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

Mathematical modeling of circulation in two-dimensional plane flow

June 1980.CER79-80VMP-SBY59.Includes bibliographical references.Final report to the National Science Foundation, Grant no. CME-7805458

A General Simulator For Reaction-Based Biogeochemical Processes

As more complex biogeochemical situations are being investigated (e.g., evolving reactivity, passivation of reactive surfaces, dissolution of sorbates), there is a growing need for biogeochemical simulators to flexibly and facilely address new reaction forms and rate laws. This paper presents an approach that accommodates this need to efficiently simulate general biogeochemical processes, while insulating the user from additional code development. The approach allows for the automatic extraction of fundamental reaction stoichiometry and thermodynamics from a standard chemistry database, and the symbolic entry of arbitrarily complex user-specified reaction forms, rate laws, and equilibria. The user-specified equilibria and kinetic rates (i.e., they are not defined in the format of the standardized database) are interpreted by the Maple V (Waterloo Maple) symbolic mathematical software package. FORTRAN 90 code is then generated by Maple for (1) the analytical Jacobian matrix (if preferred over the numerical Jacobian matrix) used in the Newton-Raphson solution procedure, and (2) the residual functions for governing equations, user-specified equilibrium expressions and rate laws. Matrix diagonalization eliminates the need to conceptualize the system of reactions as a tableau, which comprises a list of components, species, the stoichiometric matrix, and the formation equilibrium constant vector that forms the species from components (Morel and Hering, 1993), while identifying a minimum rank set of basis species with enhanced numerical convergence properties. The newly generated code, which is designed to operate in the BIOGEOCHEM biogeochemical simulator, is then compiled and linked into the BIOGEOCHEM executable. With these features, users can avoid recoding the simulator to accept new equilibrium expressions or kinetic rate laws, while still taking full advantage of the stoichiometry and thermodynamics provided by an existing chemical database. Thus, the approach introduces efficiencies in the specification of biogeochemical reaction networks and eliminates opportunities for mistakes in preparing input files and coding errors. Test problems are used to demonstrate the features of the procedure. © 2005 Elsevier Ltd. All rights reserved

A uranium bioremediation reactive transport benchmark

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailing site in Rifle, CO, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, and microbially mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introduces acetate and bromide through the upgradient boundary in 14- and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron-accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions as well as aqueous and surface complexation reactions for UO, Fe2+, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity, and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC

Influence of hydrological, biogeochemical and temperature transients on subsurface carbon fluxes in a flood plain environment

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Model simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO₂ partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe⁺² and S⁻² oxidation) to match locally-observed high CO₂ concentrations above reduced zones. Observed seasonal variations in CO₂ concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m⁻² d⁻¹, while including water table variations resulted in an overall decrease in the simulated fluxes. We conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations

Influence of hydrological, biogeochemical and temperature transients on subsurface carbon fluxes in a flood plain environment

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Model simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO₂ partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe⁺² and S⁻² oxidation) to match locally-observed high CO₂ concentrations above reduced zones. Observed seasonal variations in CO₂ concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m⁻² d⁻¹, while including water table variations resulted in an overall decrease in the simulated fluxes. We conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations