It is becoming increasingly clear that the rate of crystal growth, even at constant saturation, varies with pH, ionic strength, and solution stoichiometry. Here, we contribute to the limited data set on experimentally obtained calcite step velocities from solutions with strictly controlled parameters. We measured growth on obtuse and acute edges in solutions with five Ca2+:CO3 2– activity ratios (r): 0.1, 1.0, 10, 25, and 50, at three saturation indices: SI = 0.6, 0.8, and 1.0. The curve describing rate as a function of r is not centered at r = 1, and the maximum velocity is different for each step. Obtuse steps generally grow faster in Ca2+-rich solutions, i.e., r > 1, whereas the acute rates dominate when CO3 2– is in excess, i.e., r < 1. We show that the local arrangement of every second carbonate at the acute steps can help explain these rate differences. To further analyze the differences in growth rates, we fitted four currently used growth models to our data set, to derive growth parameters for each type of step. Some of the models worked for some of the conditions, but none could describe the results over the full range of our experiments.
Understanding mineral growth mechanism is a key to understanding biomineralisation, fossilisation and diagenesis. The presence of trace compounds affect the growth and dissolution rates and the form of the crystals produced. Organisms use ions and organic molecules to control the growth of hard parts by inhibition and enhancement. Calcite growth in the presence of Mg2+ is a good example. Its inhibiting role in biomineralisation is well known, but the controlling mechanisms are still debated. Here, we use a microkinetic model for a series of inorganic and organic inhibitors of calcite growth. With one, single, nonempirical parameter per inhibitor, i.e. its adsorption energy, we can quantitatively reproduce the experimental data and unambiguously establish the inhibition mechanism(s) for each inhibitor. Our results provide molecular scale insight into the processes of crystal growth and biomineralisation, and open the door for logical design of mineral growth inhibitors through computational methods.
In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis.
Ring artifacts on tomogram slices hinder image interpretation. They are caused by minor variation in the response from individual elements in a two dimensional (2D) X-ray detector. Polar space decreases the suppression complexity by transforming the rings on the tomogram slice to linear stripes. However, it requires that the center of rings lie at the origin of polar transformation. If this is not the case, all methods employing polar space become ineffective. We developed a method based on Gaussian localization of the ring center in Hough parameter space to assign the origin for the polar transformation. Thus, obtained linear stripes can be effectively suppressed by already existing methods. This effectively suppresses ring artifacts in the data from a variety of experimental setups, sample types and also handles tomograms that are previously cropped. This approach functions automatically, avoids the need for assumptions and preserves fine details, all critical for synchrotron based nanometer resolution tomography.
The wettability of mineral surfaces controls a range of phenomena in natural and industrial processes. In reservoirs, rock wettability determines the effectiveness of oil production; thus, modification of mineral surface properties can lead to enhanced oil recovery. Recent work reports that potential determining ions in seawater, Mg2+, Ca2+, and SO4 2–, are responsible for altering the wettability of calcite surfaces. In favorable conditions, e.g., elevated temperature, calcium at the calcite surface can be replaced by magnesium, making organic molecules bind more weakly and water molecules bind more strongly, rendering the surface more hydrophilic. We used atomic force microscopy in chemical force mapping mode to probe the adhesion forces between a hydrophobic CH3-terminated AFM tip and a freshly cleaved calcite {10.4} surface to investigate wettability change in the presence of Mg2+ and SO4 2– at 75 and 80 °C. We made submicrometer scale maps of adhesion force and contact angle and demonstrated that the adhesion force between the hydrophobic tip and calcite decreases when both Mg and SO4 are present. Surface analysis with X-ray photoelectron spectroscopy showed Mg associated with calcite even after rinsing with CaCO3-saturated deionized water, suggesting sorption on or in calcite. When the calcite-saturated solution of MgSO4 was replaced by calcite-saturated NaCl at the same ionic strength, adhesion force increased again, indicating that the effect is reversible and suggesting Mg replacement by Ca. Experiments with solutions of Na2SO4 and MgCl2 suggest that Mg2+ uptake is favored when SO4 2– is also present.
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