Description: The effect of stoichiometry on the new formation and subsequent growth of CaCO3 was investigated over a large range of solution stoichiometries (10–4 〈 raq 〈 104, where raq = {Ca2+}:{CO32–}) at various, initially constant degrees of supersaturation (30 〈 Ωcal 〈 200, where Ωcal = {Ca2+}{CO32–}/Ksp), pH of 10.5 ± 0.27, and ambient temperature and pressure. At raq = 1 and Ωcal 〈 150, dynamic light scattering (DLS) showed that ion adsorption onto nuclei (1–10 nm) was the dominant mechanism. At higher supersaturation levels, no continuum of particle sizes is observed with time, suggesting aggregation of prenucleation clusters into larger particles as the dominant growth mechanism. At raq ≠ 1 (Ωcal = 100), prenucleation particles remained smaller than 10 nm for up to 15 h. Cross-polarized light in optical light microscopy was used to measure the time needed for new particle formation and growth to at least 20 μm. This precipitation time depends strongly and asymmetrically on raq. Complementary molecular dynamics (MD) simulations confirm that raq affects CaCO3 nanoparticle formation substantially. At raq = 1 and Ωcal ≫ 1000, the largest nanoparticle in the system had a 21–68% larger gyration radius after 20 ns of simulation time than in nonstoichiometric systems. Our results imply that, besides Ωcal, stoichiometry affects particle size, persistence, growth time, and ripening time toward micrometer-sized crystals. Our results may help us to improve the understanding, prediction, and formation of CaCO3 in geological, industrial, and geo-engineering settings.

Description: While burial diagenetic processes of tropical corals are well investigated, current knowledge about factors initiating early diagenesis remains fragmentary. In the present study, we focus on recent Porites microatolls, growing in the intertidal zone. This growth form represents a model organism for elevated sea surface temperatures (SSTs) and provides important but rare archives for changes close to the seawater/atmosphere interface with exceptional precision on sea level reconstruction. As other coral growth forms, microatolls are prone to the colonization by endolithic green algae. In this case, the algae can facilitate earliest diagenetic alteration of the coral skeleton. Algae metabolic activity not only results in secondary coral porosity due to boring activities, but may also initiate reprecipitation of secondary aragonite within coral pore space, a process not exclusively restricted to microatoll settings. In the samples of this initial study, we quantified a mass transfer from primary to secondary aragonite of around 4% within endolithic green algae bands. Using δ18O, δ13C, Sr/Ca, U/Ca, Mg/Ca, and Li/Mg systematics suggests that the secondary aragonite precipitation followed abiotic precipitation principles. According to their individual distribution coefficients, the different isotope and element ratios showed variable sensitivity to the presence of secondary aragonite in bulk samples, with implications for microatoll-based SST reconstructions. The secondary precipitates formed on an organic template, presumably originating from endolithic green algae activity. Based on laboratory experiments with the green algae Ostreobium quekettii, we propose a conceptual model that secondary aragonite formation is potentially accelerated by an active intracellular calcium transport through the algal thallus from the location of dissolution into coral pore spaces. The combined high-resolution imaging and geochemical approach applied in this study shows that endolithic algae can possibly act as a main driver for earliest diagenesis of coral aragonite starting already during a coral’s life span.