Clinopyroxene Thermobarometry
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Clinopyroxene thermobarometry is a
scientific method The scientific method is an Empirical evidence, empirical method for acquiring knowledge that has been referred to while doing science since at least the 17th century. Historically, it was developed through the centuries from the ancient and ...
that uses the
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid substance with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2011): Mi ...
clinopyroxene The pyroxenes (commonly abbreviated Px) are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents ions of calcium (Ca), sodium (Na), iron (Fe ...
to determine the
temperature Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measurement, measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making ...
and
pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and eve ...
of the
magma Magma () is the molten or semi-molten natural material from which all igneous rocks are formed. Magma (sometimes colloquially but incorrectly referred to as ''lava'') is found beneath the surface of the Earth, and evidence of magmatism has also ...
when the mineral crystalized. Clinopyroxene is found in many
igneous rocks Igneous rock ( ), or magmatic rock, is one of the three main Rock (geology)#Classification, rock types, the others being sedimentary rock, sedimentary and metamorphic rock, metamorphic. Igneous rocks are formed through the cooling and solidifi ...
, so the method can be used to determine information about the entire rock. Many different minerals can be used for
geothermobarometry Geothermobarometry is the methodology for estimating the pressure and temperature history of rocks (metamorphic, igneous or sedimentary). Geothermobarometry is a combination of ''geobarometry'', where the pressure attained (and retained) by a miner ...
, but clinopyroxene is especially useful because it's a common
phenocryst image:montblanc granite phenocrysts.JPG, 300px, Granites often have large feldspar, feldspathic phenocrysts. This granite, from the Switzerland, Swiss side of the Mont Blanc massif, has large white phenocrysts of plagioclase (that have trapezoid sh ...
in igneous rocks and easy to identify, and the crystallization of
jadeite Jadeite is a pyroxene mineral with composition Na Al Si2 O6. It is hard (Mohs hardness of about 6.5 to 7.0), very tough, and dense, with a specific gravity of about 3.4. It is found in a wide range of colors, but is most often found in shades ...
, a type of clinopyroxene, implies a growth in
molar volume In chemistry and related fields, the molar volume, symbol ''V''m, or \tilde V of a substance is the ratio of the volume (''V'') occupied by a substance to the amount of substance (''n''), usually at a given temperature and pressure. It is also eq ...
, making it a good indicator of pressure. The data given by this technique is used for understanding magmatic
crystallization Crystallization is a process that leads to solids with highly organized Atom, atoms or Molecule, molecules, i.e. a crystal. The ordered nature of a crystalline solid can be contrasted with amorphous solids in which atoms or molecules lack regu ...
, prograde and retrograde
metamorphism Metamorphism is the transformation of existing Rock (geology), rock (the protolith) to rock with a different mineral composition or Texture (geology), texture. Metamorphism takes place at temperatures in excess of , and often also at elevated ...
, and
ore deposit Ore is natural rock or sediment that contains one or more valuable minerals, typically including metals, concentrated above background levels, and that is economically viable to mine and process. The grade of ore refers to the concentration ...
formation. Understanding these processes can aid industries as well as the scientific community. With this data, information about the
lithosphere A lithosphere () is the rigid, outermost rocky shell of a terrestrial planet or natural satellite. On Earth, it is composed of the crust and the lithospheric mantle, the topmost portion of the upper mantle that behaves elastically on time ...
composition can be extrapolated in more detail, and the
diamond Diamond is a Allotropes of carbon, solid form of the element carbon with its atoms arranged in a crystal structure called diamond cubic. Diamond is tasteless, odourless, strong, brittle solid, colourless in pure form, a poor conductor of e ...
exploration industry can determine the probability that a
kimberlite Kimberlite is an igneous rock and a rare variant of peridotite. It is most commonly known as the main host matrix for diamonds. It is named after the town of Kimberley, Northern Cape, Kimberley in South Africa, where the discovery of an 83.5-Car ...
contains diamonds.{{Cite journal, last=Grütter, first=Herman S., date=2009, title=Pyroxene xenocyst geotherms: Techniques and Application, journal=Lithos, volume=112, pages=1167-1178, doi=10.1016/j.lithos.2009.03.023


Methods

Thermobarometry uses equilibrium constants to calculate information about the environmental conditions present during the rocks' formation. While each rock is forming, it
reacts ''React'' (from Spanish: ''Reacciona'') is a book by Rosa María Artal published in Spain in 2011 by Aguilar, which compiles articles by José Luis Sampedro, Baltasar Garzón, Federico Mayor Zaragoza, Javier Pérez de Albéniz, Javier López Faca ...
with the surrounding elements until it cools down enough to become inert. Each mineral within the rock will cool and crystalize at different points; a petrogenetic grid is a useful way to visualize each mineral crystalizing in sequence. Individual reactions of specific minerals can be used to calculate either the temperature or pressure. Therefore, two different reactions are needed to calculate both the temperature and pressure of the magma for a single rock. Some reactions are better for pressure and others are better for temperature, based on
thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed b ...
and Le Chatelier's Principle. This technique requires each reaction to be
calibrated In measurement technology and metrology, calibration is the comparison of measurement values delivered by a device under test with those of a calibration standard of known accuracy. Such a standard could be another measurement device of known ...
, which is done through
experimentation An experiment is a procedure carried out to support or refute a hypothesis, or determine the efficacy or likelihood of something previously untried. Experiments provide insight into cause-and-effect by demonstrating what outcome occurs whe ...
and
data analysis Data analysis is the process of inspecting, Data cleansing, cleansing, Data transformation, transforming, and Data modeling, modeling data with the goal of discovering useful information, informing conclusions, and supporting decision-making. Da ...
. Experimentation involves simulating the temperatures and pressures at which these rocks form and observing how the reaction proceeds at those conditions, while data analysis relies on amassing a large
database In computing, a database is an organized collection of data or a type of data store based on the use of a database management system (DBMS), the software that interacts with end users, applications, and the database itself to capture and a ...
of rock samples with pressure and temperature information. Experimental data tends to have significant variation, so using data from natural formations is more
accurate Accuracy and precision are two measures of ''observational error''. ''Accuracy'' is how close a given set of measurements (observations or readings) are to their ''true value''. ''Precision'' is how close the measurements are to each other. The ...
, if it's available.


Pressure

The reactions best for pressure ( geobarometers) are ones that have a large change in
molar volume In chemistry and related fields, the molar volume, symbol ''V''m, or \tilde V of a substance is the ratio of the volume (''V'') occupied by a substance to the amount of substance (''n''), usually at a given temperature and pressure. It is also eq ...
during the reaction. Higher pressures cause the reaction to decrease in total volume, and lighter pressures allow reaction to increase in total volume. Therefore, based on the proportion of minerals that have larger volumes versus the proportion of minerals that have smaller volumes, the pressure of the environment during the reaction can be calculated, as a function of temperature. Experiments must be done to
calibrate In measurement technology and metrology, calibration is the comparison of measurement values delivered by a device under test with those of a calibration standard of known accuracy. Such a standard could be another measurement device of known ...
each reaction and determine the rate at which the volume changes with changes in pressure.


Temperature

The reactions best for temperature ( geothermometers) are ones that have a large
enthalpy Enthalpy () is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant extern ...
of reaction, which means they release or consume a lot of
heat In thermodynamics, heat is energy in transfer between a thermodynamic system and its surroundings by such mechanisms as thermal conduction, electromagnetic radiation, and friction, which are microscopic in nature, involving sub-atomic, ato ...
. Higher temperatures allow the reaction to consume that heat while lower temperatures cause the reaction to release heat. Similarly to geobarometers, the proportion of minerals that are formed by releasing heat versus consuming heat can be used to calculate the temperature, as long as the reaction is calibrated.


Reaction Types

There are three types of reactions that clinopyroxene is involved in and can be used for thermobarometry. ''Univariant reactions or displaced equilibria reactions'' either create or destroy
phases Phase or phases may refer to: Science *State of matter, or phase, one of the distinct forms in which matter can exist *Phase (matter), a region of space throughout which all physical properties are essentially uniform *Phase space, a mathematica ...
within the magma. Each phase will eventually crystalize as a unique mineral. Based on the temperature and pressure conditions, different proportions of these phases will emerge in the final rock. An example reaction is
jadeite Jadeite is a pyroxene mineral with composition Na Al Si2 O6. It is hard (Mohs hardness of about 6.5 to 7.0), very tough, and dense, with a specific gravity of about 3.4. It is found in a wide range of colors, but is most often found in shades ...
and
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The Atom, atoms are linked in a continuous framework of SiO4 silicon–oxygen Tetrahedral molecular geometry, tetrahedra, with each oxygen being shared between two tet ...
reacting to make
analbite Albite is a plagioclase feldspar mineral. It is the sodium Endmember (mineralogy), endmember of the plagioclase solid solution series. It represents a plagioclase with less than 10% anorthite content. The pure albite endmember has the formula . I ...
. Jadeite is a type of
pyroxene The pyroxenes (commonly abbreviated Px) are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents ions of calcium (Ca), sodium (Na), iron ( ...
, so this reaction is used for clinopyroxene barometry. NaAlS2O6 + SiO2 -> NaAlS3O8 This particular reaction involves a large change in
volume Volume is a measure of regions in three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch) ...
between the
reactants 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 ...
and the
products Product may refer to: Business * Product (business), an item that can be offered to a market to satisfy the desire or need of a customer. * Product (project management), a deliverable or set of deliverables that contribute to a business solution ...
, so the reaction is very sensitive to pressure changes. ''Exchange Reactions'' occur when there are minerals with similar
structures A structure is an arrangement and organization of interrelated elements in a material object or system, or the object or system so organized. Material structures include man-made objects such as buildings and machines and natural objects such as ...
, and
ions An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
switch places with each other within that structure. This is a common method to calculate the temperature because most exchange reactions have a high
enthalpy Enthalpy () is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant extern ...
. One example reaction is an exchange of Fe2+ and Mg2+ within
garnet Garnets () are a group of silicate minerals that have been used since the Bronze Age as gemstones and abrasives. Garnet minerals, while sharing similar physical and crystallographic properties, exhibit a wide range of chemical compositions, de ...
and clinopyroxene. That causes
pyrope The mineral pyrope is a member of the garnet group. Pyrope is the only member of the garnet family to always display red colouration in natural samples, and it is from this characteristic that it gets its name: from the Greek words for ''fire'' ...
and
hedenbergite Hedenbergite, Ca Fe Si2 O6, is the iron rich end member of the pyroxene group having a monoclinic crystal system. The mineral is extremely rarely found as a pure substance, and usually has to be synthesized in a lab. It was named in 1819 after ...
(pyroxene) to change into
almandine Almandine (), also known as almandite, is a mineral belonging to the garnet group. The name is a corruption of alabandicus, which is the name applied by Pliny the Elder to a stone found or worked at Alabanda, a town in Caria in Asia Minor. Alma ...
and
diopside Diopside is a monoclinic pyroxene mineral with composition . It forms complete solid solution series with hedenbergite () and augite, and partial solid solutions with orthopyroxene and pigeonite. It forms variably colored, but typically dull ...
(pyroxene). Mg3Al2Si3O12 + 3CaFeSi2O6 -> Fe3Al2Si3O12 + 3CaMgSi2O6 ''Solvus Equilibria'' reactions occur when two phases dissolve into each other based on the temperature, so it is usually useful for geothermometry. One such reaction is when clinopyroxene and
orthopyroxene The pyroxenes (commonly abbreviated Px) are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents ions of calcium (Ca), sodium (Na), iron (Fe( ...
dissolve into each other. This changes the distribution of
calcium Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
and
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
throughout the mineral.


Applications

Clinopyroxene thermobarometry is usually used by
mining Mining is the Resource extraction, extraction of valuable geological materials and minerals from the surface of the Earth. Mining is required to obtain most materials that cannot be grown through agriculture, agricultural processes, or feasib ...
industries. It is particularly helpful to the
diamond Diamond is a Allotropes of carbon, solid form of the element carbon with its atoms arranged in a crystal structure called diamond cubic. Diamond is tasteless, odourless, strong, brittle solid, colourless in pure form, a poor conductor of e ...
industry, so many stakeholders possess pressure and temperature data regarding the formation of rocks that contain diamonds. This is important because diamonds are usually found in kimberlites, but kimberlites do not always contain diamonds. Instead of mining every kimberlite found, they can be sampled to see if they formed in an environment that would have favored the crystallization of diamonds. Other applications are largely scientific; pressure and temperature data about magma can be used to propose detailed
models A model is an informative representation of an object, person, or system. The term originally denoted the plans of a building in late 16th-century English, and derived via French and Italian ultimately from Latin , . Models can be divided int ...
of the
lithosphere A lithosphere () is the rigid, outermost rocky shell of a terrestrial planet or natural satellite. On Earth, it is composed of the crust and the lithospheric mantle, the topmost portion of the upper mantle that behaves elastically on time ...
and mantle. These models enhance understanding of geological and volcanic activity, which may contribute to scientists' ability to predict events such as eruptions or
earthquakes An earthquakealso called a quake, tremor, or tembloris the shaking of the Earth's surface resulting from a sudden release of energy in the lithosphere that creates seismic waves. Earthquakes can range in intensity, from those so weak they c ...
.


References

Geochemistry Igneous rocks Geologic modelling