Calcite interaction with acidic sulphate solutions: a vertical scanning interferometry and energy-dispersive XRF study

Atanassova, Radostina; Cama, Jordi; Soler, Josep M.; Offeddu, Francesco G.; Queralt, Ignasi; Casanova, Ignasi

doi:10.1127/0935-1221/2013/0025-2279

Cited by 16 publications

(22 citation statements)

References 63 publications

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“…1) in scanned flat regions with similar initial roughness. The measured calcite dissolution rate, R AFM , was 1.45 × 10 −10 mol·cm −2 ·s −1 , which agrees with that at nearly neutral pH reported elsewhere [19,42–43]. The etch pit expansion rate, R s , was measured to be 1.82 ± 0.12 nm·s −1 and falls within the range of those calculated for deionized water by Jordan and Rammensee (velocity of slow step 0.5 ± 0.2 nm/s and of fast steps 2.5 ± 0.5 nm/s) [44].…”

Section: Resultssupporting

confidence: 90%

Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum

Offeddu¹,

Cama²,

Soler³

et al. 2014

Beilstein J. Nanotechnol.

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SummaryIn-situ atomic force microscopy (AFM) experiments were performed to study the overall process of dissolution of common carbonate minerals (calcite and dolomite) and precipitation of gypsum in Na2SO4 and CaSO4 solutions with pH values ranging from 2 to 6 at room temperature (23 ± 1 °C). The dissolution of the carbonate minerals took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gypsum, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to calcite. The calculated dissolution rates of calcite at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gypsum, gypsum precipitation coupled with calcite dissolution showed short gypsum nucleation induction times. The gypsum precipitate quickly coated the calcite surface, forming arrow-like forms parallel to the crystallographic orientations of the calcite etch pits. Gypsum precipitation coupled with dolomite dissolution was slower than that of calcite, indicating the dissolution rate to be the rate-controlling step. The resulting gypsum coating partially covered the surface during the experimental duration of a few hours.

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Section: Resultssupporting

confidence: 90%

Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum

Offeddu¹,

Cama²,

Soler³

et al. 2014

Beilstein J. Nanotechnol.

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“…These have been calculated from height differences of profile lines over the reacted surface, but the criterion for choosing the location of those profiles was not given and might justify to some extent the difference. However, from what we saw here, the orientation and the size difference between our grains and the single crystals used in [53] might have played the most significant role.…”

Section: Relevance To Previous Research and Implicationsmentioning

confidence: 81%

“…This method might underestimate the contribution of etch pits to the rates. Two orders of magnitude lower calcite dissolution rates are also found in literature [53]. These have been calculated from height differences of profile lines over the reacted surface, but the criterion for choosing the location of those profiles was not given and might justify to some extent the difference.…”

Section: Relevance To Previous Research and Implicationsmentioning

confidence: 95%

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

2019

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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.

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“…The most probable rates are shown in Table 3 and range from 0.13 µmol m −2 s −1 to 0.33 µmol m −2 s −1 . Atanassova et al (2013) proposed the following rate equation for calcite dissolution, based on an extensive dissolution dataset measured by VSI,

R false(normalμ mol m^{- 2} s^{- 1} false) = false(3.3 \pm 1.8 false) \times 10^{4} \cdot {false(a_{H^{+}} false)}^{false(0.94 \pm 0.08 false)} + false(0.25 \pm 0.08 false)

where a H + is the chemical activity of H + , assumed to be 10 −7 in pure flowing water. Eq.…”

Section: Discussionmentioning

confidence: 99%

“…The calcite (104) surface was chosen for this study primarily to enable comparisons to the many VSI and AFM examinations of dissolution of the same surface (Hillner et al, 1993; Dove and Platt, 1996; Lea et al, 2001; Arvidson et al, 2003; Duckworth and Martin, 2004; Bisschop et al, 2006; Harstad and Stipp, 2007; Vinson et al, 2007; Ruiz-Agudo et al, 2010; Xu et al, 2010; Fischer et al, 2012; Atanassova et al, 2013; Klasa et al, 2013; Smith et al, 2013; Ueta et al, 2013; Renard et al, 2015). As will be shown, the average or modal dissolution rates measured here fall comfortably within the range of values reported in those studies.…”

Section: Introductionmentioning

confidence: 99%

Calcite dissolution rate spectra measured by in situ digital holographic microscopy

Brand

Pan

Bullard

2017

Geochimica et Cosmochimica Acta

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Digital holographic microscopy in reflection mode is used to track in situ, real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s−1. Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates (e.g., 0.1 µmol m−2 s−1 to 0.3 µmol m−2 s−1). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

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Calcite interaction with acidic sulphate solutions: a vertical scanning interferometry and energy-dispersive XRF study

Cited by 16 publications

References 63 publications

Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum

Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

Calcite dissolution rate spectra measured by in situ digital holographic microscopy

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