Calcite Dissolution Rates Research Articles

Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution

Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.

Sources of limestone dissolution from surface water-groundwater interaction in the carbonate critical zone

Dissolution of carbonate minerals in karst aquifers has long been recognized to result from recharge of surface water undersaturated with respect to calcite from carbonic acid produced by hydration of dissolved atmospheric and respired CO2. However, dissolution also results from additional acids produced by reactions of redox sensitive solutes in the subsurface, which may represent a source of CO2 to Earth's atmosphere. Because the magnitude of dissolution by these additional acids is poorly constrained, we compare here fractions of dissolution from initial surface water undersaturation and subsurface redox reactions. Estimates are based on chemical mixing and geochemical (PHREEQC) modeling of time series measurements of water compositions at a spring vent that receives surface water during stream flooding and a stream sink-rise system in north-central Florida. During a single spring reversal, 9.2 × 105 kg of limestone dissolved. At the stream sink-rise system, where subsurface residence times are shorter than during the spring reversal, both limestone dissolution (102–104 kg) and precipitation (102–105 kg) occur as water flows through the conduits with residence times ranging from 10 to 70 h. At both sites, maximum calcite dissolution rates of ∼10 μM hr−1 occurs at subsurface residence times between 30 and 50 h. For subsurface residence time > ∼20–60 h, the models indicate that production of additional acid in the subsurface is required for ∼53 ± 7% of dissolution. Oxidation of organic carbon, ammonium, pyrite, iron, and/or manganese produce sufficient acid for additional dissolution, but dissolved oxygen is insufficient for these reactions, indicating some acidity is generated under anerobic conditions. Dissolution caused by subsurface reactions in our samples represents mobilization of 20 × 104-30 × 104 kg of CO2 via remineralization of organic carbon or carbonate dissolution by nitric and sulfuric acids. Acid produced by subsurface redox reactions during surface water-groundwater interactions, including non‑carbonic acids, are important in conduit development and carbon cycling in the carbonate critical zone.

Reaction order of near equilibrium calcite dissolution: Uncertainties and ambiguities of isotopic tracer methods

Dissolution of calcite in water is fundamental to geochemistry. Laboratory methods generally give consistent dissolution rates under conditions far from equilibrium, but close to equilibrium the measurement of dissolution using isotopes is complicated by poorly understood calcite-fluid isotopic exchange processes. This near-equilibrium isotopic exchange occurs in laboratory experiments at rates of order 10-9 to 10-13 mol/m2/s and decreases with experiment duration approximately as 1/time where time is measured from the start of the experiment. Such rates are fast enough to compete with dissolution in days-long experiments and consequently, net dissolution rates may not be measurable with isotopic tracer methods except in experiments carried out for long enough to allow the background exchange to dissipate sufficiently. To better define what should be expected for isotopic signals during dissolution, we develop a quasi-1D model for calcite dissolution that includes the mechanistically unconstrained isotopic exchange as well as solid state diffusion. We use the model, the observations reported in the literature, and the calcite dissolution rates in seawater reported by Naviaux et al., (2019a) to illustrate ambiguities in measurement of near-equilibrium calcite dissolution rates. The results suggest that the reaction order of calcite dissolution close to equilibrium could be 2 at both room temperature and the lower temperatures of the seafloor. The reaction order of near-equilibrium calcite dissolution is important for understanding calcite mineral surface processes, long-term behavior of dissolution on the seafloor, and alkalinity fluxes from modern seafloor sediments. Distinguishing between net dissolution, which affects fluid saturation state, and “exchange,” which doesn’t, is important but typically cannot be done with isotopic tracers alone.

Testing the hypothesis that solvent exchange limits the rates of calcite growth and dissolution.

It is established that the rates of solvent exchange at interfaces correlate with the rates of a number of mineral reactions, including growth, dissolution and ion sorption. To test if solvent exchange is limiting these rates, quasi-elastic neutron scattering (QENS) is used here to benchmark classical molecular dynamics (CMD) simulations of water bound to nanoparticulate calcite. Four distributions of solvent exchanges are found with residence times of 8.9 ps for water bound to calcium sites, 14 ps for that bound to carbonate sites and 16.7 and 85.1 ps for two bound waters in a shared calcium-carbonate conformation. By comparing rates and activation energies, it is found that solvent exchange limits reaction rates neither for growth nor dissolution, likely due to the necessity to form intermediate states during ion sorption. However, solvent exchange forms the ceiling for reaction rates and yields insight into more complex reaction pathways.

Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb2+ Solutions.

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb2+ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb2+ concentrations ([Pb2+] = 0 to 5 × 10-2 M) and flow velocities (v = 1.67-53.3 mm s-1). Calcite (104) surface dissolution rates decreased with increasing [Pb2+]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb2+] ≥ 5 × 10-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.

Laboratory Observation of the Buffering Effect of Aragonite Dissolution at the Seafloor

AbstractCarbon dioxide entering and acidifying the ocean can be neutralized by the dissolution of calcium carbonate, which is mainly found in two mineral forms. Calcite is the more stable form and is often found in deep‐sea sediments, whilst aragonite is more soluble and therefore rarely preserved. Recent research shows aragonite may account for a much larger portion of marine calcium carbonate export to the ocean interior via the biological pump than previously thought, and that aragonite does reach the deep sea and seafloor despite rarely being buried. If aragonite is present and dissolving at the seafloor it will raise local pH and calcium and carbonate concentrations, potentially enough to inhibit calcite dissolution, representing a deep‐sea, carbonate version of galvanization. Here, we test this hypothesis by simulating aragonite dissolution at the sediment‐water interface in the laboratory and measuring its effects on pH using microsensors. We show that the addition of aragonite to calcite sediment, overlain by seawater undersaturated with respect to both minerals, results in an unchanged alkalinity flux out of the dissolving sediment, suggesting a decrease the net dissolution rate of calcite. In combination with a diagenetic model, we show that aragonite dissolution can suppress calcite dissolution in the top millimeters of the seabed, locally leading to calcite precipitation within 1 day. Future research efforts should quantify this galvanization effect in situ, as this process may represent an important component of the marine carbon cycle, assigning a key role to aragonite producers in controlling ocean alkalinity and preserving climatic archives.

The solubility product controls the rate of calcite dissolution in pure water and seawater.

Quantification of calcite dissolution underpins climate and oceanographic modelling. We report the factors controlling the rate at which individual crystals of calcite dissolved. Clear, generic criteria based on the change of calcite particle dimensions measured microscopically with time are established to indicate if dissolution occurs under kinetic or thermodynamic control. The dissolution of calcite crystals into water is unambiguously revealed to be under thermodynamic control such that the rate at which the crystal dissolved is controlled by the rate of diffusion of ions from a saturated surface layer adjacent to the calcite surface. As such the dissolution rate is controlled by the true stoichiometric solubility product which is inferred from the microscopic measurement as a function of the concentration of NaCl. Comparison with accepted literature values shows that the role of ion pairing at high ionic strengths as in seawater, specifically that of CaCO3 and other ion pairs, exerts a significant influence since these equilibria control the amount of dissolved calcium and carbonate ions in the later of solution immediately adjacent to the solid.

Cu2(OH)3Cl microspheres with self-assembled nanostructures through a dissolution regulation reaction and exhibits excellent antibacterial activity

Basic copper chloride (Cu2(OH)3Cl) microspheres with different surface nanostructure were synthesized via the dissolution regulation of calcite in CuCl2 solution. We studied the influence of CuCl2 concentration, reaction time and reaction temperature on the formation of Cu2(OH)3Cl, and the products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and transmission electron microscopy. The concentration of CuCl2 has a great influence on the dissolution rate of calcite, dispersed microsphere particles assembled by nano-blocks formed in 20 mM CuCl2 solution. The surface of Cu2(OH)3Cl microsphere change from nano-block to nano-rod with increasing the reaction time from 20 min to 2 h Cu2(OH)3Cl microspheres with surface structure changed from nano-sheet, nano-plate to nano-block with the reaction temperature increase from 37 °C to 70 °C. The Cu2(OH)3Cl microsphere also displays superior antibacterial properties against S. aureus and E. coli. This work displays a new strategy to synthesize functional materials by the use of dissolution regulation methods.

Origin and significance of ultra-slow calcite dissolution rates in deep sea sediments

Prediction of mineral-fluid reaction rates in geologic materials is subject to large uncertainties even though the rates are critical for many applications, from studies of past climate change to the engineering of carbon removal and storage. Deep sea carbonate sediments, which have been extensively cored and characterized at dozens of sites by ocean drilling programs, provide unique opportunities to examine how minerals and fluids react over multi-million-year timescales in natural conditions at low temperature. It has already been established that the calcite-fluid reaction in these systems is extremely slow, but the explanation for the ultra-slow rates, and the fact that non-zero rates persist for tens of millions of years, remains elusive. We extend the analysis of pore fluid Sr and Ca concentration data in the literature from ocean drilling archives to 21 drill sites in sediment sections where the fraction of carbonate is larger than 80% to systematically estimate the rates at which calcite dissolves and precipitates as a function of depth and sediment age. Pore fluid Sr/Ca used in this study, and Sr and Ca isotopes in other published analyses, provide estimates of the gross calcite dissolution rates, which are mostly balanced by secondary calcite precipitation. Pore fluid Ca concentration data provide key, previously underappreciated, information on the net calcite dissolution rates. Using these data we evaluate simple models for calcite reaction kinetics and pore fluid sediment evolution and conclude that (1) reaction rates are extremely slow because the reactive site density of the bulk sediment decreases continuously and systematically approximately as age−1, and (2) reaction persists to hundreds of meters burial depth and tens of millions of years because pore fluids never become closed due to diffusive communication with the oceans, and hence remain slightly undersaturated with respect to calcite. The systematic decrease in bulk reactive site density begins immediately upon deposition, greatly slowing the rate of dissolution and hence affecting models of calcite dissolution on the seafloor. The failure to reach equilibrium after millions of years and hundreds of meters of burial, is a consequence of extremely slow net reaction rates that cannot drive the pore fluids to equilibrium against the diffusive loss of Ca and DIC to the ocean. The existence of two or more calcite phases of different solubility is a likely source of a long-lived, but small, driving force for reaction, but its effect decreases with continued recrystallization and pore fluid evolution.

Equilibrium Ca isotope fractionation and the rates of isotope exchange in the calcite-fluid and aragonite-fluid systems at 25 °C

The Ca isotope composition of calcite and aragonite can provide insights into their formation conditions. The accurate interpretation of the Ca isotope composition of natural samples, however, requires precise knowledge of the equilibrium Ca isotope fractionation between the solid and fluid phases. In this study, the three-isotope method with 42Ca, 43Ca and 44Ca has been used to estimate the equilibrium isotope fractionation of Ca between the CaCO3 minerals calcite and aragonite and the Ca2+ aquo ion. Reactive fluids were enriched with 43Ca and equilibrated with synthetic calcite and aragonite of natural Ca isotope distribution up to 3745 h at 25°C. The isotopic composition of solids and fluids was measured using MC-ICP-MS and the estimated equilibrium fractionation for calcite-Ca2+(aq) and aragonite-Ca2+(aq) was Δ44/42Casolid-fluid=−0.02±0.13‰ and −0.80±0.10‰, respectively. Textural observations of the reacted solids suggest that isotope equilibration in aragonite experiments occurs via extensive Ostwald ripening, yielding large crystalline needles at the end of the experiments. In contrast, calcite did not exhibit an observable increase in size during the course of the experiments. Isotope exchange rates in the case of calcite are similar to those reported in previous studies and ∼4 orders of magnitude lower than the far-from-equilibrium calcite dissolution rate. Calcium isotope exchange rates for aragonite are more rapid than calcite driven by a greater extent of Ostwald ripening occurring via dissolution/precipitation reactions. The results of this study suggest that the Ca isotope compositions of calcite and aragonite crystals in chemical equilibrium, but isotope disequilibrium, with natural fluids could be significantly altered without overt evidence of diagenesis, especially in the case of calcite. The extent to which Ca isotope compositions are altered, however, would depend strongly on the environmental conditions, such as fluid:solid ratio and permeability of the solid facilitating fluid transport.

Rates of carbon and oxygen isotope exchange between calcite and fluid at chemical equilibrium

The isotopic composition of carbonate minerals provides a record of historical geochemical and environmental conditions, but the ability to interpret these compositions as paleo-proxies hinges on their preservation over thousand to million year timescales. At chemical equilibrium, alteration of initial isotopic compositions of calcite can occur in the presence of a fluid without visible changes in morphology at the submicron scale, complicating the interpretation of stable isotope compositions of carbonates. However, the rates and mechanisms of isotope exchange at chemical equilibrium are poorly understood. To evaluate the rates and processes by which C and O isotopes are exchanged between calcite and fluid, batch reactor experiments were conducted at chemical equilibrium between calcite and a fluid enriched in 13C and 18O relative to the solid at 25 °C. Both natural and synthetic calcite of different grain sizes were investigated to evaluate the impact of mineral surface area and size on C and O isotope exchange rates. Our experimental results indicate that rapid exchange of both C and O isotopes occurs within 72 h for all calcite grain sizes studied, likely indicative of exchange of surface species in combination with a backward reaction during dissolution and Ostwald ripening of high energy surface sites. After 72 h, C and O isotope exchange rates were slower but near constant for timescales of thousands of hours. Surface-area normalized C and O isotope exchange rates were similar for all calcite grain sizes studied, and O and C were exchanged in a ∼3:1 ratio consistent with exchange of CO32–. The rates of C and O exchange were ∼4 orders of magnitude lower than far-from-equilibrium calcite dissolution rates, suggesting exchange was controlled either by dissolution-precipitation of pre-existing reactive sites alone, or a combination of dissolution-precipitation and solid state/aqueous mediated diffusion. Overall, the results of this study suggest alteration of O and C isotope compositions of calcite at ambient temperatures can proceed readily over short time scales, though the extent to which this process continues to operate over geologic time scales is difficult to predict at present. The results of this study further highlight the importance of generating a mechanistic understanding of the process of isotope exchange at chemical equilibrium, and represent a step towards this understanding.

Upscaling calcite dissolution rates in a tight reservoir sandstone

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) 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}}}} showed to be reasonably suitable for upscaling the mineral surface rates to the core scale.

Shallow Calcium Carbonate Cycling in the North Pacific Ocean

AbstractThe cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situ coccolith and foraminiferal calcite dissolution rates. We combine these rates with solid phase fluxes, dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean. The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution rates of all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods) are too slow to explain the patterns of both CaCO3 sinking flux and alkalinity regeneration in the North Pacific. Using a combination of dissolved and solid‐phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3 dissolution with a combination of ambient saturation state and oxygen consumption simultaneously explains solid‐phase CaCO3 flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. We do not need to invoke the presence of carbonate phases with higher solubilities. Instead, biomineralization and metabolic processes intimately associate the acid (CO2) and the base (CaCO3) in the same particles, driving the coupled shallow remineralization of organic carbon and CaCO3. The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration within degrading particle aggregates. The coupling of these cycles acts as a major filter on the export of both organic and inorganic carbon to the deep ocean.

Oxygen isotopes of calcite precipitated at high ionic strength: CaCO3-DIC fractionation and carbonic anhydrase inhibition

Background electrolytes affect calcite precipitation and dissolution rates and hence have the potential to impact kinetic isotope fractionation between calcite and the dissolved inorganic carbon (DIC) species. We grew inorganic calcite from NaCl-CaCl2 solutions (T = 25 °C, pH = 8.3, and crystal growth rate = 10−6.3 ± 0.3 mol m−2 s−1) to test for potential ionic strength effects on the oxygen isotope fractionation between calcite and an isotopically equilibrated inorganic carbon pool (αc/EIC). Calcite was grown in the presence of the enzyme carbonic anhydrase from bovine erythrocytes (bCA) to promote isotopic equilibration of the DIC pool.No evidence of an ionic strength effect on αc/EIC was found for NaCl concentrations up to 0.35 M (1000lnαc/w = 28.0 ± 0.1; n = 7). For experiments conducted with [NaCl] > 0.35 M, the DIC pool could not be maintained in isotopic equilibrium with water due to the inhibitory effect of NaCl on bCA. The use of other types of CA may be required to maintain isotopic equilibration of DIC in solution with ionic strength close to or above that of seawater.The oxygen isotope results were modeled successfully with an isotopic box model for a CO2-fed solution that tracks the isotopic composition of each DIC species and CaCO3. The experimental and modeling results suggest that the efficacy of bCA decreases exponentially with increasing [NaCl]. We quantify the salt effect on the quantity kcat/KM, which relates the catalyzed rate constant for CO2 hydration to the concentration of bCA. The salt effect can be implemented in models of biomineralization with potential to extend our knowledge of oxygen isotope vital effects in marine organisms.

The Effect of Pore-Scale Two-Phase Flow on Mineral Reaction Rates

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.

Implementing Heterogeneous Crystal Surface Reactivity in Reactive Transport Simulations: The Example of Calcite Dissolution

Both surface reactivity and fluid dynamics control the dissolution kinetics of crystalline material. In this study, we performed a 3D reactive transport simulation to investigate the impact of surface topography heterogeneity superimposed to fluid transport heterogeneity on the dissolution rate of calcite. The model simulates the chemical reaction of calcite dissolution, solute transport, and crystal surface geometry evolution. Importantly, we introduce heterogeneous surface reactivity into the reactive transport simulation. We test the surface slope factor as a proxy value for the intrinsic surface reactivity of dissolving crystal surface nanotopographies. Experimental data sets collected using vertical scanning interferometry validate this approach. The novel parametrization allows for the simulation of surface-controlled heterogeneous reactivity in reactive transport simulations of mineral surface dissolution.

Statistical Characterization of Heterogeneous Dissolution Rates of Calcite from In situ and Real-Time AFM Imaging

The evolution of the surface topography of a calcite crystal subject to dissolution is documented through in situ real-time imaging obtained via atomic force microscopy (AFM). The dissolution process takes place by exposing the crystal surface to deionized water. AFM data allow detection of nucleation and expansion of mono- and multilayer rhombic etch pits and are employed to estimate the spreading rate of these structures. Spatially heterogeneous distributions of local dissolution rate are evaluated from the difference between topographic measurements taken at prescribed time intervals. We rest on a stochastic framework of analysis viewing the dissolution rate as a generalized sub-Gaussian (GSG) spatially correlated random process. Our analysis yields: (i) a quantitative assessment of the temporal evolution of the statistics of the dissolution rates as well as their spatial increments; (ii) a characterization of the degree of spatial correlation of dissolution rates and of the way this is linked to the various mechanisms involved in the dissolution process and highlighted through the experimental evidences. Our results indicate that the parameters driving the statistics of the GSG distribution and the spreading rate of the multilayer pits display a similar trend in time, thus suggesting that the evolution of these structures imprints the statistical features of local dissolution rates.Article HighlightsWe investigate dynamics of dissolution patterns on a calcite crystal in contact with deionized water via AFM imagingTemporal behavior of parameters of our statistical model is consistent with surface pattern evolutionA nested model for the spatial correlation of rates embeds multiple mechanisms driving dissolution rate.

The contribution of hydrodynamic processes to calcite dissolution rates and rate spectra

Recent measurements on the dissolution rate of nano- and micron-scale rough calcite surfaces have shown lateral variations in dissolution rate, which can be quantified using rate spectra. This study uses numerical simulations to investigates the hydrodynamic processes during such experiments to explore whether hydrodynamic effects can explain the observed dissolution rate spectra. For this purpose, we simulated the dissolution processes of nano- and micron-scale rough calcite surfaces in COMSOL Multiphysics. We imposed surface topographies and local reaction rates measured using Vertical Scanning Interferometry (VSI), and implemented the same flow rate (i.e., 6 × 10−8 m3 s−1), solution chemistry (pH 8.8, alkalinity 4.4 meq/kg-H2O and pCO2 10−3.48 bar) and flow-cell geometry as those used in the experiment. We have compared the simulated rate spectra against the experimentally measured values at a calcite surface having the same surface topography and reactive-flow conditions.Simulations using a single dissolution rate for the rough calcite surface did not produce similarly wide dissolution rate spectra like those observed experimentally. Our results have shown that only by explicitly incorporating the rate spectra in the model the simulated and the measured rate spectra would match. Sensitivity analyses by varying chemical composition and flow velocity were performed to examine the effects of these parameters on the calculated rate spectra. This study concludes that for the reactive-flow regimes where dissolution rate spectra are observed experimentally, the chemical heterogeneity, topography of the crystal surface and the resulting heterogeneity in the free energy landscape at the surface play a major role in controlling the dissolution rate spectra. With the injection of more acidic (pH 2) solutions at higher velocities (i.e., 0.04 m s−1), we observed an increase in the hydrodynamics-induced rate variability at microscopically rough surfaces.

Topographic Analysis of Calcite (104) Cleavage Surface Dissolution in Ethanol–Water Solutions

The interaction of organic molecules with calcite surfaces plays a key role in many geochemical, industrial and biomineralization processes, and exploring the influences of organic molecules on calcite reactions is crucial for a fundamental understanding of the reaction mechanisms. Here, we used digital hologram microscopy to explore the in situ evolution of the calcite (104) surfaces when dissolved in ethanol–water solutions, and total organic carbon analysis was applied to confirm the adsorption of ethanol by calcite. The results showed that the bulk dissolution rate of calcite decreases as the volume fraction of ethanol increases, and the topographic features of etch pits were also altered by the presence of ethanol. When exposed to too much ethanol, the etch pits’ growth was inhibited and their shapes tended to change from rhombuses in ultrapure water to triangles. Our results provide insights into the interaction between adsorbed ethanol and evolving calcite crystal, which highlights the dissolution regulation of calcite by organic molecules that could benefit a broad range of fields.

Effect of polyacrylamide friction reducer on calcite dissolution rate at 25 °C and implication for hydraulic fracturing

Hydraulic fracturing is widely used to create cracks and increase the size and connectivity of existing fractures, leading to higher permeability of shale rocks and production of unconventional hydrocarbon sources. The main chemicals used in hydraulic fracturing fluids can initiate fractures in shale reservoirs by acid induced carbonate dissolution, and minimise energy loss during the pumping process by friction reducer enhanced fluid viscosity. Here, using batch reactor experiments we investigate the effect of non-ionic polyacrylamide polymer (friction reducer) on the dissolution rate of calcite in acidic solutions (0.2 M buffer solution of sodium acetate/acetic acid) at 25 °C. The results demonstrate that polyacrylamide (from 0 to 30 mg) slows down the dissolution rate by a factor of 4. Hydrogen bonding and surface complexation between non-ionic polyacrylamide and calcite potentially trigger an adsorption mechanism that protects calcite from dissolving. This research provides new insights into friction reducer (polyacrylamide) influenced pore generation, enabling engineers to optimise the fracturing fluid design (amount of polyacrylamide) and to consider suitable actions to prevent the polymer from having a negative impact on productivity.