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

Sedimentary cycling and environmental change in the Late Proterozoic: Evidence from stable and radiogenic isotopes

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/98PA01793

High‐resolution δ13C stratigraphy through the Early Aptian “Livello selli” of the Alpine tethys

Stable carbon and oxygen isotopes (δ18O and δ13C values) and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years. As valuable as these insights have been, many problems regarding the interpretation of geochemical signals within mature rocks remain. For example, while the δ18O values of carbonate rocks are dependent both upon the temperature and the δ18O value of the fluid, and additional information including trace element composition aids in interpreting such signals, direct evidence of either the temperature or the composition of the fluids is required. Such information can be obtained by analysing the δ18O value of any fluid inclusions or by measuring the temperature using a method such as the ‘clumped’ isotope technique. Such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well-known tendency for δ18O values of carbonate rocks to decrease with increasing age. Unlike the δ18O, δ13C values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time. However, many studies have not sufficiently emphasized the effects of diagenesis and other post-depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored. Finally, many additional proxies are poised to contribute to the interpretation of carbonate diagenesis. Although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods, care should be taken to understand both old and new proxies before applying them to the ancient record.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/sed.12205

The geochemistry of carbonate diagenesis: The past, present and future

Late Tertiary dolomites form the Bahamas exhibit a strong inverse correlation between Sr and mol% MgCO{sub 3}. It is proposed that this relation is a result of a distribution coefficient dependent on the concentration of Ca in dolomite. Because these dolomites precipitated from water with a Sr{sup 2+}/Ca{sup 2+} ratio similar to that of seawater, a distribution coefficient (D{sub Sr}{sup dolomite}) of 0.0118 is calculated for Sr in stoichiometric dolomite. This coefficient increases by about 0.0039 for every additional mol% CaCO{sub 3} in nonstoichiometric dolomite. These data have three important implication. First, the new D{sub Sr}{sup dolomite} is substantially lower than previously suggested. Second, a relation has been established among the Sr{sup 2+}/Ca{sup 2+} ratio of dolomite-forming waters, the major element composition of dolomites, and the Sr content of dolomites, allowing the determination of the Sr{sup 2+}/Ca{sup 2+} ratio of fluids involved in the formation of ancient dolomites. Third, some published data sets on dolomites show a similar relation between Sr content and major element composition suggesting that these dolomites may also have formed from seawater. Other data sets deviate from the correlation defined by Little Bahama Bank dolomites, indicating either dolomitization in fluids other than seawater or changes ofmore » the Sr{sup 2+}/Ca{sup 2+} ratio of seawater through time.« less

New distribution coefficient for the incorporation of strontium into dolomite and its implications for the formation of ancient dolomites

Pore system characterisation in heterogeneous carbonates: An alternative approach to widely-used rock-typing methodologies

The carbon isotope profiles of shallow-marine carbonates from the Barremian-Aptian Kharaib and Shuaiba formations of the Arabian Gulf region range between 0.5 and 7^pmil ^dgr13C PDB (Peedee belemnite). Systematic variations can be correlated with isotope profiles reported from Tethyan pelagic limestone sequences. The detailed correspondence between the isotopic signature of the relatively well-dated pelagic limestones and the poorly dated shallow-water limestones from the Arabian Gulf region suggests that global marine carbon isotope changes apparently affected deep-sea and shallow-water carbonate sediments similarly and at a similar time resolution. Although oxygen isotopes have been reset during diagenesis, carbon isotopes appear to have maintained their primary marine signature through time. No evidence has been found to connect carbon isotope trends to subaerial exposure or later meteoric diagenesis. In combination with other data, the investigated carbon isotope profiles can be used for basin-to-platform and regional correlations beyond the current resolution of biostratigraphy in shallow-water limestones. Carbon isotope stratigraphy confirms significant hiatuses in the investigated shallow-water carbonate sequences. Using carbon isotope trends as a proxy for sea level fluctuations, the carbon isotope cycles of the late Early Cretaceous of the Arabian Gulf region may represent four cycles of rising and falling sea level with a duration corresponding to that of third-order sea level fluctuations. Regional correlations derived from isotope trends provide a scenario for the larger scale stratigraphic evolution of the Arabian peninsula during the end of the Early Cretaceous. Differential rates of aggradation between realms influenced by siliciclastics and those characterized by siliciclastic-poor ("clean") carbonate deposition apparently caused the development of a pronounced basin-platform topography during the early Aptian (Shuaiba intrashelf basin and platform).

Carbon Isotope Stratigraphy of the Upper Kharaib and Shuaiba Formations: Implications for the Early Cretaceous Evolution of the Arabian Gulf Region

A Barremian to Albian succession on Mount Kanala, part of a Tethyan isolated carbonate platform, was investigated for its δ13C variations. The limestone sequence is composed of a series of peritidal shallowing-upward cycles with clear petrographic evidence for strong early diagenetic overprinting related to repeated subaerial exposure. Despite significant impact of diagenesis, the observed changes in δ13C can be very well correlated with deep-water sections from different ocean basins and shallow water carbonate platforms in the Middle East. This lends further support to the applicability of δ13C variations for stratigraphic purposes in shallow-water limestones. Using the δ13C signal, time resolution in Lower Cretaceous platform carbonates can be significantly increased, independent of bio-zonations often hampered by ecological variability.



Cyclostratigraphic analysis of the Aptian part of the section shows that strong positive excursions of the cumulative departure from mean cycle thickness of the peritidal shallowing-upward cycles coincide with global positive δ13C excursions. This, and the fact that positive shifts in the δ13C record are preserved within shallow water limestones, provide evidence that black-shale accumulation in the ocean basins occurred during sea-level rise and flooding of platform tops. Integration of carbon-isotope-, cyclo- and sequence-stratigraphic results from different carbonate platforms indicate that strong positive global δ13C shifts and concurrent organic-carbon burial during black-shale deposition are ultimately caused by rapid rises of eustatic sea level. Hence, the rate of change of eustatic sea level is considered to play a crucial role in black-shale accumulation in the global ocean basins during the Cretaceous.

Volker Vahrenkamp

Papers

New distribution coefficient for the incorporation of strontium into dolomite and its implications for the formation of ancient dolomites

Pore system characterisation in heterogeneous carbonates: An alternative approach to widely-used rock-typing methodologies

Carbon Isotope Stratigraphy of the Upper Kharaib and Shuaiba Formations: Implications for the Early Cretaceous Evolution of the Arabian Gulf Region

Carbon-isotope stratigraphy in shallow-water carbonates: implications for Cretaceous black-shale deposition

Late Cenozoic Dolomites of the Bahamas: Metastable Analogues for the Genesis of Ancient Platform Dolomites