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The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with “floes” forming at the atmosphere-water interface, “snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO3 precipitation occurring in waters with low Mg/Ca ( The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in δ13C (−9 to −28‰ VPDB) and δ18O (0 to −20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO2 hydroxylation but the controls on the δ13C-δ18O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (∼0.5 km2) and the limited range of water sources and temperatures, combined with our sampling strategy, allow us to place tight constraints on the processes involved in generating the systematic C and O isotope variations. We develop an isotopic reaction–diffusion model and an isotopic box model for a CO2-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO3. The box model includes four sources or sinks of DIC (atmospheric CO2, high pH spring water, fresh creek water, and CaCO3 precipitation). Model parameters are informed by new floe Δ44Ca data (−0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8 × 10−7 mol/m2/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO2 and the kinetic isotope fractionation factor (KFF (‰) = (α − 1) × 1000) accompanying CO2 hydroxylation, estimated here to be −17.1 ± 0.8‰ (vs. CO2(aq)) for carbon and −7.1 ± 1.1‰ (vs. ‘CO2(aq) + H2O’) for oxygen at 17.4 ± 1.0 °C. Combining our results with revised CO2 hydroxylation KFF values based on previous work suggests consistent KFF values of −17.0 ± 0.3‰ (vs. CO2(aq)) for carbon and −6.8 ± 0.8‰ for oxygen (vs. ‘CO2(aq) + H2O’) over the 17–28 °C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly HC O 3 - , pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate δ13C and δ18O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water δ18O and atmospheric δ13C values. There is evidence that older travertine at The Cedars recorded atmospheric δ13C that predates large-scale combustion of fossil fuels.

Subsurface biological processes, such as biofilm development, modify flow and permeability in fractured rocks, greatly impacting energy production or treatment efficiencies. This study aims to understand biological–hydrological interactions at a bench scale during the progression and treatment of souring (microbially mediated sulfide production). Few bench-scale studies investigate the role of a biofilm on the flow and permeability evolution, sulfidogensis, and nitrate treatment efficacy in fractured rocks. Our experiment consisted of three sandstone columns that represent differing fracture characteristics due to the mode of fracture initiation: one column with no fracture (as a control), one column with a sawcut fracture, and a third column with a fracture induced by Brazilian loading (tensile). We seek to understand the effects of the biofilm-permeability feedback on flow and nutrient transport characteristics of fractured rocks; specifically, we (1) demonstrate how fracture geometries impact the development of the biomass-permeability feedback within the rock fractures and (2) observe the souring trajectory and effects of nitrate treatment. Observed permeability trends demonstrated that bioclogging modified the flow properties of fractured columns such that they became hydrologically similar to those of the control column. While fractures were initially the main sites of sulfate reduction, when fractures were clogged, the flow in the fractured columns transitioned from a fracture-dominated flow to a matrix-dominated flow, impacting the delivery of an electron acceptor/donor to the microbial population, reducing sulfate reduction rates. Experimental data also demonstrated two distinct stages in the biofilm-permeability development. During the initial biofilm development stage, the growing microbial population had increased reaction rates but decreased permeability, i.e., a negative correlation between reaction rates and permeability. In the later stage, when the biofilm had clogged the columns, a series of biofilm shedding and regrowth directly led to reopening and clogging of the flow channels, affecting microbial accessibility to limiting nutrients. As such, a positive correlation between reaction rates and permeability was observed in this later stage. Post experimental measurements of surface elevations of the fractured surfaces revealed that surface elevations in the sawcut column were lower and more evenly distributed than the surface elevations in the tensile column where the more unevenly fractured surfaces potentially better supported the microbial establishment.

Flow-through fractures dominate the movement of fluids in a variety of natural as well as engineered subsurface systems. Microbial activities in fractured rock impact subsurface energy recovery, storage, and waste disposal. It has been recognized that understanding how the contrasting permeability between fracture and matrix interacts with microbial metabolism under thermal and hydrological gradients is key to effective utilization of the subsurface, yet such studies are sparse. Microorganisms mediate the production of hydrogen sulfide (also known as souring) in oil-bearing geological formations. We conducted a comprehensive experimental study of a novel 2D fractured rock system to understand these complex interactions and demonstrated how biofilm development can impact fracture flow, which subsequently feedbacks to moderate sulfidogenesis. Elevated temperature relevant to reservoir conditions interacted with the injection of cold fluid and formed a thermal gradient away from fractures, creating thermal niches for microbial activities in the fractured rock. Results showed that while fracture flows were dominant in the beginning, with time, growth of the biofilm in the fractures reduced permeability, effectively moderating the initial fracture-matrix contrast, and limited microbial accessibility to nutrients and subsequent reactions rates.

The proppant embedment due to creep in shales is a known issue affecting the useable lifetime of wells in unconventional oil and gas recovery. One of the factors influencing creep is the presence of organics, whose properties can be very sensitive to temperature. In this work we investigated for the first time the role of temperature-induced creep increase in proppant embedment in an organics-rich Green River oil shale sample via in-situ synchrotron X-ray micro-computed tomography. We observed that temperatures as low as 75 °C already induce fast creep, with a fracture aperture closing rate of 13 μm/h and a loss of fracture conductivity rate of 8.7%/h, due only to proppant embedment, in the measured interval at the first heating stage. Local displacement data analysis provided evidence for markedly plastic deformation around the proppant-shale contacts, in contrast with the brittle proppant embedment observed on more cemented and less organics-rich shales at room temperature. The results highlight how the problem of temperature-dependent mechanical behavior might be more important than previously thought, in shales with a high content in organics, and that in-situ micro-imaging techniques can play a key role in understanding the underlying mechanisms, contributing to solve creep-related problems associated with hydraulic fracturing in complex scenarios.

This paper describes a new modeling framework for microscopic to reservoir-scale simulations of hydraulic fracturing and production. The approach builds upon a fusion of two existing high-performance simulators for reservoir-scale behavior: the GEOS code for hydromechanical evolution during stimulation and the TOUGH+ code for multi-phase flow during production. The reservoir-scale simulations are informed by experimental and modeling studies at the laboratory scale to incorporate important micro-scale mechanical processes and chemical reactions occurring within the fractures, the shale matrix, and at the fracture-fluid interfaces. These processes include, among others, changes in stimulated fracture permeability as a result of proppant behavior rearrangement or embedment, or mineral scale precipitation within pores and microfractures, at µm to cm scales. In our new modeling framework, such micro-scale testing and modeling provides upscaled hydromechanical parameters for the reservoir scale models. We are currently testing the new modeling framework using field data and core samples from the Hydraulic Fracturing Field Test (HFTS), a recent field-based joint research experiment with intense monitoring of hydraulic fracturing and shale production in the Wolfcamp Formation in the Permian Basin (USA). Below, we present our approach coupling the reservoir simulators GEOS and TOUGH+ informed by upscaled parameters from micro-scale experiments and modeling. We provide a brief overview of the HFTS and the available field data, and then discuss the ongoing application of our new workflow to the HFTS data set.

Author(s): Dobson, PF; Kneafsey, TJ; Nakagawa, S; Sonnenthal, EL; Voltolini, M; Smith, JT; Borglin, SE | Abstract: Enhanced geothermal systems (EGS) offer the potential for a much larger energy source than conventional hydrothermal systems. Hot, low-permeability rocks are prevalent at depth around the world, but the challenge of extracting thermal energy depends on the ability to create and sustain open fracture networks. Laboratory experiments were conducted using a suite of selected rock cores (granite, metasediment, rhyolite ash-flow tuff, and silicified rhyolitic tuff) at relevant pressures (uniaxial loading up to 20.7 MPa and fluid pressures up to 10.3 MPa) and temperatures (150-250 °C) to evaluate the potential impacts of circulating fluids through fractured rock by monitoring changes in fracture aperture, mineralogy, permeability, and fluid chemistry. Because a fluid in disequilibrium with the rocks (deionized water) was used for these experiments, there was net dissolution of the rock sample: This increased with increasing temperature and experiment duration. Thermal-hydrological-mechanical-chemical (THMC) modeling simulations were performed for the rhyolite ash-flow tuff experiment to test the ability to predict the observed changes. These simulations were performed in two steps: A thermal-hydrological-mechanical (THM) simulation to evaluate the effects of compression of the fracture, and a thermal-hydrological-chemical (THC) simulation to evaluate the effects of hydrothermal reactions on the fracture mineralogy, porosity, and permeability. These experiments and simulations point out how differences in rock mineralogy, fluid chemistry, and geomechanical properties influence how long asperity-propped fracture apertures may be sustained. Such core-scale experiments and simulations can be used to predict EGS reservoir behavior on the field scale.

The Hydraulic Fracturing Test Site (HFTS) project, fielded a few years ago within the Wolfcamp Formation in the Permian Basin in the United States, provides an excellent opportunity to further develop our understanding of the geomechanical response to hydraulic stimulation and associated production in shale lithologies. In addition to a full set of geophysical and tracer observations, the project obtained core samples from wells drilled through the stimulated region, characterizing the propagation of fractures, reactivation of pre-existing natural fractures, and placement of proppant. In addition to providing an overview of the available field data from the field test, we describe here a multi-scale modeling effort to investigate the hydrologic, mechanical and geochemical response of the Wolfcamp Formation to stimulation and production. The ultimate outcome of this project is the application and validation of a new framework for microscopic to reservoir scale simulations, built upon a fusion of existing high performance simulation capabilities.The modeling occurs across two spatial domains – the “reservoir scale”, which encompasses the intra- and inter-well regions, and the “inter-fracture scale”, which is the region between stimulated fractures. Physics-based simulations of the fracture network evolution upon stimulation at the reservoir scale using the simulator GEOS provide input for reservoir-scale production simulations conducted with the TOUGH family of codes. At the inter-fracture scale, the fluid dynamics and reactive transport Chombo-Crunch code is used simulate the micro-scale pore-resolved physical processes occurring at the fracture and rock interfaces upon stimulation and production, tested against laboratory studies of proppant transport and pore-scale reactions. Micro-scale modeling and imaging provides upscaled flow and transport parameters for larger-scale reservoir modeling and production optimization.

Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism.

Oil and gas shales are a system where understanding the mechanical properties at the microscale is of paramount importance, e.g. to better understand the behavior of proppant-shale contacts and their role in the evolution of propped fractures in unconventional reservoirs. This work shows for the first time an experiment coupling indentation testing with in situ X-ray imaging in a Green River shale sample. A full compliance curve has been measured with the sample in water, allowing to visualize the indentation of the sample in function of axial load, in a purpose-built system for combined in situ indentation and X-ray imaging. A series of 3D datasets were used for a digital volume correlation study to obtain local strain fields. This analysis has been complemented with the analysis of cracks. Finally, geomechanical modeling has been carried out to replicate and generalize the observed behavior in the shale. This study validated this experimental approach, providing a breakthrough in understanding micro-mechanics in shales, and demonstrates how this class of experiments can be important for studies involving the prediction of the evolution of propped fractures in shale reservoirs, with possible applications in a much larger number of application fields (geothermal, materials science, etc.)

Soil microaggregates are the fundamental building block, at the micron scale, of the highly hierarchical structure of soils, and can exert a significant control on the local biological metabolism and microbial community partitioning. In this study we propose an analysis protocol for the morphometric characterization of complete soil microaggregates based on sub-micron resolution synchrotron X-ray microtomography. A comprehensive characterization of the aggregate morphology is the first step towards a complete characterization of the soil microaggregates, when trying to correlate morphometric parameters with physical and/or biological properties, or when building models (e.g., effective diffusivity, microbial distribution, etc.). We demonstrate our characterization approach on two single microaggregate samples from dramatically different soil environments: one from Kansas, primarily composed by inorganic particles, and one from Barrow (Alaska) dominated by plant fragments. A series of state-of-the-art morphometric analysis techniques have been employed providing quantitative results highlighting specific differences of the two samples. The role of the microstructure in a scenario microbial population development has been discussed and it has been found that the Barrow microaggregate seems to be more favorable, from a purely geometrical point of view, as also confirmed by a simple model presented in this work. The potential of this approach, when coupled with chemical and biological analysis for a fully comprehensive characterization of soil aggregates in the larger picture of enhanced biological activity, is evident.

© 2017 American Chemical Society. The performance of geologic CO2sequestration (GCS) can be affected by CO2mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO2(scCO2) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO3) at 60 °C and 100 bar in water-bearing scCO2. After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO2across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO2. The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO2.

© 2017 American Chemical Society. 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 CO2saturated 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.

A CO 2 -brine drainage and imbibition cycle was performed in a Boise sandstone sample at reservoir conditions (1300 PSI, 44 °C) at the Advanced Light Source, LBNL. The sample was repeatedly imaged, at the pore-scale, using synchrotron-based X-ray microtomography. In particular the temporal evolution of residually trapped CO 2 was monitored for about 30 hours in order to quantify fluid stability at early stages following imbibition. The data show that fluid phase distribution distribution was not stable with time over the course of the experiment. We hypothesize that fluid displacement is caused by local capillary equilibration following the imbibition process.

Recent studies of carbonate surface reactivity have underscored the fundamental variability of dissolution rates and the heterogeneous distribution of the reaction over the mineral surface due to the inhomogeneous distribution of surface energy. Dolomite dissolution rates relative to different cleavage planes (r-planes) and surfaces cut approximately perpendicular to the c-axis (c-planes) were studied at 50 °C as a function of pH (3.4 ≤ pH ≤ 9.0) and solution composition by vertical scanning interferometry (VSI) and atomic force microscopy (AFM), with the aim of providing an estimate of the intrinsic rate variation of dolomite single crystals and describing the surface reaction distribution and the rate controlling mechanisms. Surface normal retreat rates measured under acidic conditions increased linearly with time and were not visibly affected by the parallel increase of surface roughness. Mean total dissolution rates of r-planes decreased by over 200 times from pH 3.4 to pH 9.0 and CO32–-rich solutions, whereas corresponding rate variations spanned over 3 orders of magnitude when also c-plane rate distributions were included in the analysis. At acid to near neutral pH, c-planes dissolved ∼ three times faster than the adjoining r-planes but slower at basic pH and high total carbon concentration, displaying a distinctive morphologic evolution in these two regimes. The comparison of polished and unpolished crystals showed that polished cleavage planes dissolved about three times faster than the unpolished counterpart at near neutral to basic conditions, whereas no significant difference in reactivity was observed at pH Although experimental data and observations indicate a tendency of dolomite faces to reach a low-energy topography over the course of the reaction, the evolution of the entire crystal morphology depends also on the reactivity of edge and corner regions, whose contribution to measured rates is not generally taken into account by laboratory experiments. The study of time-dependent mineral morphology and reactivity requires an integrated approach of kinetic modeling and experimentation, where measured rate variance and observed reaction mechanisms represent fundamental parameters for the improvement of geochemical models in predicting long-term reaction rates in a wide range of environmental conditions.

The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10–20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10–20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.

The injection of CO2-rich fluids in carbonate rocks results in an evolution of the pore space, with consequent changes in the hydraulic properties of the reservoir; how these properties evolve, particularly for parameters relevant to multiphase flow e.g. Pc(s), remains a topic of active research despite several decades of study. We have carried out an in situ synchrotron X-ray microtomography experiment to monitor pore structure evolution during dissolution of an Indiana Limestone core; the experiment involved flowing CO2-saturated water through the core for 36 h and resulted in 10 volumes corresponding to different temporal stages of the dissolution process. The injection parameters corresponded to the flow velocities expected near the well-bore region of a shallow aqueous CO2 injection; fast flow rates with high reactant availability. Analysis of the tomographic data shows flow-enhanced dissolution i.e. channeling, and provides a time-resolved map of pore space alteration. Using the resulting 4D pore space volume, we modeled the evolution of capillary-pressure curves; this exercise demonstrates how pore structure evolution could impact the invasion and remobilization of non-wetting fluids, dramatically decreasing the entry pressure and the PC in some parts of the sample. The modeling of permeability, using a Stokes solver approach, quantified the relationship of porosity vs. permeability; we found that a modest increase in porosity, especially when the channeling system is more developed, greatly affects permeability. These results demonstrate how movement of CO2 saturated brine near injected plumes might alter drainage dynamics near the plume boundary, thus leading to mobilization across subtle capillary barriers.

A new experimental triaxial cell for in situ synchrotron X-ray micro-computed tomography aimed at imaging small samples of (6 mm × 19 mm) at high temperatures (up to 400°C) and pressures (up to 24 MPa confining) is presented. The system has flow-through capabilities, independent axial and radial pressure control, and has been developed and tested at the 8.3.2. beamline at the Advanced Light Source. The characteristics of this new experimental rig are described, along with the challenges, mainly concerning the combination of X-ray transparency with vessel strength at high temperature, and solutions found during the development stage. An experiment involving oil shale pyrolysis under subsurface conditions, highlighting the importance of a device able to operate in this pressure and temperature range, is also introduced. The availability of this cell enables an unprecedented range of experiments in the Earth Sciences, with a special focus on subsurface geothermal processes.

Our limited understanding of mineral reactive surface area contributes to significant uncertainties in quantitative simulations of reactive chemical transport in subsurface processes. Continuum formulations for reactive transport typically use a number of different approximations for reactive surface area, including geometric, specific, and effective surface area. In this study, reactive surface area estimates are developed and evaluated for their ability to predict dissolution rates in a well-stirred flow-through reactor experiment using disaggregated samples from the Nagaoka pilot CO2 injection site (Japan). The disaggregated samples are reacted with CO2 acidified synthetic brine under conditions approximating the field conditions and the evolution of solute concentrations in the reactor effluent is tracked over time. The experiments, carried out in fluid-dominated conditions at a pH of 3.2 for 650 h, resulted in substantial dissolution of the sample and release of a disproportionately large fraction of the divalent cations. Traditional reactive surface area estimation methods, including an adjusted geometric surface area and a BET-based surface area, are compared to a newly developed image-based method. Continuum reactive transport modeling is used to determine which of the reactive surface area models provides the best match with the effluent chemistry from the well-stirred reactor. The modeling incorporates laboratory derived mineral dissolution rates reported in the literature and the initial modal mineralogy of the Nagaoka sediment was determined from scanning electron microscopy (SEM) characterization. The closest match with the observed steady-state effluent concentrations was obtained using specific surface area estimates from the image-based approach supplemented by literature-derived BET measurements. To capture the evolving effluent chemistry, particularly over the first 300 h of the experiment, it was also necessary to account for the grain size distribution in the sediment and the presence of a highly reactive volcanic glass phase that shows preferential cation leaching.

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.

Clinopyroxene and plagioclase (andesine) microlites in an obsidian flow from Glass Mountain (NE California, USA) display strong alignment. Synchrotron X-ray diffraction, coupled with Rietveld analysis, was used to quantify crystallographic-preferred orientation (CPO). Clinopyroxene, with a rod-shaped morphology, shows a strong alignment of [001] in the flow direction and (010) aligned parallel to the inferred flow plane. Andesine, with a platy morphology, displays an alignment of (010) platelets in the flow plane. Some pole densities exceed 90 multiples of random distribution. Applying a model of rigid ellipsoidal inclusions in a viscous matrix, the local pure shear strains are between 2 and 3.

Significance Reliable estimates of geologic carbon storage capacities (needed for policymaking) in both saline aquifers and unconventional gas/oil shales rely on understanding trapping mechanisms. We found that CO2 uptake by muscovite (a common mineral and a conservative proxy for illite) far exceeds the maximum adsorption capacity of its external surface area. Our measurements using different methods collectively suggest that CO2 enters muscovite interlayers without bulk interlayer expansion, contrary to the conventional wisdom that only swelling clays take up CO2 into interlayers. Because the nonswelling illitic clay is the major clay mineral in deep subsurface tight rocks, their excess uptake of CO2 may significantly contribute to CO2 storage capacity and warrants further in-depth studies., Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism.

Volcanogenic sandstones are typically rich in volcanic rock fragments that can provide reactive minerals for CO 2 mineralization in a scenario of CO 2 sequestration. To quantitatively evaluate the extent and time scale of CO 2 mineralization in potential reservoir formations, we characterized example high‐porosity volcanic sand from the San Joaquin Valley of southern Central California. Samples were collected from the volcanic‐rich members of the Etchegoin Formation in the San Joaquin Basin near Coalinga, California. Thin sections made from these samples were examined under petrographic microscope to identify mineral compositions, and then scanning electron microscopy (SEM) and energy dispersive x‐ray spectroscopy (EDX) were used to gather quantitative information on mineral abundances, distribution, and reactive surface areas. Porosity and permeability were also measured using core plugs made from outcrop samples. Results show that the Etchegoin volcanic sandstone has a high percentage (10–15%) of reactive minerals (pyroxenes, Fe‐Ti spinel and clays), and high reactive surface areas at about 1 m-super-2/kg. Reactive transport modeling is conducted and shows that these reactive minerals could mineralize 92% of injected and capillary‐trapped CO 2 within 1000 years of injection. Possible effects of heterogeneity on CO 2 injection and mineralization are also studied using the reactive transport code TOUGHREACT. Vertical heterogeneity of mineralogy and hydrology increases both CO 2 injectivity and mineralization. Available volcanogenic sandstones worldwide like the Etchegoin sandstone are summarized from the literature, with formations from the western USA that have CO 2 sequestration potential emphasized.© 2015 Society of Chemical Industry and John Wiley & Sons, Ltd

International audience; The nucleation and growth processes of spherulitic alkali feldspar have been investigated in this study through X-ray microtomography and electron backscatter diffraction (EBSD) data. Here we present the first data on Shape Preferred Orientation (SPO) and Crystal Preferred Orientation (CPO) of alkali feldspar within spherulites. The analysis of synchrotron X-ray microtomography and EBSD datasets allowed us to study the morphometric characteristics of spherulites in trachytic melts in quantitative fashion, highlighting the three-dimensional shape, preferred orientation, branching of lamellae and crystal twinning, providing insights about the nucleation mechanism involved in the crystallization of the spherulites. The nucleation starts with a heterogeneous nucleus (pre-existing crystal or bubble) and subsequently it evolves forming “bow tie” morphologies, reaching radially spherulitic shapes in few hours. Since each lamella within spherulite is also twinned, these synthetic spherulites cannot be considered as single nuclei but crystal aggregates originated by heterogeneous nucleation. A twin boundary may have a lower energy than general crystal–crystal boundaries and many of the twinned grains show evidence of strong local bending which, combined with twin plane, creates local sites for heterogeneous nucleation.This study shows that the growth rates of the lamellae (10− 6–10− 7 cm/s) in spherulites are either similar or slightly higher than that for single crystals by up to one order of magnitude. Furthermore, the highest volumetric growth rates (10− 11–10− 12 cm3/s) show that the alkali feldspar within spherulites can grow fast reaching a volumetric size of ~ 10 μm3 in 1 s.

The properties of cementitious materials are related to the microstructure of their binder matrix, which develops, during cement hydration, by a sequence of dissolution–precipitation reactions. Here, microstructural development is monitored during hydration by synchrotron X-ray diffraction-enhanced computed microtomography (XRD-CT). This innovative, noninvasive technique yields images of the crystallographic phases present in the hydrating cement paste at different stages, which are combined to map the sites where dissolution and precipitation occur. The results indicate that the nucleation mechanism of the main hydration product (a calcium-silicate hydrate commonly referred to as C–S–H) changes in the presence of polycarboxylate ether (PCE) superplasticizers. The observed change is essential to understand the development of the cement microstructure and to provide a direct link between the reaction kinetics and the physicomechanical properties of the system.

© International Union of Crystallography, 2017. Continuous improvements at X-ray imaging beamlines at synchrotron light sources have made dynamic synchrotron X-ray micro-computed tomography (SXR-μCT) experiments more routinely available to users, with a rapid increase in demand given its tremendous potential in very diverse areas. In this work a survey of five different four-dimensional SXR-μCT experiments is presented, examining five different parameters linked to the evolution of the investigated system, and tackling problems in different areas in earth sciences. SXR-μCT is used to monitor the microstructural evolution of the investigated sample with the following variables: (i) high temperature, observing in situ oil shale pyrolysis; (ii) low temperature, replicating the generation of permafrost; (iii) high pressure, to study the invasion of supercritical CO2in deep aquifers; (iv) uniaxial stress, to monitor the closure of a fracture filled with proppant, in shale; (v) reactive flow, to observe the evolution of the hydraulic properties in a porous rock subject to dissolution. For each of these examples, it is shown how dynamic SXR-μCT was able to provide new answers to questions related to climate and energy studies, highlighting the significant opportunities opened recently by the technique.Recent developments in in situ synchrotron X-ray micro-computed tomography allow novel time-resolved experiments. Five different dynamic micro-computed tomography experiments addressing carbon sequestration, permafrost evolution and unconventional oil recovery topics are presented.

Author(s): Voltolini, M; Kwon, TH; Ajo-Franklin, J | Abstract: Pore-scale distribution of supercritical CO2 (scCO2) exerts significant control on a variety of key hydrologic as well as geochemical processes, including residual trapping and dissolution. Despite such importance, only a small number of experiments have directly characterized the three-dimensional distribution of scCO2 in geologic materials during the invasion (drainage) process. We present a study which couples dynamic high-resolution synchrotron X-ray micro-computed tomography imaging of a scCO2/brine system at in situ pressure/temperature conditions with quantitative pore-scale modeling to allow direct validation of a pore-scale description of scCO2 distribution. The experiment combines high-speed synchrotron radiography with tomography to characterize the brine saturated sample, the scCO2 breakthrough process, and the partially saturated state of a sandstone sample from the Domengine Formation, a regionally extensive unit within the Sacramento Basin (California, USA). The availability of a 3D dataset allowed us to examine correlations between grains and pores morphometric parameters and the actual distribution of scCO2 in the sample, including the examination of the role of small-scale sedimentary structure on CO2 distribution. The segmented scCO2/brine volume was also used to validate a simple computational model based on the local thickness concept, able to accurately simulate the distribution of scCO2 after drainage. The same method was also used to simulate Hg capillary pressure curves with satisfactory results when compared to the measured ones. This predictive approach, requiring only a tomographic scan of the dry sample, proved to be an effective route for studying processes related to CO2 invasion structure in geological samples at the pore scale.

This study utilizes synchrotron X-ray micro-tomography and pore scale modeling to investigate the process of gas exsolution and how it affects non-wetting phase relative permeability. Exsolved gas distributions are measured on Domengine and Boise sandstone samples using synchrotron X-ray micro-tomography. Observed gas phase distributions are compared to a new model that simulates the growth and distribution of exsolved gas phase at the pore-scale. Water relative permeability curves are calculated using a Stokes flow simulator with modeled and observed gas distributions, under various conditions, such as rock geometry, and pressure depletion rates. By comparing the actual bubble distributions with modeled distributions, we conclude that exsolved gas is more likely to form and accumulate at locations with higher water velocities. This suggests that convective delivery of CO2 to the gas bubble is a primary mechanism for bubble growth, as compared to diffusive transport through the aqueous phase. For carbonated brine flowing up a fault at half a meter per day, with 5% exsolved gas, the water relative permeability is estimated to be 0.6∼0.8 for various sandstones. The reduction of water mobility reduces upward brine migration when even a small amount of exsolution occurs.

© 2017 Elsevier Ltd A multi-scale synchrotron-based X-ray microtomographic dataset of residually trapped air after gravity-driven brine imbibition was acquired for three samples with differing pore topologies and morphologies; image volumes were reconstructed with voxel sizes from 4.44 µm down to 0.64 µm. Capillary pressure distributions among the population of trapped ganglia were investigated by calculating interfacial curvature in order to assess the potential for remobilization of residually-trapped non-wetting ganglia due to differences in capillary pressure presented by neighbor ganglia. For each sample, sintered glass beads, Boise sandstone and Fontainebleau sandstone, sub-volumes with different voxel sizes were analyzed to quantify air/brine interfaces and interfacial curvatures and investigate the effect of image resolution on both fluid phase identification and curvature estimates. Results show that the method developed for interfacial curvature estimation leads to reliable capillary pressure estimates for gas ganglia. Higher resolution images increase confidence in curvature calculations, especially for the sandstone samples that display smaller gas-brine interfaces which are then represented by a higher number of voxels when imaged with a micron or sub-micron voxels size. The analysis of sub-volumes from the Boise and Fontainebleau dataset highlights the presence of a residually-trapped gas phase consisting of ganglia located in one or few pores and presenting significantly different capillary pressures, especially in the case of Fontainebleau sandstone. As a result, Ostwald ripening could occur, leading to gas transfer from ganglia with higher capillary pressure to surrounding ganglia with lower capillary pressures. More generally, at the pore-scale, most gas ganglia do present similar capillary pressures and Ostwald ripening would then not represent a major mechanism for residually-trapped gas transfer and remobilization.

The 3D phase distribution of cement pastes evolves during hydration and controls the rheology and mechanical properties of the paste. Synchrotron powder-diffraction micro-tomographic imaging is here employed to assess the cement phase spatial distribution in a totally non-invasive way. This technique can be used to produce distribution maps of the phases present in the hydrating cement paste. The method is applied to an ordinary Portland cement, hydrated in pure water or in the presence of nucleation seeds. The quantitative description of the phase spatial distribution by radial distribution functions allows the discrimination of different nucleation mechanisms.

Two complementary 3D techniques, neutron diffraction and synchrotron X-ray microtomography (SXR-μCT), were used to compare the Shape and Lattice Preferred Orientations of a mylonitised metagranite from the Monte Rosa unit (Western Alps, Italy). The goal of using these techniques was to obtain two different orientation distribution functions. Although the two functions describe relatively independent characteristics of the rock fabric, nonetheless they also exhibit close relationships to macroscopic fabrics and may be complementarily used to quantify rock fabrics and microstructures, thereby highlighting 3D features that cannot be obtained with either technique, if used independently. We describe an approach that can be potentially useful in various disciplines, e.g., structural geology, rock mechanics, tectonics and geophysics, when a complete data set of preferred orientations and size distribution is needed. Micas display a strong orthorhombic symmetry between mesoscopic lineation and microscopic SPO and LPO, whereas quartz and feldspars are characterised by a monoclinic symmetry between mesoscopic lineation and LPO. These observations suggest a rheological decoupling between the weak phase mica layers and the stronger quartz + feldspar layers. This mechanical decoupling occurred during the Alpine subduction-collision, when the Monte Rosa unit was part of the Insubric Line system and accommodated large vertical strain.

This article describes a single-shot methodology to derive an average coating thickness in multi-particle core–shell systems exhibiting high X-ray absorption. Powder composed of U–Mo alloy particles surrounded by a micrometre-thick UO2protective layer has been used as a test sample. Combining high-energy X-ray diffraction and laser granulometry, the average shell thickness could be accurately characterized. These results have been validated by additional measurements on single particles by two techniques: X-ray nanotomography and high-energy X-ray diffraction. The presented single-shot approach gives rise to many potential applications on core–shell systems and in particular on as-fabricated heterogeneous nuclear fuels.

Absorption-based X-ray micro-tomography (X-μCT) provides fundamental in-situ information on the 3D microstructure of complex multiphase materials such as cements. However, since the phases present in a hydrating cement paste may be characterized by similar values of the attenuation coefficient, leading to low absorption contrast between different crystalline or amorphous phases, micro-structural interpretation can be equivocal. 3D phase mapping by X-ray diffraction micro-tomography proved to be a successful technique for investigating the spatial distribution of the products in the paste during the hydration process, in a totally non-invasive mode and with enhanced phase selectivity compared to absorption tomography. Phase-selective maps, in the case of crystalline phases, can be extracted from single Bragg peaks or from the Rietveld-refined scale factor. However, even poorly crystalline and/or amorphous phases present in the cement paste, such as calcium silicate hydrates, can be successfully mapped by the use of selected portions of the measured powder data containing the relevant scattering of the phase. The reconstructed maps can be directly modeled by multifractal analysis and compared with computer-generated distributions.

Reliable assessment of the potential alkali reactivity of aggregate to develop deleterious alkali–silica reaction is essential for construction of durable concrete structures. The potential alkali reactivity of silicified limestone and two limestones has been investigated. Preliminary characterisation of aggregate was performed by optical and environmental scanning electron microscopy. X-ray powder diffraction peak profile analysis was used to predict the aggregates’ potential alkali reactivity. Samples were aged in accordance to the RILEM AAR-2 procedure and further characterised by means of optical and environmental scanning electron microscopy as well as by synchrotron X-ray microtomography, where quantitative analysis relative to damage due to the alkali–silica reaction (ASR) was performed by morphometric analysis of volume data. Results highlight that (1) the microstructural domain size and microstrain values extracted form XRPD line profile analysis seem to be good parameters for predicting the potential alkali reactivity of quartz in aggregate, and (2) the mineralogy of the aggregate influences the weathering products (i.e. aggregate dissolution, ASR gel growth and microcracking) due to ASR in cement-based materials.