Alteration and Erosion of Rock Matrix Bordering a Carbonate-Rich Shale Fracture.

A novel reactive transport model has been developed to examine the processes that affect fracture evolution in a carbonate-rich shale. An in situ synchrotron X-ray microtomography experiment, flowing CO2 saturated water through a single fracture mini-core of Niobrara Shale provided the experimental observations for the development and testing of the model. The phenomena observed included the development of a porous altered layer, flow channeling, and increasingly limited calcite dissolution. The experimental observations cannot be explained by models that consider only mineral dissolution and development of an altered layer. The difference between the fracture volume change recorded by the microtomography images and what would be expected from mineral dissolution alone suggest that there is erosion of the altered layer as it develops. The numerical model includes this additional mechanism, with the erosion rate based on the thickness of the altered layer, and successfully captures the evolution of the geochemical reactions and morphology of the fracture. The findings imply that the abundance (with a threshold of approximately 35%) and reactivity of the rapidly reacting mineral control the development and erodibility of the altered layer on the fracture surfaces, and therefore fracture opening.

Reoxidation of Chromium(III) Products Formed under Different Biogeochemical Regimes.

Hexavalent chromium, Cr(VI), is a widespread and toxic groundwater contaminant. Reductive immobilization to Cr(III) is a treatment option, but its success depends on the long-term potential for reduced chromium precipitates to remain immobilized under oxidizing conditions. In this unique long-term study, aquifer sediments subjected to reductive Cr(VI) immobilization under different biogeochemical regimes were tested for their susceptibility to reoxidation. After reductive treatment for 1 year, sediments were exposed to oxygenated conditions for another 2 years in flow-through, laboratory columns. Under oxidizing conditions, immobilized chromium reduced under predominantly denitrifying conditions was mobilized at low concentrations (≪1 µM Cr(VI); ∼ 3% of Cr(III) deposited) that declined over time. A conceptual model of a limited pool of more soluble Cr(III), and a larger pool of relatively insoluble Cr(III), is proposed. In contrast, almost no chromium was mobilized from columns reduced under predominantly fermentative conditions, and where reducing conditions persisted for several months after introduction of oxidizing conditions, presumably due to the presence of a reservoir of reduced species generated during reductive treatment. The results from this 3-year study demonstrate that biogeochemical conditions present during reductive treatment, and the potential for buildup of reducing species, will impact the long-term sustainability of the remediation effort.

A 2.5D Reactive Transport Model for Fracture Alteration Simulation.

Understanding fracture alteration resulting from geochemical reactions is critical in predicting fluid migration in the subsurface and is relevant to multiple environmental challenges. Here, we present a novel 2.5D continuum reactive transport model that captures and predicts the spatial pattern of fracture aperture change and the development of an altered layer in the near-fracture region. The model considers permeability heterogeneity in the fracture plane and updates fracture apertures and flow fields based on local reactions. It tracks the reaction front of each mineral phase and calculates the thickness of the altered layer. Given this treatment, the model is able to account for the diffusion limitation on reaction rates associated with the altered layer. The model results are in good agreement with an experimental study in which a CO2-acidified brine was injected into a fracture in the Duperow Dolomite, causing dissolution of calcite and dolomite that result in the formation of a preferential flow channel and an altered layer. With an effective diffusion coefficient consistent with the experimentally observed porosity of the altered layer, the model captures the progressive decrease in the dissolution rate of the fast-reacting mineral in the altered layer.

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.

Pore-scale controls on calcite dissolution rates from flow-through laboratory and numerical experiments.

A combination of experimental, imaging, and modeling techniques were applied to investigate the pore-scale transport and surface reaction controls on calcite dissolution under elevated pCO2 conditions. The laboratory experiment consisted of the injection of a solution at 4 bar pCO2 into a capillary tube packed with crushed calcite. A high resolution pore-scale numerical model was used to simulate the experiment based on a computational domain consisting of reactive calcite, pore space, and the capillary wall constructed from volumetric X-ray microtomography images. Simulated pore-scale effluent concentrations were higher than those measured by a factor of 1.8, with the largest component of the discrepancy related to uncertainties in the reaction rate model and its parameters. However, part of the discrepancy was apparently due to mass transport limitations to reactive surfaces, which were most pronounced near the inlet where larger diffusive boundary layers formed around grains and in slow-flowing pore spaces that exchanged mass by diffusion with fast flow paths. Although minor, the difference between pore- and continuum-scale results due to transport controls was discernible with the highly accurate methods employed and is expected to be more significant where heterogeneity is greater, as in natural subsurface materials.

Divergent aquifer biogeochemical systems converge on similar and unexpected Cr(VI) reduction products.

In this study of reductive chromium immobilization, we found that flow-through columns constructed with homogenized aquifer sediment and continuously infused with lactate, chromate, and various native electron acceptors diverged to have very different Cr(VI)-reducing biogeochemical regimes characterized by either denitrifying or fermentative conditions (as indicated by effluent chemical data, 16S rRNA pyrotag data, and metatranscriptome data). Despite the two dramatically different biogeochemical environments that evolved in the columns, these regimes created similar Cr(III)-Fe(III) hydroxide precipitates as the predominant Cr(VI) reduction product, as characterized by micro-X-ray fluorescence and micro-X-ray absorption near-edge structure analysis. We discuss two conflicting scenarios of microbially mediated formation of Cr(III)-Fe(III) precipitates, each of which is both supported and contradicted by different lines of evidence: (1) enzymatic reduction of Cr(VI) to Cr(III) followed by coprecipitation of Cr(III) and Fe(III) and (2) both regimes generated at least small amounts of Fe(II), which abiotically reduced Cr(VI) to form a Cr-Fe precipitate. Evidence of zones with different levels of Cr(VI) reduction suggest that local heterogeneity may have confounded interpretation of processes based on bulk measurements. This study indicates that the bulk redox status and biogeochemical regime, as categorized by the dominant electron-accepting process, do not necessarily control the final product of Cr(VI) reduction.

Understanding the hydrological response of a headwater-dominated catchment by analysis of distributed surface-subsurface interactions.

We computationally explore the relationship between surface-subsurface exchange and hydrological response in a headwater-dominated high elevation, mountainous catchment in East River Watershed, Colorado, USA. In order to isolate the effect of surface-subsurface exchange on the hydrological response, we compare three model variations that differ only in soil permeability. Traditional methods of hydrograph analysis that have been developed for headwater catchments may fail to properly characterize catchments, where catchment response is tightly coupled to headwater inflow. Analyzing the spatially distributed hydrological response of such catchments gives additional information on the catchment functioning. Thus, we compute hydrographs, hydrological indices, and spatio-temporal distributions of hydrological variables. The indices and distributions are then linked to the hydrograph at the outlet of the catchment. Our results show that changes in the surface-subsurface exchange fluxes trigger different flow regimes, connectivity dynamics, and runoff generation mechanisms inside the catchment, and hence, affect the distributed hydrological response. Further, changes in surface-subsurface exchange rates lead to a nonlinear change in the degree of connectivity-quantified through the number of disconnected clusters of ponding water-in the catchment. Although the runoff formation in the catchment changes significantly, these changes do not significantly alter the aggregated streamflow hydrograph. This hints at a crucial gap in our ability to infer catchment function from aggregated signatures. We show that while these changes in distributed hydrological response may not always be observable through aggregated hydrological signatures, they can be quantified through the use of indices of connectivity.

Timing the onset of sulfate reduction over multiple subsurface acetate amendments by measurement and modeling of sulfur isotope fractionation.

Stable isotope fractionations of sulfur are reported for three consecutive years of acetate-enabled uranium bioremediation at the US Department of Energy's Rifle Integrated Field Research Challenge (IFRC) site. The data show a previously undocumented decrease in the time between acetate addition and the onset of sulfate reducing conditions over subsequent amendments, from 20 days in the 2007 experiment to 4 days in the 2009 experiment. Increased sulfide concentrations were observed at the same time as δ(34)S of sulfate enrichment in the first year, but in subsequent years elevated sulfide was detected up to 15 days after increased δ(34)S of sulfate. A biogeochemical reactive transport model is developed which explicitly incorporates the stable isotopes of sulfur to simulate fractionation during the 2007 and 2008 amendments. A model based on an initially low, uniformly distributed population of sulfate reducing bacteria that grow and become spatially variable with time reproduces measured trends in solute concentration and δ(34)S, capturing the change in onset of sulfate reduction in subsequent years. Our results demonstrate a previously unrecognized hysteretic effect in the spatial distribution of biomass growth during stimulated subsurface bioremediation.