Magnesite

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Magnesite
Magnesite-121892.jpg
Magnesite crystals from Brazil (11.4 × 9.2 × 3.6 cm)
General
Category Carbonate mineral
Formula
(repeating unit)		MgCO3
IMA symbol Mgs [1]
Strunz classification 5.AB.05
Crystal system Trigonal
Crystal class Hexagonal scalenohedral (3m)
H-M symbol: (3 2/m)
Space group R3c
Identification
ColorColorless, white, pale yellow, pale brown, faintly pink, lilac-rose
Crystal habit Usually massive, rarely as rhombohedrons or hexagonal prisms
Cleavage [1011] perfect
Fracture Conchoidal
Tenacity Brittle
Mohs scale hardness3.5–4.5
Luster Vitreous
Streak white
Diaphaneity Transparent to translucent
Specific gravity 3.0–3.2
Optical propertiesUniaxial (−)
Refractive index nω=1.508 – 1.510 nε=1.700
Birefringence 0.191
Fusibility infusible
Solubility Effervesces in hot HCl
Other characteristicsMay exhibit pale green to pale blue fluorescence and phosphorescence under UV; triboluminescent
References [2] [3] [4] [5]

Magnesite is a mineral with the chemical formula Mg C O
3 (magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts.

Contents

Occurrence

Magnesite occurs as veins in and an alteration product of ultramafic rocks, serpentinite and other magnesium rich rock types in both contact and regional metamorphic terrains. These magnesites are often cryptocrystalline and contain silica in the form of opal or chert.

Magnesite is also present within the regolith above ultramafic rocks as a secondary carbonate within soil and subsoil, where it is deposited as a consequence of dissolution of magnesium-bearing minerals by carbon dioxide in groundwaters.

Formation

Magnesite can be formed via talc carbonate metasomatism of peridotite and other ultramafic rocks. Magnesite is formed via carbonation of olivine in the presence of water and carbon dioxide at elevated temperatures and high pressures typical of the greenschist facies.

Magnesite can also be formed via the carbonation of magnesium serpentine (lizardite) via the following reaction:

2 Mg3Si2O5(OH)4 + 3 CO2 → Mg3Si4O10(OH)2 + 3 MgCO3 + 3 H2O

However, when performing this reaction in the laboratory, the trihydrated form of magnesium carbonate (nesquehonite) will form at room temperature. [6] This very observation led to the postulation of a "dehydration barrier" being involved in the low-temperature formation of anhydrous magnesium carbonate. [7] Laboratory experiments with formamide, a liquid resembling water, have shown how no such dehydration barrier can be involved. The fundamental difficulty to nucleate anhydrous magnesium carbonate remains when using this non-aqueous solution. Not cation dehydration, but rather the spatial configuration of carbonate anions creates the barrier in the low-temperature nucleation of magnesite. [8]

Magnesite has been found in modern sediments, caves and soils. Its low-temperature (around 40 °C [104 °F]) formation is known to require alternations between precipitation and dissolution intervals. [9] [10] [11] The low-temperature formation of magnesite might well be of significance toward large-scale carbon sequestration. [12] A major step forward toward the industrial production of magnesite at atmospheric pressure and a temperature of 316 K was described by Vandeginste. [13] [14] In those experiments small additions of hydrochloric acid alternated periodically with additions of sodium carbonate solution. New was also the very short duration of only a few hours for the alternating dissolution and precipitation cycles.

Magnesite was detected in meteorite ALH84001 and on planet Mars itself. Magnesite was identified on Mars using infrared spectroscopy from satellite orbit. [15] Near Jezero Crater, Mg-carbonates have been detected and reported to have formed in lacustrine environment prevailing there. [16] Controversy still exists over the temperature of formation of these carbonates. Low-temperature formation has been suggested for the magnesite from the Mars-derived ALH84001 meteorite. [17] [18]

Magnesium-rich olivine (forsterite) favors production of magnesite from peridotite. Iron-rich olivine (fayalite) favors production of magnetite-magnesite-silica compositions.

Magnesite can also be formed by way of metasomatism in skarn deposits, in dolomitic limestones, associated with wollastonite, periclase, and talc.

Resistant to high temperature and able to withstand high pressure, magnesite has been proposed to be one of the major carbonate bearing phase in Earth's mantle [19] and possible carriers for deep carbon reservoirs. [20] For similar reason, it is found in metamorphosed peridotite rocks in Central Alps, Switzerland [21] and high pressure eclogitic rocks from Tianshan, China. [22]

Magnesite can also precipitate in lakes in presence of bacteria either as hydrous Mg-carbonates or magnesite. [23] [24]

Uses

Refractory material

Polished and Dyed magnesite beads Dyed magnesite beads.jpg
Polished and Dyed magnesite beads
Magnesite of Salem Magnesite of Salem.jpg
Magnesite of Salem

Similar to the production of lime, magnesite can be burned in the presence of charcoal to produce MgO, which, in the form of a mineral, is known as periclase. Large quantities of magnesite are burnt to make magnesium oxide: an important refractory (heat-resistant) material used as a lining in blast furnaces, kilns and incinerators.

Calcination temperatures determine the reactivity of resulting oxide products and the classifications of light burnt and dead burnt refer to the surface area and resulting reactivity of the product (this is typically determined by an industry metric of the iodine number).

'Light burnt' product generally refers to calcination commencing at 450 °C and proceeding to an upper limit of 900 °C – which results in good surface area and reactivity.

Above 900 °C, the material loses its reactive crystalline structure and reverts to the chemically inert 'dead-burnt' product- which is preferred for use in refractory materials such as furnace linings.

In fire assay, magnesite cupels can be used for cupellation, as the magnesite cupel will resist the high temperatures involved.

Other uses

Magnesite can also be used as a binder in flooring material (magnesite screed). [25] Furthermore, it is being used as a catalyst and filler in the production of synthetic rubber and in the preparation of magnesium chemicals and fertilizers.

Research is proceeding to evaluate the practicality of sequestering the greenhouse gas carbon dioxide in magnesite on a large scale. [26] This has focused on peridotites from ophiolites (obducted mantle rocks on crust) where magnesite can be created by letting carbon dioxide react with these rocks. Some progress has been made in ophiolites from Oman. [27] But the major problem is that these artificial processes require sufficient porosity-permeability so that the fluids can flow but this is hardly the case in peridotites.

Artworks

Magnesite can be cut, drilled, and polished to form beads that are used in jewelry-making. Magnesite beads can be dyed into a broad spectrum of bold colors, including a light blue color that mimics the appearance of turquoise.

The Japanese-American artist Isamu Noguchi used magnesite as a sculptural material for some of his artworks. [28]

Isotopic structure

The recent advancement in the field of stable isotope geochemistry is the study of isotopic structure of minerals and molecules. This requires study of molecules with high resolutions looking at bonding scenario (how heavy isotopes are bonded to each other)- leading to knowledge of stability of molecule depending on its isotopic structure.

Isotopic structure of CO2 and MgCO3 illustrating singly and doubly substituted species of CO2. Isotopic structure of CO2 and MgCO3.pdf
Isotopic structure of CO2 and MgCO3 illustrating singly and doubly substituted species of CO2.

Isotopically substituted molecules have higher mass. As a consequence, molecular vibration reduces and the molecule develops a lower zero point energy (see Kinetic isotope effect).

The abundances of certain bonds in certain molecules are sensitive to temperature at which it formed (e.g., abundance of 13C16O18O in carbonates [29] as 13C-18O bond). This information has been exploited to form the foundation of clumped isotope geochemistry. Clumped isotope thermometers have been established for carbonate minerals like dolomite, [30] [31] calcite, [32] siderite [33] etc and non-carbonate compounds like methane [34] and oxygen. [35] Depending on the strength of cation-carbonate oxygen (ie, Mg-O, Ca-O) bonds- different carbonate minerals can form or preserve clumped isotopic signatures differently.

Measurements and reporting

Clumped isotopic analysis has certain aspects to it. These are:

Digestion, analysis and acid fractionation correction

Clumped isotopic analysis is usually done by gas source mass spectrometry where the CO2 liberated from magnesite by phosphoric acid digestion is fed into the isotope ratio mass spectrometer. In such scenario, one needs to ensure that liberation of CO2 from magnesite is complete. Digesting magnesite is hard since it takes a long time and different labs report different digestion times and temperatures (from 12 hours at 100 °C [36] to 1 hour at 90 °C [37] in phosphoric acid). Due to digestion at this high temperature, some of the 13C-18O bonds in the liberated CO2 are broken (leading to reduction in abundance of 'clumped' CO2) during phosphoric acid digestion of carbonates. To account for this additional (analytical artifact), a correction called the 'acid fractionation correction' is added to the magnesite clumped isotope value obtained at temperature of digestion.

Calibration curve expressing clumped isotope composition as a function of temperature. Clumped isotope-temperature relation.pdf
Calibration curve expressing clumped isotope composition as a function of temperature.

Since the CO2 gas is liberated from carbonate mineral during acid digestion, leaving one O behind- a fractionation occurs, and the isotopic composition of the analyzed CO2 gas needs to be corrected for this. For magnesite, the most reliable fractionation factor(α) equation is given as: [38]

103ln(α) = [(6.845 ± 0.475)∗105/T2] + (4.22 ± 0.08); T in K

Different researchers have also used other fractionation factors like dolomite fractionation factor. [39]

Standards

While measuring samples of unknown composition, it is required to measure some standard materials (see Reference materials for stable isotope analysis). With internal standards and reference materials, analytical session is routinely monitored. Standard materials are majorly calcite and marble.

Δ47 – Temperature calibration

To convert clumped isotope data into temperature, a calibration curve is required which expresses the functional form of temperature dependence of clumped isotope composition. No mineral specific calibration exists for magnesite. Based on some experimental data [37] where mineral precipitation temperature and clumped isotope derived temperature doesn't match, a need of mineral specific calibration emerges. The mismatch arises since bonding in magnesite is different from calcite/dolomite and/or acid digestion is conducted at higher temperature.

Magnesite-water and CO2-magnesite isotope fractionation factors

Using clumped isotope derived temperature, C and O isotopic composition of the parental fluid can be calculated using known magnesite-fluid isotope fractionation factors, since fractionation is temperature dependent. Reported magnesite-fluid O and C isotope fractionation factors in literature are not in agreement with each other. [37] The fractionation behaviors have not been substantiated by experimental observation.

Factors controlling isotopic structure in magnesite

Difference between cryptocrystalline and crystalline magnesite. Two types of magnesite.jpg
Difference between cryptocrystalline and crystalline magnesite.

Conversion from hydrous Mg-carbonates to magnesite

In low temperature, thus, hydrous Mg-carbonates (hydromagnesite, nesquehonite etc.) form. It is possible to convert these phases into magnesite by changing temperature by mineral dissolution-precipitation or dehydration. While so happens, an isotope effect associated can control the isotopic composition of precipitated magnesite.

Disequilibrium

Disequilibrium processes like degassing, rapid CO2 uptake etc. modify clumped isotopic composition of carbonate minerals specifically at low temperatures. They variably enrich or deplete the system in heavy isotopes of C and O. Since clumped isotope abundance depends on abundance of isotopes of C and O, they are also modified. Another very prominent effect here is that of pH of precipitating fluid. [40] As pH of precipitating fluid changes, DIC pool is affected and isotopic composition of precipitating carbonate changes.

Mineral structure and later thermal effects

Crystalline and cryptocrystalline magnesites have very different mineral structures. While crystalline magnesite has a well developed crystal structure, the cryptocrystalline magnesite is amorphous- mostly aggregate of fine grains. Since clumped isotopic composition depends on specific bonding, difference in crystal structure is very likely to affect the way clumped isotopic signatures are recorded in these different structures. This leads to the fact that their pristine signatures might be modified differently by later thermal events like diagenesis/burial heating etc.

Information on formation from isotopic structure

Clumped isotopes have been used in interpreting conditions of magnesite formation and the isotopic composition of the precipitating fluid. Within ultramafic complexes, magnesites are found within veins and stockworks in cryptocrystalline form as well as within carbonated peridotite units in crystalline form. These cryptocrystalline forms are mostly variably weathered and yield low temperature of formation. [41] On the other hand, coarse magnesites yield very high temperature indicating hydrothermal origin. It is speculated that coarse high temperature magnesites are formed from mantle derived fluids whereas cryptocrystalline ones are precipitated by circulating meteoric water, taking up carbon from dissolved inorganic carbon pool, soil carbon and affected by disequilibrium isotope effects.

Magnesites forming in lakes and playa settings are in general enriched in heavy isotopes of C and O because of evaporation and CO2 degassing. This reflects in the clumped isotope derived temperature being very low. These are affected by pH effect, biological activity as well as kinetic isotope effect associated with degassing. Magnesite forms as surface moulds in such conditions but more generally occur as hydrous Mg-carbonates since their precipitation is kinetically favored. Most of the times, they derive C from DIC or nearby ultramafic complexes (e.g., Altin Playa, British Columbia, Canada [42] ).

Magnesites in metamorphic rocks, on the other hand, indicate very high temperature of formation. Isotopic composition of parental fluid is also heavy- generally metamorphic fluids. This has been verified by fluid inclusion derived temperature as well as traditional O isotope thermometry involving co-precipitating quartz-magnesite.

Often, magnesite records lower clumped isotope temperature than associated dolomite, calcite. [43] The reason might be that calcite, dolomite form earlier at higher temperature (from mantle like fluids) which increases Mg/Ca ratio in the fluid sufficiently so as to precipitate magnesite. As this happens with increasing time, fluid cools, evolves by mixing with other fluids and when it forms magnesite, it decreases its temperature. So the presence of associated carbonates have a control on magnesite isotopic composition.

Origin of Martian carbonates can be deconvolved with the application of clumped isotope. Source of the CO2, climatic-hydrologic conditions on Mars could be assessed from these rocks. Recent study has shown (implementing clumped isotope thermometry) that carbonates in ALH84001 indicate formation at low temperature evaporative condition from subsurface water and derivation of CO2 from Martian atmosphere. [44]

Occupational safety and health

People can be exposed to magnesite in the workplace by inhaling it, skin contact, and eye contact.

United States

The Occupational Safety and Health Administration (OSHA) has set the legal limit (permissible exposure limit) for magnesite exposure in the workplace as 15 mg/m3 total exposure and 5 mg/m3 respiratory exposure 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. [45]

Related Research Articles

<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">Magnesium carbonate</span> Chemical compound

Magnesium carbonate, MgCO3, is an inorganic salt that is a colourless or white solid. Several hydrated and basic forms of magnesium carbonate also exist as minerals.

<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">Peridotite</span> Coarse-grained ultramafic igneous rock type

Peridotite ( PERR-ih-doh-tyte, pə-RID-ə-) is a dense, coarse-grained igneous rock consisting mostly of the silicate minerals olivine and pyroxene. Peridotite is ultramafic, as the rock contains less than 45% silica. It is high in magnesium (Mg2+), reflecting the high proportions of magnesium-rich olivine, with appreciable iron. Peridotite is derived from Earth's mantle, either as solid blocks and fragments, or as crystals accumulated from magmas that formed in the mantle. The compositions of peridotites from these layered igneous complexes vary widely, reflecting the relative proportions of pyroxenes, chromite, plagioclase, and amphibole.

<span class="mw-page-title-main">Dolomite (rock)</span> Sedimentary carbonate rock that contains a high percentage of the mineral dolomite

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). One of the first geologists 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.

<span class="mw-page-title-main">Serpentinization</span> Formation of serpentinite by hydration and metamorphic transformation of olivine

Serpentinization is a hydration and metamorphic transformation of ferromagnesian minerals, such as olivine and pyroxene, in mafic and ultramafic rock to produce serpentinite. Minerals formed by serpentinization include the serpentine group minerals, brucite, talc, Ni-Fe alloys, and magnetite. The mineral alteration is particularly important at the sea floor at tectonic plate boundaries.

A paleothermometer is a methodology that provides an estimate of the ambient temperature at the time of formation of a natural material. Most paleothermometers are based on empirically-calibrated proxy relationships, such as the tree ring or TEX86 methods. Isotope methods, such as the δ18O method or the clumped-isotope method, are able to provide, at least in theory, direct measurements of temperature.

<span class="mw-page-title-main">Compatibility (geochemistry)</span> Partitioning of elements in a mineral

Compatibility is a term used by geochemists to describe how elements partition themselves in the solid and melt within Earth's mantle. In geochemistry, compatibility is a measure of how readily a particular trace element substitutes for a major element within a mineral.

<span class="mw-page-title-main">Monohydrocalcite</span>

Monohydrocalcite is a mineral that is a hydrous form of calcium carbonate, CaCO3·H2O. It was formerly also known by the name hydrocalcite, which is now discredited by the IMA. It is a trigonal mineral which is white when pure. Monohydrocalcite is not a common rock-forming mineral, but is frequently associated with other calcium and magnesium carbonate minerals, such as calcite, aragonite, lansfordite, and nesquehonite.

<span class="mw-page-title-main">Amorphous calcium carbonate</span>

Amorphous calcium carbonate (ACC) is the amorphous and least stable polymorph of calcium carbonate. ACC is extremely unstable under normal conditions and is found naturally in taxa as wide-ranging as sea urchins, corals, mollusks, and foraminifera. It is usually found as a monohydrate, holding the chemical formula CaCO3·H2O; however, it can also exist in a dehydrated state, CaCO3. ACC has been known to science for over 100 years when a non-diffraction pattern of calcium carbonate was discovered by Sturcke Herman, exhibiting its poorly-ordered nature.

<span class="mw-page-title-main">Listwanite</span>

Listwanite (also sometimes spelled listvenite, listvanite, or listwaenite) is a rock type that forms when the groundmass of ultramafic rocks, most commonly mantle peridotites, is partially altered to carbonate minerals and cut by ubiquitous carbonate veins containing one or more of magnesite, calcite, dolomite, ankerite, and/or siderite. Original pyroxene and olivine in the peridotite are commonly altered to Mg- or Ca-carbonate and hydrous Mg-silicates, such as serpentine and talc. Complete carbonation of peridotite means that every single atom of magnesium and calcium as well as some of the iron atoms have combined with CO2 to form secondary carbonate minerals such a magnesite, calcite, and siderite, while the remaining silica atoms, formerly found in pyroxene and olivine (prior to alteration), are found in quartz, serpentine, and talc. Thus, in terms of bulk mineralogy, listwanites consist primarily of quartz (often of a rusty red colour), carbonate, serpentine, talc, ± mariposite/fuchsite (i.e., Cr-muscovite) ± gold.

Clumped isotopes are heavy isotopes that are bonded to other heavy isotopes. The relative abundance of clumped isotopes (and multiply-substituted isotopologues) in molecules such as methane, nitrous oxide, and carbonate is an area of active investigation. The carbonate clumped-isotope thermometer, or "13C–18O order/disorder carbonate thermometer", is a new approach for paleoclimate reconstruction, based on the temperature dependence of the clumping of 13C and 18O into bonds within the carbonate mineral lattice. This approach has the advantage that the 18O ratio in water is not necessary (different from the δ18O approach), but for precise paleotemperature estimation, it also needs very large and uncontaminated samples, long analytical runs, and extensive replication. Commonly used sample sources for paleoclimatological work include corals, otoliths, gastropods, tufa, bivalves, and foraminifera. Results are usually expressed as Δ47 (said as "cap 47"), which is the deviation of the ratio of isotopologues of CO2 with a molecular weight of 47 to those with a weight of 44 from the ratio expected if they were randomly distributed.

Carbonate-associated sulfates (CAS) are sulfate species found in association with carbonate minerals, either as inclusions, adsorbed phases, or in distorted sites within the carbonate mineral lattice. It is derived primarily from dissolved sulfate in the solution from which the carbonate precipitates. In the ocean, the source of this sulfate is a combination of riverine and atmospheric inputs, as well as the products of marine hydrothermal reactions and biomass remineralisation. CAS is a common component of most carbonate rocks, having concentrations in the parts per thousand within biogenic carbonates and parts per million within abiogenic carbonates. Through its abundance and sulfur isotope composition, it provides a valuable record of the global sulfur cycle across time and space.

Methane clumped isotopes are methane molecules that contain two or more rare isotopes. Methane (CH4) contains two elements, carbon and hydrogen, each of which has two stable isotopes. For carbon, 98.9% are in the form of carbon-12 (12C) and 1.1% are carbon-13 (13C); while for hydrogen, 99.99% are in the form of protium (1H) and 0.01% are deuterium (2H or D). Carbon-13 (13C) and deuterium (2H or D) are rare isotopes in methane molecules. The abundance of the clumped isotopes provides information independent from the traditional carbon or hydrogen isotope composition of methane molecules.

CM chondrites are a group of chondritic meteorites which resemble their type specimen, the Mighei meteorite. The CM is the most commonly recovered group of the 'carbonaceous chondrite' class of meteorites, though all are rarer in collections than ordinary chondrites.

Sulfur isotope biogeochemistry is the study of the distribution of sulfur isotopes in biological and geological materials. In addition to its common isotope, 32S, sulfur has three rare stable isotopes: 34S, 36S, and 33S. The distribution of these isotopes in the environment is controlled by many biochemical and physical processes, including biological metabolisms, mineral formation processes, and atmospheric chemistry. Measuring the abundance of sulfur stable isotopes in natural materials, like bacterial cultures, minerals, or seawater, can reveal information about these processes both in the modern environment and over Earth history.

<span class="mw-page-title-main">Lithium cycle</span>

The lithium cycle (Li) is the biogeochemical cycle of lithium through the lithosphere and hydrosphere.

In stable isotope geochemistry, the Urey–Bigeleisen–Mayer equation, also known as the Bigeleisen–Mayer equation or the Urey model, is a model describing the approximate equilibrium isotope fractionation in an isotope exchange reaction. While the equation itself can be written in numerous forms, it is generally presented as a ratio of partition functions of the isotopic molecules involved in a given reaction. The Urey–Bigeleisen–Mayer equation is widely applied in the fields of quantum chemistry and geochemistry and is often modified or paired with other quantum chemical modelling methods to improve accuracy and precision and reduce the computational cost of calculations.

<span class="mw-page-title-main">Diamond inclusions</span>

Diamond inclusions are the non-diamond materials that get encapsulated inside diamond during its formation process in the mantle. The trapped materials can be other minerals or fluids like water. Since diamonds have high strength and low reactivity with either the inclusion or the volcanic host rocks which carry the diamond to the Earth's surface, the diamond serves as a container that preserves the included material intact under the changing conditions from the mantle to the surface. Although diamonds can only place a lower bound on the pressure of their formation, many inclusions provide additional constraints on the pressure, temperature and even age of formation.

<span class="mw-page-title-main">Silicon isotope biogeochemistry</span> The study of environmental processes using the relative abundance of Si isotopes

Silicon isotope biogeochemistry is the study of environmental processes using the relative abundance of Si isotopes. As the relative abundance of Si stable isotopes varies among different natural materials, the differences in abundance can be used to trace the source of Si, and to study biological, geological, and chemical processes. The study of stable isotope biogeochemistry of Si aims to quantify the different Si fluxes in the global biogeochemical silicon cycle, to understand the role of biogenic silica within the global Si cycle, and to investigate the applications and limitations of the sedimentary Si record as an environmental and palaeoceanographic proxy.

References

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