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Geochemically driven alterations of fractures in multi-mineral media can create altered layers (ALs) at the fracture-matrix interface. Spatial variations in the AL significantly influence mass transfer across the interface, and the hydraulic and mechanical properties of the fractured medium. A real-rock based microfluidic experiment reported spatial variations in AL thickness despite the initially smooth fracture surface, suggesting potential effects of matrix heterogeneity on AL development. However, the respective contribution of structural and mineralogical characteristics is still poorly understood. Using the microfluidic experimental data and a micro-continuum reactive transport model, we systematically evaluated how micro-porosity and initial mineral texture impact AL development and thus the overall reactive transport behaviors. Our simulation results confirmed that the extent of AL spatial variations, mainly controlled by mineralogical texture, influences the evolution of reaction and permeability in different ways. Accounting for spatial heterogeneity in mineral distribution produces “channeling” structures in ALs and lower overall reaction (by up to 35.6%), but larger permeability increase (by up to 9.8%). The characteristic length of the reactive mineral cluster was observed to dominate the internal texture of ALs. Whereas the presence of micro-porosity can enhance mineral accessibility via improving connectivity for flow and transport, and lead to both higher bulk reaction, that is, thicker ALs, and permeability enhancement. Considerations of surface roughness with characteristic length on the same order of magnitude as mineral texture did not change the overall development of AL, which further highlights the importance of accounting for rock matrix properties in predicting long-term evolution of fractured media. The resulting spatial variations of ALs and their impacts on bulk properties, however, are expected to be further complicated by the coupling of chemical and mechanical processes, and may trigger matrix disaggregation, erosion and other mechanisms of fractured media alteration.

Fracture initiation and propagation in brittle materials is promoted in surface-reactive (sorptive) environments, a phenomenon known as subcritical crack growth (SCG). Laboratory measured crack-propagation velocity vs. stress intensity factor relationships typically exhibit highly nonlinear, multi-stage characteristics that are sensitive to environmental factors such as adsorbate concentration and temperature. For practical purposes, empirical relationships (e.g., a power law) have been used to describe this complex phenomenon. However, how the overall SCG behavior emerges from the underlying fundamental processes near the crack tip, such as the interaction of the crack surfaces separated by only a few nanometers and mass transport within the nano-confined space, is still not well understood. This paper develops a mechanistic, surface-force-based fracture theory (SFFT) which integrates surface force models, fluid transport models, and linear elastic fracture mechanics to quantitatively explain the multi-stage characteristics of SCG in brittle solids. A numerical model is developed based on SFFT and solved through an implicit partitioned scheme for efficiency and modularity. The results are validated by Wiederhorn's data on crack propagation in soda-lime glasses at a wide range of relative humidity levels. We show that, for the first time, the entire range of an SCG curve can be captured by a single physics-based model. The predicted SCG curves reveal that the development of repulsive disjoining pressure behind the crack tip can be responsible for the reduced apparent fracture toughness in a sorptive environment. The shape of the SCG curve, and its changes with respect to the environment, is found to critically depend on the assumed transport models.

Enhanced rock weathering (ERW) in soils is a promising carbon removal technology, but the realistically achievable efficiency, controlled primarily by in situ weathering rates of the applied rocks, is highly uncertain. Here we explored the impacts of coupled biogeochemical and transport processes and a set of primary environmental and operational controls, using forsterite as a proxy mineral in soils and a multiphase multi-component reactive transport model considering microbe-mediated reactions. For a onetime forsterite application of ~ 16 kg/m2, complete weathering within five years can be achieved, giving an equivalent carbon removal rate of ~ 2.3 kgCO2/m2/yr. However, the rate is highly variable based on site-specific conditions. We showed that the in situ weathering rate can be enhanced by conditions and operations that maintain high CO2 availability via effective transport of atmospheric CO2 (e.g. in well-drained soils) and/or sufficient biogenic CO2 supply (e.g. stimulated plant-microbe processes). Our results further highlight that the effect of increasing surface area on weathering rate can be significant-so that the energy penalty of reducing the grain size may be justified-only when CO2 supply is nonlimiting. Therefore, for ERW practices to be effective, siting and engineering design (e.g. optimal grain size) need to be co-optimized.

In interface coupled dissolution-precipitation systems, the dynamics of the mineral-fluid interface depends on two intertwining processes: the dissolution of the primary mineral that is needed for subsequent precipitation and the passivation of the dissolution reaction as a result of secondary mineral precipitation. The resulting thickness and texture of the precipitating coating layer will affect the progression of geochemical reactions, flow and transport processes at the macroscopic scale. Understanding the interplay between macroscopic flow regimes and microscopic reaction mechanisms (e.g., nucleation and crystal growth pathways) in controlling the dynamics of the mineral-fluid interface has important implications for predicting natural weathering processes, scaling in the subsurface energy production systems, etc. In this study, we use a micro-continuum pore-scale reactive transport model to investigate the feedback loop between reaction rate and solute transport with explicit consideration of the surface passivation and the diffusion process through the coating layer, as well as the impacts of saturation-dependent nucleation rate on the textures of precipitates that will largely dictate the diffusion properties of the coating layer. Our model results highlight that the drastically different coating behaviors at the macroscopic scale and their dependence on solution supersaturation observed in previous column experiments are primarily controlled by the interplay between mineral reaction rates, advective flow, and diffusion through the dynamically forming coating layer. The diffusion properties of the coating layer also play a secondary but non-negligible role in shaping the evolution of the co-dissolution and precipitation system. The probabilistic nucleation model building on the framework of classical nucleation theory highlights the complex dependence of precipitates’ texture on solution chemistry and substrate properties, which can affect the diffusion process within the precipitates. The modeling observations also underscore the necessity of further investigations to better characterize the properties of the coating layer and to improve modeling descriptions of the nucleation processes.

In multi-mineral fractured rocks, the altered porous layer on the fracture surface resulting from preferential dissolution of the fast-reacting minerals can have profound impacts on subsequent chemical-physical alteration of the fractures. This study adopts the micro-continuum approach to provide further understanding of reactive transport processes in the altered layer (AL), and mass exchanges with the bordering matrix and fracture. The modeling framework couples the Darcy-Brinkman-Stokes (DBS) solver in COMSOL Multiphysics and the geochemical modeling capability of CrunchFlow. Three-dimensional steady state simulations with systematically varied chemical-physical parameters of the AL were performed to examine the impacts of individual factors and processes. Our simulation results confirm previous observations that dissolution of the fast-reacting mineral (i.e., calcite) is largely controlled by diffusion across the AL. We also show that dissolution of the slow-reacting mineral (i.e., dolomite), which controls AL development and fracture enlargement, increases with surface area and has a complex dependence on different local rate-limiting processes. In particular, advection can result in evident spatial variations in the local dissolution rates of dolomite, although it does not affect the bulk chemistry significantly. The difference in the spatial patterns between simulations with and without advection in the AL is more noticeable in the locations with smaller apertures, with up to 20% difference in local reaction rates. Therefore, it is important to include a full depiction of advection, diffusion, and reactions for accurately capturing local dynamics that control long-term fracture evolution.

In various natural and engineered systems, mineral–fluid interactions take place in the presence of multiple fluid phases. While there is evidence that the interplay between multiphase flow processes and reactions controls the evolution of these systems, investigation of the dynamics that shape this interplay at the pore scale has received little attention. Specifically, continuum scale models rarely consider the effect of multiphase flow parameters on mineral reaction rates or apply simple corrections as a function of the reactive surface area or saturation of the aqueous phase, without developing a mechanistic understanding of the pore-scale dynamics. In this study, we developed a framework that couples the two-phase flow simulator of OpenFOAM (open field operation and manipulation) with the geochemical reaction capability of CrunchTope to examine pore-scale dynamics of two phase flow and their impacts on mineral reaction rates. For our investigations, flat 2D channels and single sine wave channels were used to represent smooth and rough geometries. Calcite dissolution in these channels was quantified with single phase flow and two phase flow at a range of velocities. We observed that the bulk calcite dissolution rates were not only affected by the loss of reactive surface area as it becomes occupied by the non-reactive non-aqueous phase, but also largely influenced by the changes in local velocity profiles, e.g., recirculation zones, due to the presence of the non-aqueous phase. The extent of the changes in reaction rates in the two-phase systems compared to the corresponding single phase system is dependent on the flow rate (i.e., capillary number) and channel geometry, and follows a non-monotonic relationship with respect to aqueous saturation. The pore-scale simulation results highlight the importance of interfacial dynamics in controlling mineral reactions and can be used to better constrain reaction rate descriptions in multiphase continuum scale models. These results also emphasize the need for experimental studies that underpin the development of mechanistic models for multiphase flow in reactive systems.

Objective： A method based on high-performance liquid chromatography-mass spectrometry was developed for the simultaneous determination of bisphenol A and nonylphenol in food packaging material. Methods: The extraction solvent and extraction method were investigated. Solid-phase extraction （SPE） conditions were optimized. The effects of solid phase extraction column, loading solvent, eluting solvent and elution solvent on the purification effect were systematically analyzed. The samples were ultrasonic extracted with dichloromethaneand cleaned up on a solid-phase extraction （SPE） cartridge equipped with packing material of silicone. The separation was performed on a Venusil MP C18（2）（100 mm×2.1 mm,2.6 μm）by gradient elution with 0.1% ammonia solution and methanol as mobile phase. The analytes were determined with multiple reaction monitoring （MRM） mode under electrospray negative ionization mode and quantified by an internal standard method. Results: The results indicated that good linearities was obtained for bisphenol A and nonylphenol both within the concentration range of 1.0~200.0 μg/L. The average recoveries of each analyte at three spiked levels of 1.0, 10.0, 200.0 μg/kg were in the range of 89.2%~101.2%, with relative standard deviations （RSD） of 3.1%~6.2%. The limits of detection （LODs） and limits of quantification （LOQs） were 0.5 μg/kg and 1.0 μg/kg, respectively. Conclusion: The method was proved to be a simple, accurate and sensitive method and was successfully applied to detect bisphenol A and nonylphenol in food packaging material. It can also provide reference for the determination of bisphenol A and nonylphenol in food.

Reactive transport in fractured media is conceptualized as a multi-scale problem that couples a pore-scale component, which comprises Navier–Stokes flow, multi-component transport and aqueous equilibrium in the fracture, and a Darcy-scale component, which comprises multi-component diffusive transport, aqueous equilibrium and mineral reactions in the porous matrix. The model that implements this multi-scale approach builds on an existing pore-scale model and is able to capture complex fracture geometries with the embedded-boundary method. The embedded boundary acts as the interface between pore- and Darcy-scale domains. Adaptive mesh refinement is used to match resolutions at the interface while using coarser resolution away from the interface when not needed in the Darcy-scale domain. The new model is validated and then compared to results from a pore-scale model. Multi-scale model results are shown to be equivalent to pore-scale results under diffusion-controlled reactions in the pore scale and very fast dissolution in the Darcy scale. The multi-scale model provides a more accurate solution for a given resolution as it effectively sets the equilibrium concentrations as boundary conditions. The multi-scale model is capable to capture flow channelization observed in an experimental fractured core and, at the same time, limitations in the dissolution of calcite by diffusive transport through an altered porous layer. Discrepancies in effluent calcium concentrations between the multi-scale results and results from a reduced-dimension Darcy-scale model for this fractured core experiment are attributed to the solution of the flow field and the gradients that develop inside the fracture. Discrepancies in effluent magnesium concentrations exemplify the limitations of the approach because the multi-scale model requires calibration of reactive surface areas as Darcy-scale continuum models.

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.

The processes that affect the evolution of fracture geometry and reactive transport in limestone fractures were evaluated using an integrated experimental and modeling approach. Flow-through experiments were performed to investigate the alteration of three artificially made planar limestone fractures, which were exposed to HCl-acidified water flow (pH 3.8 ± 0.1) at three different rates. Reactive infiltration instability developed in the fractures because of small fracture aperture variations and naturally occurring heterogeneity in the rock, i.e., the presence of clay spots of higher porosity. The dissolution regime changed from conical to dominant and ramified wormhole with increasing flow rate, i.e., Péclet number. Maps of fracture aperture obtained from X-ray micro-tomography imaging, together with measurements of permeability and analyses of fluid chemistry, provided experimental constraints for modeling. Numerical simulations were performed using a 2.5D continuum reactive transport model to examine the development of flow patterns and the reactivity and permeability evolution over time, and to interrogate the impacts of fluid reactivity, mineral heterogeneity and diffusive boundary layer. The modeling results showed that fracture alteration is very sensitive to initial fluid reactivity and mineralogical heterogeneity, in addition to flow rate. The changes of local transport processes during fracture opening also affected the reactivity of the fractured samples.

The roughness of solid surfaces influences mineral dissolution rates by affecting flow and transport in the near-surface regions and by increasing the surface area available for reaction. The impact of surface area is commonly accounted for by using the surface roughness factor (SRF), which is the ratio between the total surface area and the nominal or geometric surface area. The coupled impacts of hydrodynamics and transport, however, are rarely considered. In this study, we performed pore-scale reactive transport simulations in a series of synthetic 2D rough fractures to investigate the compound effects of surface roughness on the reaction rates in fractures. Simulation results show that while reaction rates increase with SRF, the increase is not linearly proportional to that of the surface area. Rather, local concentration gradients resulting from flow and transport processes limit the increase in the rate. In addition, surface roughness gives rise to concentration gradients that do not otherwise develop in the flat-surface geometries typically considered in modeling studies. To describe the impacts of the surface area increase on reaction rate at different roughness and flow velocities, three distinct regimes were identified. A unified mathematical relationship was also developed that allows the reaction rate in a rough fracture to be approximated by the well-mixed reactor reaction rate and a correction factor. The correction factor follows a power-law function of SRF, with the multiplying factor and exponent expressed as exponential functions of the Péclet and Damköhler number. This mathematical formulation provides a valuable upscaling approach for effective integration of sub-grid scale surface roughness in larger scale continuum models.

Accurate assessment of the long-term security of geologic carbon sequestration requires knowledge of the mobility of carbon dioxide in brines under pressure and temperature conditions that prevail in subsurface aquifers. Here, we report Raman spectroscopic measurements of the rate of CO2 diffusion in water and brines as a function of pressure, salinity, and concentration of CO2. In pure water at 50 ± 2 °C and 90 ± 2 bar, we find the diffusion coefficient, D, to be (3.08 ± 0.03) × 10-9 m2/s, a value that is consistent with a recent microfluidic study but lower than earlier PVT measurements. Under reservoir conditions, salinity affects the mobility of CO2 significantly and D decreased by 45% for a 4 M solution of NaCl. We find significant differences of diffusivity of CO2 in brines (0-4 M NaCl), in both the absolute values and the trend compared to the Stokes-Einstein prediction under our experimental conditions. We observe that D decreases significantly at the high CO2 concentrations expected in subsurface aquifers (∼15% reduction at 0.55 mol/kg of CO2) and provides an empirical correction to the commonly reported D values that assume a tracer concentration dependence on diffusivity.

Geochemical reactions add complexity to the characterization and prediction of fracture hydraulic properties because they depend on factors that are highly heterogeneous, such as mineral composition. However, systematic analyses of fracture evolution in mineralogically heterogeneous systems are still limited. In this study, we investigated fracture evolution in multimineral systems using a reduced dimension reactive transport model. The model was developed and tested based on experimental studies and addresses the complex morphological and geochemical changes that arise from the presence of multiple minerals of different reactivities. Numerical experiments were performed using randomly generated initial fracture geometries based on representative geostatistics, different categories of mineral composition, and a range of flow rates that are relevant to geologic carbon storage systems. The simulation results showed distinct dissolution regimes at different flow rates, each of which produced characteristic dissolution patterns and temporal evolutions of chemical reactions and fracture hydraulic properties. Overall, as flow rate increases, fracture evolution shifts from compact dissolution to fracture channelization to uniform dissolution. The corresponding flow rate for a given dissolution regime, however, varies considerably with mineral composition. Fracture evolution, especially in the flow regime that induces fracture channelization, is also affected by initial fracture geometry. The numerical experiments were used to develop a multireaction Damköhler number (mDa) for the prediction of fracture evolution, and fracture channelization in particular, in multimineral systems. The multireaction Damköhler number also provides a useful framework for the evaluation of caprock integrity in geologic carbon storage systems.