated dissolved oxygen and nitrate decreased along the intrameander flow paths while iron (Fe2+) concentration increased. The simulation results further demonstrated that the reductive potential of the lateral redox zonation was controlled by groundwater velocities resulting from river stage fluctuations, with low‐water conditions promoting reducing conditions. The sensitivity analysis results showed that permeability had a more significant impact on biogeochemical zonation compared to the reaction pathways under transient hydrologic conditions. The simulation results further indicated that the meander acted as a sink for organic and inorganic carbon as well as iron during the extended baseflow and high‐water conditions; however, these geochemical species were released into the river during the falling limb of the hydrograph.

Soil and crop management practices have been found to modify soil structure and alter macropore densities. An ability to accurately determine soil hydraulic parameters and their variation with changes in macropore density is crucial for assessing potential contamination from agricultural chemicals. This study investigates the consequences of using consistent matrix and macropore parameters in simulating preferential flow and bromide transport in soil columns with different macropore densities (no macropore, single macropore, and multiple macropores). As used herein, the term“macropore density” is intended to refer to the number of macropores per unit area. A comparison between continuum-scale models including single-porosity model (SPM), mobile-immobile model (MIM), and dual-permeability model (DPM) that employed these parameters is also conducted. Domain-specific parameters are obtained from inverse modeling of homogeneous (no macropore) and central macropore columns in a deterministic framework and are validated using forward modeling of both low-density (3 macropores) and high-density (19 macropores) multiple-macropore columns. Results indicate that these inversely modeled parameters are successful in describing preferential flow but not tracer transport in both multiple-macropore columns. We believe that lateral exchange between matrix and macropore domains needs better accounting to efficiently simulate preferential transport in the case of dense, closely spaced macropores. Increasing model complexity from SPM to MIM to DPM also improved predictions of preferential flow in the multiple-macropore columns but not in the single-macropore column. This suggests that the use of a more complex model with resolved domain-specific parameters is recommended with an increase in macropore density to generate forecasts with higher accuracy.