Reactive Transport Simulation of Fracture Channelization and Transmissivity Evolution.
ABSTRACT: Underground fractures serve as flow conduits, and they may produce unwanted migration of water and other fluids in the subsurface. An example is the migration and leakage of greenhouse gases in the context of geologic carbon sequestration. This study has generated new understanding about how acids erode carbonate fracture surfaces and the positive feedback between reaction and flow. A two-dimensional reactive transport model was developed and used to investigate the extent to which geochemical factors influence fracture permeability and transmissivity evolution in carbonate rocks. The only mineral modeled as reactive is calcite, a fast-reacting mineral that is abundant in subsurface formations. The X-ray computed tomography dataset from a previous experimental study of fractured cores exposed to carbonic acid served as a testbed to benchmark the model simulation results. The model was able to capture not only erosion of fracture surfaces but also the specific phenomenon of channelization, which produces accelerating transmissivity increase. Results corroborated experimental findings that higher reactivity of the influent solution leads to strong channelization without substantial mineral dissolution. Simulations using mineral maps of calcite in a specimen of Amherstburg limestone demonstrated that mineral heterogeneity can either facilitate or suppress the development of flow channels depending on the spatial patterns of reactive mineral. In these cases, fracture transmissivity may increase rapidly, increase slowly, or stay constant, and for all these possibilities, the calcite mineral continues to dissolve. Collectively, these results illustrate that fluid chemistry and mineral spatial patterns need to be considered in predictions of reaction-induced fracture alteration and risks of fluid migration.
Project description:Soil stabilization involves methods used to turn unconsolidated and unstable soil into a stiffer, consolidated medium that could support engineered structures, alter permeability, change subsurface flow, or immobilize contamination through mineral precipitation. Among the variety of available methods carbonate precipitation is a very promising one, especially when it is being induced through common soil borne microbes (MICP - microbial induced carbonate precipitation). Such microbial mediated precipitation has the added benefit of not harming the environment as other methods can be environmentally detrimental. Carbonate precipitation, typically in the form of calcite, is a naturally occurring process that can be manipulated to deliver the expected soil strengthening results or permeability changes. This study investigates the ability of spectral induced polarization and shear-wave velocity for monitoring calcite driven soil strengthening processes. The results support the use of these geophysical methods as soil strengthening characterization and long term monitoring tools, which is a requirement for viable soil stabilization projects. Both tested methods are sensitive to calcite precipitation, with SIP offering additional information related to long term stability of precipitated carbonate. Carbonate precipitation has been confirmed with direct methods, such as direct sampling and scanning electron microscopy (SEM). This study advances our understanding of soil strengthening processes and permeability alterations, and is a crucial step for the use of geophysical methods as monitoring tools in microbial induced soil alterations through carbonate precipitation.
Project description:Karstic caves represent one of the most important subterranean carbon storages on Earth and provide windows into the subsurface. The recent discovery of the Herrenberg Cave, Germany, gave us the opportunity to investigate the diversity and potential role of bacteria in carbonate mineral formation. Calcite was the only mineral observed by Raman spectroscopy to precipitate as stalactites from seepage water. Bacterial cells were found on the surface and interior of stalactites by confocal laser scanning microscopy. Proteobacteria dominated the microbial communities inhabiting stalactites, representing more than 70% of total 16S rRNA gene clones. Proteobacteria formed 22 to 34% of the detected communities in fluvial sediments, and a large fraction of these bacteria were also metabolically active. A total of 9 isolates, belonging to the genera Arthrobacter, Flavobacterium, Pseudomonas, Rhodococcus, Serratia, and Stenotrophomonas, grew on alkaline carbonate-precipitating medium. Two cultures with the most intense precipitate formation, Arthrobacter sulfonivorans and Rhodococcus globerulus, grew as aggregates, produced extracellular polymeric substances (EPS), and formed mixtures of calcite, vaterite, and monohydrocalcite. R. globerulus formed idiomorphous crystals with rhombohedral morphology, whereas A. sulfonivorans formed xenomorphous globular crystals, evidence for taxon-specific crystal morphologies. The results of this study highlighted the importance of combining various techniques in order to understand the geomicrobiology of karstic caves, but further studies are needed to determine whether the mineralogical biosignatures found in nutrient-rich media can also be found in oligotrophic caves.
Project description:The Umm er Radhuma (UER) Formation is a major karst aquifer in Saudi Arabia. This study investigated the hydraulic and petrophysical characteristics of the folded UER carbonate aquifer using integrated hydrological and geophysical logging datasets to understand its complex hydraulic setting as well as detect possible water flow. Petrophysical analysis showed that the UER aquifer has three zones with different lithologic and hydraulic properties. The upper zone attains the best properties with average values of 20%,?>100?mD, 3.30?×?10<sup>-5</sup>-1.34?×?10<sup>-3</sup>?m/s, and 1.49?×?10<sup>-3</sup>-6.04?×?10<sup>-2</sup>?m<sup>2</sup>/s, with respect to effective porosity, permeability, hydraulic conductivity and transmissivity. The gamma-ray logs indicate a good fracture system near the upper zone of the UER Formation. Pumping test measurements of transmissivity, hydraulic conductivity and storage coefficients were matched with those from geophysical logs and found to be within the expected range for confined and leaky aquifers. Hydrogeological properties were mapped to detect possible groundwater flow in relation to the dominant structure. The underground water of the folded UER aquifer was forced along meandering flow patterns from W-E to SW-NE through the anticlinal axes. The integrated approach can be further used to enhance local aquifer models and improve strategies for identifying the most productive zones in similar aquifer systems.
Project description:The engineered removal of atmospheric CO2 is now considered a key component of mitigating climate warming below 1.5 °C. Mineral carbonation is a potential negative emissions technique that, in the case of Iceland's CarbFix experiment, precipitates dissolved CO2 as carbonate minerals in basaltic groundwater settings. Here we use calcium (Ca) isotopes in both pre- and post-CO2 injection waters to quantify the amount of carbonate precipitated, and hence CO2 stored. Ca isotope ratios rapidly increase with the pH and calcite saturation state, indicating calcite precipitation. Calculations suggest that up to 93% of dissolved Ca is removed into calcite during certain phases of injection. In total, our results suggest that 165 ± 8.3 t CO2 were precipitated into calcite, an overall carbon storage efficiency of 72 ± 5%. The success of this approach opens the potential for quantification of similar mineral carbonation efforts where drawdown rates cannot be estimated by other means.
Project description:In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth.
Project description:Chicken eggshell is a biomineral composed of 95% calcite calcium carbonate mineral and of 3.5% organic matrix proteins. The assembly of mineral and its structural organization is controlled by its organic matrix. In a recent study , we have used quantitative proteomic, bioinformatic and functional analyses to explore the distribution of 216 eggshell matrix proteins at four key stages of shell mineralization defined as: (1) widespread deposition of amorphous calcium carbonate (ACC), (2) ACC transformation into crystalline calcite aggregates, (3) formation of larger calcite crystal units and (4) rapid growth of calcite as columnar structure with preferential crystal orientation. The current article detailed the quantitative analysis performed at the four stages of shell mineralization to determine the proteins which are the most abundant. Additionally, we reported the enriched GO terms and described the presence of 35 antimicrobial proteins equally distributed at all stages to keep the egg free of bacteria and of 81 proteins, the function of which could not be ascribed.
Project description:Calcite (CaCO<sub>3</sub>) is one of the most abundant minerals in the Earth's crust, and it is susceptible to subcritical chemically-driven fracturing. Understanding chemical processes at individual fracture tips, and how they control the development of fractures and fracture networks in the subsurface, is critical for carbon and nuclear waste storage, resource extraction, and predicting earthquakes. Chemical processes controlling subcritical fracture in calcite are poorly understood. We demonstrate a novel approach to quantify the coupled chemical-mechanical effects on subcritical fracture. The calcite surface was indented using a Vickers-geometry indenter tip, which resulted in repeatable micron-scale fractures propagating from the indent. Individual indented samples were submerged in an array of aqueous fluids and an optical microscope was used to track the fracture growth in situ. The fracture propagation rate varied from 1.6?×?10<sup>-8</sup>?m?s<sup>-1</sup> to 2.4?×?10<sup>-10</sup>?m?s<sup>-1</sup>. The rate depended on the type of aqueous ligand present, and did not correlate with the measured dissolution rate of calcite or trends in zeta-potential. We postulate that chemical complexation at the fracture tip in calcite controls the growth of subcritical fracture. Previous studies indirectly pointed to the zeta-potential being the most critical factor, while our work indicates that variation in the zeta-potential has a secondary effect.
Project description:Major hydrocarbon accumulations occur in traps associated with salt domes. Whereas some of these hydrocarbons remain to be extracted for economic use, significant amounts have degraded in the subsurface, yielding mineral precipitates as byproducts. Salt domes of the Gulf of Mexico Basin typically exhibit extensive deposits of carbonate that form as cap rock atop salt structures. Despite previous efforts to model cap rock formation, the details of subsurface reactions (including the role of microorganisms) remain largely unknown. Here we show that cap rock mineral precipitation occurred via closed-system sulfate reduction, as indicated by new sulfur isotope data. 13C-depleted carbonate carbon isotope compositions and low clumped isotope-derived carbonate formation temperatures indicate that microbial, sulfate-dependent, anaerobic oxidation of methane (AOM) contributed to carbonate formation. These findings suggest that AOM serves as an unrecognized methane sink that reduces methane emissions in salt dome settings perhaps associated with an extensive, deep subsurface biosphere.
Project description:Carbon dioxide (CO2) sequestration in subsurface reservoirs is important for limiting atmospheric CO2 concentrations. However, a complete physical picture able to predict the structure developing within the porous medium is lacking. We investigate theoretically reactive transport in the long-time evolution of carbon in the brine-rock environment. As CO2 is injected into a brine-rock environment, a carbonate-rich region is created amid brine. Within the carbonate-rich region minerals dissolve and migrate from regions of high-to-low concentration, along with other dissolved carbonate species. This causes mineral precipitation at the interface between the two regions. We argue that precipitation in a small layer reduces diffusivity, and eventually causes mechanical trapping of the CO2. Consequently, only a small fraction of the CO2 is converted to solid mineral; the remainder either dissolves in water or is trapped in its original form. We also study the case of a pure CO2 bubble surrounded by brine and suggest a mechanism that may lead to a carbonate-encrusted bubble owing to structural diffusion.
Project description:Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface.