Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in Earth sciences and engineering. Samples of Carrara marble were reacted with an ammonium fluoride (NH 4 F) solution for different reaction times and temperatures. The microstructure of the product phase (fluorite) was analyzed using SEM. The kinetics of replacement was monitored using Rietveld analysis of X-ray powder diffraction patterns of the products. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement). The grain boundaries of the original marble were preserved although each calcite grain was replaced by multiple fine crystals of fluorite creating inter-crystal porosity. The empirical activation energy E a (kJ/mol) of the replacement reaction was determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the modelfitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. These results suggest that the replacement reaction is dependent on the ion diffusion rate in the fluid phase through the newly formed porosity.

No abstract

Mineral replacement reactions are common phenomena in natural and laboratory environments where solids have re-equilibrated with aqueous solutions and are characterized by the generation or destruction of porosity in the product phase(s). Here, the evolution of porosity during the replacement of calcite by fluorite is used as a model system to characterize the kinetics of volume variations. Non-porous single crystals of calcite were reacted with sodium fluoride solutions for different reaction times. The crystals were pseudomorphically replaced by highly porous fluorite. Complementary use of porosimetry techniques, high resolution imaging, and mass-balance calculations revealed the total, open, and closed porosity in the samples. The infiltration of aqueous fluids in the Earth depends on the evolution of porosity and hence porosity variations are important in various geological processes such as, rock weathering and soil formation, fluid-controlled metamorphism, mineral ore emplacement, or oil and gas reservoir compaction.Such mechanisms can also be used to develop geo-inspired materials designed for industrial and medical applications.

The replacement of a natural carbonate rock (Carrara marble) by apatite was used as a model to study the role of fluid chemistry in replacement reactions, focusing on the mineralogy, chemical composition, and porosity of the replacementproduct.Carrara marble was reacted with ammonium phosphate solutions ((NH 4) 2 HPO 4), in the presence and absence of four salt solutions (NH 4 Cl, NaCl, NH 4 F, and NaF) at different ionic strengths, at 200°C and autogenous pressure. The replacement products were analysed usingpowder X-ray diffraction,Scanning electron microscopy (SEM), electron microprobe analysis(EMPA), and Raman spectroscopy. The reaction in all samples resulted in pseudomorphic replacements and shared the characteristics of an interface-coupled dissolution-precipitation mechanism. Increasing theionic strength of the phosphatefluid increased the replacement rates. With a fixedconcentration of phosphate, replacement rates were reduced with the addition of NH 4 Cl and NaCland increased significantly with the addition of NaF and NH 4 F. The addition of different salts resulted in specific porosity structures resulting from the formation of different phosphate phases. Chlorine-containing fluids showed a higher degree of fluid percolation through grain boundaries. This study illustrates the significant impact that small differences in solvent composition can have in the progress of replacement reactions, the nature of the products and the resultant porosity.

Understanding mineral dissolution is relevant for natural and industrial processes that involve the interaction of crystalline solids and fluids. The dissolution of slow dissolving minerals is typically surface controlled as opposed to diffusion/transport controlled. At these conditions, the dissolution rate is no longer constant in time or space, an outcome observed in rate maps and correspondent rate spectra. The contribution and statistical prevalence of different dissolution mechanisms is not known. Aiming to contribute to close this gap, we present a statistical analysis of the variability of calcite dissolution rates at the nano- to micrometer scale. A calcite-cemented sandstone was used to perform flow experiments. Dissolution of the calcite-filled rock pores was measured using vertical scanning interferometry. The resultant types of surface morphologies influenced the outcome of dissolution. We provide a statistical description of these morphologies and show their temporal evolution as an alternative to the lack of rate spatial variability in rate constants. Crystal size impacts dissolution rates most probably due to the contribution of the crystal edges. We propose a new methodology to analyze the highest rates (tales of rate spectra) that represent the formation of deeper etch pits. These results have application to the parametrization and upscaling of geochemical kinetic models, the characterization of industrial solid materials and the fundamental understanding of crystal dissolution.

No abstract

The application of rock powder on agricultural land to ameliorate soils and remove carbon dioxide (CO2) from the air by chemical weathering is still subject to many uncertainties. To elucidate the effects of grain size distribution and soil partial pressure of carbon dioxide (pCO2) levels on CO2 uptake rates, two simple column experiments were designed and filled nearly daily with an amount of water that simulates humid tropical conditions, which prevail in areas known for being hotspots of weathering. Multiple materials (dunite, basanite, agricultural oxisol, a combination of the latter two, and loess) were compared under ambient and 100% CO2 atmosphere. In a second series, single material columns (dunite) were filled with three different grain size distributions. Total alkalinity, pH, major ions, and dissolved silica were determined in the outflow water of the columns for about 300 days. Under ambient atmospheric conditions, the CO2 consumption was the lowest in the oxisol column, with 100 t CO2 km−2 year−1, while dunite and basanite showed similar consumption rates (around 220 t CO2 km−2 year−1). The values are comparable to high literature values for ultramafic lithologies. Interestingly, the mixture of basanite and oxisol has a much higher consumption rate (around 430 t CO2 km−2 year−1) than the basanite alone. The weathering fluxes under saturated CO2 conditions are about four times higher in all columns, except the dunite column, where fluxes are increased by a factor of more than eleven. Grain size distribution differences also play a role, with the highest grain surface area normalized weathering rates observed in the columns with coarser grains, which at first seems counterintuitive. Our findings point to some important issues to be considered in future experiments and a potential rollout of EW as a carbon dioxide removal method. Only in theory do small grain sizes of the spread-material yield higher CO2 drawdown potentials than coarser material. The hydrologic conditions, which determine the residence times in the pore space, i.e., the time available for weathering reactions, can be more important than small grain size. Saturated-CO2 column results provide an upper limit for weathering rates under elevated CO2.

Calcite is a highly abundant mineral in the Earth’s crust and occurs as a cement phase in numerous siliciclastic sediments, where it often represents the most reactive component when a fluid percolates through the rock. Hence, the objective of this study is to derive calcite dissolution rates on different scales in a reservoir sandstone using mineral surface experiments combined with vertical scanning interferometry (VSI) and two types of core plug experiments. The 3D geometry of the calcite cement phase inside the rock cores was characterized by X-ray micro-computed tomography (µXCT) and was used to attempt dissolution rate upscaling from the mineral surface to the core scale. Initially (without upscaling), our comparison of the far-from-equilibrium dissolution rates at the mineral surface (µm-mm-scale, low fluid residence time) and the surface normalized dissolution rates obtained from the core experiments (cm-scale, high fluid residence time) revealed differences of 0.5–2 orders of magnitude. The µXCT geometric surface area connected to the open pore space $$\left( {GSA_{{Cc,{\text{open}}}} } \right)$$ G S A C c , open considers the fluid accessibility of the heterogeneously distributed calcite cement that can largely vary between individual samples, but greatly affects the effective dissolution rates. Using this parameter to upscale the rates from the µm- to the cm-scale, the deviation of the upscaled total dissolution rates from the measured total dissolution rates was less than one order of magnitude for all investigated rock cores. Thus, $$GSA_{{Cc,{\text{open}}}}$$ G S A C c , open showed to be reasonably suitable for upscaling the mineral surface rates to the core scale.