Transformation of protodolomite to dolomite proceeds under dry-heating conditions

Abstract

The genesis of sedimentary dolomite remains an unresolved issue. Protodolomite has been considered as a metastable precursor for some sedimentary dolomites. Through laboratory experiments, much has been learnt about the transformation of protodolomite into dolomite under hydrothermal conditions mimicking those in open diagenetic systems. However, it is still unclear whether such mineral transformation could proceed in closed diagenetic systems, in which the supply of externally-derived fluids is often limited. Here through dry-heating experiments we demonstrated that low-temperature protodolomite converts into dolomite in the absence of external fluid. The starting materials for the recrystallization reactions included two types of protodolomite: biotic protodolomite and its abiotic counterpart. Biotic protodolomite was synthesized by means of a halophilic bacterium at 30°C. Since the synthesis of abiotic protodolomite normally requires higher temperatures than biotic ones, the abiotic protodolomite samples used herein were prepared at 60°C and 100°C. These protodolomites were spherical in shape and composed of nano-globular subunits. Our protodolomite samples contained considerable structural water in the range of 1.4-7 wt%. The water content of protodolomites was linearly correlated with their synthesis temperature, that is, biotic protodolomite had a higher amount of water than its abiotic counterparts. The protodolomite samples were then dry-annealed at temperatures of 100 to 300°C for two months. The results indicated that the rate of protodolomite-to-dolomite transformation was higher in the reactors using biotic protodolomite than those using abiotic protodolomites. This conversion was likely triggered by the dehydration of structural water within protodolomite. The resulting dolomite mostly retained spherical morphology, whereas its nanosized subunits tended to become rhombohedral. Calcite neoformation was also found to accompany the dolomite formation. Our findings suggest that structural water within protodolomite is an overlooked internal fluid and it might have an impact on the genesis of sedimentary dolomite during burial diagenesis.