Long-time evolution of sequestered CO2_2 in porous media

CO$_2$ sequestration in subsurface reservoirs is important for limiting atmospheric CO$_2$ 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 CO$_2$ 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 concentration 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 CO$_2$. Consequently, only a small fraction of the CO$_2$ 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 CO$_2$ bubble surrounded by brine and suggest a mechanism that may lead to a carbonate-encrusted bubble due to structural diffusion

Dynamic reservoir-condition microtomography of reactive transport in complex carbonates: effect of initial pore structure and initial brine pH

We study the impact of brine acidity and initial pore structure on the dynamics of fluid/solid reaction at high Péclet numbers and low Damköhler numbers. A laboratory μ-CT scanner was used to image the dissolution of Ketton, Estaillades, and Portland limestones in the presence of CO2-acidified brine at reservoir conditions (10 MPa and 50°C) at two injected acid strengths for a period of 4 hours. Each sample was scanned between 6 and 10 times at ∼4 μm resolution and multiple effluent samples were extracted. The images were used as inputs into flow simulations, and analysed for dynamic changes in porosity, permeability, and reaction rate. Additionally, the effluent samples were used to verify the image-measured porosity changes. We find that initial brine acidity and pore structure determine the type of dissolution. Dissolution is either uniform where the porosity increases evenly both spatially and temporally, or occurs as channelling where the porosity increase is concentrated in preferential flow paths. Ketton, which has a relatively homogeneous pore structure, dissolved uniformly at pH = 3.6 but showed more channelized flow at pH = 3.1. In Estaillades and Portland, increasingly complex carbonates, channelized flow was observed at both acidities with the channel forming faster at lower pH. It was found that the effluent pH, which is higher than that injected, is a reasonably good indicator of effective reaction rate during uniform dissolution, but a poor indicator during channelling. The overall effective reaction rate was up to 18 times lower than the batch reaction rate measured on a flat surface at the effluent pH, with the lowest reaction rates in the samples with the most channelized flow, confirming that transport limitations are the dominant mechanism in determining reaction dynamics at the fluid/solid boundary

Reactive-infiltration instabilities in rocks. Fracture dissolution

A reactive fluid dissolving the surface of a uniform fracture will trigger an instability in the dissolution front, leading to spontaneous formation of pronounced well-spaced channels in the surrounding rock matrix. Although the underlying mechanism is similar to the wormhole instability in porous rocks there are significant differences in the physics, due to the absence of a steadily propagating reaction front. In previous work we have described the geophysical implications of this instability in regard to the formation of long conduits in soluble rocks. Here we describe a more general linear stability analysis, including axial diffusion, transport limited dissolution, non-linear kinetics, and a finite length system.Comment: to be published in J. Fluid. Mec

PADAMOT : project overview report

Background and relevance to radioactive waste management International consensus confirms that placing radioactive wastes and spent nuclear fuel deep underground in a geological repository is the generally preferred option for their long-term management and disposal. This strategy provides a number of advantages compared to leaving it on or near the Earth’s surface. These advantages come about because, for a well chosen site, the geosphere can provide: • a physical barrier that can negate or buffer against the effects of surface dominated natural disruptive processes such as deep weathering, glaciation, river and marine erosion or flooding, asteroid/comet impact and earthquake shaking etc. • long and slow groundwater return pathways from the facility to the biosphere along which retardation, dilution and dispersion processes may operate to reduce radionuclide concentration in the groundwater. • a stable, and benign geochemical environment to maximise the longevity of the engineered barriers such as the waste containers and backfill in the facility. • a natural radiation shield around the wastes. • a mechanically stable environment in which the facility can be constructed and will afterwards be protected. • an environment which reduces the likelihood of the repository being disturbed by inadvertent human intrusion such as land use changes, construction projects, drilling, quarrying and mining etc. • protection against the effects of deliberate human activities such as vandalism, terrorism and war etc. However, safety considerations for storing and disposing of long-lived radioactive wastes must take into account various scenarios that might affect the ability of the geosphere to provide the functionality listed above. Therefore, in order to provide confidence in the ability of a repository to perform within the deep geological setting at a particular site, a demonstration of geosphere “stability” needs to be made. Stability is defined here to be the capacity of a geological and hydrogeological system to minimise the impact of external influences on the repository environment, or at least to account for them in a manner that would allow their impacts to be evaluated and accounted for in any safety assessments. A repository should be sited where the deep geosphere is a stable host in which the engineered containment can continue to perform according to design and in which the surrounding hydrogeological, geomechanical and geochemical environment will continue to operate as a natural barrier to radionuclide movement towards the biosphere. However, over the long periods of time during which long-lived radioactive wastes will pose a hazard, environmental change at the surface has the potential to disrupt the stability of the geosphere and therefore the causes of environmental change and their potential consequences need to be evaluated. As noted above, environmental change can include processes such as deep weathering, glaciation, river and marine erosion. It can also lead to changes in groundwater boundary conditions through alternating recharge/discharge relationships. One of the key drivers for environmental change is climate variability. The question then arises, how can geosphere stability be assessed with respect to changes in climate? Key issues raised in connection with this are: • What evidence is there that 'going underground' eliminates the extreme conditions that storage on the surface would be subjected to in the long term? • How can the additional stability and safety of the deep geosphere be demonstrated with evidence from the natural system? As a corollary to this, the capacity of repository sites deep underground in stable rock masses to mitigate potential impacts of future climate change on groundwater conditions therefore needs to be tested and demonstrated. To date, generic scenarios for groundwater evolution relating to climate change are currently weakly constrained by data and process understanding. Hence, the possibility of site-specific changes of groundwater conditions in the future can only be assessed and demonstrated by studying groundwater evolution in the past. Stability of groundwater conditions in the past is an indication of future stability, though both the climatic and geological contexts must be taken into account in making such an assertion

Application of mineralogical, petrological and geochemical tools for evaluating the palaeohdrogeological evolution of the PADAMOT study sites

The role of Work Package (WP) 2 of the PADAMOT project – ‘Palaeohydrogeological Data Measurements’ - has been to study late-stage fracture mineral and water samples from groundwater systems in Spain, Sweden, United Kingdom and the Czech Republic, with the aim of understanding the recent palaeohydrogeological evolution of these groundwater systems. In particular, the project sought to develop and evaluate methods for obtaining information about past groundwater evolution during the Quaternary (about the last 2 million years) by examining how the late-stage mineralization might record mineralogical, petrographical and geochemical evidence of how the groundwater system may have responded to past geological and climatological changes. Fracture-flow groundwater systems at six European sites were studied: • Melechov Hill, in the Bohemian Massif of the Czech Republic: a shallow (0-100 m) dilute groundwater flow system within the near-surface weathering zone in fractured granitic rocks; • Cloud Hill, in the English Midlands: a (~100 m) shallow dilute groundwater flow system in fractured and dolomitized Carboniferous limestone; • Los Ratones, in southwest Spain: an intermediate depth (0-500 m) dilute groundwater flow system in fractured granitic rocks; • Laxemar, in southeast Sweden: a deep (0-1000 m) groundwater flow system in fractured granitic rocks. This is a complex groundwater system with potential recharge and flushing by glacial, marine, lacustrine and freshwater during the Quaternary; • Sellafield, northwest England: a deep (0-2000 m) groundwater flow system in fractured Ordovician low-grade metamorphosed volcaniclastic rocks and discontinuous Carboniferous Limestone, overlain by a Permo-Triassic sedimentary sequence with fracture and matrix porosity. This is a complex coastal groundwater system with deep hypersaline sedimentary basinal brines, and deep saline groundwaters in crystalline basement rocks, overlain by a shallow freshwater aquifer system. The site was glaciated several times during the Quaternary and may have been affected by recharge from glacial meltwater; • Dounreay, northeast Scotland: a deep (0-1400 m) groundwater flow system in fractured Precambrian crystalline basement overlain by fractured Devonian sedimentary rocks. This is within the coastal discharge area of a complex groundwater system, comprising deep saline groundwater hosted in crystalline basement, overlain by a fracture-controlled freshwater sedimentary aquifer system. Like Sellafield, this area experienced glaciation and may potentially record the impact of glacial meltwater recharge. In addition, a study has been made of two Quaternary sedimentary sequences in Andalusia in southeastern Spain to provide a basis of estimating the palaeoclimatic history of the region that could be used in any reconstruction of the palaeoclimatic history at the Los Ratones site: • The Cúllar-Baza lacustrine sequence records information about precipitation and palaeotemperature regimes, derived largely from the analysis of the stable isotope (δ18O and δ13C) signatures from biogenic calcite (ostracod shells). • The Padul Peat Bog sequence provided information on past vegetation cover and palaeogroundwater inputs based on the study of fossil pollen and biomarkers as proxies for past climate change. Following on from the earlier EC 4th Framework EQUIP project, the focus of the PADAMOT studies has been on calcite mineralization. Calcite has been identified as a late stage mineral, closely associated with hydraulically-conductive fractures in the present-day groundwater systems at the Äspö-Laxemar, Sellafield, Dounreay and Cloud Hill sites. At Los Ratones and Melechov sites late-stage mineralization is either absent or extremely scarce, and both the quantity and fine crystal size of any late-stage fracture mineralization relevant to Quaternary palaeohydrogeological investigations is difficult to work with. The results from the material investigated during the PADAMOT studies indicate that the fracture fillings at these sites are related to hydrothermal activity, and so do not have direct relevance as Quaternary indicators. Neoformed calcite has not been found at these two sites at the present depth of the investigations. Furthermore, the HCO3 - concentration in all the Los Ratones groundwaters is mainly controlled by complex carbonate dissolution. The carbonate mineral saturation indices do not indicate precipitation conditions, and this is consistent with the fact that neoformed calcite, ankerite or dolomite have not been observed petrographically

The initial stages of cave formation: Beyond the one-dimensional paradigm

The solutional origin of limestone caves was recognized over a century ago, but the short penetration length of an undersaturated solution made it seem impossible for long conduits to develop. This is contradicted by field observations, where extended conduits, sometimes several kilometers long, are found in karst environments. However, a sharp drop in the dissolution rate of CaCO_3 near saturation provides a mechanism for much deeper penetration of reactant. The notion of a "kinetic trigger" - a sudden change in rate constant over a narrow concentration range - has become a widely accepted paradigm in speleogenesis modeling. However, it is based on one-dimensional models for the fluid and solute transport inside the fracture, assuming that the dissolution front is planar in the direction perpendicular to the flow. Here we show that this assumption is incorrect; a planar dissolution front in an entirely uniform fracture is unstable to infinitesimal perturbations and inevitably breaks up into highly localized regions of dissolution. This provides an alternative mechanism for cave formation, even in the absence of a kinetic trigger. Our results suggest that there is an inherent wavelength to the erosion pattern in dissolving fractures, which depends on the reaction rate and flow rate, but is independent of the initial roughness. In contrast to one-dimensional models, two-dimensional simulations indicate that there is only a weak dependence of the breakthrough time on kinetic order; localization of the flow tends to keep the undersaturation in the dissolution front above the threshold for non-linear kinetics.Comment: to be published in Earth and Planetary Science Letter

Frictional Instabilities and Carbonation of Basalts Triggered by Injection of Pressurized H2O- and CO2- Rich Fluids

The safe application of geological carbon storage depends also on the seismic hazard associated with fluid injection. In this regard, we performed friction experiments using a rotary shear apparatus on precut basalts with variable degree of hydrothermal alteration by injecting distilled H2O, pure CO2, and H2O + CO2fluid mixtures under temperature, fluid pressure, and stress conditions relevant for large-scale subsurface CO2storage reservoirs. In all experiments, seismic slip was preceded by short-lived slip bursts. Seismic slip occurred at equivalent fluid pressures and normal stresses regardless of the fluid injected and degree of alteration of basalts. Injection of fluids caused also carbonation reactions and crystallization of new dolomite grains in the basalt-hosted faults sheared in H2O + CO2fluid mixtures. Fast mineral carbonation in the experiments might be explained by shear heating during seismic slip, evidencing the high chemical reactivity of basalts to H2O + CO2mixtures