A comprehensive dataset for the thermal conductivity of ice Ih for application to planetary ice shells.

Contemporary models representing the thermal conductivity of ice Ih as a function of temperature are based on data from published experiments that span over a century. Each model is derived using specific datasets with distinct experimental setups, temperature ranges, and uncertainties. Model errors introduced by inaccurate digitization and biased datapoints are challenging to trace due to a lack of transparency of the primary data. This dataset is a collection of published thermal conductivity data for ice Ih, including both tabulated and digitized data, presented in the original units. Specific samples or pressure conditions are noted where applicable. The dataset also includes a survey of published thermal conductivity models, providing the valid temperature range, accuracy and uncertainty (where noted in the original publication), and the primary data sources. Importantly, the dataset includes notes that were contained in the original publication or subsequent publications that provide additional context for the data. This dataset is used to derive a new thermal conductivity model which best represents the thermal conductivity of ice Ih for temperatures greater than 30 K. Statistics are provided to evaluate the fit of each thermal conductivity model in the survey of published models to the comprehensive dataset presented here. This dataset is constructed in support of the work "New insights into temperature-dependent ice properties and their effect on ice shell convection for icy ocean worlds" [1].

Dispersion of charged solute in charged micro- and nanochannel with reversible sorption.

We study dispersion of a charged solute in a charged micro- and nanochannel with reversible sorption and derive an analytical solution for mass fraction in the fluid, transport velocity and dispersion coefficient. Electrical double layer formed on the charged surface gives rise to a charge-dependent solute transport by modifying the transverse distribution of the solute. We discuss the effect of sorption and electrical double layer on solute transport and show that the coupling between sorption and electrical double layer gives rise to charge-dependent transport even for a thin double layer. However, in this case, it can be reduced to a simple non-charge-dependent case by introducing the intrinsic sorption equilibrium constant.

Reactive Transport of Protons in Electro-Osmotic Displacements with Electrolyte Concentration Difference in a Microcapillary.

In this work, we model electro-osmotic displacement with electrolyte concentration difference in a microcapillary by incorporating proton transport coupled with surface complexation reaction and carbonate equilibrium. The hysteretic effect observed in experiments is well-captured by the model. By deriving the semianalytical solution of the nonlinear transport equation using method of characteristics, we elucidate the transport mechanism of protons by classifying their nonlinear transport behavior (shock/rarefaction/discontinuity) into several regimes depending on the concentration ratio and the pH. The model can be used to predict pH variation and characterizes surface property in electro-osmotic experiments.

Chromatographic analysis of the acidity-salinity transport system.

The effects of acidity and salinity on solute transport in porous media are important to a diverse range of fields from seawater intrusion to nuclear waste storage. Recent transport experiments in quartz sand show the difficulty in capturing the coupling of acidity and salinity under acidic conditions for this system. Here we study the ability of different surface complexation models to capture this coupling, through an analysis of the reactive transport equations in the limit of no diffusion. This chromatographic analysis leads to a graphical representation of the full set of solutions in the phase plane, thus allowing a comprehensive comparison of the transport behavior arising from different SCMs. The analysis shows that the predicted coupling is improved by including amphoteric behavior of the quartz surface. The inclusion of a secondary proton sorption reaction increases the magnitude of surface charge under acidic conditions strengthening the acidity-salinity coupling. This suggests that even though the overall surface is negative above the point of zero charge, positively charged sites play an important role in the reactive transport of acidity and salinity.

Percolative core formation in planetesimals enabled by hysteresis in metal connectivity.

The segregation of dense core-forming melts by porous flow is a natural mechanism for core formation in early planetesimals. However, experimental observations show that texturally equilibrated metallic melt does not wet the silicate grain boundaries and tends to reside in isolated pockets that prevent percolation. Here we use pore-scale simulations to determine the minimum melt fraction required to induce porous flow, the percolation threshold. The composition of terrestrial planets suggests that typical planetesimals contain enough metal to overcome this threshold. Nevertheless, it is currently thought that melt segregation is prevented by a pinch-off at melt fractions slightly below the percolation threshold. In contrast to previous work, our simulations on irregular grain geometries reveal that a texturally equilibrated melt network remains connected down to melt fractions of only 1 to 2%. This hysteresis in melt connectivity allows percolative core formation in planetesimals that contain enough metal to exceed the percolation threshold. Evidence for the percolation of metallic melt is provided by X-ray microtomography of primitive achondrite Northwest Africa (NWA) 2993. Microstructural analysis shows that the metal-silicate interface has characteristics expected for a texturally equilibrated pore network with a dihedral angle of ∼85°. The melt network therefore remained close to textural equilibrium despite a complex history. This suggests that the hysteresis in melt connectivity is a viable process for percolative core formation in the parent bodies of primitive achondrites.

Challenges in Coupling Acidity and Salinity Transport in Porous Media.

Salinity is an increasingly prescient issue in reactive transport, from low salinity water flooding to fracking brine leakage. Of primary concern is the effect of salinity on surface chemistry. Transport and batch experiments show a strong coupling of salinity and acidity through chemical interactions at the mineral-liquid interface. This coupling is ascribed to the combined effects of ionic strength on electrostatic behavior of the interface and competitive sorption between protons and other cations for binding sites on the surface. The effect of these mechanisms is well studied in batch settings and readily describes observed behavior. In contrast, the transport literature is sparse, primarily applied to synthetic materials, and offers only qualitative agreement with observations. To address, this gap in knowledge, we conduct a suite of column flood experiments through silica sand, systematically varying salinity and acidity conditions. Experiments are compared to a reactive transport model incorporating the proposed coupling mechanisms. The results highlight the difficulty in applying such models to realistic media under both basic and acidic conditions with a single set of parameters. The analysis and experimental results show the observed error is the result of electrostatic assumptions within the surface chemistry model and provide a strong constraint on further model development.

Deformation-assisted fluid percolation in rock salt.

Deep geological storage sites for nuclear waste are commonly located in rock salt to ensure hydrological isolation from groundwater. The low permeability of static rock salt is due to a percolation threshold. However, deformation may be able to overcome this threshold and allow fluid flow. We confirm the percolation threshold in static experiments on synthetic salt samples with x-ray microtomography. We then analyze wells penetrating salt deposits in the Gulf of Mexico. The observed hydrocarbon distributions in rock salt require that percolation occurred at porosities considerably below the static threshold due to deformation-assisted percolation. Therefore, the design of nuclear waste repositories in salt should guard against deformation-driven fluid percolation. In general, static percolation thresholds may not always limit fluid flow in deforming environments.

Constraints on the magnitude and rate of CO2 dissolution at Bravo Dome natural gas field.

The injection of carbon dioxide (CO2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO2 emissions from fossil fuels. Dissolution of the injected CO2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO2 storage. We use thermochronology to estimate the timing of CO2 emplacement at Bravo Dome, a large natural CO2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraints on the magnitude, mechanisms, and rates of CO2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2-1.5 Ma. The CO2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO2 storage is possible. Integrating geophysical and geochemical data, we estimate that 1.3 Gt CO2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m(2)y). The similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO2 on the 10-ky timescale typically considered for storage projects.

Percolation and grain boundary wetting in anisotropic texturally equilibrated pore networks.

In texturally equilibrated porous media the pore geometry evolves to minimize the energy of the liquid-solid interfaces, while maintaining the dihedral angle θ at solid-solid-liquid contact lines. We present computations of three-dimensional texturally equilibrated pore networks using a level-set method. Our results show that the grain boundaries with the smallest area can be fully wetted by the pore fluid even for θ > 0. This was previously not thought to be possible at textural equilibrium and reconciles the theory with experimental observations. Even small anisotropy in the fabric of the porous medium allows the wetting of these faces at very low porosities, ϕ<3%. Percolation and orientation of the wetted faces relative to the anisotropy of the fabric are controlled by θ. The wetted grain boundaries are perpendicular to the direction of stretching for θ > 60° and the pores do not percolate for any investigated ϕ. For θ < 60°, in contrast, the grain boundaries parallel to the direction of stretching are wetted and a percolating pore network forms for all ϕ investigated. At low θ even small anisotropy in the fabric induces large anisotropy in the permeability, due to the concentration of liquid on the grain boundaries and faces.

Experimental evidence for self-limiting reactive flow through a fractured cement core: implications for time-dependent wellbore leakage.

We present a set of reactive transport experiments in cement fractures. The experiments simulate coupling between flow and reaction when acidic, CO(2)-rich fluids flow along a leaky wellbore. An analog dilute acid with a pH between 2.0 and 3.15 was injected at constant rate between 0.3 and 9.4 cm/s into a fractured cement core. Pressure differential across the core and effluent pH were measured to track flow path evolution, which was analyzed with electron microscopy after injection. In many experiments reaction was restricted within relatively narrow, tortuous channels along the fracture surface. The observations are consistent with coupling between flow and dissolution/precipitation. Injected acid reacts along the fracture surface to leach calcium from cement phases. Ahead of the reaction front, high pH pore fluid mixes with calcium-rich water and induces mineral precipitation. Increases in the pressure differential for most experiments indicate that precipitation can be sufficient to restrict flow. Experimental data from this study combined with published field evidence for mineral precipitation along cemented annuli suggests that leakage of CO(2)-rich fluids along a wellbore may seal the leakage pathway if the initial aperture is small and residence time allows mobilization and precipitation of minerals along the fracture.