K. K. Sand

ACC and Vaterite as Intermediates in the Solution-Based Crystallization of CaCO 3

Amorphous calcium carbonate (ACC) and vaterite are not very common in abiotic systems, but they play a very significant role in biomineralization processes and are key in the global carbon cycle. Despite their importance, many questions about the factors affecting the mechanisms of formation and stabilization during biomineralization processes remain unanswered, because most of the information so far is obtained from experimental synthesis in abiotic conditions. In recent years, it has been shown that ACC and vaterite have complex structures and chemistries. Their formation and stability are drastically affected by pH, the presence of (in)organics (e.g., Mg2+, SO42−, aspartic acid, glutamic acid, citric acid, etc.), temperature, and supersaturation. Changes in any of these variables affect the lifetime of ACC and the crystallization rates and pathways to vaterite or other CaCO3 polymorphs. In addition, the morphologies, composition, sizes, and properties of ACC and vaterite are highly affected. This chapter provides a perspective on the current state-of-the-art research on the formation and crystallization mechanisms of ACC to vaterite.

Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths--do we observe the mineral surface?

We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

A Microkinetic Model of Calcite Step Growth

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.

The mechanisms of crystal growth inhibition by organic and inorganic inhibitors

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.Although trace compounds are known to inhibit crystal growth, the mechanisms by which they do so are unclear. Here, the authors use a microkinetic model to study the mechanisms of several inhibitors of calcite growth, finding that the processes are quite different for inorganic and organic inhibitors.

Quantifying the free energy landscape between polymers and minerals

Higher organisms as well as medical and technological materials exploit mineral-polymer interactions, however, mechanistic understanding of these interactions is poorly constrained. Dynamic force spectroscopy can probe the free energy landscape of interacting bonds, but interpretations are challenged by the complex mechanical behavior of polymers. Here we restate the difficulties inherent to applying DFS to polymer-linked adhesion and present an approach to gain quantitative insight into polymer-mineral binding.