Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates. The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can be an effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.

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Dissolution of silica, silicate, and calcite minerals in the presence of a chelating agent (NTA) at a high pH has been successfully performed in the laboratory using a high-temperature flow reactor. The mineral dissolution and porosity enhancement in the laboratory experiment has been reproduced by reactive transport simulation using TOUGHREACT. The chemical stimulation method has been applied by numerical modeling to a field geothermal injection well system, to investigate its effectiveness. Parameters from the quartz monzodiorite unit at the Enhanced Geothermal System (EGS) site at Desert Peak (Nevada) were used. Results indicate that the injection of a high pH chelating solution results in dissolution of both calcite and plagioclase minerals, and avoids precipitation of calcite at high temperature conditions. Consequently reservoir porosity and permeability can be enhanced especially near the injection well.

Dissolution of silica and calcite in the presence of a chelating agent (NTA) at a high pH was successfully demonstrated in laboratory experiments using a high-temperature flow reactor. (Note that the term 'silica' used here includes amorphous silica, quartz, and silicate glass bead). The mineral dissolution and associated porosity enhancement in the experiments were reproduced by reactive transport modeling using TOUGHREACT. The chemical stimulation method was applied by numerical modeling to a field geothermal injection well system to investigate its effectiveness. Parameters applicable to the quartz monzodiorite unit at the Enhanced Geothermal Systems (EGS) site at Desert Peak (Nevada) were used. Results indicate that the injection of a high pH chelating solution results in dissolution of both calcite and plagioclase, while avoiding precipitation of calcite at high temperature conditions. Consequently reservoir porosity and permeability can be enhanced especially near the injection well. Injection at a lower temperature of 120 C (over 160 C in the base-case) results in a porosity increase that is smaller close to the injection point, but extends to a larger radial distance. A slower kinetic rate results in less aggressive mineral dissolution close to the injection point and larger extent along the flow path, which is …

Hyperspectral plant signatures can be used as a short-term, as well as long-term (100-yr timescale) monitoring technique to verify that CO2 sequestration fields have not been compromised. An influx of CO2 gas into the soil can stress vegetation, which causes changes in the visible to nearinfrared reflectance spectral signature of the vegetation. For 29 days, beginning on July 9th, 2008, pure carbon dioxide gas was released through a 100-meter long horizontal injection well, at a flow rate of 300 kg/day. Spectral signatures were recorded almost daily from an unmown patch of plants over the injection with a ''FieldSpec Pro'' spectrometer by Analytical Spectral Devices, Inc. Measurements were taken both inside and outside of the CO2 leak zone to normalize observations for other environmental factors affecting the plants.

A major concern in the development of enhanced geothermal systems (EGS) is achieving and maintaining adequate injectivity, while avoiding the development of preferential short-circuiting flow paths such as those caused by thermally-induced stress cracking. Past researches have tended to focus primarily on thermal and hydraulic stimulation. Recent studies suggest that chemical stimulation may improve the performance of EGS reservoirs. Geothermal injection wells are often drilled into formations containing reactive minerals such as calcite. Injecting aqueous chemical agents such as mineral acids, could be effective for mineral dissolution and porosity enhancement at distances of several meters around a well. An alternative to treatment with strong acids is the use of supercritical (SC) CO{sub 2} as stimulation agent for an aqueous-based EGS. Reactive transport modeling is used to investigate the effectiveness of this method. We used the thermal condition and mineralogical composition from a well of Desert Peak EGS site, to examine ways in which mixtures of water and CO{sub 2} can be injected to enhance porosity.

Approximately 300 kg/day of food-grade CO2 was injected through a perforated pipe placed horizontally 2-2.3 m deep during July 9-August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO2. As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1-6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during and following CO2 injection. The main objective of study was to investigate changes in the concentrations of major, minor and trace inorganic and organic compounds during and following CO2 injection.

The hydrodynamic behavior of carbon dioxide (CO{sub 2}) injected into a deep saline formation is investigated, focusing on trapping mechanisms that lead to CO{sub 2} plume stabilization. A numerical model of the subsurface at a proposed power plant with CO{sub 2} capture is developed to simulate a planned pilot test, in which 1,000,000 metric tons of CO{sub 2} is injected over a four-year period, and the subsequent evolution of the CO{sub 2} plume for hundreds of years. Key measures are plume migration distance and the time evolution of the partitioning of CO{sub 2} between dissolved, immobile free-phase, and mobile free-phase forms. Model results indicate that the injected CO{sub 2} plume is effectively immobilized at 25 years. At that time, 38% of the CO{sub 2} is in dissolved form, 59% is immobile free phase, and 3% is mobile free phase. The plume footprint is roughly elliptical, and extends much farther up-dip of the injection well than down-dip. The pressure increase extends far beyond the plume footprint, but the pressure response decreases rapidly with distance from the injection well, and decays rapidly in time once injection ceases. Sensitivity studies that were carried out to investigate the effect of poorly constrained model parameters …

Injection of CO{sub 2} into saline aquifers may cause formation dry-out and precipitation of salt near the injection well, which may reduce formation porosity, permeability, and injectivity. This paper uses numerical simulation to explore the role of different processes and parameters in the salt precipitation process and to examine injection strategies that could mitigate the effects. The main physical mechanisms affecting the dry-out and salt precipitation process include (1) displacement of brine away from the injection well by injected CO{sub 2}, (2) dissolution (evaporation) of brine into the flowing CO{sub 2} stream, (3) upflow of CO{sub 2} due to gravity effects (buoyancy), (4) backflow of brine toward the injection point due to capillary pressure gradients that oppose the pressure gradient in the CO{sub 2}-rich ('gas') phase, and (5) molecular diffusion of dissolved salt. The different mechanisms operate on a range of spatial scales. CO{sub 2} injection at constant rate into a homogeneous reservoir with uniform initial conditions is simulated in 1-D radial geometry, to resolve multiscale processes by taking advantage of the similarity property, i.e., the evolution of system conditions as a function of radial distance R and time t depends only on the similarity variable R{sup 2}/t. Simulations in …

Gene probe hybridization was used to determine distribution and expression of co-metabolic genes at a contaminated site as it underwent in situ methanotrophic bioremediation of trichloroethylene (TCE). The bioremediation strategies tested included a series of air, air:methane, and air:methane:nutrient pulses of the test plot using horizontal injection wells. During the test period, the levels of TCE reduced drastically in almost all test samples. Sediment core samples (n = 367) taken from 0 m (surface)-43 m depth were probed for gene coding for methanotrophic soluble methane monooxygenase (sMMO) and heterotrophic toluene dioxygenase (TOD), which are known to co-metabolize TCE. The same sediment samples were also probed for genes coding for methanol dehydrogenase (MDH) (catalyzing the oxidation of methanol to formaldehyde) to assess specifically changes in methylotrophic bacterial populations in the site. Gene hybridization results showed that the frequency of detection of sMMO genes were stimulated approximately 250% following 1% methane:air (v/v) injection. Subsequent injection of 4% methane:air (v/v) resulted in an 85% decline probably due to nutrient limitations, since addition of nutrients (gaseous nitrogen and phosphorus) thereafter caused an increase in the frequency of detection of sMMO genes. Detection of TOD genes declined during the process, and eventually they were non-detectable …

Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO{sub 3} and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO{sub 3} as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO{sub 3} dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO{sub 3} forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO{sub 3} precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

If carbon dioxide stored in deep saline aquifers were to leak into an overlying aquifer containing potable groundwater, the intruding CO{sub 2} would change the geochemical conditions and cause secondary effects mainly induced by changes in pH In particular, hazardous trace elements such as lead and arsenic, which are present in the aquifer host rock, could be mobilized. In an effort to evaluate the potential risks to potable water quality, reactive transport simulations were conducted to evaluate to what extent and mechanisms through which lead and arsenic might be mobilized by intrusion of CO{sub 2}. An earlier geochemical evaluation of more than 38,000 groundwater quality analyses from aquifers throughout the United States and an associated literature review provided the basis for setting up a reactive transport model and examining its sensitivity to model variation. The evaluation included identification of potential mineral hosts containing hazardous trace elements, characterization of the modal bulk mineralogy for an arenaceous aquifer, and augmentation of the required thermodynamic data. The reactive transport simulations suggest that CO{sub 2} ingress into a shallow aquifer can mobilize significant lead and arsenic, contaminating the groundwater near the location of intrusion and further downstream. Although substantial increases in aqueous concentrations are …

We have developed a certification framework (CF) for certifying the safety and effectiveness of geologic carbon sequestration (GCS) sites. Safety and effectiveness are achieved if CO{sub 2} and displaced brine have no significant impact on humans, other living things, resources, or the environment. In the CF, we relate effective trapping to CO{sub 2} leakage risk which takes into account both the impact and probability of leakage. We achieve simplicity in the CF by using (1) wells and faults as the potential leakage pathways, (2) compartments to represent environmental resources that may be impacted by leakage, (3) CO{sub 2} fluxes and concentrations in the compartments as proxies for impact to vulnerable entities, (4) broad ranges of storage formation properties to generate a catalog of simulated plume movements, and (5) probabilities of intersection of the CO{sub 2} plume with the conduits and compartments. We demonstrate the approach on a hypothetical GCS site in a Texas Gulf Coast saline formation. Through its generality and flexibility, the CF can contribute to the assessment of risk of CO{sub 2} and brine leakage as part of the certification process for licensing and permitting of GCS sites around the world regardless of the specific regulations in place …

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low ({approx}10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that {sup 230}Th/{sup 238}U activity ratios range from 0.005-0.48 and {sup 226}Ra/{sup 238}U activity ratios range from 0.006-113. {sup 239}Pu/{sup 238}U mass ratios for the saturated zone are <2 x 10{sup -14}, and Pu mobility in the saturated zone is >1000 times lower than the U mobility. Saturated zone mobility decreases in the order {sup 238}U{approx}{sup 226}Ra > {sup 230}Th{approx}{sup 239}Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on …

Large-scale storage of carbon dioxide in saline aquifers may cause considerable pressure perturbation and brine migration in deep rock formations, which may have a significant influence on the regional groundwater system. With the help of parallel computing techniques, we conducted a comprehensive, large-scale numerical simulation of CO{sub 2} geologic storage that predicts not only CO{sub 2} migration, but also its impact on regional groundwater flow. As a case study, a hypothetical industrial-scale CO{sub 2} injection in Tokyo Bay, which is surrounded by the most heavily industrialized area in Japan, was considered, and the impact of CO{sub 2} injection on near-surface aquifers was investigated, assuming relatively high seal-layer permeability (higher than 10 microdarcy). A regional hydrogeological model with an area of about 60 km x 70 km around Tokyo Bay was discretized into about 10 million gridblocks. To solve the high-resolution model efficiently, we used a parallelized multiphase flow simulator TOUGH2-MP/ECO2N on a world-class high performance supercomputer in Japan, the Earth Simulator. In this simulation, CO{sub 2} was injected into a storage aquifer at about 1 km depth under Tokyo Bay from 10 wells, at a total rate of 10 million tons/year for 100 years. Through the model, we can examine …

in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a …

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To demonstrate the potential for geologic storage of CO{sub 2} in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO{sub 2} were injected into a high-permeability sandstone and the resulting subsurface plume of CO{sub 2} was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO{sub 2} injection for baseline geochemical characterization, during the CO{sub 2} injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO{sub 2} breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO{sub 3}{sup -} and aqueous Fe, and significant shifts in the isotopic compositions of H{sub 2}O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The …

Peat cores were collected in 4 remnant marsh islands and 4 drained, farmed islands throughout the Sacramento - San Joaquin Delta of California in order to characterize the peat accretion history of this region. Radiocarbon age determination of marsh macrofossils at both marsh and farmed islands showed that marshes in the central and western Delta started forming between 6030 and 6790 cal yr BP. Age-depth models for three marshes were constructed using cubic smooth spline regression models. The resulting spline fit models were used to estimate peat accretion histories for the marshes. Estimated accretion rates range from 0.03 to 0.49 cm yr{sup -1} for the marsh sites. The highest accretion rates are at Browns Island, a marsh at the confluence of the Sacramento and San Joaquin rivers. Porosity was examined in the peat core from Franks Wetland, one of the remnant marsh sites. Porosity was greater than 90% and changed little with depth indicating that autocompaction was not an important process in the peat column. The mean contribution of organic matter to soil volume at the marsh sites ranges from 6.15 to 9.25% with little variability. In contrast, the mean contribution of inorganic matter to soil volume ranges from 1.40 …

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Microbial ureolysis-induced calcite precipitation may offer an in situ remediation for heavy metal and radionuclide contamination, as well as an alternative to traditional soil strengthening techniques. A microbially mediated calcite precipitation model was built in TOUGHREACT v2 and calibrated to batch and columnar experimental data. Kinetic ureolysis and calcite precipitation-rate expressions were parameterized by coupling TOUCHREACT with UCODE.

Although recent research suggests that contaminant plumes behave as geobatteries that produce an electrical current in the ground, no associated model exists that honors both geophysical and biogeochemical constraints. Here, we develop such a model to explain the two main electrochemical contributions to self-potential signals in contaminated areas. Both contributions are associated with the gradient of the activity of two types of charge carriers, ions and electrons. In the case of electrons, bacteria act as catalysts for reducing the activation energy needed to exchange the electrons between electron donor and electron acceptor. Possible mechanisms that facilitate electron migration include iron oxides, clays, and conductive biological materials, such as bacterial conductive pili or other conductive extracellular polymeric substances. Because we explicitly consider the role of biotic processes in the geobattery model, we coined the term 'biogeobattery'. After theoretical development of the biogeobattery model, we compare model predictions with self-potential responses associated with laboratory and field-scale conducted in contaminated environments. We demonstrate that the amplitude and polarity of large (>100 mV) self-potential signatures requires the presence of an electronic conductor to serve as a bridge between electron donors and acceptors. Small self-potential anomalies imply that electron donors and electron acceptors are not …

For guiding optimal design and interpretation of in-situ treatments that strongly perturb subsurface systems, knowledge about the spatial and temporal patterns of mass transport and reaction intensities are important. Here, a procedure was developed and applied to time-lapse concentrations of a conservative tracer (bromide), an injected amendment (acetate) and reactive species (iron(II), uranium(VI) and sulfate) associated with two field scale biostimulation experiments, which were conducted successively at the same field location over two years. The procedure is based on a temporal moment analysis approach that relies on a streamtube approximation. The study shows that biostimulated reactions can be considerably influenced by subsurface hydrological and geochemical heterogeneities: the delivery of bromide and acetate and the intensity of the sulfate reduction is interpreted to be predominantly driven by the hydrological heterogeneity, while the intensity of the iron reduction is interpreted to be primarily controlled by the geochemical heterogeneity. The intensity of the uranium(VI) reduction appears to be impacted by both the hydrological and geochemical heterogeneity. Finally, the study documents the existence of feedbacks between hydrological heterogeneity and remediation-induced biogeochemical transformations at the field scale, particularly the development of precipitates that may cause clogging and flow rerouting.

Fluid-rock interaction (or water-rock interaction, as it was more commonly known) is a subject that has evolved considerably in its scope over the years. Initially its focus was primarily on interactions between subsurface fluids of various temperatures and mostly crystalline rocks, but the scope has broadened now to include fluid interaction with all forms of subsurface materials, whether they are unconsolidated or crystalline ('fluid-solid interaction' is perhaps less euphonious). Disciplines that previously carried their own distinct names, for example, basin diagenesis, early diagenesis, metamorphic petrology, reactive contaminant transport, chemical weathering, are now considered to fall under the broader rubric of fluid-rock interaction, although certainly some of the key research questions differ depending on the environment considered. Beyond the broadening of the environments considered in the study of fluid-rock interaction, the discipline has evolved in perhaps an even more important way. The study of water-rock interaction began by focusing on geochemical interactions in the absence of transport processes, although a few notable exceptions exist (Thompson 1959; Weare et al. 1976). Moreover, these analyses began by adopting a primarily thermodynamic approach, with the implicit or explicit assumption of equilibrium between the fluid and rock. As a result, these early models were fundamentally …