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Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals
calcite Calcite is a Carbonate minerals, carbonate mineral and the most stable Polymorphism (materials science), polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on ...
and aragonite, which are different crystal forms of . 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. About 20% to 25% of sedimentary rock is carbonate rock, and most of this is limestone. The remaining carbonate rock is mostly dolomite, a closely related rock, which contains a high percentage of the mineral dolomite, . ''Magnesian limestone'' is an obsolete and poorly-defined term used variously for dolomite, for limestone containing significant dolomite (''dolomitic limestone''), or for any other limestone containing a significant percentage of magnesium. Most limestone was formed in shallow marine environments, such as
continental shelves A continental shelf is a portion of a continent that is submerged under an area of relatively shallow water, known as a shelf sea. Much of these shelves were exposed by drops in sea level during glacial periods. The shelf surrounding an island ...
or platforms, though smaller amounts were formed in many other environments. Much dolomite is secondary dolomite, formed by chemical alteration of limestone. Limestone is exposed over large regions of the Earth's surface, and because limestone is slightly soluble in rainwater, these exposures often are eroded to become
karst Karst is a topography formed from the dissolution of soluble rocks such as limestone, dolomite, and gypsum. It is characterized by underground drainage systems with sinkholes and caves. It has also been documented for more weathering-resistant ro ...
landscapes. Most cave systems are found in limestone bedrock. Limestone has numerous uses: as a chemical
feedstock A raw material, also known as a feedstock, unprocessed material, or primary commodity, is a basic material that is used to produce goods, finished goods, energy, or intermediate materials that are feedstock for future finished products. As feedst ...
for the production of lime used for cement (an essential component of concrete), as aggregate for the base of roads, as white pigment or filler in products such as toothpaste or
paint Paint is any pigmented liquid, liquefiable, or solid mastic composition that, after application to a substrate in a thin layer, converts to a solid film. It is most commonly used to protect, color, or provide texture. Paint can be made in many ...
s, as a
soil conditioner A soil conditioner is a product which is added to soil to improve the soil’s physical qualities, usually its fertility (ability to provide nutrition for plants) and sometimes its mechanics. In general usage, the term "soil conditioner" is often ...
, and as a popular decorative addition to
rock gardens A rock garden, also known as a rockery and formerly as a rockwork, is a garden, or more often a part of a garden, with a landscaping framework of rocks, stones, and gravel, with planting appropriate to this setting. Usually these are small A ...
. Limestone formations contain about 30% of the world's
petroleum reservoir A petroleum reservoir or oil and gas reservoir is a subsurface accumulation of hydrocarbons contained in porous or fractured rock formations. Such reservoirs form when kerogen (ancient plant matter) is created in surrounding rock by the presence ...
s.


Description

Limestone is composed mostly of the minerals
calcite Calcite is a Carbonate minerals, carbonate mineral and the most stable Polymorphism (materials science), polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on ...
and aragonite, which are different crystal forms of calcium carbonate (). Dolomite, , is an uncommon mineral in limestone, and siderite or other carbonate minerals are rare. However, the calcite in limestone often contains a few percent of magnesium. Calcite in limestone is divided into low-magnesium and high-magnesium calcite, with the dividing line placed at a composition of 4% magnesium. High-magnesium calcite retains the calcite mineral structure, which is distinct from dolomite. Aragonite does not usually contain significant magnesium. Most limestone is otherwise chemically fairly pure, with clastic sediments (mainly fine-grained quartz and
clay mineral Clay minerals are hydrous aluminium phyllosilicates (e.g. kaolin, Al2 Si2 O5( OH)4), sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations found on or near some planetary surfaces. Clay minerals ...
s) making up less than 5% to 10% of the composition. Organic matter typically makes up around 0.2% of a limestone and rarely exceeds 1%. Limestone often contains variable amounts of silica in the form of chert or siliceous skeletal fragments (such as sponge spicules, diatoms, or radiolarians). Fossils are also common in limestone. Limestone is commonly white to gray in color. Limestone that is unusually rich in organic matter can be almost black in color, while traces of iron or manganese can give limestone an off-white to yellow to red color. The density of limestone depends on its porosity, which varies from 0.1% for the densest limestone to 40% for chalk. The density correspondingly ranges from 1.5 to 2.7 g/cm3. Although relatively soft, with a Mohs hardness of 2 to 4, dense limestone can have a crushing strength of up to 180 MPa. For comparison, concrete typically has a crushing strength of about 40 MPa. Although limestones show little variability in mineral composition, they show great diversity in texture. However, most limestone consists of sand-sized grains in a carbonate mud matrix. Because limestones are often of biological origin and are usually composed of sediment that is deposited close to where it formed, classification of limestone is usually based on its grain type and mud content.


Grains

Most grains in limestone are skeletal fragments of marine organisms such as coral or foraminifera. These organisms secrete structures made of aragonite or calcite, and leave these structures behind when they die. Other carbonate grains composing limestones are
ooids Ooids are small (commonly ≤2 mm in diameter), 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, ...
, peloids, and limeclasts ( intraclasts and extraclasts). Skeletal grains have a composition reflecting the organisms that produced them and the environment in which they were produced. Low-magnesium calcite skeletal grains are typical of articulate brachiopods, planktonic (free-floating) foraminifera, and coccoliths. High-magnesium calcite skeletal grains are typical of benthic (bottom-dwelling) foraminifera, echinoderms, and coralline algae. Aragonite skeletal grains are typical of
mollusc Mollusca is the second-largest phylum of invertebrate animals after the Arthropoda, the members of which are known as molluscs or mollusks (). Around 85,000  extant species of molluscs are recognized. The number of fossil species is esti ...
s, calcareous
green algae The green algae (singular: green alga) are a group consisting of the Prasinodermophyta and its unnamed sister which contains the Chlorophyta and Charophyta/Streptophyta. The land plants (Embryophytes) have emerged deep in the Charophyte alga as ...
,
stromatoporoid Stromatoporoidea is an extinct clade of sea sponges common in the fossil record from the Ordovician through the Devonian. They were especially abundant and important reef-formers in the Silurian and most of the Devonian.Stock, C.W. 2001, Stro ...
s, corals, and tube worms. The skeletal grains also reflect specific geological periods and environments. For example, coral grains are more common in high-energy environments (characterized by strong currents and turbulence) while bryozoan grains are more common in low-energy environments (characterized by quiet water). Ooids (sometimes called ooliths) are sand-sized grains (less than 2mm in diameter) consisting of one or more layers of calcite or aragonite around a central quartz grain or carbonate mineral fragment. These likely form by direct precipitation of calcium carbonate onto the ooid. Pisoliths are similar to ooids, but they are larger than 2 mm in diameter and tend to be more irregular in shape. Limestone composed mostly of ooids is called an ''
oolite Oolite or oölite (''egg stone'') is a sedimentary rock formed from ooids, spherical grains composed of concentric layers. The name derives from the Ancient Greek word for egg (ᾠόν). Strictly, oolites consist of ooids of diameter 0.25–2 ...
'' or sometimes an ''oolitic limestone''. Ooids form in high-energy environments, such as the Bahama platform, and oolites typically show crossbedding and other features associated with deposition in strong currents. ''Oncoliths'' resemble ooids but show a radial rather than layered internal structure, indicating that they were formed by algae in a normal marine environment. Peloids are structureless grains of microcrystalline carbonate likely produced by a variety of processes. Many are thought to be fecal pellets produced by marine organisms. Others may be produced by endolithic (boring) algae or other microorganisms or through breakdown of mollusc shells. They are difficult to see in a limestone sample except in thin section and are less common in ancient limestones, possibly because compaction of carbonate sediments disrupts them. Limeclasts are fragments of existing limestone or partially lithified carbonate sediments. Intraclasts are limeclasts that originate close to where they are deposited in limestone, while extraclasts come from outside the depositional area. Intraclasts include ''grapestone'', which is clusters of peloids cemented together by organic material or mineral cement. Extraclasts are uncommon, are usually accompanied by other clastic sediments, and indicate deposition in a tectonically active area or as part of a turbidity current.


Mud

The grains of most limestones are embedded in a matrix of carbonate mud. This is typically the largest fraction of an ancient carbonate rock. Mud consisting of individual crystals less than 5 microns in length is described as ''micrite''. In fresh carbonate mud, micrite is mostly small aragonite needles, which may precipitate directly from seawater, be secreted by algae, or be produced by abrasion of carbonate grains in a high-energy environment. This is converted to calcite within a few million years of deposition. Further recrystallization of micrite produces ''microspar'', with grains from 5 to 15 microns in diameter. Limestone often contains larger crystals of calcite, ranging in size from 0.02 to 0.1 mm, that are described as ''sparry calcite'' or ''sparite''. Sparite is distinguished from micrite by a grain size of over 20 microns and because sparite stands out under a hand lens or in thin section as white or transparent crystals. Sparite is distinguished from carbonate grains by its lack of internal structure and its characteristic crystal shapes. Geologists are careful to distinguish between sparite deposited as cement and sparite formed by recrystallization of micrite or carbonate grains. Sparite cement was likely deposited in pore space between grains, suggesting a high-energy depositional environment that removed carbonate mud. Recrystallized sparite is not diagnostic of depositional environment.


Other characteristics

Limestone outcrops are recognized in the field by their softness (calcite and aragonite both have a Mohs hardness of less than 4, well below common silicate minerals) and because limestone bubbles vigorously when a drop of dilute hydrochloric acid is dropped on it. Dolomite is also soft but reacts only feebly with dilute hydrochloric acid, and it 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. Impurities (such as clay, sand, organic remains,
iron oxide Iron oxides are chemical compounds composed of iron and oxygen. Several iron oxides are recognized. All are black magnetic solids. Often they are non-stoichiometric. Oxyhydroxides are a related class of compounds, perhaps the best known of whic ...
, and other materials) will cause limestones to exhibit different colors, especially with
weathered ''Weathered'' is the third studio album by American rock band Creed, released on November 20, 2001. It was the last Creed album to be released until '' Full Circle'' came out in October 2009, with Creed disbanding in June 2004. It is the only Cr ...
surfaces. The makeup of a carbonate rock outcrop can be estimated in the field by etching the surface with dilute hydrochloric acid. This etches away the calcite and aragonite, leaving behind any silica or dolomite grains. The latter can be identified by their rhombohedral shape. Crystals of calcite, quartz, dolomite or
barite Baryte, barite or barytes ( or ) is a mineral consisting of barium sulfate ( Ba S O4). Baryte is generally white or colorless, and is the main source of the element barium. The ''baryte group'' consists of baryte, celestine (strontium sulfate), ...
may line small cavities ('' vugs'') in the rock. Vugs are a form of secondary porosity, formed in existing limestone by a change in environment that increases the solubility of calcite. Dense, massive limestone is sometimes described as "marble". For example, the famous Portoro "marble" of Italy is actually a dense black limestone. True marble is produced by recrystallization of limestone during regional metamorphism that accompanies the mountain building process (
orogeny Orogeny is a mountain building process. An orogeny is an event that takes place at a convergent plate margin when plate motion compresses the margin. An ''orogenic belt'' or ''orogen'' develops as the compressed plate crumples and is uplifted t ...
). It is distinguished from dense limestone by its coarse crystalline texture and the formation of distinctive minerals from the silica and clay present in the original limestone.


Classification

Two major classification schemes, the Folk and Dunham, are used for identifying the types of carbonate rocks collectively known as limestone.


Folk classification

Robert L. Folk developed a classification system that places primary emphasis on the detailed composition of grains and interstitial material in carbonate rocks. Based on composition, there are three main components: allochems (grains), matrix (mostly micrite), and cement (sparite). The Folk system uses two-part names; the first refers to the grains and the second to the cement. For example, a limestone consisting mainly of ooids, with a crystalline matrix, would be termed an oosparite. It is helpful to have a petrographic microscope when using the Folk scheme, because it is easier to determine the components present in each sample.


Dunham classification

Robert J. Dunham published his system for limestone in 1962. It focuses on the depositional fabric of carbonate rocks. Dunham divides the rocks into four main groups based on relative proportions of coarser clastic particles, based on criteria such as whether the grains were originally in mutual contact, and therefore self-supporting, or whether the rock is characterized by the presence of frame builders and algal mats. Unlike the Folk scheme, Dunham deals with the original porosity of the rock. The Dunham scheme is more useful for hand samples because it is based on texture, not the grains in the sample. A revised classification was proposed by Wright (1992). It adds some diagenetic patterns to the classification scheme.


Other descriptive terms

'' Travertine'' is a term applied to calcium carbonate deposits formed in freshwater environments, particularly
hot springs A hot spring, hydrothermal spring, or geothermal spring is a spring produced by the emergence of geothermally heated groundwater onto the surface of the Earth. The groundwater is heated either by shallow bodies of magma (molten rock) or by circ ...
. Such deposits are typically massive, dense, and banded. When the deposits are highly porous, so that they have a spongelike texture, they are typically described as '' tufa''. Secondary calcite deposited by
supersaturated In physical chemistry, supersaturation occurs with a solution when the concentration of a solute exceeds the concentration specified by the value of solubility at equilibrium. Most commonly the term is applied to a solution of a solid in a liqu ...
meteoric waters ( groundwater) in caves is also sometimes described as travertine. This produces speleothems, such as
stalagmite A stalagmite (, ; from the Greek , from , "dropping, trickling") is a type of rock formation that rises from the floor of a cave due to the accumulation of material deposited on the floor from ceiling drippings. Stalagmites are typically ...
s and
stalactite A stalactite (, ; from the Greek 'stalaktos' ('dripping') via ''stalassein'' ('to drip') is a mineral formation that hangs from the ceiling of caves, hot springs, or man-made structures such as bridges and mines. Any material that is soluble an ...
s. ''
Coquina Coquina () is a sedimentary rock that is composed either wholly or almost entirely of the transported, abraded, and mechanically sorted fragments of the shells of mollusks, trilobites, brachiopods, or other invertebrates. The term ''coquina'' ...
'' is a poorly consolidated limestone composed of abraded pieces of coral, shells, or other fossil debris. When better consolidated, it is described as ''coquinite''. '' Chalk'' is a soft, earthy, fine-textured limestone composed of the tests of planktonic microorganisms such as foraminifera, while ''
marl Marl is an earthy material rich in carbonate minerals, clays, and silt. When hardened into rock, this becomes marlstone. It is formed in marine or freshwater environments, often through the activities of algae. Marl makes up the lower part o ...
'' is an earthy mixture of carbonates and silicate sediments.


Formation

Limestone forms when calcite or aragonite precipitate out of water containing dissolved calcium, which can take place through both biological and nonbiological processes. The solubility of calcium carbonate () is controlled largely by the amount of dissolved carbon dioxide () in the water. This is summarized in the reaction: :: Increases in temperature or decreases in pressure tend to reduce the amount of dissolved and precipitate . Reduction in salinity also reduces the solubility of , by several orders of magnitude for fresh water versus seawater. Near-surface water of the earth's oceans are oversaturated with by a factor of more than six. The failure of to rapidly precipitate out of these waters is likely due to interference by dissolved magnesium ions with
nucleation In thermodynamics, nucleation is the first step in the formation of either a new thermodynamic phase or structure via self-assembly or self-organization within a substance or mixture. Nucleation is typically defined to be the process that deter ...
of calcite crystals, the necessary first step in precipitation. Precipitation of aragonite may be suppressed by the presence of naturally occurring organic phosphates in the water. Although
ooids Ooids are small (commonly ≤2 mm in diameter), 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, ...
likely form through purely inorganic processes, the bulk of precipitation in the oceans is the result of biological activity. Much of this takes place on carbonate platforms. The origin of carbonate mud, and the processes by which it is converted to micrite, continue to be a subject of research. Modern carbonate mud is composed mostly of aragonite needles around 5 microns in length. Needles of this shape and composition are produced by calcareous algae such as '' Penicillus'', making this a plausible source of mud. Another possibility is direct precipitation from the water. A phenomenon known as ''whitings'' occurs in shallow waters, in which white streaks containing dispersed micrite appear on the surface of the water. It is uncertain whether this is freshly precipitated aragonite or simply material stirred up from the bottom, but there is some evidence that whitings are caused by biological precipitation of aragonite as part of a
bloom Bloom or blooming may refer to: Science and technology Biology * Bloom, one or more flowers on a flowering plant * Algal bloom, a rapid increase or accumulation in the population of algae in an aquatic system * Jellyfish bloom, a collective n ...
of
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...
or
microalgae Microalgae or microphytes are microscopic algae invisible to the naked eye. They are phytoplankton typically found in freshwater and marine systems, living in both the water column and sediment. They are unicellular species which exist indiv ...
. However, stable isotope ratios in modern carbonate mud appear to be inconsistent with either of these mechanisms, and abrasion of carbonate grains in high-energy environments has been put forward as a third possibility. Formation of limestone has likely been dominated by biological processes throughout the
Phanerozoic The Phanerozoic Eon is the current geologic eon in the geologic time scale, and the one during which abundant animal and plant life has existed. It covers 538.8 million years to the present, and it began with the Cambrian Period, when anima ...
, the last 540 million years of the Earth's history. Limestone may have been deposited by microorganisms in the
Precambrian The Precambrian (or Pre-Cambrian, sometimes abbreviated pꞒ, or Cryptozoic) is the earliest part of Earth's history, set before the current Phanerozoic Eon. The Precambrian is so named because it preceded the Cambrian, the first period of the ...
, prior to 540 million years ago, but inorganic processes were probably more important and likely took place in an ocean more highly oversaturated in calcium carbonate than the modern ocean.


Diagenesis

Diagenesis is the process in which sediments are compacted and turned into solid rock. During diagenesis of carbonate sediments, significant chemical and textural changes take place. For example, aragonite is converted to low-magnesium calcite. Diagenesis is the likely origin of ''pisoliths'', concentrically layered particles ranging from in diameter found in some limestones. Pisoliths superficially resemble ooids but have no nucleus of foreign matter, fit together tightly, and show other signs that they formed after the original deposition of the sediments. Silicification occurs early in diagenesis, at low pH and temperature, and contributes to fossil preservation. Silicification takes place through the reaction: :: Fossils are often preserved in exquisite detail as chert. Cementing takes place rapidly in carbonate sediments, typically within less than a million years of deposition. Some cementing occurs while the sediments are still under water, forming hardgrounds. Cementing accelerates after the retreat of the sea from the depositional environment, as rainwater infiltrates the sediment beds, often within just a few thousand years. As rainwater mixes with groundwater, aragonite and high-magnesium calcite are converted to low-calcium calcite. Cementing of thick carbonate deposits by rainwater may commence even before the retreat of the sea, as rainwater can infiltrate over into sediments beneath the continental shelf. As carbonate sediments are increasingly deeply buried under younger sediments, chemical and mechanical compaction of the sediments increases. Chemical compaction takes place by ''pressure solution'' of the sediments. This process dissolves minerals from points of contact between grains and redeposits it in pore space, reducing the porosity of the limestone from an initial high value of 40% to 80% to less than 10%. Pressure solution produces distinctive
stylolite Stylolites (Greek: ''stylos'', pillar; ''lithos'', stone) are serrated surfaces within a rock mass at which mineral material has been removed by pressure dissolution, in a deformation process that decreases the total volume of rock. Minerals whi ...
s, irregular surfaces within the limestone at which silica-rich sediments accumulate. These may reflect dissolution and loss of a considerable fraction of the limestone bed. At depths greater than , burial cementation completes the lithification process. Burial cementation does not produce stylolites. When overlying beds are eroded, bringing limestone closer to the surface, the final stage of diagenesis takes place. This produces ''secondary porosity'' as some of the cement is dissolved by rainwater infiltrating the beds. This may include the formation of vugs, which are crystal-lined cavities within the limestone. Diagenesis may include conversion of limestone to dolomite by magnesium-rich fluids. There is considerable evidence of replacement of limestone by dolomite, including sharp replacement boundaries that cut across bedding. The process of dolomitization remains an area of active research, but possible mechanisms include exposure to concentrated brines in hot environments (''evaporative reflux'') or exposure to diluted seawater in delta or estuary environments (''Dorag dolomitization''). However, Dorag dolomitization has fallen into disfavor as a mechanism for dolomitization, with one 2004 review paper describing it bluntly as "a myth". Ordinary seawater is capable of converting calcite to dolomite, if the seawater is regularly flushed through the rock, as by the ebb and flow of tides (tidal pumping). Once dolomitization begins, it proceeds rapidly, so that there is very little carbonate rock containing mixed calcite and dolomite. Carbonate rock tends to be either almost all calcite/aragonite or almost all dolomite.


Occurrence

About 20% to 25% of sedimentary rock is carbonate rock, and most of this is limestone. Limestone is found in sedimentary sequences as old as 2.7 billion years. However, the compositions of carbonate rocks show an uneven distribution in time in the geologic record. About 95% of modern carbonates are composed of high-magnesium calcite and aragonite. The aragonite needles in carbonate mud are converted to low-magnesium calcite within a few million years, as this is the most stable form of calcium carbonate. Ancient carbonate formations of the
Precambrian The Precambrian (or Pre-Cambrian, sometimes abbreviated pꞒ, or Cryptozoic) is the earliest part of Earth's history, set before the current Phanerozoic Eon. The Precambrian is so named because it preceded the Cambrian, the first period of the ...
and Paleozoic contain abundant dolomite, but limestone dominates the carbonate beds of the Mesozoic and
Cenozoic The Cenozoic ( ; ) is Earth's current geological era, representing the last 66million years of Earth's history. It is characterised by the dominance of mammals, birds and flowering plants, a cooling and drying climate, and the current configura ...
. Modern dolomite is quite rare. There is evidence that, while the modern ocean favors precipitation of aragonite, the oceans of the Paleozoic and middle to late Cenozoic favored precipitation of calcite. This may indicate a lower Mg/Ca ratio in the ocean water of those times. This magnesium depletion may be a consequence of more rapid sea floor spreading, which removes magnesium from ocean water. The modern ocean and the ocean of the Mesozoic have been described as "aragonite seas". Most limestone was formed in shallow marine environments, such as
continental shelves A continental shelf is a portion of a continent that is submerged under an area of relatively shallow water, known as a shelf sea. Much of these shelves were exposed by drops in sea level during glacial periods. The shelf surrounding an island ...
or platforms. Such environments form only about 5% of the ocean basins, but limestone is rarely preserved in continental slope and deep sea environments. The best environments for deposition are warm waters, which have both a high organic productivity and increased saturation of calcium carbonate due to lower concentrations of dissolved carbon dioxide. Modern limestone deposits are almost always in areas with very little silica-rich sedimentation, reflected in the relative purity of most limestones. Reef organisms are destroyed by muddy, brackish river water, and carbonate grains are ground down by much harder silicate grains. Unlike clastic sedimentary rock, limestone is produced almost entirely from sediments originating at or near the place of deposition. Limestone formations tend to show abrupt changes in thickness. Large moundlike features in a limestone formation are interpreted as ancient reefs, which when they appear in the geologic record are called ''bioherms''. Many are rich in fossils, but most lack any connected organic framework like that seen in modern reefs. The fossil remains are present as separate fragments embedded in ample mud matrix. Much of the sedimentation shows indications of occurring in the intertidal or supratidal zones, suggesting sediments rapidly fill available
accommodation space Accommodation is a fundamental concept in sequence stratigraphy, a subdiscipline of geology. It is defined as the space that is available for the Deposition (geology), deposition of sediments. Accommodation space can be pictured as the volume b ...
in the shelf or platform. Deposition is also favored on the seaward margin of shelves and platforms, where there is upwelling deep ocean water rich in nutrients that increase organic productivity. Reefs are common here, but when lacking, ooid shoals are found instead. Finer sediments are deposited close to shore. The lack of deep sea limestones is due in part to rapid
subduction Subduction is a geological process in which the oceanic lithosphere is recycled into the Earth's mantle at convergent boundaries. Where the oceanic lithosphere of a tectonic plate converges with the less dense lithosphere of a second plate, the ...
of oceanic crust, but is more a result of dissolution of calcium carbonate at depth. The solubility of calcium carbonate increases with pressure and even more with higher concentrations of carbon dioxide, which is produced by decaying organic matter settling into the deep ocean that is not removed by photosynthesis in the dark depths. As a result, there is a fairly sharp transition from water saturated with calcium carbonate to water unsaturated with calcium carbonate, the '' lysocline'', which occurs at the ''calcite compensation depth'' of . Below this depth, foraminifera tests and other skeletal particles rapidly dissolve, and the sediments of the ocean floor abruptly transition from carbonate ooze rich in foraminifera and coccolith remains ('' Globigerina'' ooze) to silicic mud lacking carbonates. In rare cases, turbidites or other silica-rich sediments bury and preserve benthic (deep ocean) carbonate deposits. Ancient benthic limestones are microcrystalline and are identified by their tectonic setting. Fossils typically are foraminifera and coccoliths. No pre-Jurassic benthic limestones are known, probably because carbonate-shelled plankton had not yet evolved. Limestones also form in freshwater environments. These limestones are not unlike marine limestone, but have a lower diversity of organisms and a greater fraction of silica and clay minerals characteristic of
marl Marl is an earthy material rich in carbonate minerals, clays, and silt. When hardened into rock, this becomes marlstone. It is formed in marine or freshwater environments, often through the activities of algae. Marl makes up the lower part o ...
s. The Green River Formation is an example of a prominent freshwater sedimentary formation containing numerous limestone beds. Freshwater limestone is typically micritic. Fossils of charophyte (stonewort), a form of freshwater green algae, are characteristic of these environments, where the charophytes produce and trap carbonates. Limestones may also form in evaporite depositional environments. Calcite is one of the first minerals to precipitate in marine evaporites.


Limestone and living organisms

Most limestone is formed by the activities of living organisms near reefs, but the organisms responsible for reef formation have changed over geologic time. For example, '' stromatolites'' are mound-shaped structures in ancient limestones, interpreted as colonies of
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...
that accumulated carbonate sediments, but stromatolites are rare in younger limestones. Organisms precipitate limestone both directly as part of their skeletons, and indirectly by removing carbon dioxide from the water by photosynthesis and thereby decreasing the solubility of calcium carbonate. Limestone shows the same range of sedimentary structures found in other sedimentary rocks. However, finer structures, such as lamination, are often destroyed by the burrowing activities of organisms (
bioturbation Bioturbation is defined as the reworking of soils and sediments by animals or plants. It includes burrowing, ingestion, and defecation of sediment grains. Bioturbating activities have a profound effect on the environment and are thought to be a pr ...
). Fine lamination is characteristic of limestone formed in playa lakes, which lack the burrowing organisms. Limestones also show distinctive features such as ''geopetal structures'', which form when curved shells settle to the bottom with the concave face downwards. This traps a void space that can later be filled by sparite. Geologists use geopetal structures to determine which direction was up at the time of deposition, which is not always obvious with highly deformed limestone formations. The cyanobacterium ''Hyella balani'' can bore through limestone; as can the green alga ''Eugamantia sacculata'' and the fungus ''Ostracolaba implexa''.


Micritic mud mounds

Micricitic mud mounds are subcircular domes of micritic calcite that lacks internal structure. Modern examples are up to several hundred meters thick and a kilometer across, and have steep slopes (with slope angles of around 50 degrees). They may be composed of peloids swept together by currents and stabilized by '' Thallasia'' grass or mangroves. Bryozoa may also contribute to mound formation by helping to trap sediments. Mud mounds are found throughout the geologic record, and prior to the early Ordovician, they were the dominant reef type in both deep and shallow water. These mud mounds likely are microbial in origin. Following the appearance of frame-building reef organisms, mud mounds were restricted mainly to deeper water.


Organic reefs

Organic reefs form at low latitudes in shallow water, not more than a few meters deep. They are complex, diverse structures found throughout the fossil record. The frame-building organisms responsible for organic reef formation are characteristic of different geologic time periods: Archaeocyathids appeared in the early Cambrian; these gave way to sponges by the late Cambrian; later successions included stromatoporoids, corals, algae, bryozoa, and rudists (a form of bivalve mollusc). The extent of organic reefs has varied over geologic time, and they were likely most extensive in the middle Devonian, when they covered an area estimated at . This is roughly ten times the extent of modern reefs. The Devonian reefs were constructed largely by stromatoporoids and
tabulate corals Tabulata, commonly known as tabulate corals, are an order of extinct forms of coral. They are almost always colonial, forming colonies of individual hexagonal cells known as corallites defined by a skeleton of calcite, similar in appearance to ...
, which were devastated by the late Devonian extinction. Organic reefs typically have a complex internal structure. Whole body fossils are usually abundant, but ooids and interclasts are rare within the reef. The core of a reef is typically massive and unbedded, and is surrounded by a talus that is greater in volume than the core. The talus contains abundant intraclasts and is usually either ''floatstone'', with 10% or more of grains over 2mm in size embedded in abundant matrix, or ''rudstone'', which is mostly large grains with sparse matrix. The talus grades to planktonic fine-grained carbonate mud, then noncarbonate mud away from the reef.


Limestone landscape

Limestone is partially soluble, especially in acid, and therefore forms many erosional landforms. These include limestone pavements, pot holes, cenotes, caves and gorges. Such erosion landscapes are known as
karsts Karst is a topography formed from the dissolution of soluble rocks such as limestone, dolomite, and gypsum. It is characterized by underground drainage systems with sinkholes and caves. It has also been documented for more weathering-resistant ro ...
. Limestone is less resistant to erosion than most igneous rocks, but more resistant than most other sedimentary rocks. It is therefore usually associated with hills and downland, and occurs in regions with other sedimentary rocks, typically clays. Karst regions overlying limestone bedrock tend to have fewer visible above-ground sources (ponds and streams), as surface water easily drains downward through joints in the limestone. While draining, water and organic acid from the soil slowly (over thousands or millions of years) enlarges these cracks, dissolving the calcium carbonate and carrying it away in solution. Most cave systems are through limestone bedrock. Cooling groundwater or mixing of different groundwaters will also create conditions suitable for cave formation. Coastal limestones are often eroded by organisms which bore into the rock by various means. This process is known as
bioerosion Bioerosion describes the breakdown of hard ocean substrates – and less often terrestrial substrates – by living organisms. Marine bioerosion can be caused by mollusks, polychaete worms, phoronids, sponges, crustaceans, echinoids, and ...
. It is most common in the tropics, and it is known throughout the fossil record. Bands of limestone emerge from the Earth's surface in often spectacular rocky outcrops and islands. Examples include the
Rock of Gibraltar The Rock of Gibraltar (from the Arabic name Jabel-al-Tariq) is a monolithic limestone promontory located in the British territory of Gibraltar, near the southwestern tip of Europe on the Iberian Peninsula, and near the entrance to the Mediterr ...
, the Burren in County Clare, Ireland; Malham Cove in North Yorkshire and the Isle of Wight, England; the Great Orme in Wales; on Fårö near the Swedish island of
Gotland Gotland (, ; ''Gutland'' in Gutnish), also historically spelled Gottland or Gothland (), is Sweden's largest island. It is also a province, county, municipality, and diocese. The province includes the islands of Fårö and Gotska Sandön to the ...
, the
Niagara Escarpment The Niagara Escarpment is a long escarpment, or cuesta, in Canada and the United States that runs predominantly east–west from New York through Ontario, Michigan, Wisconsin, and into Illinois. The escarpment is most famous as the cliff over ...
in Canada/United States; Notch Peak in Utah; the Ha Long Bay National Park in Vietnam; and the hills around the
Lijiang River The Li River or Li Jiang () is the name for the upper reaches of the Gui River in northwestern Guangxi, China. It is part of the Xijiang River system in the Pearl River Basin. The river flows from Xing'an County to Pingle County, where the kars ...
and Guilin city in China. The
Florida Keys The Florida Keys are a coral cay archipelago located off the southern coast of Florida, forming the southernmost part of the continental United States. They begin at the southeastern coast of the Florida peninsula, about south of Miami, and e ...
, islands off the south coast of Florida, are composed mainly of oolitic limestone (the Lower Keys) and the carbonate skeletons of coral reefs (the Upper Keys), which thrived in the area during interglacial periods when sea level was higher than at present. Unique habitats are found on alvars, extremely level expanses of limestone with thin soil mantles. The largest such expanse in Europe is the Stora Alvaret on the island of Öland, Sweden. Another area with large quantities of limestone is the island of Gotland, Sweden. Huge quarries in northwestern Europe, such as those of Mount Saint Peter (Belgium/Netherlands), extend for more than a hundred kilometers.


Uses

Limestone is a raw material that is used globally in a variety of different ways including construction, agriculture and as industrial materials. Limestone is very common in architecture, especially in Europe and North America. Many landmarks across the world, including the Great Pyramid and its associated complex in Giza, Egypt, were made of limestone. So many buildings in
Kingston Kingston may refer to: Places * List of places called Kingston, including the five most populated: ** Kingston, Jamaica ** Kingston upon Hull, England ** City of Kingston, Victoria, Australia ** Kingston, Ontario, Canada ** Kingston upon Thames, ...
, Ontario, Canada were, and continue to be, constructed from it that it is nicknamed the 'Limestone City'. Limestone, metamorphosed by heat and pressure produces marble, which has been used for many statues, buildings and stone tabletops. On the island of Malta, a variety of limestone called
Globigerina limestone The Geology of Malta consists of a sequence of sedimentary rocks of late Oligocene to late Miocene age cut through by a set of extensional faults of Pliocene age. Tectonics The Maltese archipelago is situated on the mainly shallow water contin ...
was, for a long time, the only building material available, and is still very frequently used on all types of buildings and sculptures. Limestone can be processed into many various forms such as brick, cement, powdered/crushed, or as a filler. Limestone is readily available and relatively easy to cut into blocks or more elaborate carving. Ancient American sculptors valued limestone because it was easy to work and good for fine detail. Going back to the Late Preclassic period (by 200–100 BCE), the Maya civilization (Ancient Mexico) created refined sculpture using limestone because of these excellent carving properties. The Maya would decorate the ceilings of their sacred buildings (known as lintels) and cover the walls with carved limestone panels. Carved on these sculptures were political and social stories, and this helped communicate messages of the king to his people. Limestone is long-lasting and stands up well to exposure, which explains why many limestone ruins survive. However, it is very heavy ( density 2.6), making it impractical for tall buildings, and relatively expensive as a building material. Limestone was most popular in the late 19th and early 20th centuries. Railway stations, banks and other structures from that era were made of limestone in some areas. It is used as a facade on some skyscrapers, but only in thin plates for covering, rather than solid blocks. In the United States, Indiana, most notably the Bloomington area, has long been a source of high-quality quarried limestone, called Indiana limestone. Many famous buildings in London are built from Portland limestone. Houses built in
Odessa Odesa (also spelled Odessa) is the third most populous city and municipality in Ukraine and a major seaport and transport hub located in the south-west of the country, on the northwestern shore of the Black Sea. The city is also the administrativ ...
in Ukraine in the 19th century were mostly constructed from limestone and the extensive remains of the mines now form the Odessa Catacombs. Limestone was also a very popular building block in the Middle Ages in the areas where it occurred, since it is hard, durable, and commonly occurs in easily accessible surface exposures. Many medieval churches and castles in Europe are made of limestone.
Beer stone Beer Quarry Caves is a man-made limestone underground complex located about a mile west of the village of Beer, Devon, and the main source in England for beer stone. The tunnels resulted from 2,000 years of quarrying beer stone, which was part ...
was a popular kind of limestone for medieval buildings in southern England. File:Limestone Mines at Cedar Creek.jpg, Limestone quarry at Cedar Creek, Virginia, USA File:Pargas Quarry-24.jpg, Nordkalk's limestone quarry in Pargas, Finland File:Gozo, limestone quarry - cutting the stone.JPG, Cutting limestone blocks at a quarry in
Gozo Gozo (, ), Maltese: ''Għawdex'' () and in antiquity known as Gaulos ( xpu, 𐤂𐤅𐤋, ; grc, Γαῦλος, Gaúlos), is an island in the Maltese archipelago in the Mediterranean Sea. The island is part of the Republic of Malta. After t ...
, Malta File:Kalkstein (nahe).JPG, Limestone as building material File:Bermuda (UK) Number 178 limestone used as building material for walls.jpg, Limestone is used worldwide as building material.
Limestone is the raw material for production of lime, primarily known for treating soils, purifying water and smelting copper. Lime is an important ingredient used in chemical industries.Bliss, J. D., Hayes, T. S., & Orris, G. J. (2012, August). Limestone—A Crucial and Versatile Industrial Mineral Commodity. Retrieved February 23, 2021, from https://pubs.usgs.gov/fs/2008/3089/fs2008-3089.pdf Limestone and (to a lesser extent) marble are reactive to acid solutions, making
acid rain Acid rain is rain or any other form of precipitation that is unusually acidic, meaning that it has elevated levels of hydrogen ions (low pH). Most water, including drinking water, has a neutral pH that exists between 6.5 and 8.5, but acid ...
a significant problem to the preservation of artifacts made from this stone. Many limestone statues and building surfaces have suffered severe damage due to acid rain. Likewise limestone gravel has been used to protect lakes vulnerable to acid rain, acting as a pH buffering agent. Acid-based cleaning chemicals can also etch limestone, which should only be cleaned with a neutral or mild
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
-based cleaner. Other uses include: * It is the raw material for the manufacture of
quicklime Calcium oxide (CaO), commonly known as quicklime or burnt lime, is a widely used chemical compound. It is a white, caustic, alkaline, crystalline solid at room temperature. The broadly used term "''lime''" connotes calcium-containing inorganic ma ...
(calcium oxide),
slaked lime Calcium hydroxide (traditionally called slaked lime) is an inorganic compound with the chemical formula Ca( OH)2. It is a colorless crystal or white powder and is produced when quicklime (calcium oxide) is mixed or slaked with water. It has ma ...
(calcium hydroxide), cement and mortar. * Pulverized limestone is used as a soil conditioner to neutralize acidic soils ( agricultural lime). * Is crushed for use as
aggregate Aggregate or aggregates may refer to: Computing and mathematics * collection of objects that are bound together by a root entity, otherwise known as an aggregate root. The aggregate root guarantees the consistency of changes being made within the ...
—the solid base for many roads as well as in
asphalt concrete Asphalt concrete (commonly called asphalt, blacktop, or pavement in North America, and tarmac, bitumen macadam, or rolled asphalt in the United Kingdom and the Republic of Ireland) is a composite material commonly used to surface roads, parkin ...
. * As a
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
in
flue-gas desulfurization Flue-gas desulfurization (FGD) is a set of technologies used to remove sulfur dioxide () from exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulfur oxide emitting processes such as waste incineration. Methods ...
, where it reacts with
sulfur dioxide Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic activ ...
for air pollution control. * In glass making, particularly in the manufacture of soda–lime glass. * As an additive toothpaste, paper, plastics, paint, tiles, and other materials as both white pigment and a cheap filler. * As rock dust, to suppress methane explosions in underground coal mines. * Purified, it is added to bread and cereals as a source of calcium. * As a calcium supplement in livestock feed, such as for poultry (when ground up). * For remineralizing and increasing the alkalinity of purified water to prevent pipe corrosion and to restore essential nutrient levels. * In
blast furnace A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, generally pig iron, but also others such as lead or copper. ''Blast'' refers to the combustion air being "forced" or supplied above atmospheric ...
s, limestone binds with silica and other impurities to remove them from the iron. *It can aid in the removal of toxic components created from coal burning plants and layers of polluted molten metals.Bliss, J. D., Hayes, T. S., & Orris, G. J. (2012, August). Limestone—A Crucial and Versatile Industrial Mineral Commodity. Retrieved February 23, 2021, from https://pubs.usgs.gov/fs/2008/3089/fs2008-3089.pdf Many limestone formations are porous and permeable, which makes them important
petroleum reservoir A petroleum reservoir or oil and gas reservoir is a subsurface accumulation of hydrocarbons contained in porous or fractured rock formations. Such reservoirs form when kerogen (ancient plant matter) is created in surrounding rock by the presence ...
s. About 20% of North American hydrocarbon reserves are found in carbonate rock. Carbonate reservoirs are very common in the petroleum-rich Middle East, and carbonate reservoirs hold about a third of all petroleum reserves worldwide. Limestone formations are also common sources of metal ores, because their porosity and permeability, together with their chemical activity, promotes ore deposition in the limestone. The lead- zinc deposits of Missouri and the
Northwest Territories The Northwest Territories (abbreviated ''NT'' or ''NWT''; french: Territoires du Nord-Ouest, formerly ''North-Western Territory'' and ''North-West Territories'' and namely shortened as ''Northwest Territory'') is a federal territory of Canada. ...
are examples of ore deposits hosted in limestone.


Scarcity

Limestone is a major industrial raw material that is in constant demand. This raw material has been essential in the iron and
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
industry since the nineteenth century. Companies have never had a shortage of limestone; however, it has become a concern as the demand continues to increase and it remains in high demand today. The major potential threats to supply in the nineteenth century were regional availability and accessibility. The two main accessibility issues were transportation and property rights. Other problems were high capital costs on plants and facilities due to environmental regulations and the requirement of zoning and mining permits. These two dominant factors led to the adaptation and selection of other materials that were created and formed to design alternatives for limestone that suited economic demands. Limestone was classified as a critical raw material, and with the potential risk of shortages, it drove industries to find new alternative materials and technological systems. This allowed limestone to no longer be classified as critical as replacement substances increased in production; minette ore is a common substitute, for example.


Occupational safety and health

Powdered limestone as a food additive is generally recognized as safe and limestone is not regarded as a hazardous material. However, limestone dust can be a mild respiratory and skin irritant, and dust that gets into the eyes can cause corneal abrasions. Because limestone contains small amounts of silica, inhalation of limestone dust could potentially lead to
silicosis Silicosis is a form of occupational lung disease caused by inhalation of crystalline silica dust. It is marked by inflammation and scarring in the form of nodular lesions in the upper lobes of the lungs. It is a type of pneumoconiosis. Silicos ...
or cancer.


United States

The Occupational Safety and Health Administration (OSHA) has set the legal limit ( permissible exposure limit) for limestone exposure in the workplace as 15 mg/m3
total exposure Total may refer to: Mathematics * Total, the summation of a set of numbers * Total order, a partial order without incomparable pairs * Total relation, which may also mean ** connected relation (a binary relation in which any two elements are compa ...
and 5 mg/m3
respiratory exposure The respiratory system (also respiratory apparatus, ventilatory system) is a biological system consisting of specific organs and structures used for gas exchange in animals and plants. The anatomy and physiology that make this happen varies grea ...
over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 10 mg/m3 total exposure and 5 mg/m3 respiratory exposure over an 8-hour workday.


Graffiti

Removing graffiti from weathered limestone is difficult because it is a porous and permeable material. The surface is fragile so usual abrasion methods run the risk of severe surface loss. Because it is an acid-sensitive stone some cleaning agents cannot be used due to adverse effects.


Gallery

File:OrdOutcropTN.JPG, A
stratigraphic section A stratigraphic section is a sequence of layers of rocks in the order they were deposited. It is based on the principle of original horizontality, which states that layers of sediment are originally deposited horizontally under the action of gr ...
of Ordovician limestone exposed in central Tennessee, U.S. The less-resistant and thinner beds are composed of
shale 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, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especial ...
. The vertical lines are drill holes for explosives used during road construction. File:Limestone etched section KopeFm new.jpg, Photo and etched section of a sample of fossiliferous limestone from the
Kope Formation The Kope Formation is one of the three component bedrock formations of the Maquoketa Group that primarily consists of shale (75%) with some limestone (25%) interbedded. In general, it has a bluish-gray color that weathers light gray to yellowish- ...
(Upper Ordovician) near Cincinnati, Ohio, U.S. File:BrassfieldEncrinite042112.jpg, Biosparite limestone of the Brassfield Formation (Lower
Silurian The Silurian ( ) is a geologic period and system spanning 24.6 million years from the end of the Ordovician Period, at million years ago ( Mya), to the beginning of the Devonian Period, Mya. The Silurian is the shortest period of the Paleozo ...
) near
Fairborn Fairborn is a city in Greene County, Ohio, United States. The population was 34,620 at the 2020 census. Fairborn is a suburb of Dayton, and part of the Dayton Metropolitan Statistical Area. It is the only city in the world named Fairborn, a port ...
, Ohio, U.S., showing grains mainly composed of crinoid fragments File:大连国家地质公园12-龟背石.jpg, A concretionary nodular (septarian) limestone at
Jinshitan Coastal National Geopark Golden Pebble Beach is a station on Line 3 of the Dalian Metro in Liaoning Province, China. It is located in the Jinzhou District of Dalian City Dalian () is a major sub-provincial port city in Liaoning province, People's Republic of Chin ...
,
Dalian Dalian () is a major sub-provincial port city in Liaoning province, People's Republic of China, and is Liaoning's second largest city (after the provincial capital Shenyang) and the third-most populous city of Northeast China. Located on the ...
, China File:太湖賞石-Rock in the form of a fantastic mountain MET DT208239.jpg, Limestone from Lake Tai, used in gongshi, a Chinese stone art File:Folded Rock Provo Canyon.JPG, Folded limestone layers on Cascade Mountain in Provo Canyon, Utah File:Calcined fossils.jpg, Fossils in limestone from the northern Black Sea region File:Geography of Ohio - DPLA - aaba7b3295ff6973b6fd1e23e33cde14 (page 96) (cropped).jpg, Limestone distribution in Ohio, from "Geography of Ohio," 1923 File:Chalk ("Upper Chalk" Formation, Upper Cretaceous; White Cliffs of Dover, England, southern Britain).jpg, Chalk is a variety of limestone. It is a softer, and more powdery material.


See also

* * * * * * *


References


Further reading

* {{Authority control Industrial minerals