Compatibility (geochemistry)
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Compatibility is a term used by geochemists to describe how elements partition themselves in the solid and melt within Earth's mantle. In
geochemistry Geochemistry is the science that uses the tools and principles of chemistry to explain the mechanisms behind major geological systems such as the Earth's crust and its oceans. The realm of geochemistry extends beyond the Earth, encompassing the e ...
, compatibility is a measure of how readily a particular
trace element __NOTOC__ A trace element, also called minor element, is a chemical element whose concentration (or other measure of amount) is very low (a "trace amount"). They are classified into two groups: essential and non-essential. Essential trace elements ...
substitutes for a major element within a
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. ( ...
. Compatibility of an
ion 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 conve ...
is controlled by two things: its valence and its
ionic radius Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation ...
. Both must approximate those of the major element for the trace element to be compatible in the mineral. For instance,
olivine The mineral olivine () is a magnesium iron silicate with the chemical formula . It is a type of nesosilicate or orthosilicate. The primary component of the Earth's upper mantle, it is a common mineral in Earth's subsurface, but weathers quickl ...
(an abundant mineral in the
upper mantle The upper mantle of Earth is a very thick layer of rock inside the planet, which begins just beneath the crust (at about under the oceans and about under the continents) and ends at the top of the lower mantle at . Temperatures range from appro ...
) has the chemical formula .
Nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
, with very similar chemical behaviour to
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
and
magnesium Magnesium is a chemical element with the 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 of the periodic ta ...
, substitutes readily for them and hence is very compatible in the mantle. Compatibility controls the partitioning of different elements during
melting Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid. This occurs when the internal energy of the solid increases, typically by the application of heat or pressure, which incre ...
. The compatibility of an element in a
rock Rock most often refers to: * Rock (geology), a naturally occurring solid aggregate of minerals or mineraloids * Rock music, a genre of popular music Rock or Rocks may also refer to: Places United Kingdom * Rock, Caerphilly, a location in Wales ...
is a
weighted average The weighted arithmetic mean is similar to an ordinary arithmetic mean (the most common type of average), except that instead of each of the data points contributing equally to the final average, some data points contribute more than others. The ...
of its compatibility in each of the minerals present. By contrast, an
incompatible element In petrology and geochemistry, an incompatible element is one that is unsuitable in size and/or charge to the cation sites of the minerals of which it is included. It is defined by the partition coefficient between rock-forming minerals and melt b ...
is one that is least stable within its
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
structure. If an element is incompatible in a rock, it partitions into a melt as soon as melting begins. In general, when an element is referred to as being “compatible” without mentioning what rock it is compatible in, the mantle is implied. Thus incompatible elements are those that are enriched in the
continental crust Continental crust is the layer of igneous, sedimentary, and metamorphic rocks that forms the geological continents and the areas of shallow seabed close to their shores, known as continental shelves. This layer is sometimes called ''sial'' be ...
and depleted in the mantle. Examples include:
rubidium Rubidium is the chemical element with the symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have a density higher ...
,
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
,
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
, and
lanthanum Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lantha ...
. Compatible elements are depleted in the crust and enriched in the mantle, with examples nickel and
titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
. Compatibility is commonly described by an element's distribution coefficient. A distribution coefficient describes how the solid and liquid phases of an element will distribute themselves in a mineral. Current studies of Earth's rare trace elements seek to quantify and examine the chemical composition of elements in the Earth's crust. There are still uncertainties in the understanding of the lower crust and upper mantle region of Earth's interior. In addition, numerous studies have focused on looking at the
partition coefficient In the physical sciences, a partition coefficient (''P'') or distribution coefficient (''D'') is the ratio of concentrations of a compound in a mixture of two immiscible solvents at equilibrium. This ratio is therefore a comparison of the solub ...
s of certain elements in the basaltic magma to characterize the composition of oceanic crust. By having a way to measure the composition of elements in the crust and mantle given a mineral sample, compatibility allows relative concentrations of a particular trace element to be determined. From a petrological point of view, the understanding of how major and rare trace elements differentiate in the melt provides deeper understanding of Earth's chemical evolution over the geologic time scale.


Quantifying compatibility


Distribution (Partition) coefficient

In a mineral, nearly all elements distribute unevenly between the solid and liquid phase. This phenomenon known as chemical fractionation and can be described by an
equilibrium constant The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency ...
, K which sets a fixed distribution of an element between any two phases ''at equilibrium''. A
distribution constant The distribution constant (or partition ratio) (KD) is the equilibrium constant for the distribution of an analyte in two immiscible solvents.i is the concentration of A remaining after extracting Vaq millilitre The litre (international sp ...
K_D is used to define the relationship between the solid and liquid phase of a reaction. This value is essentially a ratio of the concentration of an element between two phases, typically between the solid and liquid phase in this context. This constant is often referred to as D when dealing with
trace element __NOTOC__ A trace element, also called minor element, is a chemical element whose concentration (or other measure of amount) is very low (a "trace amount"). They are classified into two groups: essential and non-essential. Essential trace elements ...
s, where K_D=\frac=\frac K_D=D for trace elements The equilibrium constant is an empirically determined value. These values depend on temperature, pressure, and composition of the mineral melt. D values differ considerably between major elements and trace elements. By definition, incompatible trace elements have an equilibrium constant value of less than one because trace elements have higher concentrations in the melt than solids. This means that compatible elements have a value of D\gg1. Thus, incompatible elements are concentrated in the melt, whereas compatible elements tend to be concentrated in the solid. Compatible elements with D\gg1 are strongly fractionated and have very low concentrations in the liquid phase.


Bulk distribution coefficient

The bulk distribution coefficient is used to calculate the elemental composition for any element that makes up a mineral in a rock. The bulk distribution coefficient, \overline_i, is defined as \overline_i=\Sigma W_AD_i^A where i is the element of interest in the mineral, and W_A is the weight fraction of mineral A in the rock. D_i^A is the distribution coefficient for the element in mineral A. This constant can be used to describe how individual elements in a mineral is concentrated in two different phases. During chemical fractionation, certain elements may become more or less concentrated, which can allow geochemists to quantify the different stages of magma differentiation. Ultimately, these measurements can be used to provide further understanding of elemental behavior in different geologic settings.


Applications

One of the main sources of information about the Earth's composition comes from understanding the relationship between peridotite and basalt melting.
Peridotite Peridotite ( ) 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 prop ...
makes up most of Earth's mantle.
Basalt Basalt (; ) is an aphanite, aphanitic (fine-grained) extrusive igneous rock formed from the rapid cooling of low-viscosity lava rich in magnesium and iron (mafic lava) exposed at or very near the planetary surface, surface of a terrestrial ...
, which is highly concentrated in the Earth's oceanic crust, is formed when magma reaches the Earth's surface and cools down at a very fast rate. When magma cools, different minerals crystallize at different times depending on the cooling temperature of that respective mineral. This ultimately changes the chemical composition of the melt as different minerals begin to crystallize. Fractional crystallization of elements in basaltic liquids has also been studied to observe the composition of lava in the
upper mantle The upper mantle of Earth is a very thick layer of rock inside the planet, which begins just beneath the crust (at about under the oceans and about under the continents) and ends at the top of the lower mantle at . Temperatures range from appro ...
. This concept can be applied by scientists to give insight on the evolution of Earth's mantle and how concentrations of
lithophile Lithophiles are micro-organisms that can live within the pore interstices of sedimentary rock, sedimentary and even fractured igneous rock, igneous rocks to depths of several kilometers. Some are known to live on surface rocks, and make use of p ...
trace elements have varied over the last 3.5 billion years.


Understanding the Earth's interior

Previous studies have used compatibility of trace elements to see the effect it would have on the melt structure of the
peridotite Peridotite ( ) 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 prop ...
solidus Solidus (Latin for "solid") may refer to: * Solidus (coin), a Roman coin of nearly solid gold * Solidus (punctuation), or slash, a punctuation mark * Solidus (chemistry), the line on a phase diagram below which a substance is completely solid * S ...
. In such studies, partition coefficients of specific elements were examined and the magnitude of these values gave researchers some indication about the degree of polymerization of the melt. A study conducted in East China in 1998 looked at the chemical composition of various elements found in the crust in China. One of the parameters used to characterize and describe the crustal structure in this region was compatibility of various element pairs. Essentially, studies like this showed how compatibility of certain elements can change and be affected by the chemical compositions and conditions of Earth's interior. Oceanic volcanism is another topic that commonly incorporates the use of compatibility. Since the 1960s, the structure of Earth's mantle started being studied by geochemists. The oceanic crust, which is rich in
basalt Basalt (; ) is an aphanite, aphanitic (fine-grained) extrusive igneous rock formed from the rapid cooling of low-viscosity lava rich in magnesium and iron (mafic lava) exposed at or very near the planetary surface, surface of a terrestrial ...
s from volcanic activity, show distinct components that provides information about the evolution of the Earth's interior over the geologic timescale. Incompatible trace elements become depleted when mantle melts and become enriched in oceanic or continental crust through volcanic activity. Other times, volcanism can produce enriched mantle melt onto the crust. These phenomena can be quantified by looking at radioactive decay records of isotopes in these basalts, which is a valuable tool for mantle geochemists. More specifically, the geochemistry of
serpentinite Serpentinite is a rock composed predominantly of one or more serpentine group minerals, the name originating from the similarity of the texture of the rock to that of the skin of a snake. Serpentinite has been called ''serpentine'' or ''ser ...
s along the ocean floor, specifically subduction zones, can be examined using compatibility of specific trace elements. The compatibility of
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
(Pb) into
zircon Zircon () is a mineral belonging to the group of nesosilicates and is a source of the metal zirconium. Its chemical name is zirconium(IV) silicate, and its corresponding chemical formula is Zr SiO4. An empirical formula showing some of the r ...
s under different environments can also be an indication of zircons in rocks. When observing levels of non-radiogenic lead in zircons, this can be a useful tool for radiometric dating of zircons.{{Cite journal, last=Watson, first=E. B, last2=Chemiak, first2=D. J, last3=Hanchar, first3=J. M, last4=Harrison, first4=T. M, last5=Wark, first5=D. A, date=1997, title=The incorporation of Pb into zircon, journal=Chemical Geology, volume=141, issue=1, pages=19–31, doi=10.1016/S0009-2541(97)00054-5, bibcode=1997ChGeo.141...19W, issn=0009-2541


References

Geochemistry Geology