Dolomite: occurrence, evolution and economically important associations

Abstract Despite intensive research over more than 200 years, the origin of dolomite, the mineral and the rock, remains subject to considerable controversy. This is partly because some of the chemical and/or hydrological conditions of dolomite formation are poorly understood, and because petrographic and geochemical data commonly permit more than one genetic interpretation. This paper is a summary and critical appraisal of the state of the art in dolomite research, highlighting its major advances and controversies, especially over the last 20–25 years. The thermodynamic conditions of dolomite formation have been known quite well since the 1970s, and the latest experimental studies essentially confirm earlier results. The kinetics of dolomite formation are still relatively poorly understood, however. The role of sulphate as an inhibitor to dolomite formation has been overrated. Sulphate appears to be an inhibitor only in relatively low-sulphate aqueous solutions, and probably only indirectly. In sulphate-rich solutions it may actually promote dolomite formation. Mass-balance calculations show that large water/rock ratios are required for extensive dolomitization and the formation of massive dolostones. This constraint necessitates advection, which is why all models for the genesis of massive dolostones are essentially hydrological models. The exceptions are environments where carbonate muds or limestones can be dolomitized via diffusion of magnesium from seawater rather than by advection. Replacement of shallow-water limestones, the most common form of dolomitization, results in a series of distinctive textures that form in a sequential manner with progressive degrees of dolomitization, i.e. matrix-selective replacement, overdolomitization, formation of vugs and moulds, emplacement of up to 20 vol% calcium sulphate in the case of seawater dolomitization, formation of two dolomite populations, and — in the case of advanced burial — formation of saddle dolomite. In addition, dolomite dissolution, including karstification, is to be expected in cases of influx of formation waters that are dilute, acidic, or both. Many dolostones, especially at greater depths, have higher porosities than limestones, and this may be the result of several processes, i.e. mole-per-mole replacement, dissolution of unreplaced calcite as part of the dolomitization process, dissolution of dolomite due to acidification of the pore waters, fluid mixing (mischungskorrosion), and thermochemical sulphate reduction. There also are several processes that destroy porosity, most commonly dolomite and calcium sulphate cementation. These processes vary in importance from place to place. For this reason, generalizations about the porosity and permeability development of dolostones are difficult, and these parameters have to be investigated on a case-by-case basis. A wide range of geochemical methods may be used to characterize dolomites and dolostones, and to decipher their origin. The most widely used methods are the analysis and interpretation of stable isotopes (O, C), Sr isotopes, trace elements, and fluid inclusions. Under favourable circumstances some of these parameters can be used to determine the direction of fluid flow during dolomitization. The extent of recrystallization in dolomites and dolostones is much disputed, yet extremely important for geochemical interpretations. Dolomites that originally form very close to the surface and from evaporitic brines tend to recrystallize with time and during burial. Those dolomites that originally form at several hundred to a few thousand metres depth commonly show little or no evidence of recrystallization. Traditionally, dolomitization models in near-surface and shallow diagenetic settings are defined and/or based on water chemistry, but on hydrology in burial diagenetic settings. In this paper, however, the various dolomite models are placed into appropriate diagenetic settings. Penecontemporaneous dolomites form almost syndepositionally as a normal consequence of the geochemical conditions prevailing in the environment of deposition. There are many such settings, and most commonly they form only a few per cent of microcrystalline dolomite(s). Many, if not most, penecontemporaneous dolomites appear to have formed through the mediation of microbes. Virtually all volumetrically large, replacive dolostone bodies are post-depositional and formed during some degree of burial. The viability of the many models for dolomitization in such settings is variable. Massive dolomitization by freshwater-seawater mixing is a myth. Mixing zones tend to form caves without or, at best, with very small amounts of dolomite. The role of coastal mixing zones with respect to dolomitization may be that of a hydrological pump for seawater dolomitization. Reflux dolomitization, most commonly by mesohaline brines that originated from seawater evaporation, is capable of pervasively dolomitizing entire carbonate platforms. However, the extent of dolomitization varies strongly with the extent and duration of evaporation and flooding, and with the subsurface permeability distribution. Complete dolomitization of carbonate platforms appears possible only under favourable circumstances. Similarly, thermal convection in open half-cells (Kohout convection), most commonly by seawater or slightly modified seawater, can form massive dolostones under favourable circumstances, whereas thermal convection in closed cells cannot. Compaction flow cannot form massive dolostones, unless it is funnelled, which may be more common than generally recognized. Neither topography driven flow nor tectonically induced (‘squeegee-type’) flow is likely to form massive dolostones, except under unusual circumstances. Hydrothermal dolomitization may occur in a variety of subsurface diagenetic settings, but has been significantly overrated. It commonly forms massive dolostones that are localized around faults, but regional or basin-wide dolomitization is not hydrothermal. The regionally extensive dolostones of the Bahamas (Cenozoic), western Canada and Ireland (Palaeozoic), and Israel (Mesozoic) probably formed from seawater that was ‘pumped’ through these sequences by thermal convection, reflux, funnelled compaction, or a combination thereof. For such platform settings flushed with seawater, geochemical data and numerical modelling suggest that most dolomites form(ed) at temperatures around 50–80 °C commensurate with depths of 500 to a maximum of 2000 m. The resulting dolostones can be classified both as seawater dolomites and as burial dolomites. This ambiguity is a consequence of the historical evolution of dolomite research.

Concepts and models of dolomitization: a critical reappraisal

This textbook outlines the physical, chemical, and biologic properties of the major sedimentary rocks, as revealed by petrographic microscopy, geochemical techniques, and field study It covers the mineralogy, chemistry, textures, and sedimentary structures that characterise sedimentary rocks, and relates these features to the depositional origin of the rocks and their subsequent alteration by diagenetic processes during burial In addition to detailed sections on siliciclastic and carbonate rocks, it also discusses evaporites, cherts, iron-rich sedimentary rocks, phosphorites, and carbonaceous sedimentary rocks such as oil shales This second edition maintains the comprehensive treatment of sedimentary petrography and petrology provided in the first edition, and has been updated with new concepts and cutting-edge techniques like cathodoluminescence imaging of sedimentary rocks and backscattered electron microscopy It is ideal for advanced undergraduate and graduate courses in sedimentary petrology, and is a key reference for researchers and professional petroleum geoscientists

Petrology of sedimentary rocks

Earth's glacial record and its tectonic setting

Cenozoic dolomites of carbonate islands: their attributes and origin

Dolomites form in a range of environments by processes able to drive large volumes of magnesium-rich waters through existing carbonate sediments or rocks. These fluids need not be of unusual composition but there are kinetic barriers to crystallisation which is influenced by factors such as the Mg/Ca ratio, salinity, temperature, the /Ca2+ ratio and time. Dolomite is able to form at near-surface temperatures and pressures within a few thousand years.Textures in dolomitic rocks are controlled by their conditions of formation. A large proportion are replacive but few of these are mimetic, preserving primary structures. Crystals vary from euhedral to anhedral with boundaries ranging from planar to consertal. Solution chemistry and temperatures influence the density and distribution of nuclei together with growth rates and crystal morphology. There is still doubt whether irregular crystal faces are products of high or low temperatures or saturation. Dolomite cements are more important than has previously been realised in massively dolomitised rocks. Differential dissolution of aragonite, calcite, or evaporite minerals leaves space for these cements to occupy. Dolomitisation may also be allied to compaction, generating stylolitic rocks which are progressively enriched in dolomite. Dolomite may be replaced by calcite or it may be dissolved and the resulting pores filled with a calcite cement.There is no general correlation between any set of petrographic features and particular geological models for dolomitisation. Similar physicochemical conditions are reproduced in a range of environments and the most effective guides to origin are in the geometry and regional petrographic variation of dolomite bodies.

C. J. R. Braithwaite

Papers

Dolomites, a review of origins, geometry and textures