Dolomite (rock)

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Triassic dolomitic rocks from Slovakia 7092 pieskovna Dolinka pri Hradisti pod Vratnom dolomit.JPG
Triassic dolomitic rocks from Slovakia
Erosion of dolomite over weaker shale created the Niagara Escarpment Canadian Horseshoe Falls with city of Niagara Falls, Ontario in background.jpg
Erosion of dolomite over weaker shale created the Niagara Escarpment
Trilobite fossil preserved as an internal cast in Silurian dolomite from southwestern Ohio, US Sthenarocalymene celebra - Arthropoda, Trilobita, Polymerida, Calymenidae - Silurian - Ohio, USA.jpg
Trilobite fossil preserved as an internal cast in Silurian dolomite from southwestern Ohio, US
Erosion of dolomitic rocks in Moureze, Herault, France Cirque de Moureze, Herault 32.jpg
Erosion of dolomitic rocks in Mourèze, Hérault, France

Dolomite (also known as dolomite rock, dolostone or dolomitic rock) is a sedimentary carbonate rock that contains a high percentage of the mineral dolomite, CaMg(CO3)2. It occurs widely, often in association with limestone and evaporites, though it is less abundant than limestone and rare in Cenozoic rock beds (beds less than about 66 million years in age). The first geologist to distinguish dolomite from limestone was Déodat Gratet de Dolomieu; a French mineralogist and geologist whom it is named after. He recognized and described the distinct characteristics of dolomite in the late 18th century, differentiating it from limestone.

Contents

Most dolomite was formed as a magnesium replacement of limestone or of lime mud before lithification. [1] The geological process of conversion of calcite to dolomite is known as dolomitization and any intermediate product is known as dolomitic limestone. [2] [3] The "dolomite problem" refers to the vast worldwide depositions of dolomite in the past geologic record in contrast to the limited amounts of dolomite formed in modern times. [4] [5] Recent research has revealed sulfate-reducing bacteria living in anoxic conditions precipitate dolomite which indicates that some past dolomite deposits may be due to microbial activity. [6] [7]

Dolomite is resistant to erosion and can either contain bedded layers or be unbedded. It is less soluble than limestone in weakly acidic groundwater, but it can still develop solution features (karst) over time. Dolomite rock can act as an oil and natural gas reservoir.

Name

Dolomite takes its name from the 18th-century French mineralogist Déodat Gratet de Dolomieu (1750–1801), who was one of the first to describe the mineral. [8] [9]

The term dolomite refers to both the calcium-magnesium carbonate mineral and to sedimentary rock formed predominantly of this mineral. The term dolostone was introduced in 1948 to avoid confusion between the two. However, the usage of the term dolostone is controversial, because the name dolomite was first applied to the rock during the late 18th century and thus has technical precedence. The use of the term dolostone was not recommended by the Glossary of Geology published by the American Geological Institute. [10]

In old USGS publications, dolomite was referred to as magnesian limestone , a term now reserved for magnesium-deficient dolomites or magnesium-rich limestones.

Description

Dolomite rock is defined as sedimentary carbonate rock composed of more than 50% mineral dolomite. Dolomite is characterized by its nearly ideal 1:1 stoichiometric ratio of magnesium to calcium. It is distinct from high-magnesium limestone in that the magnesium and calcium form ordered layers within the individual dolomite mineral grains, rather than being arranged at random, as they are in high-magnesium calcite grains. [11] In natural dolomite, magnesium is typically between 44 and 50 percent of total magnesium plus calcium, indicating some substitution of calcium into the magnesium layers. A small amount of ferrous iron typically substitutes for magnesium, particularly in more ancient dolomites. [12] Carbonate rock tends to be either almost all calcite or almost all dolomite, with intermediate compositions being quite uncommon. [13]

Dolomite outcrops are recognized in the field by their softness (mineral dolomite has a Mohs hardness of 4 or less, well below common silicate minerals) and because dolomite bubbles feebly when a drop of dilute hydrochloric acid is dropped on it. This distinguishes dolomite from limestone, which is also soft but reacts vigorously with dilute hydrochloric acid. Dolomite usually weathers to a characteristic dull yellow-brown color due to the presence of ferrous iron. This is released and oxidized as the dolomite weathers. [14] Dolomite is usually granular in appearance, with a texture resembling grains of sugar. [15]

Under the microscope, thin sections of dolomite usually show individual grains that are well-shaped rhombs, with considerable pore space. As a result, subsurface dolomite is generally more porous than subsurface limestone and makes up 80% of carbonate rock petroleum reservoirs. [16] This texture contrasts with limestone, which is usually a mixture of grains, micrite (very fine-grained carbonate mud) and sparry cement. The optical properties of calcite and mineral dolomite are difficult to distinguish, but calcite almost never crystallizes as regular rhombs, and calcite is stained by Alizarin Red S while dolomite grains are not. [17] Dolomite rock consisting of well-formed grains with planar surfaces is described as planar or idiotopic dolomite, while dolomite consisting of poorly-formed grains with irregular surfaces is described as nonplanar or xenotopic dolomite. [15] The latter likely forms by recrystallization of existing dolomite at elevated temperature (over 50 to 100 °C (122 to 212 °F)). [17]

The texture of dolomite often shows that it is secondary, formed by replacement of calcium by magnesium in limestone. The preservation of the original limestone texture can range from almost perfectly preserved to completely destroyed. [18] Under a microscope, dolomite rhombs are sometimes seen to replace oolites or skeletal particles of the original limestone. [19] There is sometimes selective replacement of fossils, with the fossil remaining mostly calcite and the surrounding matrix composed of dolomite grains. Sometimes dolomite rhombs are seen cut across the fossil outline. However, some dolomite shows no textural indications that it was formed by replacement of limestone. [17]

Occurrence and origin

Dolomite is widespread in its occurrences, though not as common as limestone. [20] It is typically found in association with limestone or evaporite beds and is often interbedded with limestone. [21] There is no consistent trend in its abundance with age, but most dolomite appears to have formed at high stands of sea level. Little dolomite is found in Cenozoic beds (beds less than 65 million years old), which has been a time of generally low sea levels. [22] Times of high sea level also tend to be times of a greenhouse Earth, and it is possible that greenhouse conditions are the trigger for dolomite formation. [23]

Many dolomites show clear textural indications that they are secondary dolomites, formed by replacement of limestone. However, although much research has gone into understanding this process of dolomitization, the process remains poorly understood. There are also fine-grained dolomites showing no textural indications that they formed by replacement, and it is uncertain whether they formed by replacement of limestone that left no textural traces or are true primary dolomites. This dolomite problem was first recognized over two centuries ago but is still not fully resolved. [21]

The dolomitization reaction

2CaCO3 + Mg2+ → CaMg(CO3)2 + Ca2+

is thermodynamically favorable, with a Gibbs free energy of about -2.2 kcal/mol. In theory, ordinary seawater contains sufficient dissolved magnesium to cause dolomitization. However, because of the very slow rate of diffusion of ions in solid mineral grains at ordinary temperatures, the process can occur only by simultaneous dissolution of calcite and crystallization of dolomite. This in turn requires that large volumes of magnesium-bearing fluids are flushed through the pore space in the dolomitizing limestone. [24] Several processes have been proposed for dolomitization.

The hypersaline model (also known as the evaporative reflux model [25] ) is based on the observation that dolomite is very commonly found in association with limestone and evaporites, with the limestone often interbedded with the dolomite. According to this model, dolomitization takes place in a closed basin where seawater is subject to high rates of evaporation. This results in precipitation of gypsum and aragonite, raising the magnesium to calcium ratio of the remaining brine. The brine is also dense, so it sinks into the pore space of any underlying limestone (seepage refluxion), flushing out the existing pore fluid and causing dolomitization. The Permian Basin of North America has been put forward as an example of an environment in which this process took place. [25] A variant of this model has been proposed for sabkha environments in which brine is sucked up into the dolomitizing limestone by evaporation of capillary fluids, a process called evaporative pumping. [25]

Another model is the mixing-zone or Dorag model, in which meteoric water mixes with seawater already present in the pore space, increasing the chemical activity of magnesium relative to calcium and causing dolomitization. The formation of Pleistocene dolomite reefs in Jamaica has been attributed to this process. However, this model has been heavily criticized, [26] with one 2004 review paper describing it bluntly as "a myth". [27] A 2021 paper argued that the mixing zone serves as domain of intense microbial activity which promotes dolomitization. [28]

A third model postulates that normal seawater is the dolomitizing fluid, and the necessary large volumes are flushed through the dolomitizing limestone through tidal pumping. Dolomite formation at Sugarloaf Key may be an example of this process. A similar process might occur during rises in sea level, as large volumes of water move through limestone platform rock. [29]

Regardless of the mechanism of dolomitization, the tendency of carbonate rock to be either almost all calcite or almost all dolomite suggests that, once the process is started, it completes rapidly. [30] The process likely occurs at shallow depths of burial, under 100 meters (330 ft), where there is an inexhaustible supply of magnesium-rich seawater and the original limestone is more likely to be porous. On the other hand, dolomitization can proceed rapidly at the greater temperatures characterizing deeper burial, if a mechanism exists to flush magnesium-bearing fluids through the beds. [31]

Mineral dolomite has a 12% to 13% smaller volume than calcite per alkali cation. Thus dolomitization likely increases porosity and contributes to the sugary texture of dolomite. [16]

The dolomite problem and primary dolomite

Dolomite is supersaturated in normal seawater by a factor of greater than ten, but dolomite is not seen to precipitate in the oceans. Likewise, geologists have not been successful at precipitating dolomite from seawater at normal temperatures and pressures in laboratory experiments. This is likely due to a very high activation energy for nucleating crystals of dolomite. [32]

The magnesium ion is a relatively small ion, and it acquires a tightly bound hydration shell when dissolved in water. In other words, the magnesium ion is surrounded by a clump of water molecules that are strongly attracted to its positive charge. Calcium is a larger ion and this reduces the strength of binding of its hydration shell, so it is much easier for a calcium ion than a magnesium ion to shed its hydration shell and bind to a growing crystal. It is also more difficult to nucleate a seed crystal of ordered dolomite than disordered high-magnesium calcite. As a result, attempts to precipitate dolomite from seawater precipitate high-magnesium calcite instead. This substance, which has an excess of calcium over magnesium and lacks calcium-magnesium ordering, is sometimes called protodolomite. [32] Raising the temperature makes it easier for magnesium to shed its hydration shell, and dolomite can be precipitated from seawater at temperatures in excess of 60 °C (140 °F). [33] Protodolomite also rapidly converts to dolomite at temperatures of 250 °C (482 °F) or higher. [34] The high temperatures necessary for the formation of dolomite helps explain the rarity of Cenozoic dolomites, since Cenozoic seawater temperatures seldom exceeded 40 °C. [35]

It is possible that microorganisms are capable of precipitating primary dolomite. [7] This was first demonstrated in samples collected at Lagoa Vermelha, Brazil [6] in association with sulfate-reducing bacteria ( Desulfovibrio ), leading to the hypothesis that sulfate ion inhibits dolomite nucleation. Later laboratory experiments suggest bacteria can precipitate dolomite independently of the sulfate concentration. [36] With time other pathways of interaction between microbial activity and dolomite formation have been added to the discord regarding their role in modulation and generation of polysaccharides, [37] manganese [38] [39] and zinc [40] within the porewater. Meanwhile, a contrary view held by other researchers is that microorganisms precipitate only high-magnesium calcite but leave open the question of whether this can lead to precipitation of dolomite. [41]

Dedolomitization

Dolomitization can sometimes be reversed, and a dolomite bed converted back to limestone. This is indicated by a texture of pseudomorphs of mineral dolomite that have been replaced with calcite. Dedolomitized limestone is typically associated with gypsum or oxidized pyrite, and dedolomitization is thought to occur at very shallow depths through infiltration of surface water with a very high ratio of calcium to magnesium. [42]

Uses

Cutting dolomite in 1994. Saaremaa, Estonia. Saaremaa dolomiit 1994 (04).jpg
Cutting dolomite in 1994. Saaremaa, Estonia.

Dolomite is used for many of the same purposes as limestone, including as construction aggregate; in agriculture to neutralize soil acidity and supply calcium and magnesium; as a source of carbon dioxide; as dimension stone; as a filler in fertilizers and other products; as a flux in metallurgy; and in glass manufacturing. It cannot substitute for limestone in chemical processes that require a high-calcium limestone, such as manufacture of sodium carbonate. Dolomite is used for production of magnesium chemicals, such as Epsom salt, and is used as a magnesium supplement. [43] It is also used in the manufacture of refractory materials. [44]

Caves in dolomite rock

As with limestone caves, natural caves and solution tubes typically form in dolomite rock as a result of the dissolution by weak carbonic acid. [45] [46] Caves can also, less commonly, form through dissolution of rock by sulfuric acid. [47] Calcium carbonate speleothems (secondary deposits) in the forms of stalactites, stalagmites, flowstone etc., can also form in caves within dolomite rock. “Dolomite is a common rock type, but a relatively uncommon mineral in speleothems”. [45] Both the 'Union Internationale de Spéléologie' (UIS) and the American 'National Speleological Society' (NSS), extensively use in their publications, the terms "dolomite" or "dolomite rock" when referring to the natural bedrock containing a high percentage of CaMg(CO3)2 in which natural caves or solution tubes have formed. [45] [48]

Dolomite speleothems

Both calcium and magnesium go into solution when dolomite rock is dissolved. The speleothem precipitation sequence is: calcite, Mg-calcite, aragonite, huntite and hydromagnesite. [45] [48] Hence, the most common speleothem (secondary deposit) in caves within dolomite rock karst, is calcium carbonate in the most stable polymorph form of calcite. Speleothem types known to have a dolomite constituent include: coatings, crusts, moonmilk, flowstone, coralloids, powder, spar and rafts. [45] Although there are reports of dolomite speleothems known to exist in a number of caves around the world, they are usually in relatively small quantities and form in very fine-grained deposits. [45] [48]

See also

Related Research Articles

<span class="mw-page-title-main">Limestone</span> Type of sedimentary rock

Limestone is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of CaCO3. Limestone forms when these minerals precipitate out of water containing dissolved calcium. This can take place through both biological and nonbiological processes, though biological processes, such as the accumulation of corals and shells in the sea, have likely been more important for the last 540 million years. Limestone often contains fossils which provide scientists with information on ancient environments and on the evolution of life.

<span class="mw-page-title-main">Shale</span> Fine-grained, clastic sedimentary rock

Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2Si2O5(OH)4) and tiny fragments (silt-sized particles) of other minerals, especially quartz and calcite. Shale is characterized by its tendency to split into thin layers (laminae) less than one centimeter in thickness. This property is called fissility. Shale is the most common sedimentary rock.

<span class="mw-page-title-main">Sedimentary rock</span> Rock formed by the deposition and cementation of particles

Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles to settle in place. The particles that form a sedimentary rock are called sediment, and may be composed of geological detritus (minerals) or biological detritus. The geological detritus originated from weathering and erosion of existing rocks, or from the solidification of molten lava blobs erupted by volcanoes. The geological detritus is transported to the place of deposition by water, wind, ice or mass movement, which are called agents of denudation. Biological detritus was formed by bodies and parts of dead aquatic organisms, as well as their fecal mass, suspended in water and slowly piling up on the floor of water bodies. Sedimentation may also occur as dissolved minerals precipitate from water solution.

<span class="mw-page-title-main">Calcite</span> Calcium carbonate mineral

Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on the Mohs scale of mineral hardness, based on scratch hardness comparison. Large calcite crystals are used in optical equipment, and limestone composed mostly of calcite has numerous uses.

<span class="mw-page-title-main">Chalk</span> Soft, white, porous sedimentary rock made of calcium carbonate

Chalk is a soft, white, porous, sedimentary carbonate rock. It is a form of limestone composed of the mineral calcite and originally formed deep under the sea by the compression of microscopic plankton that had settled to the sea floor. Chalk is common throughout Western Europe, where deposits underlie parts of France, and steep cliffs are often seen where they meet the sea in places such as the Dover cliffs on the Kent coast of the English Channel.

<span class="mw-page-title-main">Dolomite (mineral)</span> Carbonate mineral - CaMg(CO₃)₂

Dolomite is an anhydrous carbonate mineral composed of calcium magnesium carbonate, ideally CaMg(CO3)2. The term is also used for a sedimentary carbonate rock composed mostly of the mineral dolomite (see Dolomite (rock)). An alternative name sometimes used for the dolomitic rock type is dolostone.

<span class="mw-page-title-main">Chert</span> Hard, fine-grained sedimentary rock composed of cryptocrystalline silica

Chert is a hard, fine-grained sedimentary rock composed of microcrystalline or cryptocrystalline quartz, the mineral form of silicon dioxide (SiO2). Chert is characteristically of biological origin, but may also occur inorganically as a chemical precipitate or a diagenetic replacement, as in petrified wood.

<span class="mw-page-title-main">Aragonite</span> Calcium carbonate mineral

Aragonite is a carbonate mineral and one of the three most common naturally occurring crystal forms of calcium carbonate, the others being calcite and vaterite. It is formed by biological and physical processes, including precipitation from marine and freshwater environments.

<span class="mw-page-title-main">Speleothem</span> Structure formed in a cave by the deposition of minerals from water

A speleothem is a geological formation by mineral deposits that accumulate over time in natural caves. Speleothems most commonly form in calcareous caves due to carbonate dissolution reactions. They can take a variety of forms, depending on their depositional history and environment. Their chemical composition, gradual growth, and preservation in caves make them useful paleoclimatic proxies.

<span class="mw-page-title-main">Lithology</span> Description of its physical characteristics of a rock unit

The lithology of a rock unit is a description of its physical characteristics visible at outcrop, in hand or core samples, or with low magnification microscopy. Physical characteristics include colour, texture, grain size, and composition. Lithology may refer to either a detailed description of these characteristics, or a summary of the gross physical character of a rock. Examples of lithologies in the second sense include sandstone, slate, basalt, or limestone.

<span class="mw-page-title-main">Ooid</span> Small sedimentary grain that forms on shallow tropical seabeds

Ooids are small, spheroidal, "coated" (layered) sedimentary grains, usually composed of calcium carbonate, but sometimes made up of iron- or phosphate-based minerals. Ooids usually form on the sea floor, most commonly in shallow tropical seas. After being buried under additional sediment, these ooid grains can be cemented together to form a sedimentary rock called an oolite. Oolites usually consist of calcium carbonate; these belong to the limestone rock family. Pisoids are similar to ooids, but are larger than 2 mm in diameter, often considerably larger, as with the pisoids in the hot springs at Carlsbad in the Czech Republic.

<span class="mw-page-title-main">Mudstone</span> Fine grained sedimentary rock whose original constituents were clays or muds

Mudstone, a type of mudrock, is a fine-grained sedimentary rock whose original constituents were clays or muds. Mudstone is distinguished from shale by its lack of fissility.

<span class="mw-page-title-main">Carbonate rock</span> Class of sedimentary rock

Carbonate rocks are a class of sedimentary rocks composed primarily of carbonate minerals. The two major types are limestone, which is composed of calcite or aragonite (different crystal forms of CaCO3), and dolomite rock (also known as dolostone), which is composed of mineral dolomite (CaMg(CO3)2). They are usually classified based on texture and grain size. Importantly, carbonate rocks can exist as metamorphic and igneous rocks, too. When recrystallized carbonate rocks are metamorphosed, marble is created. Rare igneous carbonate rocks even exist as intrusive carbonatites and, even rarer, there exists volcanic carbonate lava.

<span class="mw-page-title-main">Cementation (geology)</span> Process of chemical precipitation bonding sedimentary grains

Cementation involves ions carried in groundwater chemically precipitating to form new crystalline material between sedimentary grains. The new pore-filling minerals forms "bridges" between original sediment grains, thereby binding them together. In this way, sand becomes sandstone, and gravel becomes conglomerate or breccia. Cementation occurs as part of the diagenesis or lithification of sediments. Cementation occurs primarily below the water table regardless of sedimentary grain sizes present. Large volumes of pore water must pass through sediment pores for new mineral cements to crystallize and so millions of years are generally required to complete the cementation process. Common mineral cements include calcite, quartz, and silica phases like cristobalite, iron oxides, and clay minerals; other mineral cements also occur.

<span class="mw-page-title-main">Caymanite</span> Variety of dolomite

Caymanite at its type area is an uncommon variety of dolomite, also known as dolostone, originally reported from locations in the Miocene Cayman Formation in the Cayman Islands: the Bluff in Cayman Brac and the East End on Grand Cayman.

<span class="mw-page-title-main">Shallow water marine environment</span>

Shallow water marine environment refers to the area between the shore and deeper water, such as a reef wall or a shelf break. This environment is characterized by oceanic, geological and biological conditions, as described below. The water in this environment is shallow and clear, allowing the formation of different sedimentary structures, carbonate rocks, coral reefs, and allowing certain organisms to survive and become fossils.

<span class="mw-page-title-main">Dolomitization</span> Geological process producing dolomite

Dolomitization is a geological process by which the carbonate mineral dolomite is formed when magnesium ions replace calcium ions in another carbonate mineral, calcite. It is common for this mineral alteration into dolomite to take place due to evaporation of water in the sabkha area. Dolomitization involves substantial amount of recrystallization. This process is described by the stoichiometric equation:

<span class="mw-page-title-main">Calcite rafts</span> Cave-crystallized calcite crusts

Calcite crystals form on the surface of quiescent bodies of water, even when the bulk water is not supersaturated with respect to calcium carbonate. The crystals grow, attach to one other and appear to be floating rafts of a white, opaque material. The floating materials have been referred to as calcite rafts or "leopard spots".

<span class="mw-page-title-main">Lawrence Alexander Hardie</span> American geologist (1933–2013)

Lawrence Alexander Hardie was an American geologist, sedimentologist, and geochemist.

Automicrite is autochthonous micrite, that is, a carbonate mud precipitated in situ and made up of fine-grained calcite or aragonite micron-sized crystals. It precipitates on the sea floor or within the sediment as an authigenic mud thanks to physicochemical, microbial, photosynthetic and biochemical processes. It has peculiar fabrics and uniform mineralogical and chemical composition.

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