Nicolas Spycher

CO2-H2O mixtures in the geological sequestration of CO2. I. Assessment and calculation of mutual solubilities from 12 to 100°C and up to 600 bar

Abstract Evaluating the feasibility of CO 2 geologic sequestration requires the use of pressure-temperature-composition ( P - T - X ) data for mixtures of CO 2 and H 2 O at moderate pressures and temperatures (typically below 500 bar and below 100°C). For this purpose, published experimental P - T - X data in this temperature and pressure range are reviewed. These data cover the two-phase region where a CO 2 -rich phase (generally gas) and an H 2 O-rich liquid coexist and are reported as the mutual solubilities of H 2 O and CO 2 in the two coexisting phases. For the most part, mutual solubilities reported from various sources are in good agreement. In this paper, a noniterative procedure is presented to calculate the composition of the compressed CO 2 and liquid H 2 O phases at equilibrium, based on equating chemical potentials and using the Redlich-Kwong equation of state to express departure from ideal behavior. The procedure is an extension of that used by King et al. (1992), covering a broader range of temperatures and experimental data than those authors, and is readily expandable to a nonideal liquid phase. The calculation method and formulation are kept as simple as possible to avoid degrading the performance of numerical models of water-CO 2 flows for which they are intended. The method is implemented in a computer routine, and inverse modeling is used to determine, simultaneously, (1) new Redlich-Kwong parameters for the CO 2 -H 2 O mixture, and (2) aqueous solubility constants for gaseous and liquid CO 2 as a function of temperature. In doing so, mutual solubilities of H 2 O from 15 to 100°C and CO 2 from 12 to 110°C and up to 600 bar are generally reproduced within a few percent of experimental values. Fugacity coefficients of pure CO 2 are reproduced mostly within one percent of published reference data.

Reactive transport codes for subsurface environmental simulation

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 high-level list of capabilities for each of the codes, along with a selective list of applications that highlight their capabilities and historical development.

Effect of dissolved CO2 on a shallow groundwater system: a controlled release field experiment.

Capturing carbon dioxide (CO(2)) emissions from industrial sources and injecting the emissions deep underground in geologic formations is one method being considered to control CO(2) concentrations in the atmosphere. Sequestering CO(2) underground has its own set of environmental risks, including the potential migration of CO(2) out of the storage reservoir and resulting acidification and release of trace constituents in shallow groundwater. A field study involving the controlled release of groundwater containing dissolved CO(2) was initiated to investigate potential groundwater impacts. Dissolution of CO(2) in the groundwater resulted in a sustained and easily detected decrease of ~3 pH units. Several trace constituents, including As and Pb, remained below their respective detections limits and/or at background levels. Other constituents (Ba, Ca, Cr, Sr, Mg, Mn, and Fe) displayed a pulse response, consisting of an initial increase in concentration followed by either a return to background levels or slightly greater than background. This suggests a fast-release mechanism (desorption, exchange, and/or fast dissolution of small finite amounts of metals) concomitant in some cases with a slower release potentially involving different solid phases or mechanisms. Inorganic constituents regulated by the U.S. Environmental Protection Agency remained below their respective maximum contaminant levels throughout the experiment.

Experimental and numerical simulation of dissolution and precipitation: implications for fracture sealing at Yucca Mountain, Nevada

Plugging of flow paths caused by mineral precipitation in fractures above the potential repository at Yucca Mountain, Nevada could reduce the probability of water seeping into the repository. As part of an ongoing effort to evaluate thermal-hydrological-chemical (THC) effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation under anticipated temperature and pressure conditions in the repository. To replicate mineral dissolution by vapor condensate in fractured tuff, water was flowed through crushed Yucca Mountain tuff at 94 degrees C. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/l; silica was the dominant dissolved constituent. A portion of the steady-state mineralized water was flowed into a vertically oriented planar fracture in a block of welded Topopah Spring Tuff that was maintained at 80 degrees C at the top and 130 degrees C at the bottom. The fracture began to seal with amorphous silica within 5 days.A 1-D plug-flow numerical model was used to simulate mineral dissolution, and a similar model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The mineral precipitation simulations predicted the precipitation of amorphous silica at the base of the boiling front, leading to a greater than 50-fold decrease in fracture permeability in 5 days, consistent with the laboratory experiment.These results help validate the use of a numerical model to simulate THC processes at Yucca Mountain. The experiment and simulations indicated that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. However, differences in fluid flow rates and thermal gradients between the experimental setup and anticipated conditions at Yucca Mountain need to be factored into scaling the results of the dissolution/precipitation experiments and associated simulations to THC models for the potential Yucca Mountain repository.

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.

Advances in subsurface modeling using the TOUGH suite of simulators

The TOUGH suite of nonisothermal multiphase flow and transport simulators is continually updated to improve the analysis of complex subsurface processes through numerical modeling. Driven by research questions in the Earth sciences and by application needs in industry and government organizations, the codes are extended to include the coupling of relevant processes and subsystems, to improve computational performance, to support model development and analysis tasks, and to provide more convenient pre- and post-processing capabilities. This review paper briefly describes the history of the simulator, discusses recent advances, and comments on potential future developments and applications.

Reoxidation of Biogenic Reduced Uranium: A Challenge Toward Bioremediation

Uraninite (UO2) is the most desirable end product of in situ bioreduction because of its low solubility under reducing conditions. For effective long-term immobilization of uranium (U), there should be no biotic or abiotic reoxidation of the insoluble biogenic U(IV). It is therefore critical to understand the long-term stability of U(IV) under oxic- and nutrient-limited conditions at U-contaminated subsurface sites. It has now been established that following in situ bioremediation of U(VI) via nutrient addition in the subsurface, a range of physical, chemical, and biological factors control the rate and extent of long-term stability of U(IV). Some of these factors are tied to site specific conditions including existence of oxidants such as Fe(III)(hydr)oxides, Mn(IV) oxides, oxygen, and nitrate; the presence of organic carbon and the reduced forms of U (e.g., mononuclear U(IV) or nanometer-sized uraninite particles); and the carbonate concentration and pH of groundwater. This review analyzes the contribution of these factors in controlling U(IV)-reoxidation, and highlights the competition among U(IV) and other electron acceptors and possible mechanisms of reoxidation of various forms of U(IV).

Influence of chelating agents on biogenic uraninite reoxidation by Fe(III) (Hydr)oxides.

Microbially mediated reduction of soluble U(VI) to U(IV) with subsequent precipitation of uraninite, UO(2(S)), has been proposed as a method for limiting uranium (U) migration. However, microbially reduced UO(2) may be susceptible to reoxidation by environmental factors, with Fe(III) (hydr)oxides playing a significant role. Little is known about the role that organic compounds such as Fe(III) chelators play in the stability of reduced U. Here, we investigate the impact of citrate, DFB, EDTA, and NTA on biogenic UO(2) reoxidation with ferrihydrite, goethite, and hematite. Experiments were conducted in anaerobic batch systems in PIPES buffer (10 mM, pH 7) with bicarbonate for approximately 80 days. Results showed EDTA accelerated UO(2) reoxidation the most at an initial rate of 9.5 μM day(-1) with ferrihydrite, 8.6 μM day(-1) with goethite, and 8.8 μM day(-1) with hematite. NTA accelerated UO(2) reoxidation with ferrihydrite at a rate of 4.8 μM day(-1); rates were less with goethite and hematite (0.66 and 0.71 μM day(-1), respectively). Citrate increased UO(2) reoxidation with ferrihydrite at a rate of 1.8 μM day(-1), but did not increase the extent of reaction with goethite or hematite, with no reoxidation in this case. In all cases, bicarbonate increased the rate and extent of UO(2) reoxidation with ferrihydrite in the presence and absence of chelators. The highest rate of UO(2) reoxidation occurred when the chelator promoted both UO(2) and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO(2) dissolution did not occur, UO(2) reoxidation likely proceeded through an aqueous Fe(III) intermediate with lower reoxidation rates observed. Reaction modeling suggests that strong Fe(II) chelators promote reoxidation whereas strong Fe(III) chelators impede it. These results indicate that chelators found in U contaminated sites may play a significant role in mobilizing U, potentially affecting bioremediation efforts.

Modeling Reactive Multiphase Flow and Transport of Concentrated Solutions

Abstract A Pitzer ion-interaction model for concentrated aqueous solutions was added to the reactive multiphase flow and transport code TOUGHREACT. The model is described and verified against published experimental data and the geochemical code EQ3/6. The model is used to simulate water-rock-gas interactions caused by boiling and evaporation within and around nuclear waste emplacement tunnels at the proposed high-level waste repository at Yucca Mountain, Nevada. The coupled thermal, hydrological, and chemical processes considered consist of water and air/vapor flow, evaporation, boiling, condensation, solute and gas transport, formation of highly concentrated brines, precipitation of deliquescent salts, generation of acid gases, and vapor-pressure lowering caused by the high salinity of the concentrated brine.

A reactive transport benchmark on heavy metal cycling in lake sediments

Sediments are active recipients of anthropogenic inputs, including heavy metals, but may be difficult to interpret without the use of numerical models that capture sediment-metal interactions and provide an accurate representation of the intricately coupled sedimentological, geochemical, and biological processes. The focus of this study is to present a benchmark problem on heavy metal cycling in lake sediments and to compare reactive transport models (RTMs) in their treatment of the local-scale physical and biogeochemical processes. This benchmark problem has been developed based on a previously published reactive-diffusive model of metal transport in the sediments of Lake Coeur d’Alene, Idaho. Key processes included in this model are microbial reductive dissolution of iron hydroxides (i.e., ferrihydrite), the release of sorbed metals into pore water, reaction of these metals with biogenic sulfide to form sulfide minerals, and sedimentation driving the burial of ferrihydrite and other minerals. This benchmark thus considers a multicomponent biotic reaction network with multiple terminal electron acceptors (TEAs), Fickian diffusive transport, kinetic and equilibrium mineral precipitation and dissolution, aqueous and surface complexation, as well as (optionally) sedimentation. To test the accuracy of the reactive transport problem solution, four RTMs—TOUGHREACT (TR), CrunchFlow (CF), PHREEQC, and PHT3D—have been used. Without sedimentation, all four models are able to predict similar trends of TEAs and dissolved metal concentrations, as well as mineral abundances. TR and CF are further used to compare sedimentation and compaction test cases. Results with different sedimentation rates are captured by both models, but since the codes do not use the same formulation for compaction, the results differ for this test case. Although, both TR and CF adequately capture the trends of aqueous concentrations and mineral abundances, the difference in results highlights the need to consider further the conceptual and numerical models that link transport, biogeochemical reactions, and sedimentation.