K. Ulrich Mayer

Reactive transport modeling of an in situ reactive barrier for the treatment of hexavalent chromium and trichloroethylene in groundwater

Multicomponent reactive transport modeling was conducted for the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, North Carolina. The zero-valent iron barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated solvents. The simulations were performed using the reactive transport model MIN3P, applied to an existing site-specific conceptual model. Reaction processes controlling the geochemical evolution within and down gradient of the barrier were considered. Within the barrier, the treatment of the contaminants, the reduction of other electron acceptors present in the ambient groundwater, microbially mediated sulfate reduction, the precipitation of secondary minerals, and degassing of hydrogen gas were included. Down gradient of the barrier, water-rock interactions between the highly alkaline and reducing pore water emanating from the barrier and the aquifer material were considered. The model results illustrate removal of Cr(VI) and the chlorinated solvents by the reactive barrier and highlight that reactions other than the remediation reactions most significantly affect the water chemistry in the barrier. In particular, sulfate reduction and iron corrosion by water control the evolution of the pore water while passing through the treatment system. The simulation results indicate that secondary mineral formation has the potential to decrease the porosity in the barrier over the long term and illustrate that the precipitation of minerals is concentrated in the upgradient portion of the barrier. Two-dimensional simulations demonstrate how preferential flow can affect the reduction of electron acceptors, the consumption of the treatment material, and the formation of secondary minerals. In addition, the model results indicate that deprotonation and the adsorption of cations down gradient of the barrier can potentially explain the observed pH buffering.

Effectiveness of various cover scenarios on the rate of sulfide oxidation of mine tailings

Long term environmentally sound disposal of the millions of tons of mining residue is a serious challenge to the international mining industry. This paper evaluates, through a numerical investigation, the potential performance of desulfurized tailings as a cover material for the reduction of acidic drainage from sulfidic tailings. This evaluation is facilitated through a comparison of various cover types as decommissioning options. The cover types considered consist of a desulfurized tailings material cover exposed to ambient climate conditions, a water cover (flooded tailings), and a combination cover type. As part of the evaluation of cover performances, the effect of climatic variability on the potential rate of sulfide oxidation in tailings with an open ground surface, was also assessed. The numerical analysis was conducted using the model PYROX, which was modified to allow for variably-saturated conditions, time varying moisture contents, and to account for the temperature dependence of Henrys law and gas diffusion. In the case study presented here, the benign cover material consists of a low sulfide waste stream (cassiterite float tails, CFT), a by-product of the production of tin concentrate (cassiterite, SnO2). Modelling results after a simulation period of 100 years indicate that a water cover alone or an exposed CFT cover alone are both less effective options than the combined cover type. A water cover alone leads to a reduction of approximately 99.1%, in the oxidation rate relative to uncovered tailings while the combined cover type results in the lowest potential extent of sulfide oxidation after mine closure-an approximately 99.8% reduction. Importantly, a CFT cover exposed to ambient environmental conditions can still substantially reduce the sulfide oxidation rate, by approximately 75–82% over a 100-year time period, relative to uncovered tailings. Variability in precipitation (and hence percent saturation of the surface layer) had less of an effect on the potential sulfide oxidation rate than did the cover type. The performance of the exposed CFT cover varied by less than 10%, within the range of climatic conditions expected at the Renison Bell mine site in southwest Tasmania, Australia. Although the modelling results indicate that the combined water and CFT cover is the best option, this approach achieves only a minor improvement over the water cover alone.

CO2-efflux measurements for evaluating source zone natural attenuation rates in a petroleum hydrocarbon contaminated aquifer.

In order to gain regulatory approval for source zone natural attenuation (SZNA) at hydrocarbon-contaminated sites, knowledge regarding the extent of the contamination, its tendency to spread, and its longevity is required. However, reliable quantification of biodegradation rates, an important component of SZNA, remains a challenge. If the rate of CO(2) gas generation associated with contaminant degradation can be determined, it may be used as a proxy for the overall rate of subsurface biodegradation. Here, the CO(2)-efflux at the ground surface is measured using a dynamic closed chamber (DCC) method to evaluate whether this technique can be used to assess the areal extent of the contaminant source zone and the depth-integrated rate of contaminant mineralization. To this end, a field test was conducted at the Bemidji, MN, crude oil spill site. Results indicate that at the Bemidji site the CO(2)-efflux method is able to both delineate the source zone and distinguish between the rates of natural soil respiration and contaminant mineralization. The average CO(2)-efflux associated with contaminant degradation in the source zone is estimated at 2.6 μmol m(-2) s(-1), corresponding to a total petroleum hydrocarbon mineralization rate (expressed as C(10)H(22)) of 3.3 g m(-2) day(-1).

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate.

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO(4)). Both the high density (1025 gL(-1)) and reactivity of the treatment solution influence the fate of permanganate (MnO(4)) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO(4) utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer-aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO(4) have a negligible effect on solution density and MnO(4) delivery.

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol.

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 μmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 μmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.

Transport implications resulting from internal redistribution of arsenic and iron within constructed soil aggregates.

Soils are an aggregate-based structured media that have a multitude of pore domains resulting in varying degrees of advective and diffusive solute and gas transport. Consequently, a spectrum of biogeochemical processes may function at the aggregate scale that collectively, and coupled with solute transport, determine element cycling in soils and sediments. To explore how the physical structure impacts biogeochemical processes influencing the fate and transport of As, we examined temporal changes in speciation and distribution of As and Fe within constructed aggregates through experimental measurement and reactive transport simulations. Spherical aggregates were made with As(V)-bearing ferrihydrite-coated sand inoculated with Shewanella sp. ANA-3; aerated solute flow around the aggregate was then induced. Despite the aerated aggregate exterior, where As(V) and ferrihydrite persist as the dominant species, anoxia develops within the aggregate interior. As a result, As and Fe redox gradients emerge, and the proportion of As(III) and magnetite increases toward the aggregate interior. Arsenic(III) and Fe(II) produced in the interior migrate toward the aggregated exterior and result in coaccumulation of As and Fe(III) proximal to preferential flow paths as a consequence of oxygenic precipitation. The oxidized rind of aggregates thus serves as a barrier to As release into advecting pore-water, but also leads to be a buildup of this hazardous element at preferential flow boundaries that could be released upon shifting geochemical conditions.

Benchmarks for multicomponent reactive transport across a cement/clay interface

The use of the subsurface for CO2 storage, geothermal energy generation, and nuclear waste disposal will greatly increase the interaction between clay(stone) and concrete. The development of models describing the mineralogical transformations at this interface is complicated, because contrasting geochemical conditions (Eh, pH, solution composition, etc.) induce steep concentration gradients and a high mineral reactivity. Due to the complexity of the problem, analytical solutions are not available to verify code accuracy, rendering code intercomparisons as the most efficient method for assessing code capabilities and for building confidence in the used model. A benchmark problem was established for tackling this issue. We summarize three scenarios with increasing geochemical complexity in this paper. The processes considered in the simulations are diffusion-controlled transport in saturated media under isothermal conditions, cation exchange reactions, and both local equilibrium and kinetically controlled mineral dissolution-precipitation reactions. No update of the pore diffusion coefficient as a function of porosity changes was considered. Seven international teams participated in this benchmarking exercise. The reactive transport codes used (TOUGHREACT, PHREEQC, with two different ways of handling transport, CRUNCH, HYTEC, ORCHESTRA, MIN3P-THCm) gave very similar patterns in terms of predicted solute concentrations and mineral distributions. Some differences linked to the considered activity models were observed, but they do not bias the general system evolution. The benchmarking exercise thus demonstrates that a reactive transport modelling specification for long-term performance assessment can be consistently addressed by multiple simulators.

Implementation and evaluation of permeability-porosity and tortuosity-porosity relationships linked to mineral dissolution-precipitation

Changes of porosity, permeability, and tortuosity due to physical and geochemical processes are of vital importance for a variety of hydrogeological systems, including passive treatment facilities for contaminated groundwater, engineered barrier systems (EBS), and host rocks for high-level nuclear waste (HLW) repositories. Due to the nonlinear nature and chemical complexity of the problem, in most cases, it is impossible to verify reactive transport codes analytically, and code intercomparisons are the most suitable method to assess code capabilities and model performance. This paper summarizes model intercomparisons for six hypothetical scenarios with generally increasing geochemical or physical complexity using the reactive transport codes CrunchFlow, HP1, MIN3P, PFlotran, and TOUGHREACT. Benchmark problems include the enhancement of porosity and permeability through mineral dissolution, as well as near complete clogging due to localized mineral precipitation, leading to reduction of permeability and tortuosity. Processes considered in the benchmark simulations are advective-dispersive transport in saturated media, kinetically controlled mineral dissolution-precipitation, and aqueous complexation. Porosity changes are induced by mineral dissolution-precipitation reactions, and the Carman-Kozeny relationship is used to describe changes in permeability as a function of porosity. Archie’s law is used to update the tortuosity and the pore diffusion coefficient as a function of porosity. Results demonstrate that, generally, good agreement is reached amongst the computer models despite significant differences in model formulations. Some differences are observed, in particular for the more complex scenarios involving clogging; however, these differences do not affect the interpretation of system behavior and evolution.

Manganese valence in oxides formed from in situ chemical oxidation of TCE by KMnO4.

Batch and column experiments designed to simulate in situ chemical oxidation (ISCO) in a sand aquifer were conducted to create Mn-oxides (MnOx) by oxidation of trichloroethylene (TCE) with permanganate (MnO4-). Electron energy-loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) were used to quantify Mn valence in the oxides. The valence of Mn in the MnOx generated in near-source ISCO conditions was 2.2 and 2.3 when formed at low (<3) and neutral (6-7) pH conditions, respectively. There is no significant difference between these values. Valence was found to be sensitive to the preparation method and to aging. When formed in the presence of excess MnO4-, or aged for 3 months, Mn valence ranged from 2.5 to 3.6. Aging in a lower pH environment inhibited Mn oxidation. The EELS and XPS methods provided similar results, but there was a slight bias to higher values for XPS. This work demonstrates that MnO2(s) may not be the main product of MnO4- reaction with chlorinated solvents as is commonly assumed and that the efficiency of ISCO treatment may be greater than previously known.

Solubility controls for molybdenum in neutral rock drainage

Mineral controls on molybdate (MoO42−) solubility were studied to better understand the fate of molybdenum (Mo) in neutral rock drainage. Batch and column experiments lasting from 46–110 days predict that molybdate (MoO42−) mobility is limited by powellite (CaMoO4) and wulfenite (PbMoO4) precipitation under neutral pH conditions with aqueous Ca and Pb present. Batch experiments demonstrate that wulfenite forms almost instantaneously and effectively removes Pb from solution to concentrations below detection limits. Powellite formation is kinetically limited, but has the capacity to significantly reduce Mo concentrations in the presence of calcite. An initial inhibition of powellite formation is observed, likely due to a lack of available nucleation sites. After the nucleation phase, powellite formation from supersaturated conditions follows a second order rate expression with linear dependence on Ca2+ and MoO42−. A column experiment provides further evidence of rapid wulfenite formation and kinetically limited powellite formation. Both powellite and wulfenite have also been identified in molybdenum-bearing carbonate-rich waste rock sampled from barrel-sized field cell weathering experiments, providing direct evidence that these minerals affect Mo mobility under field conditions. In contrast to Pb and Ca, both Cu and Zn did not form distinct molybdate precipitates.