Chemistry and Environments of Dolomitization —A Reappraisal

Abstract

Dolomitization of calcium carbonate can best be expressed by mass transfer reactions that allow for volume gain, preservation, or loss during the replacement process. Experimental data, as well as textures and porosities of natural dolomites, indicate that these reactions must include CO 3 2− and/or HCO 3 − supplied by the solution to the reaction site. Since dolomite formation is thermodynamically favoured in solutions of (a) low Ca 2+/Mg 2+ ratios, (b) low Ca 2+/CO 3 2− (or Ca 2+/HCO 3 −) ratios, and (c) high temperatures, the thermodynamic stability for the system calcite-dolomite-water is best represented in a diagram with these three parameters as axes. Kinetic considerations favour dolomitization under the same conditions, and additionally at low as well as at high salinities. If thermodynamic and kinetic considerations are combined, the following conditions and environments are considered chemically conducive to dolomitization: (1) environments of any salinity above thermodynamic and kinetic saturation with respect to dolomite (i.e. freshwater/seawater mixing zones, normal saline to hypersaline subtidal environments, hypersaline supratidal environments, schizohaline environments); (2) alkaline environments (i.e. those under the influence of bacterial reduction and/or fermentation processes, or with high input of alkaline continental groundwaters); and (3) many environments with temperatures greater than about 50°C (subsurface and hydrothermal environments). Whether or not massive, replacive dolostones are formed in these environments depends on a sufficient supply of magnesium, and thus on hydrologic parameters. Most massive dolostones, particularly those consisting of shallowing-upward cycles and capped by regional unconformities, have been interpreted to be formed according to either the freshwater/seawater mixing model or the sabkha with reflux model. However, close examination of natural mixing zones and exposed evaporitic environments reveals that the amounts of dolomite formed are small and texturally different from the massive, replacive dolostones commonly inferred to have been formed in these environments. Many shallowing-upward sequences are devoid of dolomite. It is therefore suggested that massive, replacive dolomitization during exposure is rare, if not impossible. Rather, only small quantities of dolomite (cement or replacement) are formed which may act as nuclei for later subsurface dolomitization. Alternatively, large-scale dolomitization may take place in shallow subtidal environments of moderate to strong hypersalinity. The integration of stratigraphic, petrographic, geochemical, and hydrological parameters suggests that the only environments capable of forming massive, replacive dolostones on a large scale are shallow, hypersaline subtidal environments and certain subsurface environments.