The disposal of spent nuclear fuel and high-level radioactive waste in the subsurface represents one of the greatest challenges for the geosciences. Most disposal strategies rely on a multiple barrier system, consisting of both natural and engineered materials, to prevent or delay the contact of groundwater with the waste and radionuclide release to the environment. Reactive transport models have been central to understanding and assessing how thermal, hydrological, and geochemical processes are coupled in these containment barriers, which are expected to experience a range of temperatures and geochemical conditions, yet, must maintain their integrity for millions of years.

We have investigated the hydrothermal alteration of polished wafers of tuff reacted with dilute groundwater at 90 °C, 150 °C and 250 °C for time periods ranging from 2 months to nearly 1 year. The polished rock wafer provided a convenient surface upon which to grow secondary minerals. Reaction product minerals were identified and analyzed at the end of each experiment and, along with the evolving fluid chemistry, were compared to computational results from corresponding reaction progress models. At 250 °C after a few months the run products in the experiment were dominantly the mordenite group zeolite minerals: dachiardite (a Ca-rich variety) and mordenite, itself. At 150 °C after a few months of reaction only minor amounts of clay were produced, but after 1 year of reaction at this temperature both mordenite group zeolites were again present. At this lower temperature the total amount of run products was much smaller. At 90 °C no run products could be seen at all, even after 1 year of reaction. The reaction progress modeling results for reaction products were in good relative agreement with the experimental results. The higher the temperature, and the greater the extent of reaction, the better the fluid phase modeling results agreed with the actual experimental results. At 250 °C the agreement was good for nearly all elements. At 150 °C agreement for pH, SiO2, Na and K were good, but less good for Al, Mg and Ca, especially after short reaction times. At 90 °C agreement for pH, SiO2 and Na was reasonable, but not as good for the other elements, and all modeling results for short reaction times did not match experimental results as well as the longer time results. This study demonstrates that reaction progress modeling provides a powerful tool for predicting hydrothermal rock-water interactions, with results expected to improve, as more and better quality thermodynamic and kinetic data become available and as process-oriented simulators incorporate better and more comprehensive sub-models for mineral dissolution and growth.

A non-electrostatic generalized composite surface complexation model (SCM) was developed for U(VI) sorption on contaminated F-Area sediments from the U.S. Department of Energy Savannah River Site, South Carolina. The objective of this study was to test if a simpler, semi-empirical, non-electrostatic U(VI) sorption model (NEM) could achieve the same predictive performance as a SCM with electrostatic correction terms in describing U(VI) plume evolution and long-term mobility. One-dimensional reactive transport simulations considering key hydrodynamic processes, Al and Fe minerals, as well as H⁺ and U surface complexation, with and without electrostatic correction terms, were conducted. The NEM was first calibrated with laboratory batch H⁺ and U(VI) sorption data on F-Area sediments, and then the surface area of the NEM was adjusted to match field observations of dissolved U(VI). Modeling results indicate that the calibrated NEM was able to perform as well as the previously developed electrostatic model in predicting the long-term evolution of H⁺ and U(VI) at the site, given the variability of field-site data. The electrostatic and NEM models yield somewhat different results for the time period when basin discharge was active; however, it is not clear which modeling approach may be better to model this early time period because groundwater quality data during this period were not available. A key finding of this study is that the applicability of NEM (and thus robustness of its predictions) to the field system evolves with time and is strongly dependent on the pH range that was used to develop the model.

A demonstration project for the geological storage of CO2 is currently being considered in the deep Precipice Sandstone formation of the Surat Basin, Queensland, Australia. Because of the presence of potential fresh water resources in this formation, a reservoir-scale two-dimensional reactive-transport model was developed to assess temporal and spatial changes in water quality imposed by co-injecting CO2 with SO2, NO2, and O2 at this location. The model shows that because the injection rate is relatively low (60,000 tons/year), flow is buoyancy-dominated and under these conditions the predicted CO2 flow pattern is quite sensitive to fine-scale heterogeneities and the resolution of the numerical mesh. The model also shows that SO2 and NO2 readily partition into the aqueous phase in close vicinity of their injection point, lowering pH somewhat beyond the acidification from CO2 dissolution. Only O2 under redox disequilibrium conditions is modeled to persist in the CO2 plume away from the injection point, however at sub-ppm levels. This modeling effort demonstrates acidification near the wellbore due to the preferential stripping of gas impurities, and accumulation of CO2 around a lithostratigraphic boundary above the target formation, where relatively rapid mineral dissolution (muscovite, chlorite and calcite) and precipitation (ankerite, kaolinite and chalcedony) occur.

Agricultural managed aquifer recharge (AgMAR) is a strategy whereby surface water is used to intentionally flood croplands to recharge underlying aquifers. However, nitrate (NO3−) contamination in agriculturally intensive regions poses a threat to groundwater resources under AgMAR. We use a reactive transport model to understand the effects of AgMAR management strategies (i.e., by varying the frequency, duration between flooding events, and amount of water) on NO3− leaching to groundwater under different stratigraphic configurations and antecedent moisture conditions. We examine the potential of denitrification and nitrogen retention in deep vadose zone sediments (∼15 m) using variable AgMAR application rates on two-dimensional representations of differently textured soils, soils with discontinuous bands/channels, and with preferential flow paths characteristic of agricultural fields. Simulations indicate finer textured sediments, alone or embedded within/adjacent to high flow regions, are important reducing zones providing conditions needed for denitrification. Simulation results suggest that applying water all-at-once rather than in increments transports higher concentrations of NO3− deeper into the profile, which may exacerbate groundwater quality. This transport into deeper depths can be aggravated by wetter antecedent soil moisture conditions. However, applying water all-at-once also increases denitrification within the vadose zone by promoting anoxic conditions. We conclude that AgMAR can be designed to enhance denitrification in the subsurface and reduce NO3− leaching to groundwater, while specifically accounting for lithologic heterogeneity, antecedent soil moisture conditions, and depth to the water table. Our findings are potentially relevant to other systems that experience flooding inundation such as floodplains and dedicated recharge basins.

The region surrounding the Modoc Plateau, encompassing parts of northeastern California, southern Oregon, and northwestern Nevada, lies at an intersection between two tectonic provinces; the Basin and Range province and the Cascade volcanic arc. Both of these provinces have substantial geothermal resource base and resource potential. Geothermal systems with evidence of magmatic heat, associated with Cascade arc magmatism, typify the western side of the region. Systems on the eastern side of the region appear to be fault controlled with heat derived from high crustal heat flow, both of which are typical of the Basin and Range. As it has the potential to host Cascade arc-type geothermal resources, Basin and Range-type geothermal resources, and/or resources with characteristics of both provinces, and because there is relatively little current development, the Modoc Plateau region represents an intriguing potential for undiscovered geothermal resources. It remains unclear however, what specific set(s) of characteristics are diagnostic of Modoc-type geothermal systems and how or if those characteristics are distinct from Basin and Range-type or Cascade arc-type geothermal systems. In order to evaluate the potential for undiscovered geothermal resources in the Modoc area, we integrate a wide variety of existing data in order to evaluate geothermal resource potential and exploration risk utilizing ‘play-fairway’ analysis. We consider that the requisite parameters for hydrothermal circulation are: 1) heat that is sufficient to drive circulation, and 2) permeability that is sufficient to allow for fluid circulation in the subsurface. We synthesize data that indicate the extent and distribution of these parameters throughout the Modoc region. ‘Fuzzy logic’ is used to incorporate expert opinion into the utility of each dataset as an indicator of either heat or permeability, and thus geothermal favorability. The results identify several geothermal prospects, areas that are highly favorable for the occurrence of both heat and permeability. These are also areas where there is sufficient data coverage, quality, and consistency that the exploration risk is relatively low. These unknown, undeveloped, and under-developed prospects are well-suited for continued exploration efforts. The results also indicate to what degree the two ‘play-types,’ i.e. Cascade arc-type or Basin and Range-type, apply to each of the geothermal prospects, a useful guide in exploration efforts.

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 CO₂ 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 CO₂ concentrations above reduced zones. Observed seasonal variations in CO₂ 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.

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.