Pyroxenes☆

DM Buchs, Cardiff University, Cardiff, UK

RA Howie{, Royal Holloway, University of London, London, UK
ã 2016 Elsevier Inc. All rights reserved.

Pyroxenes are an important group of rock-forming ferromagnesian silicates that occur as stable phases in almost every type of
igneous rock, a wide range of metamorphic rocks formed under conditions of both regional and contact/thermal metamorphism,
and some classes of meteorites.
Pyroxenes are inosilicate minerals that crystallize in the orthorhombic and monoclinic systems to form orthopyroxene and
clinopyroxene, respectively. All the pyroxenes have a common structure that consists of infinite single chains of linked silicon-
oxygen tetrahedra, the [Si2O6] groups, these chains being linked laterally by octahedral layers of (Ca, Mg, Fe, Na, etc.) cations
(Figure 1). The general formula of pyroxenes can be expressed as (M2)(M1)(T)2O6, where M1 represents a nearly regular
octahedron site coordinated with 6 non-bridging oxygens (notably accommodating Mg, Fe2+, Al, Cr, and Fe3+) (Figure 2). M2
represents a regular to distorted octahedron site coordinated with 6 to 8 bridging and non-bridging oxygens (notably accommo-
dating Ca, Mg, Fe2+, Na, and rare earth elements). T is the tetrahedral site essentially occupied by Si and, to lesser extent,
Al. Substitution of cations in the M1 and M2 sites is a significant characteristic of pyroxenes, which results in several solid solution
series and large compositional spectrum of the pyroxene group.
The pyroxene group includes twenty mineral species accepted by the Commission on New Minerals and Mineral Names of the
International Mineralogical Association based on their occurrence as end members of definite chemical compositions or end
members of common binary solution series (Table 1). For broad classification purpose the pyroxenes are generally subdivided into
three chemical groups: Ca–Mg–Fe pyroxenes, Ca–Na and Na pyroxenes, and other pyroxenes. The Mg–Fe pyroxenes and some of
the Ca pyroxenes are the most common rock-forming pyroxenes and are classified using the pyroxene quadrilateral of the ternary
system CaSiO3–MgSiO3–FeSiO3 (where the CaSiO3 component is not a pyroxene but a pyroxenoid, wollastonite) (Figure 3).
Pyroxenes of the MgSiO3–FeSiO3 series occur in five polymorphs; the most common natural example in terrestrial rocks is
orthorhombic enstatite/ferrosilite (or orthoenstatite/orthoferrosilite), whereas clinoenstatite/clinoferrosilite is a much rarer,
monoclinic polymorph. In more calcic pyroxenes, a complete solid solution exists between diopside and hedenbergite that also
forms a continuous range of compositions with augite. However, a miscibility gap occurs between augite and pigeonite, which
expands with decreasing temperature due to reduced stability of pigeonite. Temperature and compositional dependence of solid
solutions of quadriletal pyroxenes (i.e., pyroxenes included in Figure 3 quadrilateral) have been used to develop two-pyroxene
thermometers applicable to a large range of igneous and metamorphic rocks. The Ca–Na and most common Na pyroxenes are
classified using the Ca–Mg–Fe pyroxenes–jadeite–aegirine diagram (Figure 4), which accounts for extensive solid solution of
jadeite and aegirine with Ca–Mg–Fe pyroxenes (leading to the Ca–Na pyroxenes).

Figure 1 Idealized illustration of a single pyroxene chain formed by (SiO4)4 tetrahedra, as seen in projections on (A) along x, (B) along z,
and (C) along y. (D) Oblique view with oxygen anions on the shared edges of the Si octahedra (O1 and O2) and oxygen anions shared between the
tetrahedra (O3).

☆
Change History: December 2015. DM Buchs and RA Howie introduced small edits in the text of the article and added Figures 5 and 6.
{
Deceased.

Reference Module in Earth Systems and Environmental Sciences http://dx.doi.org/10.1016/B978-0-12-409548-9.09697-4 1

2 Pyroxenes

Figure 2 Projection along z of an idealized pyroxene structure, showing the pyroxene chains and the two distinct cation sites M1 and M2. The latter are
in oxygen polyhedra which also form chains or bands parallel to z.

Table 1 Pyroxene mineral names accepted by the Commission on New Minerals and
Mineral Names of the International Mineralogical Association (names in bold are for pyroxenes
displayed in Figures 3 and 4)

Mg–Fe pyroxenes
Orthopyroxenes Enstatite–ferrosilite (Mg,Fe)2Si2O6

Clinopyroxenes Clinoenstatite–clinoferrosilite (Mg,Fe)2Si2O6

Pigeonite (Mg,Fe2+,Ca)(Mg,Fe2+)Si2O6
Mn–Mg pyroxenes
Orthopyroxene Donpeacorite (Mn,Mg)MgSi2O6
Kanoite (Mn,Mg)MgSi2O6
Ca pyroxenes
Augite (Ca,Mg,Fe2+,Al)2 (Si,Al)2O6
Diopside–hedenbergite Ca(Mg,Fe)Si2O6
Joannsenite CaMnSi2O6
Petedunnite CaZnSi2O6
Esseneite CaFe3+AlSi2O6
Ca–Na pyroxenes
Omphacite (Ca,Na)(Mg,Fe2+,Fe3+,Al)Si2O6
Clinopyroxenes Aegirine–augite (Ca,Na)(Mg,Fe2+,Fe3+)Si2O6
Na pyroxenes
Jadeite NaAlSi2O6
Aegirine NaFe3+Si2O6
Kosmochlor NaCr3+Si2O6
Jervisite NaSc3+Si2O6
Li pyroxenes
Spodumene LiAlSi2O6

Optically, the orthopyroxenes are colourless to greenish under the microscope and bronze to black in hand specimen. They have
a good {210} cleavage and straight extinction. Their other properties vary with the Fe/Mg ratio. The clinopyroxenes are colourless
to greenish or brownish under the microscope, have a good {110} cleavage, but with variable extinction angles from 0 to 45 .
Within the CaMgSi2O6–CaFeSi2O6–Fe2Si2O6–Mg2Si2O6 quadrilateral, which covers 90% of the common rock-forming clinopyr-
oxenes, their optical properties vary systematically, allowing their composition to be estimated. All pyroxenes have cleavages
intersecting with an angle of approximately 90 and they commonly display a nearly squared, octahedral basal section (i.e., a
section perpendicular to the cleavages and c crystallographic axis) (Figure 5). Exsolution lamellae are common in slowly cooled
volcanic and subvolcanic rocks due to inversion of the high temperature phase pigeonite to augite  orthopyroxene (Figure 6).
 Pyroxenes 3

Figure 3 Nomenclature of (A) Ca–Fe–Mg orthopyroxenes and (B) clinopyroxenes.

Figure 4 Nomenclature of most common Na and Ca–Na clinopyroxenes.

The occurrence of members of the pyroxene group in general reflects the compositions of their parent rocks. Igneous rocks host
most of the pyroxenes on Earth, with ultramafic rocks of the upper mantle including a large proportion of Mg-rich orthopyroxene
(enstatite) and clinopyroxenes (diopside and augite). Augite is generally the most common clinopyroxene in volcanic and
subvolcanic rocks. However, pigeonite is not uncommon in high temperature, rapidly cooled lavas, and diopside can occur as
an early mineral phase in Mg-rich magmatic systems. Aegirine and aegirine-augite are mainly found in alkaline and peralkaline
igneous rocks. The lithium pyroxene spodumene is restricted to Li-rich granitic pegmatites and is the most important commercially-
mined high-grade lithium ore.
Pyroxenes are also common in metamorphic rocks, where they occur over a large range of P-T conditions. Notable examples
include diopside produced by thermal metamorphism and decarbonation reaction of siliceous limestone or dolomite; this mineral
can also result from the breakdown of the amphibole tremolite at high temperature. The sodium-bearing clinopyroxene jadeite is a
diagnostic mineral of rocks generally considered to have formed in a high-pressure environment; when near its end-member
composition of NaAlSi2O6, this pyroxene is colourless or pale green and forms one variety of the gem material jade. The Ca–Na
clinopyroxene omphacite forms in the highest pressure metamorphic facies and is a major mineral component of eclogite.
In clastic sedimentary rocks, pyroxenes can form a significant fraction of heavy minerals, in particular in eroding volcanic
environments. However, high susceptibility of these minerals to chemical and mechanical weathering makes them relatively
uncommon in mature sedimentary rocks.
4 Pyroxenes

Figure 5 Augite phenocryst in a picrite from an accreted oceanic island (Azuero Peninsula, Panama), with (A) plain polarized light view, and
(B) cross-polarized light view. The field of view is approximately perpendicular to the c crystallographic axis, with {110} and {110} cleavages crosscutting
at nearly right angle, and a simple twinning along {100}. Chemical zonation of the crystal (resulting from magma mixing during formation of the
accreted volcano) is outlined by changes in the birefringence (B).

Figure 6 Exsolution lamellae in a clinopyroxene from an abyssal peridotite (Gakkel Ridge, Arctic Ocean). Shown in cross-polarized light view (photo
credit: Matthew Loocke).

The occurrence of pyroxenes is not restricted to the Earth and has been showed to extend to other rocky planets and extra-
terrestrial bodies in the solar system. Low-calcium Mg–Fe orthopyroxenes and clinopyroxenes are commonly found in some classes
of meteorites. High- and low-Ca pyroxenes have been remotely detected at the surface of Mars; augite was unambiguously
identified on this planet by in situ measurements. Pyroxenes may also be an important mineral component beyond the solar
system, as notably suggested by the composition of extrasolar silicate dust.

Further Reading
Cameron M and Papike JJ (1981) Structural and chemical variations in pyroxenes. American Mineralogist 66: 1–50.
Deer WA, Howie RA, and Zussman J (2013) An introduction to the rock-forming minerals, 3rd edn. London: Longman.
Gasparik T (2014) Phase diagrams for geoscientists: An atlas of the Earth’s interior, 2nd edn. Berlin: Springer.
Lindsley DH (1983) Pyroxene thermometry. American Mineralogist 68: 477–493.
Morimoto N, Fabries J, Ferguson AK, Ginzburg IV, Ross M, Seifert FA, Zussman J, Aoki K, and Gottardi G (1988) Nomenclature of pyroxenes. Mineralogy and Petrology 39: 55–76.