The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

Many organisms use amorphous calcium carbonate (ACC) during crystalline calcium carbonate biomineralization, as a means to control particle shape/size and phase stability. Here, we present an in situ small-and wide-angle X-ray scattering (SAXS/WAXS) study of the mechanisms and kinetics of ACC crystallization at rapid time scales (seconds). Combined with offline solid and solution characterization, we show that ACC crystallizes to vaterite via a threestage process. First, hydrated and disordered ACC forms, then rapidly transforms to more ordered and dehydrated ACC; in conjunction with this, vaterite forms via a spherulitic growth mechanism. Second, when the supersaturation of the solution with respect to vaterite decreases sufficiently, the mechanism changes to ACC dissolution and vaterite crystal growth. The third stage is controlled by Ostwald ripening of the vaterite particles. Combining this information with previous studies, allowed us to develop a mechanistic understanding of the abiotic crystallization process from ACC to vaterite and all the way to calcite. We propose this is the underlying abiotic mechanism for calcium carbonate biomineralization from ACC. This process is then augmented or altered by organisms (e.g., using organic compounds) to form intricate biominerals. This study also highlights the applicability of in situ time-resolved SAXS/WAXS to study rapid crystallization reactions.

No abstract

Monohydrocalcite is a member of the carbonate family which forms in Mg-rich environments at a wide range of Mg Ca ratios Mg aq Ca aq Although found in modern sedimentary deposits and as a product of biomineralization, there is a lack of information about its formation mechanisms and about the role of Mg during its crystallization. In this work we have quantitatively assessed the mechanism of crystallization of monohydrocalcite through in situ synchrotron-based small and wide angle X-ray scattering (SAXS/WAXS) and off-line spectroscopic, microscopic and wet chemical analyses. Monohydrocalcite crystallizes via a 4-stage process beginning with highly supersaturated solutions from which a Mg-bearing, amorphous calcium carbonate (ACC) precursor precipitates. This precursor crystallizes to monohydrocalcite via a nucleation-controlled reaction in stage two, while in stage three it is further aged through Ostwald-ripening at a rate of 1.8±0.1 nm/h1/2. In stage four, a secondary Ostwald ripening process (66.3±4.3 nm/h1/2) coincides with the release of Mg from the monohydrocalcite structure and the concomitant formation of minor hydromagnesite. Our data reveal that monohydrocalcite can accommodate significant amounts of Mg in its structure MgCO and that its Mg content and dehydration temperature are directly proportional to the saturation index for monohydrocalcite (SIMHC) immediately after mixing the stock solutions. However, its crystallite and particle size are inversely proportional to these parameters. At high supersaturations (SIMHC=3.89) nanometer-sized single crystals of monohydrocalcite form, while at low values (SIMHC=2.43) the process leads to low-angle branching spherulites. Many carbonates produced during biomineralization form at similar conditions to most synthetic monohydrocalcites, and thus we hypothesize that some calcite or aragonite deposits found in the geologic record that have formed at high Mg/Ca ratios could be secondary in origin and may have originally formed via a metastable monohydrocalcite intermediate. This manuscript describes an experimental study in which we elucidated the formation mechanism of monohydrocalcite from a poorly-ordered precursor and the role of Mg in its crystallization. Combining in situ synchrotron-based with various off-line laboratory characterizations allowed us to derive complementary quantitative data that explain the monohydrocalcite crystallization via a multiple stage process. School of Earth and EnvironmentWe believe that our paper is of interest to a broad geochemical community and that our results may help explain a number of important biogeochemical processes (including biomineralization and their link to past variations in ocean chemistry).All authors have read and accepted the manuscript in its current format and we all confirm that this paper represents original work from which no part has been published, nor is being considered for publication, elsewhere. Dear Frank, Thank you very much for the comments and suggestions to improve our manuscript.P...

No abstract

No abstract

No abstract

The direct crystallization of dolomite from an aqueous solution at temperatures between 60-220 °C was followed in situ through time-resolved synchrotron-based energy-dispersive X-ray diffraction combined with offline high-resolution imaging, X-ray diffraction, and infrared spectroscopy. Crystalline CaMg(CO 3 ) 2 phases form through a three-stage process. In the first stage, a nanoparticulate magnesium-deficient, amorphous calcium carbonate (Mg-ACC) with a nominal formula of Ca 0.606 Mg 0.394 CO 3 ·1.37H 2 O forms. After a temperature-dependent induction time, during stage 2 the Mg-ACC partially dehydrates and orders prior to its rapid (<5 min) crystallization to non-stoichiometric proto-dolomite. This occurs via the dissolution of Mg-ACC, followed by the secondary nucleation of proto-dolomite from solution. The proto-dolomite crystallization proceeds via spherulitic growth that follows a growth front nucleation mechanism with a de-nuovo and continuous formation of nanocrystalline proto-dolomite subunits that form spherical aggregates. In stage three of the reaction, the proto-dolomite transforms to highly crystalline and stoichiometric dolomite on a much longer timescale (hours to days), via an Ostwald-ripening mechanism. Such a three-stage crystallization can explain microbially induced proto-dolomites observed in modern hypersaline settings and may also be the route by which the Cryogenian cap dolomite deposits of the Neoproterozoic formed.