Vicky L. Freedman

Changes in hydrologic properties of aquifer media due to chemical reactions: A review

Hydrologic properties that govern fluid flow through the subsurface are porosity, permeability, relative permeability, fluid-fluid and fluid-solid interfacial areas, pore and particle size distributions, which may change due to dissolution/precipitation of minerals, fine particle release and capture, ion exchange, and clay swelling. Provided here is a review on the change of hydrologic properties in subsurface media due to chemical processes, and the modeling of such changes. Precipitation and dissolution processes affecting the hydrologic properties, their kinetics and the effect of hydrodynamic factors on such processes are discussed. Precipitation in carbonaceous, siliceous, alkaline and acidic environments, and the role of dissolution and clay swelling in formation damage are reviewed. Changes in properties of unsaturated and fractured media were also discussed. Traditionally, different approaches were used to model various physico-chemical processes and their effect on the hydrologic properties. A detailed review of these methods, including the geochemical equilibrium and kinetic models, chemical divide pathway models, flow and transport models, precipitation/dissolution wave theory, network models, porosity and permeability reduction models, is presented. Recommendations are provided for the assessment of changes in the hydrologic properties of subsurface media attributable to chemical reactions, and modeling flow and transport in their presence. Further, research needs on the changes in hydrologic properties and constitutive relationships among such properties in unsaturated media are identified.

Groundwater Data Package for Hanford Assessments

This report presents data and interpreted information that supports the groundwater module of the System Assessment Capability (SAC) used in Hanford Assessments. The objective of the groundwater module is to predict movement of radioactive and chemical contaminants through the aquifer to the Columbia River or other potential discharge locations. This data package is being revised as part of the deliverables under the Characterization of Systems Project (#49139) aimed at providing documentation for assessments being conducted under the Hanford Assessments Project (#47042). Both of these projects are components of the Groundwater Remediation and Closure Assessments Projects, managed by the Management and Integration Project (#47043).

Vadose Zone Transport Field Study: Summary Report

From FY 2000 through FY 2003, a series of vadose zone transport field experiments were conducted as part of the U.S. Department of Energy’s Groundwater/Vadose Zone Integration Project Science and Technology Project, now known as the Remediation and Closure Science Project, and managed by the Pacific Northwest National Laboratory (PNNL). The series of experiments included two major field campaigns, one at a 299-E24-11 injection test site near PUREX and a second at a clastic dike site off Army Loop Road. The goals of these experiments were to improve our understanding of vadose zone transport processes; to develop data sets to validate and calibrate vadose zone flow and transport models; and to identify advanced monitoring techniques useful for evaluating flow-and-transport mechanisms and delineating contaminant plumes in the vadose zone at the Hanford Site. This report summarizes the key findings from the field studies and demonstrates how data collected from these studies are being used to improve conceptual models and develop numerical models of flow and transport in Hanford’s vadose zone. Results of these tests have led to a better understanding of the vadose zone. Fine-scale geologic heterogeneities, including grain fabric and lamination, were observed to have a strong effect on the large-scale behavior of contaminant plumes, primarily through increased lateral spreading resulting from anisotropy. Conceptual models have been updated to include lateral spreading and numerical models of unsaturated flow and transport have revised accordingly. A new robust model based on the concept of a connectivity tensor was developed to describe saturation-dependent anisotropy in strongly heterogeneous soils and has been incorporated into PNNL’s Subsurface Transport Over Multiple Phases (STOMP) simulator. Application to field-scale transport problems have led to a better understanding plume behavior at a number of sites where lateral spreading may have dominated waste migration (e.g. BC Cribs and Trenches). The improved models have been also coupled with inverse models and newly-developed parameter scaling techniques to allow estimation of field-scale and effective transport parameters for the vadose zone. The development and utility of pedotransfer functions for describing fine-scale hydrogeochemical heterogeneity and for incorporating this heterogeneity into reactive transport models was explored. An approach based on grain-size statistics appears feasible and has been used to describe heterogeneity in hydraulic properties and sorption properties, such as the cation exchange capacity and the specific surface area of Hanford sediments. This work has also led to the development of inverse modeling capabilities for time-dependent, subsurface, reactive transport with transient flow fields using an automated optimization algorithm. In addition, a number of geophysical techniques investigated for their potential to provide detailed information on the subtle changes in lithology and bedding surfaces; plume delineation, leak detection. High-resolution resistivity is now being used for detecting saline plumes at several waste sites at Hanford, including tank farms. Results from the field studies and associated analysis have appeared in more than 46 publications generated over the past 4 years. These publications include test plans and status reports, in addition to numerous technical notes and peer reviewed papers.

Influence of mineral precipitation and dissolution on hydrologic properties of porous media in static and dynamic systems

A critical component in determining the suitability of disposing glassified, low activity waste is the identification of key mineral assemblages affecting the porosity and permeability of both the glass and near- and far-field materials. In this study, two different classes of geochemical models are used to identify mineral precipitation and dissolution potentials for an immobilized low-activity waste (ILAW) disposal facility in Hanford, Washington. The first is a static geochemical model that does not consider the effects of transport. The second model is dynamic, and combines geochemical reactions with hydrogeological processes such as advection, diffusion and dispersion. This reactive transport model also includes an innovative application of a depositional film model for determining changes in permeability due to mineral precipitation and dissolution reactions. Although both models describe solid-aqueous phase reactions kinetically, the two models identify two different sets of mineral assemblages affecting the porosity and permeability of the media. These markedly different results are due to transport considerations, the most significant of which are the spatial variability in aqueous concentrations, and advection and diffusion of dissolved glass constituents into the backfill materials. This work shows that for the prediction of geochemical behavior of engineered systems, such as the ILAW disposal facility, the traditional reaction path modeling approach is not sufficient for an accurate assessment of the precipitation of key mineral assemblages and their effect on the geochemical and hydraulic behavior of the waste glass. Reactive transport modeling improves this assessment significantly. The static model is useful in identifying potential minerals to be included in the reactive transport simulations. The dynamic model, however, ultimately determines the key mineral assemblages affecting both the geochemical behavior and the hydraulic properties of the waste glass in the presence of a flowing aqueous phase.

Laboratory and Modeling Evaluations in Support of Field Testing for Desiccation at the Hanford Site

The Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau includes testing of the desiccation technology as a potential technology to be used in conjunction with surface infiltration control to limit the flux of technetium and other contaminants in the vadose zone to the groundwater. Laboratory and modeling efforts were conducted to investigate technical uncertainties related to the desiccation process and its impact on contaminant transport. This information is intended to support planning, operation, and interpretation of a field test for desiccation in the Hanford Central Plateau.

A high-performance workflow system for subsurface simulation

The U.S. Department of Energy (DOE) recently invested in developing a numerical modeling toolset called ASCEM (Advanced Simulation Capability for Environmental Management) to support modeling analyses at legacy waste sites. This investment includes the development of an open-source user environment called Akuna that manages subsurface simulation workflows. Core toolsets accessible through the Akuna user interface include model setup, grid generation, sensitivity analysis, model calibration, and uncertainty quantification. Additional toolsets are used to manage simulation data and visualize results. This new workflow technology is demonstrated by streamlining model setup, calibration, and uncertainty analysis using high performance computation for the BC Cribs Site, a legacy waste area at the Hanford Site in Washington State. For technetium-99 transport, the uncertainty assessment for potential remedial actions (e.g., surface infiltration covers) demonstrates that using multiple realizations of the geologic conceptual model results in greater variation in concentration predictions than when a single model is used. Akuna provides integrated toolset needed for subsurface modeling workflow.Akuna streamlines process of executing multiple simulations in HPC environment.Akuna provides visualization tools for spatial and temporal data.Example application demonstrates risk with remediation impacting infiltration rates.

Coupled reactive mass transport and fluid flow: Issues in model verification

Abstract Model verification and validation are both important steps in the development of reactive transport models. In this paper, a distinction is made between verification and validation, and the focus is on codifying the issues of verification for a numerical, reactive transport flow model. First, the conceptual basis of model verification is reviewed, which shows that verification should be understood as a first step in model development, and be followed by a protocol that assures that the model accurately represents system behavior. Second, commonly used procedures and methods of model verification are presented. In the third part of this paper, an intercomparison of models is used to demonstrate that model verification can be performed despite differences in hydrogeochemical transport code formulations. Results of an example simulation of transport are presented in which the numerical model is tested against other hydrogeochemical codes. Different kinetic formulations between solid and aqueous phases used among numerical models complicates model verification. This test problem involves uranium transport under conditions of varying pH and oxidation potential, with reversible precipitation of calcium uranate and coffinite. Results between the different hydrogeochemical transport codes show differences in oxidation potentials, but similarities in mineral assemblages and aqueous transport patterns. Because model verification can be further complicated by differences in the approach for solving redox problems, a comparison of a fugacity approach (based on O 2 partial pressure) to both the external approach (based on hypothetical electron activity) and effective internal approach (based on conservation of electrons) is performed. The comparison demonstrates that the oxygen fugacity approach produces different redox potentials and mineral assemblages than both the effective internal and external approaches.

Performance Assessment of Low-Level Waste Disposal Facilities Using Coupled Unsaturated Flow and Reactive Transport Simulators

Recent advances in development of reactive chemical transport simulators have made it possible to use these tools in performance assessments (PAs) for nuclear waste disposal. Reactive transport codes were used to evaluate the impacts of design modifications on the performance of two shallow subsurface disposal systems for low-level radioactive waste. The first disposal system, located at the Hanford site in Richland, Washington, is for disposal of low-level waste glass. Glass waste blocks will be disposed in subsurface trenches, surrounded by backfill material. The effect of different waste package sizes and layering on technetium release to the vadose zone had a small impact on release rates. The second disposal system involves a hypothetical repository for low-activity waste in Italy. A model of uranium release from a grout waste form was developed using the STORM reactive transport code. Uranium is predicted to be relatively insoluble for several hundred years under the high-pH environment of the cement pore water. The effect of using different filler materials between the waste packages on uranium flux to the vadose zone proved to have a negligible impact on release rates.

A science data gateway for environmental management

Science data gateways are effective in providing complex science data collections to the world‐wide user communities. In this paper we describe a gateway for the Advanced Simulation Capability for Environmental Management (ASCEM) framework. Built on top of established web service technologies, the ASCEM data gateway is specifically designed for environmental modeling applications. Its key distinguishing features include (1) handling of complex spatiotemporal data, (2) offering a variety of selective data access mechanisms, (3) providing state‐of‐the‐art plotting and visualization of spatiotemporal data records, and (4) integrating seamlessly with a distributed workflow system using a RESTful interface. ASCEM project scientists have been using this data gateway since 2011. Copyright

2004 Initial Assessments of Closure for the S-SX Tank Farm: Numerical Simulations

In support of CH2M HILL Hanford Group, Inc.s (CHG) preparation of a Field Investigative Report (FIR) for the closure of the Hanford Site Single-Shell Tank (SST) Waste Management Area (WMA) tank farms, a set of numerical simulations of flow and solute transport was executed to investigate different potential contaminant source scenarios that may pose long-term risks to groundwater from the closure of the S-SX Tank Farm. This report documents the simulation of 7 cases (plus two verification) involving two-dimensional cross sections through the S Tank Farm (Tanks S-101, S102, and S-103) and the simulation of one case involving three-dimensional domain of the S Tank Farm. Using a unit release scenario at Tank S-103, three different types of leaks were simulated. These simulations assessed the effect of leaks during retrieval as well as residual wastes and ancillary equipment after closure. Two transported solutes were considered: uranium-238 (U-238) and technetium-99 (Tc 99). To evaluate the effect of sorption on contaminant transport, six different sorption coefficients were simulated for U 238. Overall, simulations results for the S Tank Farm showed that only a small fraction (< 0.4%) of the U-238 with sorption coefficients  0.6 mL/g migrated from the vadose zone in all of the cases. For the conservative solute, Tc-99, results showed that the simulations investigating leaks during retrieval demonstrated the highest peak concentrations and the earliest arrival times due to the high infiltration rate before water was added and surface barriers installed. Residual leaks were investigated with different release rate models, including uniform release, advection-dominated, diffusion-dominated, and saltcake (solubility-controlled) release models. Of the four models, peak concentrations were lowest and arrival times later for the uniform release model due to the lower release rate of the residual tank waste solids; similar high peak concentrations occurred for the advection-dominated and the salt cake models due to the higher release rate. For the tank ancillary equipment leak case, the diffusion-dominated release rate model yielded peak concentrations and arrival times that were similar to the majority of the past leak cases for residual tank wastes. Comparison between the results of the two-dimensional and those of the three-dimensional simulations show that the two-dimensional simulation significantly overestimated the peak concentrations of the contaminants by a factor of about 41 for Tc-99 and 37 for U-238 with sorption coefficient of 0.03 mL/g.