olivine

—olivinic /ol'euh vin"ik/, olivinitic /ol'euh vi nit"ik/, adj.

/ol"euh veen', ol'euh veen"/, n.

Mineral. any of a group of magnesium iron silicates, (Mg,Fe)₂SiO₄, occurring in olive-green to gray-green masses as an important constituent of basic igneous rocks. Also called chrysolite.

[1785-95; < G Olivin, equiv. to Olive OLIVE + -in -INE²]

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Any member of a group of common magnesium, iron silicate minerals.

Olivines occur in many igneous rocks and are a major constituent of the Earth's upper mantle. They also have been found in some lunar rocks and in many meteorites. Olivine forms yellow to greenish yellow crystals and is sometimes used in making bricks. Transparent green olivine (precious olivine) is called peridot.

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▪ mineral

Introduction

      any member of a group of common magnesium, iron silicate minerals.

General considerations

 Olivines are an important rock-forming mineral group. Magnesium-rich olivines are abundant in low-silica mafic and ultramafic igneous rocks and are believed to be the most abundant constituent of the Earth's upper mantle. Olivine also occurs in high-temperature metamorphic rocks, lunar basalts, and some meteorites. The name olivine derives from the unusual yellow-green to deep bottle-green colour of the magnesium-iron olivine series. Typically the name olivine is given to members of the forsterite-fayalite (forsterite-fayalite series) solid-solution series. In addition to these magnesium and ferrous iron end-members, the olivine group contains manganese ( tephroite), calcium-manganese (glaucochroite), calcium-magnesium ( monticellite), and calcium-iron (kirschsteinite) end-members (Table—>). Gem-quality forsterite olivine is known as peridot. Because of its high melting point and resistance to chemical reagents, magnesium olivine is an important refractory material—i.e., it can be used in furnace linings and in kilns when other materials are subjected to heat and chemical processes.

Chemical composition

      The composition of most olivines can be represented in the system Ca₂SiO₄-Mg₂SiO₄-Fe₂SiO₄ (Figure 1). The most abundant olivines occur in the system from forsterite (Mg₂SiO₄) to fayalite (Fe₂SiO₄). Most of the naturally occurring olivines are intermediate in composition to these two end-members and have the general formula (Mg, Fe)₂SiO₄. Members of the series monticellite (CaMgSiO₄) to kirschsteinite (CaFeSiO₄) are rare. Minor elements such as aluminum, nickel, chromium, and boron can substitute in olivine.

      The name forsterite is restricted to those species with no more than 10 percent iron substituting for magnesium; fayalite (from Fayal Island in the Azores, where it was believed to occur in a local volcanic rock but probably was obtained from slag brought to the island as ship's ballast) is restricted to species with no more than 10 percent magnesium substituting for iron. Compositions intermediate to these series end-members are identified by Fo_xFa_y, which is an expression of the molar percentage of each compound. For example, Fo₇₀Fa₃₀ denotes a composition of olivine that is 70 percent forsterite. The notation is shortened to Fo₇₀.

      The continuity in the forsterite-fayalite series has been verified experimentally. At the magnesium-rich end of the solid-solution (solid solution) series, natural crystals may contain very small amounts of calcium, nickel, and chromium; the iron-rich members near the other end of the series may incorporate small amounts of manganese and calcium. Apart from ferrous iron, the crystalline structure of the olivines is also capable of accommodating relatively small amounts of ferric iron; dendrites (small branching crystals) of magnetite or chromite found oriented with respect to some crystallographic direction within such olivines may be attributed to exsolution. The presence of relatively large amounts of ferric oxide in the analyses of olivines, however, clearly indicates either an advanced state of oxidation or the mechanical inclusion of co-precipitating magnetite upon crystallization from the magma.

      In addition to the forsterite-fayalite series, other complete solid-solution series exist among the various olivine minerals. Fayalite is soluble in all proportions with ash-gray tephroite (from Greek tephros, “ashen”), pure manganese silicate (Mn₂SiO₄); the intermediate in the series is knebelite (FeMnSiO₄). Tephroite and knebelite come from manganese and iron ore deposits, from metamorphosed manganese-rich sedimentary rocks, and from slags.

crystal structure

 All olivines crystallize in the orthorhombic (orthorhombic system) crystal system. Olivine is classified as a nesosilicate which has isolated SiO₄ tetrahedrons bound to each other only by ionic bonds from interstitial cations. The structure of olivine can be viewed as a layered closest-packed oxygen network, with silicon ions occupying some of the tetrahedral voids and the calcium, ferrous iron, and magnesium cations occupying some of the octahedral voids (Figure 2—>). The layers consist of octahedrons cross-linked by independent SiO₄ tetrahedrons. There are two symmetrically nonequivalent octahedral sites, M1 and M2. In magnesium-iron olivines there is no M1 or M2 site preference for magnesium or ferric iron. However, in calcic olivines like monticellite, calcium preferentially enters the M2 site and magnesium occupies the M1 site.

Mineralogical characteristics

Physical properties

 The specific gravity and hardness of the olivines are listed in the Table—>. There are at least two cleavages (cleavage)—i.e., the tendency to split along preferred crystallographic directions (perpendicular to the a and b axes (axis) in this case)—both of which are better-developed in the iron-rich varieties. Forsterite contained in certain ultramafic rocks may show a banded structure when observed in thin sections with a polarizing microscope; in some dunites (dunite) (a variety of rock consisting nearly entirely of olivine), for example, olivine is preferentially oriented so that the cleavage plane perpendicular to the b axis is parallel to the microscopic laminated structure of the rock. Individual grains of olivine within such rocks typically appear as oriented bands with angles of up to 10° between them. Such banding, which is undoubtedly the product of incipient mechanical deformation, also can be observed within the olivine nodules of some basalts.

      To the unaided eye, pure forsterite appears colourless, but, as the content of ferrous oxide increases, specimens show yellow-green, dark green, and eventually brown to black tints. In thin sections under the microscope, however, even pure fayalite appears pale yellow. Pure tephroite is gray, and monticellite also appears gray or colourless.

      Some variations of optical properties observed in natural olivine crystals probably result from small but varying replacements of magnesium and iron by calcium and manganese and of silicon by titanium, chromium, and ferric iron.

Crystal habit and form

      The magnesium-iron olivines occur most commonly as compact or granular masses. Except for the well-shaped phenocrysts (single crystals) of such olivines found embedded in the fine-grained matrices (groundmass) of basalts (basalt), distinctly developed crystals are relatively rare. The phenocrysts in basalts are characterized by six- or eight-sided cross sections. With fayalite the morphology is often simple. Monticellite and tephroite commonly show prominent pyramidal faces. twinning is rare. When twinning does occur, trillings (the intergrowth of three grains) may be produced, and, in monticellite, six-pointed star shapes are reported from the Highwood Mountains in Montana, U.S.

Origin and occurrence

Igneous rocks (igneous rock)

      Olivines are found most commonly in mafic and ultramafic igneous rocks such as peridotites, dunites, gabbros (gabbro), and basalts. Forsteritic olivines, which have 88 to 92 percent forsterite, are the dominant phase of dunites and are common in peridotites. Gabbros and basalts typically contain forsteritic to intermediate-composition olivine ranging from 50 to 80 percent forsterite. Olivine is typically associated with calcic plagioclase, magnesium-rich pyroxenes, and iron-titanium oxides such as magnetite and ilmenite. This mineralogical association is diagnostic of the relatively high temperatures of crystallization of mafic rock types. Forsterite and protoenstatite crystallize together from about 1,550° C to roughly 1,300° C and are among the first minerals to crystallize from a mafic melt. Magnesium-rich olivine is unstable in a high-silica environment and is never found in equilibrium with quartz. The chemical reaction that precludes the stable coexistence of forsterite and quartz due to the formation of the orthopyroxene enstatite in the presence of excess silica is

      Fayalite (Fa), however, can coexist in equilibrium with quartz in iron-rich granites and rhyolites.

      Olivines richer in iron than Fa₅₀ are less common; they do occur in the iron-enriched layers of some intrusive rocks, however. Fayalite itself occurs in small amounts in some silicic volcanic rocks, both as a primary mineral and in the lithophysae and vugs (bubblelike hollows) of rhyolites (rhyolite) and obsidians (obsidian) (volcanic glass). It also occurs in acidic plutonic rocks such as granites (granite) in association with iron-enriched amphiboles and pyroxenes.

Metamorphic rocks (metamorphic rock)

      Olivines also occur in metamorphic environments. Both forsterite and monticellite typically develop in the zones in which igneous intrusions make contact with dolomites. Forsterite tends to develop at lower temperatures than monticellite as the process of decarbonation in the contact zone progresses. Fayalitic olivines develop within metamorphosed iron-rich sediments. In the quaternary (i.e., four-component) system Fe₂O₃-FeO-SiO₂-H₂O, fayalite is associated with the minerals greenalite (iron-serpentine), minnesotaite (iron-talc), and grunerite (iron-amphibole) in various metamorphic stages. In chemically more complex environments, which, in addition to the above components, also involve lime (CaO) and alumina (Al₂O₃), fayalite may be associated with hedenbergite, orthopyroxene, grunerite, and almandine (iron-garnet).

Meteorites (meteorite) and the Earth's mantle

      In meteorites, the olivine is usually a forsteritic variety containing only Fa₁₅ to Fa₃₀. In the Nakhla (Egypt) meteorite (an achondrite meteorite), the olivine is more ferrous, however, containing as much as Fa₆₅. In the chondrites (chondrite) (stony meteorites), the olivine is commonly incorporated in the distinctive spheroidal bodies referred to as chondrules, which range up to one millimetre in diameter.

      Because the rocks of the upper mantle directly below the Mohorovičić discontinuity (Moho) are believed to consist of peridotite and garnetiferous peridotite that contain olivines as their most abundant minerals, it is important to establish their behaviour when subjected to high pressures. Study of the olivine-like compound magnesium germanate, Mg₂GeO₄, showed that it has polymorphs (polymorphism) that have both olivine and spinel structure. In the spinel structure, the oxygen atoms are arranged in cubic closest packing (in which the position of every third layer repeats that of the initial layer) instead of hexagonal closest packing (in which the position of every second layer repeats that of the initial layer) of the olivine structure. The spinel form of Mg₂GeO₄ was found to have a density exceeding that of the olivine form by 9 percent. In 1936 it was suggested that at high pressures Mg₂SiO₄ might also transform to a spinel structure; this suggestion was adopted in 1937 as a basis for explaining the so-called 20° discontinuity, an observed seismic discontinuity in the mantle at a depth of about 400 kilometres.

      In 1966 it was shown that each of the three synthetic olivines—Fe₂SiO₄, Ni₂SiO₄, and CO₂SiO₄—could be transformed directly to a spinel structure at a temperature of 700° C and at pressures below 70 kilobars (1,000,000 pounds per square inch). These spinel structures were denser by approximately 10 percent than the corresponding olivine structures. In 1968 a series of synthetic magnesium and iron olivines was subjected to a range of pressures between 50 and 200 kilobars at a temperature of 1,000° C. In the composition range Fe₂SiO₄ to (Mg_0.8Fe_0.2)₂SiO₄, these olivines were transformed completely to their spinel polymorphs, which are isometric crystals, with an accompanying increase in density of 10 percent. In the composition range (Mg_0.8Fe_0.2)₂SiO₄ to Mg₂SiO₄, however, the olivines were transformed to another orthorhombic (orthorhombic system) structure (called β-orthosilicate) at a pressure of about 130 kilobars and a temperature of 1,000° C. This β-phase polymorph, with a density only 8 percent greater than that of the corresponding olivine structure, is believed to be the stable phase in the field of its synthesis. The change in the crystalline structure of olivine to its spinel polymorph, accompanied by a change in the structure of magnesium-iron pyroxenes to a new garnetlike structure at depths of 350 to 450 kilometres in the mantle, is believed to be responsible for the observed abrupt change in the velocity of seismic waves at these depths (see also earthquake: General considerations (earthquake)).

      The spinel polymorph of olivine has been recorded in the Tenham (Queensland, Australia) chondrite as pseudomorphs after olivine. Portions of some large grains of olivine immediately adjacent to black, shock-generated veins are recognized as transforms to the spinel phase; the associated plagioclase feldspar was converted to maskelynite. The composition of the spinel phase in the meteorite has been analyzed by means of an electron probe and found to be (Mg_0.75Fe_0.25)₂SiO₄; in thin sections it appears blue-gray to violet-blue. It has been named ringwoodite after Alfred E. Ringwood, an Australian earth scientist who synthesized spinel phases with compositions and properties close to those of the mineral found in the meteorite. More recently, ringwoodite also has been found in the Coorara (Western Australia) meteorite in association with a garnet phase. The β-phase polymorph has not yet been observed in shocked meteorites—i.e., those that have undergone impact shock—but it is highly probable that it, too, exists in relative abundance within the Earth's mantle.

Other occurrences

      Knebelite olivines are restricted to iron-manganese ore deposits, to their associated skarn (lime-bearing silicate rocks) zones, and to metamorphosed manganiferous sediments. At Franklin, N.J., U.S., tephroite and glaucochroite occur in the same deposit as roepperite, a knebelite containing 10.7 percent by weight of zinc oxide (ZnO).

      Monticellite occurs in some alkali peridotites and within limestones near their contact with peridotites. Pure kirschsteinite is known only from slags and has not yet been observed as part of a natural mineral assemblage. The most plausible natural environments for kirschsteinite are altered limestones; it is possible the mineral has remained unrecognized in such rocks because its optical properties (the chief means of identification) are similar to those of the much more common magnesium-iron olivines. A kirschsteinite containing 31 percent by weight of other olivines, particularly monticellite, has been reported from a nepheline-melilite in Nord-Kivu province, Congo (Kinshasa).

       glaucochroite, pure calcium and manganese silicate (CaMnSiO₄), is rare, reported only from a deposit in Franklin, N.J., where it occurs with tephroite. The limited availability of manganese in parent magmas is thought to account for the rarity of minerals intermediate in the solid-solution series between the calcium-rich olivines monticellite, glaucochroite, and kirschsteinite.

Alteration products and weathering

      Olivines gelatinize in even weak acids and offer little resistance to attack by weathering agents and hot mineralizing (hydrothermal) solutions. The forsteritic olivines are altered principally through leaching, which results in the removal of magnesium and the addition of water and some iron. The chemical reactions are usually complex and involve hydration, oxidation, and carbonation. The fayalitic (fayalite) olivines are altered principally through oxidation and the removal of silica. The usual product of alteration is the mineral serpentine, which may occur as a pseudomorph (a form with the outward appearance of the original mineral but that has been completely replaced by another mineral). Serpentine, which is the most common alteration product of olivine in ultramafic rocks, often is accompanied by magnesite.

      The mechanical weathering of olivine-rich rocks leads to the release of olivine particles that, in the absence of much chemical weathering, may accumulate to produce green or greenish black sands. Conspicuous examples of such sands occur on the beaches of the islands of Oahu and Hawaii, particularly at Diamond Head (Oahu) and South Point (Hawaii). Alluvial sands rich in olivine are also known from Navajo county of Arizona and from New Mexico in the United States; these sands provide the clear olivine (peridot) used in jewelry.

Cecil Edgar Tilley William B. Simmons

Additional Reading

W.A. Deer, R.A. Howie, and J. Zussman, Rock-forming Minerals, 5 vol. (1962–63), with a 2nd ed. in progress (1978– ); Manual of Mineralogy (after James D. Dana), 20th ed. by Cornelis Klein and Cornelius S. Hurlbut, Jr. (1985); J.J. Papike and M. Cameron, “Crystal Chemistry of Silicate Minerals of Geophysical Interest,” Reviews of Geophysics and Space Physics, 14(1):37–80 (1976); and Paul H. Ribbe (ed.), Orthosilicates, 2nd ed. (1982).William B. Simmons

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