From poorly-ordered precursors to crystals: Factors contributing to spherulitic growth of dolomite

<p>Dolomite is one of the most abundant carbonate minerals in the geological record, yet it barely forms in the present. The contrast in the abundance of dolomite between geological and modern records combined with the impossibility of synthesizing stoichiometric dolomite in the laboratory at ambient conditions are known as the 'dolomite problem'. This enigma has been in the scope of research for decades, trying to understand dolomite formation, mechanisms and the contributing factors. Dolomite is known to form via two abiotic mechanisms; through (1) dolomitization or (2) dolomite cementation. Also, the contribution of microorganisms can result in biotic dolomite crystallization. The mechanisms of dolomite formation at the molecular and nanoscale in biotic and abiotic environments are relatively well-described, but we still struggle to develop a unified model of dolomite formation in modern and ancient settings. In this contribution, we summarize the development of research related to the dolomite formation processes and in particular the direct dolomite precipitation via spherulitic growth of proto-dolomite.</p>

Modern dolomite formation caused by seasonal cycling of oxygenic phototrophs and anoxygenic phototrophs in a hypersaline sabkha

The “Dolomite Problem” has been a controversy for over a century, owing to massive assemblages of low-temperature dolomite in ancient rocks with little dolomite forming today despite favorable geochemical conditions. Experiments show that microbes and their exopolymeric substances (EPS) nucleate dolomite. However, factors controlling ancient abundances of dolomite can still not be explained. To decode the enigma of ancient dolomite, we examined a modern dolomite forming environment, and found that a cyclic shift in microbial community between cyanobacteria and anoxygenic phototrophs creates EPS suited to dolomite precipitation. Specifically, EPS show an increased concentration of carboxylic functional groups as microbial composition cycles from cyanobacterial to anoxygenic phototroph driven communities at low-and high- salinity, respectively. Comparing these results to other low-T forming environments suggests that large turnover of organic material under anoxic conditions is an important driver of the process. Consequently, the shift in atmospheric oxygen throughout Earth’s history may explain important aspects of “The Dolomite Problem”. Our results provide new context for the interpretation of dolomite throughout Earth’s history.

Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the “dolomite problem”

Paleozoic and Precambrian sedimentary successions frequently contain massive dolomicrite [CaMg(CO3)2] units despite kinetic inhibitions to nucleation and precipitation of dolomite at Earth surface temperatures (<60 °C). This paradoxical observation is known as the “dolomite problem.” Accordingly, the genesis of these dolostones is usually attributed to burial–hydrothermal dolomitization of primary limestones (CaCO3) at temperatures of >100 °C, thus raising doubt about the validity of these deposits as archives of Earth surface environments. We present a high-resolution, >63-My-long clumped-isotope temperature (TΔ47) record of shallow-marine dolomicrites from two drillcores of the Ediacaran (635 to 541 Ma) Doushantuo Formation in South China. Our T∆47record indicates that a majority (87%) of these dolostones formed at temperatures of <100 °C. When considering the regional thermal history, modeling of the influence of solid-state reordering on our TΔ47record further suggests that most of the studied dolostones formed at temperatures of <60 °C, providing direct evidence of a low-temperature origin of these dolostones. Furthermore, calculated δ18O values of diagenetic fluids, rare earth element plus yttrium compositions, and petrographic observations of these dolostones are consistent with an early diagenetic origin in a rock-buffered environment. We thus propose that a precursor precipitate from seawater was subsequently dolomitized during early diagenesis in a near-surface setting to produce the large volume of dolostones in the Doushantuo Formation. Our findings suggest that the preponderance of dolomite in Paleozoic and Precambrian deposits likely reflects oceanic conditions specific to those eras and that dolostones can be faithful recorders of environmental conditions in the early oceans.

Can Primary Ferroan Dolomite and Ankerite Be Precipitated? Its Implications for Formation of Submarine Methane-Derived Authigenic Carbonate (MDAC) Chimney

Microbes can mediate the precipitation of primary dolomite under surface conditions. Meanwhile, primary dolomite mediated by microbes often contains more Fe2+ than standard dolomite in modern microbial culture experiments. Ferroan dolomite and ankerite have been regarded as secondary products. This paper reviews the process and possible mechanisms of microbial mediated precipitation of primary ferroan dolomite and/or ankerite. In the microbial geochemical Fe cycle, many dissimilatory iron-reducing bacteria (DIRB), sulfate-reducing bacteria (SRB), and methanogens can reduce Fe3+ to Fe2+, while SRB and methanogens can also promote the precipitation of primary dolomite. There are an oxygen respiration zone (ORZ), an iron reduction zone (IRZ), a sulfate reduction zone (SRZ), and a methanogenesis zone (MZ) from top to bottom in the muddy sediment diagenesis zone. DIRB in IRZ provide the lower section with Fe2+, which composes many enzymes and proteins to participate in metabolic processes of SRB and methanogens. Lastly, heterogeneous nucleation of ferroan dolomite on extracellular polymeric substances (EPS) and cell surfaces is mediated by SRB and methanogens. Exploring the origin of microbial ferroan dolomite may help to solve the “dolomite problem”.

Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem

The18O/16O of calcite fossils increased by ∼8‰ between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ18O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ‟clumped” isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ18O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15–158 °C and parent waters having δ18OVSMOWvalues from −2 to +12‰. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ18O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ18O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen–isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites.