Description: Sulfate-reducing bacteria are known to mediate dolomite formation under hypersaline conditions, but details of the crystal nucleation process are still poorly constrained. Our laboratory study demonstrates for the first time that Desulfobulbus mediterraneus, a marine sulfate-reducing bacterium, mediates primary precipitation of Mg-rich dolomite under anoxic conditions in media replicating modern seawater chemistry at low temperature (21 °C). Precipitation of crystals was associated with extracellular polymeric substances in a monospecific biofilm, providing templates for nucleation by altering the molar Mg/Ca ratio. After initial nucleation of single nanospherulites (∼50 nm), growth was mediated by aggregation, resulting in spherulites of ∼2–3 μm in diameter. Nucleation led to differences in Mg/Ca ratios and δ44/40Ca values among the organic material (i.e., biofilm including cells and extracellular polymeric substances; 0.87 ± 0.01 [2 SD] and 0.48‰ ± 0.11‰ [2 SE], respectively), the crystals (1.02 ± 0.11 [2 SD] and 〈−0.08‰ ± 0.24‰ [2 SE], respectively), and the liquid bulk medium after mineral precipitation (4.53 ± 0.04 [2 SD] and 1.10‰ ± 0.24‰ [2 SE], respectively). These data indicate a two-step fractionation process involved in the sequestration of Ca from the solution into the crystal lattice of the mineral precipitated. Our results demonstrate the capability of extracellular polymeric substances to overcome kinetic inhibition, fostering the formation of kinetically less favorable Mg-rich dolomite, and they also question the applicability of the Ca isotopic system as a proxy for paleogeochemistry of seawater.

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.