Magnesium inhibition of calcite dissolution kinetics

We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO₂-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 × 10⁻³ molal. At the same pH, magnesium concentrations of less than 0.05 × 10⁻³ molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch pit formation.     

An atomic force microscopy study of calcite dissolution in saline solutions: The role of magnesium ions

In situ Atomic Force Microscopy, AFM, experiments have been carried out using calcite cleavage surfaces in contact with solutions of MgSO₄, MgCl₂, Na₂SO₄ and NaCl in order to attempt to understand the role of Mg²⁺ during calcite dissolution. Although previous work has indicated that magnesium inhibits calcite dissolution, quantitative AFM analyses show that despite the fact that Mg²⁺ inhibits etch pit spreading, it increases the density and depth of etch pits nucleated on calcite surfaces and, subsequently, the overall dissolution rates: i.e., from 10^−11.75 mol cm⁻² s⁻¹ (in deionized water) up to 10^−10.54 mol cm⁻² s⁻¹ (in 2.8 M MgSO₄). Such an effect is concentration-dependent and it is most evident in concentrated solutions ([Mg²⁺] >> 50 mM). These results show that common soluble salts (especially Mg sulfates) may play a critical role in the chemical weathering of carbonate rocks in nature as well as in the decay of carbonate stone in buildings and statuary.     

A fundamental equation for calcite dissolution kinetics

A fundamental rate equation for the dissolution of calcite in a pure 0.7 M KC1 solution has been determined. Between pH 8.0 and 10.1 the kinetics of the dissolution reaction can be expressed by the equation

$\text{d[Ca}{}^{\mathrm{2+}}\text{]/dt = kA(C-[Ca}{}^{\mathrm{2+}}\text{]}\text{1}\text{2}\text{[CO}{}_3{}^{\mathrm{2?}}\text{]}\text{1}\text{2}\text{)}$

, where d[Ca²⁺]/dt is the rate in mole cm^?3s^?1, k is the apparent rate constant in s^?1 cm^?2, A is the calcite surface area and C is the square root of the calcite solubility constant. The apparent rate constant at 20°C is 9.5 × 10^?6s^?1cm^?2. The apparent activation energy for the reaction between 5 and 50°C is 8.4 kcal mole^?1.The reaction rate is pH independent above pH = 7.5. At pH values less than 8, [CO₃^2?] becomes negligible, and the rate becomes fast and should be dependent on the calcite surface area alone, if there is no change in mechanism.The stirring coefficient between 2.8 and 11.1 rev s^?1 is 0.33. This, together with the relatively high activation energy, indicates that the reaction is mainly chemically controlled.Interpolation of the experimental results into seawater systems gives a computed rate several magnitudes greater than the observed rate, but considerably less than that calculated for a diffusion-controlled reaction.     

The influence of grinding on the dissolution kinetics of calcite

This study of the dissolution of calcite in an acid environment demonstrates a significant dissolution anomaly for small particles. This cannot be attributed to very small, finely ground particles “stuck” to the grains, as there were too few to explain the magnitude of the observed anomaly. It is linked to the disruption resulting from the grinding. When observed in the electron microscope, the grains appear to be constructed of an aggregate of small crystals oriented in several principal directions. Their size increases progressively from the surface to the interior of the grain. An exothermic reaction is produced when the calcite is heated to 350° C. This causes a change in the microcrystalline structure leading to a nearly monocrystalline state. This recrystallisation retards the dissolution speed.     

The role of background electrolytes on the kinetics and mechanism of calcite dissolution

The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl⁻ < I⁻ < F⁻ for salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F⁻ and Li⁺ are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F⁻, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.     

Dissolution kinetics of calcite at 50-70 °C: An atomic force microscopic study under near-equilibrium conditions

Direct measurements of calcite faces were performed using in situ atomic force microscopy (AFM) to reveal the dissolution processes as a function of solution saturation state and temperature. Time-sequential AFM images demonstrated that step velocities at constant temperature increased with increasing undersaturation. The anisotropy of obtuse and acute step velocities appeared to become more significant as solutions approached equilibrium and temperature increased. At saturation state Ω > 0.02, a curvilinear boundary was formed at the intersection of two acute steps and the initially rhombohedral etch pit exhibited a nearly triangular shape. This suggests that the and steps may not belong to the calcite-aqueous solution equilibrium system. Further increase in the saturation state (Ω ? 0.3) led to a lack of etch pit formation and dissolution primarily occurred at existing steps, in accordance with Teng (2004). Analysis of step kinetics at different temperatures yielded activation energies of 25 ± 6 kJ/mol and 14 ± 13 kJ/mol for obtuse and acute steps, respectively. The inconsistencies in etch pit morphology, step anisotropy, and step activation energies from the present study with those of studies far-from-equilibrium can be explained by increased influence of the backward reaction, or growth, near-equilibrium. We propose that the backward reaction occurs preferentially at the acute-acute kink sites. The kinetics and effective activation energies of near-equilibrium calcite dissolution presented in this work provide accurate experimental data under likely CO₂ sequestration conditions, and thus are crucial to the development of robust geochemical models that predict the long-term performance of mineral-trapped CO₂.     

Effects of phosphate ions on intergranular pressure solution in calcite: An experimental study

Intergranular pressure solution (IPS) is a coupled chemical-mechanical process of widespread importance that occurs during diagenesis and low-temperature deformation of sedimentary rocks. Laboratory experiments on IPS in halite, quartz, and calcite have largely concentrated on the mechanical aspects of the process. In this study, we report the effects of pore fluid chemistry, specifically varying phosphate ion concentration, on the mechanical compaction by IPS of fine-grained calcite powders at room temperature and 1 to 4 MPa applied effective stress. Phosphate was investigated because of its importance as a biogenic constituent of sea and pore waters. Increasing the pore fluid phosphate concentration from 0 to 10⁻³ mol/L systematically reduced compaction strain rates by up to two orders of magnitude. The sensitivity of the compaction strain rate to phosphate concentration was the same as the sensitivity of calcite precipitation rates to the addition of phosphate ions reported in the literature, suggesting that the rate of IPS in phosphate-bearing samples was controlled by calcite precipitation on pore walls. The results imply that IPS and associated porosity/permeability reduction rates in calcite sediments may be strongly reduced when pore fluids are enriched in phosphates, for example, through high biologic productivity or a seawater origin. Future modeling of IPS-related processes in carbonates must therefore take into account the effects of pore fluid chemistry, specifically the inhibition of interfacial reactions.     

The influence of experimental design on the rate of calcite dissolution

A rotating disc system has been constructed to study calcite dissolution kinetics. The disc system is shown to obey the Levich theory and to satisfy the stringent chemical controls required by the calcite dissolution system at neutral to alkaline pH values. The errors involved in using a CO₂-free atmosphere are shown to be insignificant. It is shown that the stirring dependence of systems which are not hydrodynamically well-defined is variable and dependent on the shape of the reaction vessel. Extrapolation of such results into natural systems involves very large uncertainties.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.     

Magnesian calcite cements and their diagenesis: dissolution and dolomitization, Mururoa Atoll

The most ubiquitous syn-sedimentary cements affecting Mururoa atoll are composed of magnesian calcite. Three main types are distinguished: fibrous, bladed and sparitic on the basis of petrography, morphology and MgCO₃ concentration of the constituting crystals, while peloid infills, a particular form of HMC chemical precipitation, also exist. Petrographic evidence and isotopic signatures are compatible with marine precipitation. Mururoa atoll was exposed several times to meteoric diagenesis resulting in varied diagenetic alterations including selective dissolution and partial dolomitization of Mg-calcite cements. These alterations are responsible for substantial modifications of the initial cement fabrics and may introduce unconformities in the diagenetic chronology. The first stage of the partial dissolution of Mg-calcite induces the development of chalky, white friable zones within the initially crystalline, hard cement layers. At ultrascale, this is due to the creation of micro-voids along the elongate cement fibres. Advanced dissolution includes total disappearance of cement portions as attested to by large voids within the cement crust and/or between superposed cement layers. Mg-calcite dissolution is related to meteoric diagenesis during periods of Quaternary exposure. The creation of voids within Mg-calcite layers is due to the mechanical removal of previously altered calcium carbonate, a process suggesting marine or non-marine water flow, probably in the vadose environment. Selective dolomitization of Mururoa cements involves alternations of calcite and dolomite which form successive cement-like rinds within primary cavities. At Mururoa, these alternations are the result of selective dolomitization of the pre-existing Mg-calcite cements rather than successive precipitation of calcite and dolomite. Selective dolomitization of Mg-calcite cements at Mururoa indicates that a given cement succession is not necessarily a simple chronological sequence. Oxygen isotope values of dolomites are enriched in δ¹⁸6 by about 3‰ PDB within calcite-dolomite pseudo-alternations. The dolomitizing fluid at Mururoa seems similar to present marine water although some mixture with meteoric water is probable to favour dissolution associated with dolomitization.     

Controls by saturation state on etch pit formation during calcite dissolution

Dissolution experiments were conducted on {101?4} cleavage faces of calcite at various under-saturations to determine how the saturation state controls etch pit formation. Experimental observations were made by using in situ fluid cell Atomic Force Microscopy. Three dissolution modes were observed. When the saturation index Ω > 0.541, no etch pit formation was seen and dissolution primarily occurred at existing steps. When Ω decreased to Ω_c = 0.541-0.410, the first visible pits appeared and continuous reduction in saturation state slowly increased the pit density on terraces while dissolution simultaneously proceeded at step edges. Finally, when the saturation state fell below Ω_max = ∼0.007, a precipitous increase in pit density took place that sharply contrasted to the ordered fashion of pit formation observed at saturation conditions above this level. These observations are interpreted to be two-dimensional and unassisted pit formation at Ω < ∼0.007, defect- and step-assisted dissolution in between Ω = 0.541 and 0.007, and existing step-induced dissolution for Ω > 0.541.The values of Ω_c are in good agreement with the dislocation theory's predicted critical under-saturations for pit formation at line dislocations. The occurrence of Ω_max is not directly predicted but is a logical consequence of dissolution thermodynamics. These findings suggest that (1) dissolution near and far from equilibrium (i.e., Ω > Ω_c, Ω < Ω_max) is not controlled by dislocations, therefore (2) dislocation density should significantly impact dissolution rate only in the saturation range of Ω_max < Ω < Ω_c; (3) dissolution kinetics and chemical affinity of dissolution reactions should have a non-linear relationship: at sufficiently close to equilibrium, when dislocations cannot open up to form etch pits, the dissolution kinetics will be limited by the number of existing steps; at far from equilibrium, when pits are able to form in defect-free regions, the dissolution rate will be capped by the maximum number of achievable steps.These findings may provide explanations for several well-observed geochemical relationships, including the weak dependence of dissolution rate upon dislocation density in distilled water and the ‘plateau’ behavior of dissolution kinetics both near and far from equilibrium. The explosive occurrence of unassisted pit nucleation at Ω ∼ Ω_max is not predicted by the current dissolution rate equations. This suggests that an accurate ‘general’ rate law describing universal dissolution processes has yet to be developed.     

The influence of temperature and seawater composition on calcite crystal growth mechanisms and kinetics: Implications for Mg incorporation in calcite lattice

The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. To determine if and how temperature is kinetically responsible for the amount of Mg incorporated in calcite, we quantified the influence of temperature and specific dissolved components on the complex mechanism of calcite precipitation in seawater. A kinetic study was carried out in artificial seawater and NaCl-CaCl₂ solutions, each having a total ionic strength of 0.7 M. The constant addition technique was used to maintain [Ca²⁺] at 10.5 mmol kg⁻¹ while [] was varied to isolate the role of this variable on the precipitation rate of calcite.Our results show that the overall reaction of calcite precipitation in both seawater and NaCl-CaCl₂ solutions is dominated by the following reaction:

     

The kinetics of chlorite dissolution

A model for the dissolution of chlorite has been developed based on fast ligand assisted proton attack of the alumina tetrahedra within the alumina-silica lattice followed by slower dissolution of the remnant silica lattice. While the rate determining step is within the silica dissolution regime, the rate is a function of the H⁺ and Al³⁺ concentrations and the dominant aqueous Al species. Individual rates may be described by a generic rate equation applicable across the spectrum of Al species:

     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Molecular models of alginic acid: Interactions with calcium ions and calcite surfaces

Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these cation-organic interactions are well suited for predictive molecular modeling and the analysis of conformation and configuration of polysaccharides and their influence on cation binding. In this study, alginic acid was chosen as a model polymer system and representative disaccharide and polysaccharide subunits were developed. Molecular dynamics simulation of the torsion angles of the ether linkage between various monomeric subunits identified local and global energy minima for selected disaccharides. The simulations indicate stable disaccharide configurations and a common global energy minimum for all disaccharide models at Φ = 274 ± 7°, Ψ = 227 ± 5°, where Φ and Ψ are the torsion angles about the ether linkage. The ability of disaccharide subunits to bind calcium ions and to associate with the surface of calcite was also investigated. Molecular models of disaccharide interactions with calcite provide binding energy differences for conformations that are related to the proximity and residence densities of the electron-donating moieties with calcium ions on the calcite surface, which are controlled, in part, by the torsion of the ether linkage between monosaccharide units. Dynamically optimized configurations for polymer alginate models with calcium ions were also derived.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

Polycrystalline calcite to aragonite transformation kinetics: experiments in synthetic systems

The kinetics of the calcite to aragonite transformation have been investigated using synthetic polycrystalline calcite aggregates, with and without additional minerals present. The reaction progresses as a function of time were measured at four temperature/pressure conditions: (1) 550 °C/1.86 GPa; (2) 600 °C/2.11 GPa; (3) 650 °C/2.11 GPa, and (4) 700 °C/2.29 GPa. Experiments reveal that Mg-calcite and Fe-calcite transforms to aragonite at considerably slower rates than pure calcite, and that Sr-bearing calcite and calcite + quartz aggregates transform at significantly higher rates than pure calcite. The reaction progresses vs. time data for pure calcite were fitted to Cahns grain-boundary nucleation and interface-controlled growth model. Evidence for interface-controlled growth is provided by petrographic observations of grain boundaries. The activation energy for aragonite growth from the synthetic polycrystalline calcite determined in this study is significantly lower than that previously determined from a natural marble. The discrepancy in rates and activation energy may be attributed to the nature of grain boundaries, to deformational strain or the presence of impurities in the studied samples, and likely to uncertainties in experimental conditions. The results of this study imply that the variation of local petrologic conditions, in addition to temperature, pressure and grain size, may play an important role in determining the rates for the calcite to aragonite transformation in nature.Editorial responsibility: W. Schreyer