Malcolm Dean Siegel

Crystalline Todorokite Associated with Biogenic Debris in Manganese Nodules

Platy intergrowths of crystalline todorokite are associated with biogenic debris in the cores of manganese nodules from a site in the Pacific Ocean. Analyses by electron diffraction and transmission electron microscopy demonstrate that this material is composed of tunnels of chains of linked MnO6 octahedra. The chemical composition, morphology, and stability of the todorokite differ from those of nickel-and copper-rich manganese oxides in nodules that have been identified as todorokite or buserite in earlier investigations.

Environmental geochemistry of radioactive contamination.

This report attempts to describe the geochemical foundations of the behavior of radionuclides in the environment. The information is obtained and applied in three interacting spheres of inquiry and analysis: (1) experimental studies and theoretical calculations, (2) field studies of contaminated and natural analog sites and (3) model predictions of radionuclide behavior in remediation and waste disposal. Analyses of the risks from radioactive contamination require estimation of the rates of release and dispersion of the radionuclides through potential exposure pathways. These processes are controlled by solubility, speciation, sorption, and colloidal transport, which are strong functions of the compositions of the groundwater and geomedia as well as the atomic structure of the radionuclides. The chemistry of the fission products is relatively simple compared to the actinides. Because of their relatively short half-lives, fission products account for a large fraction of the radioactivity in nuclear waste for the first several hundred years but do not represent a long-term hazard in the environment. The chemistry of the longer-lived actinides is complex; however, some trends in their behavior can be described. Actinide elements of a given oxidation state have either similar or systematically varying chemical properties due to similarities in ionic size, coordination number, valence, and electron structure. In dilute aqueous systems at neutral to basic pH, the dominant actinide species are hydroxy- and carbonato-complexes, and the solubility-limiting solid phases are commonly oxides, hydroxides or carbonates. In general, actinide sorption will decrease in the presence of ligands that complex with the radionuclide; sorption of the (IV) species of actinides (Np, Pu, U) is generally greater than of the (V) species. The geochemistry of key radionuclides in three different environments is described in this report. These include: (1) low ionic strength reducing waters from crystalline rocks at nuclear waste research sites in Sweden; (2) oxic water from the J-13 well at Yucca Mountain, Nevada, the site of a proposed repository for high level nuclear waste (HLW) in tuffaceous rocks; and (3) reference brines associated with the Waste Isolation Pilot Plant (WIPP). The transport behaviors of radionuclides associated with the Chernobyl reactor accident and the Oklo Natural Reactor are described. These examples span wide temporal and spatial scales and include the rapid geochemical and physical processes important to nuclear reactor accidents or industrial discharges as well as the slower processes important to the geologic disposal of nuclear waste. Application of geochemical information to remediating or assessing the risk posed by radioactive contamination is the final subject of this report. After radioactive source terms have been removed, large volumes of soil and water with low but potentially hazardous levels of contamination may remain. For poorly-sorbing radionuclides, capture of contaminated water and removal of radionuclides may be possible using permeable reactive barriers and bioremediation. For strongly sorbing radionuclides, contaminant plumes will move very slowly. Through a combination of monitoring, regulations and modeling, it may be possible to have confidence that they will not be a hazard to current or future populations. Abstraction of the hydrogeochemical properties of real systems into simple models is required for probabilistic risk assessment. Simplifications in solubility and sorption models used in performance assessment calculations for the WIPP and the proposed HLW repository at Yucca Mountain are briefly described.

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.

Geochemical evolution of groundwater in the Culebra dolomite near the Waste Isolation Pilot Plant, southeastern New Mexico, USA☆

Abstract The Culebra Dolomite Member of the Rustler Formation, a thin (10 m) fractured dolomite aquifer, lies approximately 450 m above the repository horizon of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico, USA. Salinities of water in the Culebra range roughly from 10,000 to 200,000 mg/L within the WIPP site. A proposed model for the post-Pleistocene hydrochemical evolution of the Culebra tentatively identifies the major sources and sinks for many of the groundwater solutes. Reaction-path simulations with the PHRQPITZ code suggest that the Culebra dolomite is a partial chemical equilibrium system whose composition is controlled by an irreversible process (dissolution of evaporites) and equilibrium with gypsum and calcite. Net geochemical reactions along postulated modern flow paths, calculated with the NETPATH code, include dissolution of halite, carbonate and evaporite salts, and ion exchange. R-mode principal component analysis revealed correlations among the concentrations of Si, Mg, pH, Li, and B that are consistent with several clay-water reactions. The results of the geochemical calculations and mineralogical data are consistent with the following hydrochemical model: 1. (1) solutes are added to the Culebra by dissolution of evaporite minerals 2. (2) the solubilities of gypsum and calcite increase as the salinity increases; these minerals dissolve as chemical equilibrium is maintained between them and the groundwater 3. (3) equilibrium is not maintained between the waters and dolomite; sufficient Mg is added to the waters by dissolution of accessory carnallite or polyhalite such that the degree of dolomite supersaturation increases with ionic strength 4. (4) clays within the fractures and rock matrix exert some control on the distribution of Li, B, Mg, and Si via sorption, ion exchange, and dissolution.

Innovative mathematical modeling in environmental remediation

There are two different ways to model reactive transport: ad hoc and innovative reaction-based approaches. The former, such as the Kd simplification of adsorption, has been widely employed by practitioners, while the latter has been mainly used in scientific communities for elucidating mechanisms of biogeochemical transport processes. It is believed that innovative mechanistic-based models could serve as protocols for environmental remediation as well. This paper reviews the development of a mechanistically coupled fluid flow, thermal transport, hydrologic transport, and reactive biogeochemical model and example-applications to environmental remediation problems. Theoretical bases are sufficiently described. Four example problems previously carried out are used to demonstrate how numerical experimentation can be used to evaluate the feasibility of different remediation approaches. The first one involved the application of a 56-species uranium tailing problem to the Melton Branch Subwatershed at Oak Ridge National Laboratory (ORNL) using the parallel version of the model. Simulations were made to demonstrate the potential mobilization of uranium and other chelating agents in the proposed waste disposal site. The second problem simulated laboratory-scale system to investigate the role of natural attenuation in potential off-site migration of uranium from uranium mill tailings after restoration. It showed inadequacy of using a single Kd even for a homogeneous medium. The third example simulated laboratory experiments involving extremely high concentrations of uranium, technetium, aluminum, nitrate, and toxic metals (e.g., Ni, Cr, Co). The fourth example modeled microbially-mediated immobilization of uranium in an unconfined aquifer using acetate amendment in a field-scale experiment. The purposes of these modeling studies were to simulate various mechanisms of mobilization and immobilization of radioactive wastes and to illustrate how to apply reactive transport models for environmental remediation.

Pilot test specific test plan for the removal of arsenic Socorro, New Mexico.

Sandia National Laboratories (SNL) is conducting pilot scale evaluations of the performance and cost of innovative drinking water treatment technologies designed to meet the new arsenic maximum contaminant level (MCL) of 10 {micro}g/L (effective January 2006). As currently envisioned, pilots tests may include multiple phases. Phase I tests will involve side-by-side comparisons of several commercial technologies primarily using design parameters suggested by the Vendors. Subsequent tests (Phase II) may involve repeating some of the original tests, testing the same commercial technologies under different conditions and testing experimental technologies or additional commercial technologies. This Pilot Test Specific Test Plan (PTSTP) was written for Phase I of the Socorro Springs Pilot. The objectives of Phase I include evaluation of the treatment performance of five adsorptive media under ambient pH conditions (approximately 8.0) and assessment of the effect of contact time on the performance of one of the media. Addenda to the PTSTP may be written to cover Phase II studies and supporting laboratory studies. The Phase I demonstration began in the winter of 2004 and will last approximately 9 months. The information from the test will help the City of Socorro choose the best arsenic treatment technology for the Socorro Springs well. The pilot demonstration is a project of the Arsenic Water Technology Partnership program, a partnership between the American Water Works Association (AWWA) Research Foundation, SNL, and WERC (A Consortium for Environmental Education and Technology Development).

An Analysis of Waste Package Behavior for High-Level Waste

A sensitivity analysis was performed to determine the impact of the containment time criterion on compliance with the Environmental Protection Agency Draft Standard when using temperature-dependent leach rates. The results of this analysis indicate that canister design life can be shown to be important when the effects of temperature on leach rates are taken into account.

Nuclear Energy Advanced Modeling and Simulation (NEAMS) Waste Integrated Performance and Safety Codes (IPSC): Gap Analysis for High Fidelity and Performance Assessment Code Development

This report describes a gap analysis performed in the process of developing the Waste Integrated Performance and Safety Codes (IPSC) in support of the U.S. Department of Energy (DOE) Office of Nuclear Energy Advanced Modeling and Simulation (NEAMS) Campaign. The goal of the Waste IPSC is to develop an integrated suite of computational modeling and simulation capabilities to quantitatively assess the long-term performance of waste forms in the engineered and geologic environments of a radioactive waste storage or disposal system. The Waste IPSC will provide this simulation capability (1) for a range of disposal concepts, waste form types, engineered repository designs, and geologic settings, (2) for a range of time scales and distances, (3) with appropriate consideration of the inherent uncertainties, and (4) in accordance with rigorous verification, validation, and software quality requirements. The gap analyses documented in this report were are performed during an initial gap analysis to identify candidate codes and tools to support the development and integration of the Waste IPSC, and during follow-on activities that delved into more detailed assessments of the various codes that were acquired, studied, and tested. The current Waste IPSC strategy is to acquire and integrate the necessary Waste IPSC capabilities wherever feasible, and develop only those capabilities that cannot be acquired or suitably integrated, verified, or validated. The gap analysis indicates that significant capabilities may already exist in the existing THC codes although there is no single code able to fully account for all physical and chemical processes involved in a waste disposal system. Large gaps exist in modeling chemical processes and their couplings with other processes. The coupling of chemical processes with flow transport and mechanical deformation remains challenging. The data for extreme environments (e.g., for elevated temperature and high ionic strength media) that are needed for repository modeling are severely lacking. In addition, most of existing reactive transport codes were developed for non-radioactive contaminants, and they need to be adapted to account for radionuclide decay and in-growth. The accessibility to the source codes is generally limited. Because the problems of interest for the Waste IPSC are likely to result in relatively large computational models, a compact memory-usage footprint and a fast/robust solution procedure will be needed. A robust massively parallel processing (MPP) capability will also be required to provide reasonable turnaround times on the analyses that will be performed with the code. A performance assessment (PA) calculation for a waste disposal system generally requires a large number (hundreds to thousands) of model simulations to quantify the effect of model parameter uncertainties on the predicted repository performance. A set of codes for a PA calculation must be sufficiently robust and fast in terms of code execution. A PA system as a whole must be able to provide multiple alternative models for a specific set of physical/chemical processes, so that the users can choose various levels of modeling complexity based on their modeling needs. This requires PA codes, preferably, to be highly modularized. Most of the existing codes have difficulties meeting these requirements. Based on the gap analysis results, we have made the following recommendations for the code selection and code development for the NEAMS waste IPSC: (1) build fully coupled high-fidelity THCMBR codes using the existing SIERRA codes (e.g., ARIA and ADAGIO) and platform, (2) use DAKOTA to build an enhanced performance assessment system (EPAS), and build a modular code architecture and key code modules for performance assessments. The key chemical calculation modules will be built by expanding the existing CANTERA capabilities as well as by extracting useful components from other existing codes.

Evaluation of innovative arsenic treatment technologies :the arsenic water technology partnership vendors forums summary report.

The lowering of the drinking water standard (MCL) for arsenic from 50 {micro}g/L to 10 {micro}g/L in January 2006 could lead to significant increases in the cost of water for many rural systems throughout the United States. The Arsenic Water Technology Partnership (AWTP), a collaborative effort of Sandia National Laboratories, the Awwa Research Foundation (AwwaRF) and WERC: A Consortium for Environmental Education and Technology Development, was formed to address this problem by developing and testing novel treatment technologies that could potentially reduce the costs of arsenic treatment. As a member of the AWTP, Sandia National Laboratories evaluated cutting-edge commercial products in three annual Arsenic Treatment Technology Vendors Forums held during the annual New Mexico Environmental Health Conferences (NMEHC) in 2003, 2004 and 2005. The Forums were comprised of two parts. At the first session, open to all conference attendees, commercial developers of innovative treatment technologies gave 15-minute talks that described project histories demonstrating the effectiveness of their products. During the second part, these same technologies were evaluated and ranked in closed sessions by independent technical experts for possible use in pilot-scale field demonstrations being conducted by Sandia National Laboratories. The results of the evaluations including numerical rankings of the products, links to company websites and copies of presentations made by the representatives of the companies are posted on the project website at http://www.sandia.gov/water/arsenic.htm. This report summarizes the contents of the website by providing brief descriptions of the technologies represented at the Forums and the results of the evaluations.