G

Geochemical Classification of Elements environment and a trace element in another. For example,
during certain petrogenetic processes, an element initially
Cin-Ty Lee occurring at trace levels can become concentrated enough to
Department of Earth Science MS-126, Rice University, be a major or minor element. Cu ore deposits or Li-rich
Houston, TX, USA pegmatites are examples where elements normally in trace
abundances can locally become quite enriched. Other exam-
ples are H, N, and C, which are trace elements in the mantle
Definition but major constituents of the oceans, atmosphere, and life.
Redistribution of elements throughout the Earth, a process
Geochemists classify elements in various ways based on their called differentiation, is dominantly controlled by the forma-
abundance, behavior, and distribution in the Earth. tion and physical segregation of silicate liquids, aqueous
fluids, and gases, which serve as potential carriers of all
elements of the periodic table.
Introduction Exactly how elements are spatially redistributed in a plan-
etary body depends on their chemical behaviors and how they
Elements can be qualitatively classified into major (>0.4 wt partition into different phases during geologic and biochemical
%), minor (0.1–0.4 wt%), and trace elements (<0.1 wt%). processes. Chemical behavior of elements is dictated by the
Major elements are those that define the primary structure of a “stability” of the outer electrons. Elements whose outermost
given phase, which can be a mineral, liquid, or vapor. Major electron shells are nearly filled tend to readily attract electrons
elements are abundant enough that they dictate a system’s (high electronegativity), forming anions in chemical bonds.
physical properties, including the assemblage of phases. Elements with only partially filled outer shells tend to donate
Trace elements are not essential to the structure of a phase electrons (low electronegativity) and become cations in chem-
and do not directly influence the properties of a phase or ical bonds. Elements with very different electronegativities
system. Instead, trace elements occur passively as dissolved (opposite ends of the periodic table) tend to transfer electrons
constituents or in the form of minor amounts of accessory between atoms, resulting in ionic bonds. In contrast, elements
phases. The distribution of elements on Earth is heteroge- with similar electronegativities tend to share electron clouds in
neous, ranging from the scale of hundreds to thousands of chemical bonds (covalent bonds), making such bonds very
kilometers in the form of the Earth’s layered structure (core, strong. Most of the rocks on Earth are silicates, which are
mantle, crust, ocean, and atmosphere) down to the scale of composed of complexes of silica tetrahedra (SiO44 ), where
millimeters or less in the form of mineral grains or living the similar electronegativities of Si and O result in significant
organisms. Thus, although >99 % of the bulk Earth, which degree of covalent character. Cations on the left side of the
includes the crust, mantle, and metallic core, is composed of periodic table (alkali and alkali Earth metals), such as Mg2+,
Fe, O, Mg, Si, S, Ni, Ca, and Al, in order of decreasing Ca2+, Na+, and K+, generate ionic bonds with the O2 anions
abundance by weight, much of the Fe and almost all the Ni making up the apices of the silica tetrahedra to form, for
are sequestered in the core, whereas most of the Earth’s O is example, the silicate minerals that make up most of the Earth’s
locked up in the mantle and crust in the form of oxides mantle (olivine, Mg2SiO4) and crust (feldspar, e.g.,
(O makes up nearly 50 % by weight of the mantle). The CaAl2Si2O8 and NaAlSi3O8). Elements with filled energy
same element can be a major element in one geologic shells, such as the noble gases, tend to be chemically inert.

# Springer International Publishing Switzerland 2016

W.M. White (ed.), Encyclopedia of Geochemistry,
DOI 10.1007/978-3-319-39193-9_255-1
2 Geochemical Classification of Elements

Partitioning Classifications compatibility of Fe3+ if Al3+ is contained in its structure

(Frost et al., 2004). The subsolidus transformation of
The efficiency to which an element partitions into a particular wadsleyite or ringwoodite, which contains minimal Al3+, to
phase is controlled to first order by charge and ionic radius bridgmanite has been suggested to lead to disproportionation
(cations are smaller and anions are larger than their respective of Fe2+ into Fe0 and Fe3+, the latter dissolving into
atomic radii). During melting, elements can be classified into bridgmanite.
compatible or incompatible relative to the solid phase, that Another important quantity is the charge to ionic radius
is, an incompatible element preferentially partitions into the ratio, known as the ionic potential. Elements with high ionic
melt phase, whereas a compatible element partitions into the potential are referred to as high field strength elements
solid phase. A cation becomes incompatible in a particular (HFSEs) and include Ti4+, Zr4+, Nb5+, Ta5+, and Hf4+. Ele-
crystallographic site when excess electrostatic and strain ments with low ionic potential are often referred to as large
energy is generated due to charge imbalance or when an ion ion lithophile elements (LILEs) in the geochemical commu-
is too big or too small for a particular crystallographic site nity. LILEs include Na+, K+, Rb+, Cs+, Sr2+, and Ba2+. Low
(Wood and Blundy, 2003). These effects are manifested as ionic potential elements readily form inner sphere aquo-
general trends in partitioning behavior as a function of ionic complexes in aqueous solutions because they are large
radii for a given charge. For any given mineral/melt pair, there enough to be surrounded and coordinated to water molecules
is an optimum ionic radii for maximum compatibility (Wood (Langmuir, 1997). This makes LILEs soluble in aqueous
and Blundy, 2003). In the case of the rare earth elements in solutions. The high charge of HFSE and rare earth element
most mantle minerals, the heavy rare earths typically exhibit cations reduces electron shielding within their outermost
maximum compatibility because the lighter rare earths are too electron shell, resulting in significant reduction in ionic
large. This variation in ionic radius, known as the “lanthanide radii. Because of their small cationic radii and high charge,
contraction” of the f-orbital shell, thus manifests itself as a H is expelled from the solvation shell, preventing such ele-
distinct decrease in compatibility toward the left-hand side of ments from forming aquo-complexes and rendering them
the periodic table for the rare earth elements. relatively insoluble in water (Langmuir, 1997). Only by
Most of the high mass trace metals, such as Sr, Rb, and Ba, complexing with other anions, such as halides and oxyanions,
and the rare earth elements tend to be incompatible during can such elements become more soluble in water. These are
mantle melting because of their large cationic radii. First-row the reasons why geochemists generally consider LILEs fluid
transition metals, with ionic radii more similar to the cation mobile and HFSEs fluid immobile, but even fluid immobile
crystallographic sites in mantle minerals, tend to be compat- elements can become mobile under certain conditions.
ible (Ni and Co) or moderately incompatible (Sc, V, Mn)
during melting (Canil, 2004). Some highly charged transition
metals, such as high field strength elements Ti, Zr, and Nb, are Geochemical Classifications
highly incompatible in common silicates due to charge imbal-
ance. Some elements, however, can be highly compatible in a Elements are often categorized based on their general geo-
given phase, but exhibit overall incompatible behavior during chemical behaviors even though an element’s chemical
melting if that phase represents a minor constituent in the behavior depends strongly on variables such as temperature,
rock. For example, Cu is highly compatible in sulfide, but pressure, and chemical environment; the latter of which can
because sulfides are low in abundance in typical mantle rocks, dictate an element’s valence state and ability to form com-
Cu behaves effectively as an incompatible element during plexes. These classifications broadly follow Goldschmidt’s
mantle melting (Lee et al., 2012). original classifications (Goldschmidt, 1937) with the addition
Partitioning behavior for a given element is rarely ever a of organophile and fluid-mobile elements.
constant due to many factors: (1) effective oxidation, which is
controlled by the oxygen fugacity of the environment, (2) tem- Lithophile elements (“rock loving”) are preferentially
perature, (3) pressure, (4) mineral composition, and (5) melt partitioned into silicate minerals. These include cations
or fluid composition, which changes complexation behavior. that commonly form oxides, such as Ca, Mg, Mn, Ti,
An example of redox effects is seen in the difference in Na, K, the rare earth elements, U, Th, Si, and Fe in its
partitioning behaviors between Eu2+ and Eu3+ and between oxidized states.
V2+ and V3+ (Canil, 1997). An example of the influence of Siderophile elements (“iron loving”) are those that are pref-
mineral composition is the effect of coupled substitutions. erentially partitioned into the metallic core, typically in the
The presence of Al3+ as a major element in a pyroxene can form of alloys with Fe. Elements exhibiting metallic
enhance the compatibility of rare earth elements (+3) by behavior include the noble metals (Pt, Pd, Ir, Ru, Rh, and
providing a means of charge balance. Bridgmanite, a lower- Os) as well as W, Ni, and Co. Some elements in their
mantle mineral with perovskite structure, can enhance the reduced states or at high enough pressures to impart
Geochemical Classification of Elements 3

metallic behavior can alloy with Fe metal; these include more soluble if complexed with certain halogens or
Si, C, and some high field strength elements like oxyanions. Introduction of carbonate ions into fluids or
Nb. Sulfur may dissolve in the core as a sulfide complex silicate melts can also enhance solubilities of certain
and, under these conditions, is also considered siderophile. elements.
Chalcophile elements are those that commonly form sulfide-
type minerals. These include Cu, Pb, Zn, Cd, Mo, Hg, Sb, It is important to recognize that elements can behave in
Sn, Tl, Te, As, as well as noble metals. different ways. Obviously, oxygen in its molecular form can
Atmophile elements are those that readily form volatile com- be atmophile, but it also forms oxides and dominantly
pounds at relatively low temperatures (<300 K), many of behaves as a lithophile element in the presence of metals.
which are preferentially concentrated in planetary atmo- Elements like Ge can be lithophile, organophile, chalcophile,
spheres. Atmophile elements include C, O, H, N, S, and and siderophile, depending on oxidation state and chemical
the noble gases. environment (Figure 1).
Organophile elements are those that form or associate with
organic compounds (hydrocarbon molecules) in biochem-
ical and biogeochemical processes. These include C, H, N, Cosmochemical Classifications
S, and P, but also include various metal-organic com-
plexes. Many metals, such as U, V, Ge, Pb, and Mo, can There is a cosmochemical classification of elements that is
complex with organic molecules, generating organic-rich primarily used to describe the temperature interval over which
sediments with high metal contents. elements condense from a gaseous state to a solid or liquid
Fluid-mobile elements are those that readily dissolve in state during nebular condensation and planetary accretion.
fluids, typically water-rich fluids. Elements with high sol- These classifications are based on theoretical condensation
ubility in water tend to be low field strength elements, such temperatures calculated from a nebula with a solar composi-
as the alkali and alkali Earth group elements, which readily tion and a pressure of 10 4 bar (at the 50 % condensation
form inner sphere aquo-complexes or highly electronega- level) and are most applicable in the study of meteorites,
tive elements, such as the halogens. High field strength impact processes, and planetary accretion (Lodders and
elements, in the absence of complexation, tend to be insol- Fegley, 1998):
uble. Transition metals tend to have lower solubilities, but
the presence of anions in the water can greatly enhance Highly refractory (>1700 K) – Re, Os, W, Zr, and Hf
their solubilities through complexation. For example, Refractory (1500–1700 K) – Al, Sc, Ca, Ti, most rare earth
noble metals and high field strength elements can become elements, Th, and U

Geochemical Classification of Elements, Figure 1 Cosmochemical classification of elements: Cosmochemical classification of elements based
on 50 % condensation temperatures at 10 4 bar using data from Lodders and Fegley (1998)
4 Geochemical Classification of Elements

Moderately refractory (1300–1500 K) – Be, Mg, Si, Cr, Fe, and moderately compatible trace elements can also be used to
Co, Ni, Nb, Ce, Yb, Pt, and Pd evaluate phase assemblages. Together, major elements and
Moderately volatile (1100–1500 K) – Cu, Ba, Mn, Sr, P, and moderately incompatible to compatible trace elements can be
Au powerful tools for unraveling the mineralogy of the source
Volatile (700–1100 K) – Na, K, B, S, Rb, Cs, Ga, Sn, and Se regions of magmas. Incompatible trace elements are less
Highly volatile (<700 K) – Pb, Zn, Tl, In, Bi, O, C, N, H, and diagnostic of mineralogy because effects of fractionation
noble gases strongly accentuate changes in incompatible trace element
abundances. For example, continental crust is highly enriched
The use of these classifications should generally be in incompatible elements owing to extreme magmatic differ-
restricted to cosmochemical processes or during the high entiation. Contamination of mantle-derived magmas with
temperatures of planetary accretion instead of for differentia- small amounts of continental crust or fluids can lead to sig-
tion within an already condensed planetary body. For exam- nificant changes in trace element signatures with only minor
ple, refractory elements, in a cosmochemical sense, can be change in major element systematics. Because some trace
siderophile, lithophile, or even chalcophile during planetary element systems are associated with radioactive isotopic sys-
differentiation. Care must also be taken when using the terms tems, a full understanding of the geochemical behavior of
atmophile and volatile. For example, Pb and Zn are consid- parent and daughter elements is critical for interpreting isoto-
ered highly volatile from a cosmochemical perspective, but pic evolution of the Earth.
would not be considered atmophile. Nevertheless, under Because many factors influence element partitioning,
unusual situations, such as during a meteorite impact or some elements can be used to track various intensive vari-
volcanic processes, Pb and Zn can be volatilized briefly into ables, such as temperature, pressure, and oxygen fugacity,
the atmosphere before recondensing out of the atmosphere when used judiciously. For example, rare earth element
upon cooling. Ge can be volatile in a cosmochemical sense, partitioning between solid and melt and at subsolidus condi-
but can be lithophile or siderophile in a geochemical sense tions can be used indirectly as a qualitative barometer by
(Figure 2). signaling the presence of high-pressure minerals (garnet) or
as a quantitative thermobarometer with proper calibration
(Liang et al., 2013). Variations in the oxidation state of Fe,
Using Elements in Geochemistry and Eu, and Ce influence their geochemical behaviors, allowing
Cosmochemistry them to be used for tracking oxygen fugacity in the mantle,
crust, oceans, and atmosphere through time.
Major elements are best used for determining how phase Finally, elemental abundances provide first-order con-
assemblages evolve during petrogenesis of rocks. Compatible straints on how different reservoirs interact and how elements

Geochemical Classification of Elements, Figure 2 Geochemical classification of elements

Geochemical Classification of Elements 5

are cycled through these reservoirs. For example, the abun- ▶ Nobel Gas Elements
dance of an element in the ocean may shed light on the ▶ Oxidation-Reduction Reactions
element’s residence time, that is, elements in high abundance ▶ Partitioning and partition coefficients
tend to be soluble and have long residence times (Na and Cl), ▶ Periodic Table
whereas elements in low abundance tend to be insoluble and ▶ Siderophile Elements
have short residence times (e.g., rare earth elements). Tempo- ▶ Solubility
ral variations in seawater composition have been used to ▶ Trace Elements
reconstruct past variations in climate, ocean circulation, and
weathering (Holland, 1984). Similar approaches can be
applied to better understand magma chamber dynamics. References

Canil, D., 1997. Vanadium partitioning and the oxidation state of

Archaean komatiite magmas. Nature, 389, 842–845.
Summary Canil, D., 2004. Mildly incompatible elements in peridotites and the
origins of mantle lithosphere. Lithos, 77, 375–393.
The elements of the periodic table provide many different Frost, D. J., Liebske, C., Langenhorst, F., McCammon, C. A., Tronnes,
ways of investigating how the Earth system operates. In R. G., and Rubie, D. C., 2004. Experimental evidence for the exis-
tence of iron-rich metal in the Earth’s lower mantle. Nature, 428,
many cases, however, the study of major and trace elements
409–412.
is often treated separately. Many of the most interesting Goldschmidt, V. M., 1937. The principles of the distribution of chemical
advances in geochemistry have come from a holistic under- elements in minerals and rocks. Journal of Chemical Society, Lon-
standing of the periodic table. don, 140, 655–673.
Holland, H. D., 1984. The Chemical Evolution of the Atmosphere and
Oceans. Princeton: Princeton University Press.
Langmuir, D., 1997. Aqueous Environmental Geochemistry. Upper Sad-
Cross-References dle River: Prentice Hall.
Lee, C.-T. A., Luffi, P., Chin, E. J., Bouchet, R., Dasgupta, R., Morton,
D. M., Le Roux, V., Yin, Q.-Z., and Jin, D., 2012. Copper systematics
▶ Atmophile Elements
in arc magmas and implications for crust-mantle differentiation.
▶ Chalcophile Elements Science, 336, 64–68.
▶ Chemical Bonds Liang, Y., Sun, C., and Yao, L., 2013. A REE-in-two-pyroxene ther-
▶ Complexes mometer for mafic and ultramafic rocks. Geochimica et
Cosmochimica Acta, 102, 246–260.
▶ Differentiation
Lodders, K., and Fegley, J. B., 1998. The Planetary Scientist’s Compan-
▶ Earth’s Core ion. Oxford: Oxford University Press.
▶ Electronegativity Wood, B. J., and Blundy, J. D., 2003. Trace element partitioning under
▶ First Transition Series Elements crustal and uppermost mantle conditions: the influences of ionic
radius, cation charge, pressure, and temperature. Treatise on Geo-
▶ High Field Strength Elements
chemistry, 2, 395–424.
▶ Large Ion Lithophile Elements
▶ Lithophile Elements