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1 Department of Geology, University of Leicester, Leicester LE1 7RH, UK
2 Department of Earth Sciences, University of Oxford, Oxford OX1 3PR, UK
The failure to precipitate dolomite experimentally at low temperatures or from seawater in which it is both supersaturated and the most thermodynamically favoured carbonate phase, together with its unequal distribution through geological time relative to limestone, are all aspects of the ‘dolomite problem’, a subject of continuing controversy. A plethora of physicochemical models has been invoked to explain sedimentary dolomite formation, none of which satisfactorily addresses the basic problem of how kinetic barriers are overcome. These barriers are related to the disproportionate distribution of the component ions of dolomite, cation hydration and ion complexing in seawater. Competing claims for the effectiveness of sulphate as an inhibitor to dolomite formation further confuse the debate, although there are many reports of modern dolomite associated with bacterial sulphate reduction. The uppermost sediments in some lakes of the Coorong region of South Australia comprise almost 100% dolomite, and afford an ideal opportunity to study this association.
Samples of lake waters taken during late evaporative stages of several shallow hypersaline dolomitic lakes showed high initial sulphate concentrations, high pH and high carbonate alkalinities. Pore waters from unlithified lake sediment cores directly below the lake-water sample sites showed a substantial and progressive decrease in sulphate concentrations with depth, coupled with an exponential increase in carbonate concentrations, through the sulphate-reduction zone. By the end of the evaporative cycle, sulphate was entirely removed. High bacterial counts on cultures from the sediment cores, and sulphur isotope values consistent with ‘bacterial’ fractionation in lake waters, indicate that the chemical changes in ambient water chemistry can be related to active bacterial sulphate reduction. Laboratory experiments using sulphate reducers cultured from the lake sediments and simulating the anoxic microbiogeochemical environment of the lakes, have resulted in the precipitation of dolomite, demonstrating that bacterial sulphate reduction in the Coorong lakes modifies lake-water and pore-water chemistry so that dolomite precipitation is kinetically favoured.
Given the wide spatial and temporal distribution of sulphate-reducing bacteria, and their frequent association, both past and present, with cyanobacteria, it is likely that this process was more widespread in the geological past when dolomite was found in far greater abundance than limestone. Bacterial sulphate reduction may thus have played an important role in dolomite formation throughout the geological record.
