An atomic force microscopy study of the dissolution of calcite in the presence of phosphate ions

Klasa, J.; Ruíz-Agudo, Encarnación; Wang, L.; Putnis, Christine V.; Valsami-Jones, Eugénia; Menneken, Martina; Putnis, Andrew

doi:10.1016/j.gca.2013.03.025

Cited by 48 publications

(32 citation statements)

References 50 publications

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“…The evidence in favor of a kinetics‐dominated process is further supported by the accepted role of additives as kinetic inhibitors of ion‐by‐ion crystal growth and dissolution. Specifically, interactions of gels with water molecules, or interactions of phosphate ions with crystal surfaces, were shown to kinetically slow down the ion‐mediated processes. The gel induces confinement of the solution into delimited volumes.…”

Section: Discussionmentioning

confidence: 99%

Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase

Gal

Kahil

Vidavsky

et al. 2014

Adv Funct Materials

144

168

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Many biogenic minerals are composed of aggregated particles at the nanoscale. These minerals usually form through the transformation of amorphous precursors into single crystals inside a privileged space controlled by the organism. Here, in vitro experiments aimed at understanding the factors responsible for producing such single crystals with aggregated particle texture are presented. Crystallization is achieved by a two‐step reaction in which amorphous calcium carbonate (ACC) is first precipitated and then transformed into calcite in small volumes of water and in the presence of additives. The additives used are gel‐forming molecules, phosphate ions, and the organic extract from sea urchin embryonic spicules ‐ all are present in various biogenic crystals that grow via the transformation of ACC. Remarkably, this procedure yields faceted single‐crystals of calcite that maintain the nanoparticle texture. The crystals grow predominantly by the accretion of ACC nanoparticles, which subsequently crystallize. Gels and phosphate ions stabilize ACC via a different mechanism than sea urchin spicule macromolecules. It is concluded that the unique nanoparticle texture of biogenic minerals results from formation pathways that may differ from one another, but given the appropriate precursor and micro‐environment, share a common particle accretion mechanism.

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Section: Discussionmentioning

confidence: 99%

Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase

Gal

Kahil

Vidavsky

et al. 2014

Adv Funct Materials

144

168

View full text Add to dashboard Cite

show abstract

“…This 3D model investigates the influence of convection and the impact of the AFM tip/holder and general cell geometry on mass transport in a square ROI for a setup in which the bottom wall of the AFM fluid is formed by the crystal surface under investigation, as in a number of studies. 12,15,18,19,31,35,44,45 The surface concentration at the ROI is simulated at different flow rates and for different bulk concentrations. Dissolution of an ionic crystal is a stoichiometric reaction to satisfy the assumption of an electro-neutral solution and to maintain a constant charge at the crystal surface; as such, for illustrative purposes we reduce the mass transport model to the simulation of a single species.…”

Section: Theory and Modelingmentioning

confidence: 99%

“…[6][7][8][9][10][11][12][13][14][15][16][17][18] In these studies, the dissolution process is investigated through the evolution of the crystal surface morphology at a microscopic/molecular level, and kinetics are often deduced from the analysis of the surface retreat. 7,11,15,16,18 In many cases, the main mode of dissolution is by step motion, and the step position is tracked over time to determine step velocities, from which dissolution kinetics have been determined. 19,20 In-situ AFM has been particularly lauded for its capacity to capture high resolution images of dynamic processes on surfaces at the nanoscale/microscale.…”

Section: Introductionmentioning

confidence: 99%

Importance of Mass Transport and Spatially Heterogeneous Flux Processes for in Situ Atomic Force Microscopy Measurements of Crystal Growth and Dissolution Kinetics

et al. 2016

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It is well-established that important information about the dissolution and growth of crystals can be obtained by the investigation of step movement on single crystal faces via in-situ AFM.However, a potential drawback of this approach for kinetic measurements is that the small region of investigation may not be representative of the overall surface. It is shown that the investigation of local processes without accounting for the processes outside the region of interest can lead to significant misinterpretation of the data collected. Taking the case of gypsum dissolution as an exemplar, we critically analyze literature data and develop 3 different finite element method models that treat in detail the coupled mass transport -surface kinetic problem pertaining to dissolution processes in typical AFM environment. It is shown that mass transport cannot be neglected when performing in-situ AFM on macroscopic surfaces even with highconvection fluid cells. Moreover, crystal dissolution kinetics determined by AFM are mainly influenced by processes occurring in areas of the surface outside the region of interest. When this is recognized, and appropriate models are applied, step velocities due to dissolution are consistent with expectations based on macroscopic measurements and the kinetic gap that is often apparent between nanoscale and macroscopic measurements is closed. This study provides a framework for the detailed analysis of AFM kinetic data that has wide utility and applicability.3

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“…The coupling between dissolution and precipitation that results in pseudomorphic replacement suggests that the rate controlling step is dissolution (Xia et al, 2009b) and that whatever influences the dissolution step would have a similar effect on the replacement kinetics. However, atomic force microscopy (AFM) experiments by Klasa et al (2013) showed that the dissolution rate of calcite (CaCO 3 ) is significantly reduced in the presence of (NH 4 ) 2 HPO 4 in solution, but not in the presence of Na 2 HPO 4 (both solutions pH ~ 8)compared to that observed in pure deionized water, suggesting that the NH 4 + group may inhibit calcite dissolution. Moreover, the experiments performed here showed that phosphate fluids containing Cl had a negative kinetic effect on the replacement rates, both when adding Cl as NaCl and NH 4 Cl, with the addition of NaCl having a more significant effect in decreasing the reaction rate than NH 4 Cl.…”

Section: Fluid Composition and Replacement Kineticsmentioning

confidence: 99%

The pseudomorphic replacement of marble by apatite: The role of fluid composition

Pedrosa

Putnis

2016

Chemical Geology

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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.

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An atomic force microscopy study of the dissolution of calcite in the presence of phosphate ions

Cited by 48 publications

References 50 publications

Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase

Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase

Importance of Mass Transport and Spatially Heterogeneous Flux Processes for in Situ Atomic Force Microscopy Measurements of Crystal Growth and Dissolution Kinetics

The pseudomorphic replacement of marble by apatite: The role of fluid composition

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