Motivation, description, and summary status of geomechanical andgeochemical modeling studies in Task D of the InternationalDECOVALEX-THMC Project

The DECOVALEX project is an international cooperativeproject initiated by SKI, the Swedish Nuclear Power Inspectorate, withparticipation of about 10 international organizations. The general goalof this project is to encourage multidisciplinary interactive andcooperative research on modelling coupledthermo-hydro-mechanical-chemical (THMC) processes in geologic formationsin support of the performance assessment for underground storage ofradioactive waste. One of the research tasks, initiated in 2004 by theU.S. Department of Energy (DOE), addresses the long-term impact ofgeomechanical and geochemical processes on the flow conditions near wasteemplacement tunnels. Within this task, four international research teamsconduct predictive analysis of the coupled processes in two genericrepositories, using multiple approaches and different computer codes.Below, we give an overview of the research task and report its currentstatus

Reactive transport model of sulfur cycling as impacted by perchlorate and nitrate treatments

Microbial souring in oil reservoirs produces toxic, corrosive hydrogen sulfide through microbial sulfate reduction, often accompanying (sea)­water flooding during secondary oil recovery. With data from column experiments as constraints, we developed the first reactive-transport model of a new candidate inhibitor, perchlorate, and compared it with the commonly used inhibitor, nitrate. Our model provided a good fit to the data, which suggest that perchlorate is more effective than nitrate on a per mole of inhibitor basis. Critically, we used our model to gain insight into the underlying competing mechanisms controlling the action of each inhibitor. This analysis suggested that competition by heterotrophic perchlorate reducers and direct inhibition by nitrite produced from heterotrophic nitrate reduction were the most important mechanisms for the perchlorate and nitrate treatments, respectively, in the modeled column experiments. This work demonstrates modeling to be a powerful tool for increasing and testing our understanding of reservoir-souring generation, prevention, and remediation processes, allowing us to incorporate insights derived from laboratory experiments into a framework that can potentially be used to assess risk and design optimal treatment schemes

Modeling acid-gas generation from boiling chloride brines

<p>Abstract</p> <p>Background</p> <p>This study investigates the generation of HCl and other acid gases from boiling calcium chloride dominated waters at atmospheric pressure, primarily using numerical modeling. The main focus of this investigation relates to the long-term geologic disposal of nuclear waste at Yucca Mountain, Nevada, where pore waters around waste-emplacement tunnels are expected to undergo boiling and evaporative concentration as a result of the heat released by spent nuclear fuel. Processes that are modeled include boiling of highly concentrated solutions, gas transport, and gas condensation accompanied by the dissociation of acid gases, causing low-pH condensate.</p> <p>Results</p> <p>Simple calculations are first carried out to evaluate condensate pH as a function of HCl gas fugacity and condensed water fraction for a vapor equilibrated with saturated calcium chloride brine at 50-150°C and 1 bar. The distillation of a calcium-chloride-dominated brine is then simulated with a reactive transport model using a brine composition representative of partially evaporated calcium-rich pore waters at Yucca Mountain. Results show a significant increase in boiling temperature from evaporative concentration, as well as low pH in condensates, particularly for dynamic systems where partial condensation takes place, which result in enrichment of HCl in condensates. These results are in qualitative agreement with experimental data from other studies.</p> <p>Conclusion</p> <p>The combination of reactive transport with multicomponent brine chemistry to study evaporation, boiling, and the potential for acid gas generation at the proposed Yucca Mountain repository is seen as an improvement relative to previously applied simpler batch evaporation models. This approach allows the evaluation of thermal, hydrological, and chemical (THC) processes in a coupled manner, and modeling of settings much more relevant to actual field conditions than the distillation experiment considered. The actual and modeled distillation experiments do not represent expected conditions in an emplacement drift, but nevertheless illustrate the potential for acid-gas generation at moderate temperatures (<150°C).</p

Multiple-code benchmark simulation study of coupled THMC processesin the excavation disturbed zone associated with geological nuclear wasterepositories

An international, multiple-code benchmark test (BMT) studyis being conducted within the international DECOVALEX project to analysecoupled thermal, hydrological, mechanical and chemical (THMC) processesin the excavation disturbed zone (EDZ) around emplacement drifts of anuclear waste repository. This BMT focuses on mechanical responses andlong-term chemo-mechanical effects that may lead to changes in mechanicaland hydrological properties in the EDZ. This includes time-de-pendentprocesses such as creep, and subcritical crack, or healing of fracturesthat might cause "weakening" or "hardening" of the rock over the longterm. Five research teams are studying this BMT using a wide range ofmodel approaches, including boundary element, finite element, and finitedifference, particle mechanics, and elasto-plastic cellular automatamethods. This paper describes the definition of the problem andpreliminary simulation results for the initial model inception part, inwhich time dependent effects are not yet included

Mathematical Formulation Requirements and Specifications for the Process Models

The Advanced Simulation Capability for Environmental Management (ASCEM) is intended to be a state-of-the-art scientific tool and approach for understanding and predicting contaminant fate and transport in natural and engineered systems. The ASCEM program is aimed at addressing critical EM program needs to better understand and quantify flow and contaminant transport behavior in complex geological systems. It will also address the long-term performance of engineered components including cementitious materials in nuclear waste disposal facilities, in order to reduce uncertainties and risks associated with DOE EM's environmental cleanup and closure activities. Building upon national capabilities developed from decades of Research and Development in subsurface geosciences, computational and computer science, modeling and applied mathematics, and environmental remediation, the ASCEM initiative will develop an integrated, open-source, high-performance computer modeling system for multiphase, multicomponent, multiscale subsurface flow and contaminant transport. This integrated modeling system will incorporate capabilities for predicting releases from various waste forms, identifying exposure pathways and performing dose calculations, and conducting systematic uncertainty quantification. The ASCEM approach will be demonstrated on selected sites, and then applied to support the next generation of performance assessments of nuclear waste disposal and facility decommissioning across the EM complex. The Multi-Process High Performance Computing (HPC) Simulator is one of three thrust areas in ASCEM. The other two are the Platform and Integrated Toolsets (dubbed the Platform) and Site Applications. The primary objective of the HPC Simulator is to provide a flexible and extensible computational engine to simulate the coupled processes and flow scenarios described by the conceptual models developed using the ASCEM Platform. The graded and iterative approach to assessments naturally generates a suite of conceptual models that span a range of process complexity, potentially coupling hydrological, biogeochemical, geomechanical, and thermal processes. The Platform will use ensembles of these simulations to quantify the associated uncertainty, sensitivity, and risk. The Process Models task within the HPC Simulator focuses on the mathematical descriptions of the relevant physical processes

Precipitation-Front Modeling: Issues Relating to Nucleation and Metastable Precipitation in the Planned Nuclear Waste Repository at Yucca Mountain, Nevada

The focus of the presentation is on certain aspects concerning the kinetics of heterogeneous reactions involving the dissolution and precipitation of unstable and metastable phases under conditions departing from thermodynamic equilibrium. These aspects are particularly relevant to transient thermal-hydrological-chemical (THC) processes that will occur as a result of the emplacement of radioactive waste within the Yucca Mountain Repository. Most important of these is a phenomenon commonly observed in altering soils, sediments and rocks, where less stable minerals precipitate in preference to those that are more stable, referred to as the Ostwald Rule of Stages, or the Ostwald Step Rule. W. Ostwald (1897) described the phenomenon characterizing his rule (as cited in Schmeltzer et al., 1998), thus: ''...in the course of transformation of an unstable (or metastable) state into a stable one the system does not go directly to the most stable conformation (corresponding to the modification with the lowest free energy) but prefers to reach intermediate stages (corresponding to other metastable modifications) having the closest free energy to the initial state''. This phenomenon is so widespread in natural geochemical systems, particularly under hydrothermal or low temperature conditions, that few geochemical parageneses involving the subcritical aqueous phase can be described without invoking the Ostwald Rule of Stages. Commonly observed systems where this phenomenon occurs include carbonates, silica, clay minerals, iron and manganese oxides, iron sulfides and zeolites (Morse and Casey, 1988). Simulations involving natural or anthropogenically modified reactive chemical transport must therefore be consistent with field observations describable by the Ostwald Rule. Geochemists have long been familiar with the Ostwald Rule, but, with one exception (Steefel and Van Cappellen, 1990), have not incorporated the underlying chemical principles justifying the Rule in reactive chemical transport simulations, other than through arbitrary fixes involving the suppression of the thermodynamically more stable phases, and by prohibiting the re-dissolution of minerals. Another issue relating to mineral metastability is the contribution of interfacial free energy to the total free energy of a geochemical system. The interfacial free energy contribution is trivial for crystal sizes in excess of 1 micrometer. However, the alteration of soils and sediments entails both the dissolution of finely crystalline products of diagenesis and heterogeneous nucleation and precipitation of new phases. The latter phases are commonly microcrystalline or amorphous, with substantial contributions of surface free energy to the total Gibbs free energy of the phase. Such contributions must be taken into account when modeling the chemical evolution of such systems, as they stabilize metastable phases and can modify aqueous species concentrations by up to two orders of magnitude. This condition is especially relevant to anthropogenically driven geochemical processes involving extreme levels of supersaturation where nucleation processes are dominant. Furthermore, by a process known as Ostwald Ripening, larger crystallites, usually possess a lower surface free energy contribution, and being more stable, destabilize smaller coexisting crystallites of the same phase, leading to a decreased crystal size distribution, and the growth of progressively fewer crystals

Geysers Valley CO2 Cycling Geological Engine (Kamchatka, Russia)

1941–2017 period of the Valley of Geysers monitoring (Kamchatka, Kronotsky Reserve) reveals a very dynamic geyser behavior under natural state conditions: significant changes of IBE (interval between eruptions) and power of eruptions, chloride and other chemical components, and preeruption bottom temperature. Nevertheless, the total deep thermal water discharge remains relatively stable; thus all of the changes are caused by redistribution of the thermal discharge due to giant landslide of June 3, 2007, mudflow of Jan. 3, 2014, and other events of geothermal caprock erosion and water injection into the geothermal reservoir. In some cases, water chemistry and isotope data point to local meteoric water influx into the geothermal reservoir and geysers conduits. TOUGHREACT V.3 modeling of Velikan geyser chemical history confirms 20% dilution of deep recharge water and CO2 components after 2014. Temperature logging in geysers Velikan (1994, 2007, 2015, 2016, and 2017) and Bolshoy (2015, 2016, and 2017) conduits shows preeruption temperatures below boiling at corresponding hydrostatic pressure, which means partial pressure of CO2 creates gas-lift upflow conditions in geyser conduits. Velikan geyser IBE history explained in terms of gradual CO2 recharge decline (1941–2013), followed by CO2 recharge significant dilution after the mudflow of Jan. 3, 2014, also reshaped geyser conduit and diminished its power

Implications of the Drift Scale Heater Test at Yucca Mountain for Epithermal Mineralization

An 8-year long, drift scale heater test (DST) is currently underway at the underground Exploratory Studies Facility at Yucca Mountain in Nevada. The host rock for the DST is a highly fractured, welded tuff. The rock has {approx}10% matrix porosity 90% filled with water. After a little more than two years of heating, the temperature at the drift wall reached {approx}200 C and has been maintained at that temperature for the past {approx}1.5 years. Gas and water (both vapor and liquid) have been collected from monitoring boreholes since the test began. The CO{sub 2} concentration of the gas and the isotopic compositions of the water and CO{sub 2} are measured. These data are used to constrain numerical models of coupled thermal, hydrological, and chemical processes occurring in the system. Despite obvious differences from epithermal systems (e.g., the DST is being conducted in an unsaturated system), the trends observed in the isotopic compositions of the water and CO{sub 2} have interesting implications for natural systems. In areas below boiling, the isotope ratios of the water are near that of the ambient pore water ({delta}{sup 18}O about -12{per_thousand}). Where significant amounts of vapor condensate occur (above the boiling front above the drift and in fracture zones to the sides of the drift), the {delta}{sup 18}O values of the water are lower than the pore water, reflecting addition of low-{delta}{sup 18}O steam condensate. Conversely, in boiling zones, the {delta}{sup 18}O values of the water become progressively higher, representing Rayleigh fractionation of the pore water as it is vaporized. As the temperature approaches boiling, the gas phase becomes dominated by water vapor. The remainder of the gas phase consists of air with elevated CO{sub 2} (up to 15%). The source of the CO, is primarily dissolved inorganic carbon (DIC) in the pore water. As the temperature increases, the {delta}{sup 13}C values of the CO{sub 2} shift from approximate equilibrium with the pore water DIC (-15{per_thousand}) to much higher values (&gt;0{per_thousand}). Dissolution of calcite in fractures is also a significant source of CO{sub 2} in regions with drainage of vapor condensate. Isotopic data from several Mexican epithermal vein systems will be discussed in light of these findings