In geology, a redox buffer is an assemblage of minerals or compounds that constrains oxygen fugacity as a function of temperature. Knowledge of the redox conditions (or equivalently, oxygen fugacities) at which a rock forms and evolves can be important for interpreting the rock history. Iron, sulfur, and manganese are three of the relatively abundant elements in the Earth's crust that occur in more than one oxidation state. For instance, iron, the fourth most abundant element in the crust, exists as native iron, ferrous iron (Fe2+), and ferric iron (Fe3+). The redox state of a rock affects the relative proportions of the oxidation states of these elements and hence may determine both the minerals present and their compositions. If a rock contains pure minerals that constitute a redox buffer, then the oxygen fugacity of equilibration is defined by one of the curves in the accompanying fugacity-temperature diagram.
Redox buffers were developed in part to control oxygen fugacities in laboratory experiments to investigate mineral stabilities and rock histories. Each of the curves plotted in the fugacity-temperature diagram is for an oxidation reaction occurring in a buffer. These redox buffers are listed here in order of decreasing oxygen fugacity at a given temperature—in other words, from more oxidizing to more reducing conditions in the plotted temperature range. As long as all the pure minerals (or compounds) are present in a buffer assemblage, the oxidizing conditions are fixed on the curve for that buffer. Pressure has only a minor influence on these buffer curves for conditions in the Earth's crust.
NiNiO: nickel-nickel oxide:
FMQ: fayalite-magnetite-quartz:
The ratio of Fe2+ to Fe3+ within a rock determines, in part, the silicate mineral and oxide mineral assemblage of the rock. Within a rock of a given chemical composition, iron enters minerals based on the bulk chemical composition and the mineral phases which are stable at that temperature and pressure. For instance, at redox conditions more oxidizing than the MH (magnetite-hematite) buffer, at least much of the iron is likely to be present as Fe3+ and hematite is a likely mineral in iron-bearing rocks. Iron may only enter minerals such as olivine if it is present as Fe2+; Fe3+ cannot enter the lattice of fayalite olivine. Elements in olivine such as magnesium, however, stabilize olivine containing Fe2+ to conditions more oxidizing than those required for fayalite stability. Solid solution between magnetite and the titanium-bearing endmember, ulvospinel, enlarges the stability field of magnetite. Likewise, at conditions more reducing than the IW (iron-wustite) buffer, minerals such as pyroxene can still contain Fe3+. The redox buffers therefore are only approximate guides to the proportions of Fe2+ and Fe3+ in minerals and rocks.
Terrestrial igneous rocks commonly record crystallization at oxygen fugacities more oxidizing than the WM (wüstite-magnetite) buffer and more reduced than a log unit or so above the nickel-nickel oxide (NiNiO) buffer. Their oxidizing conditions thus are not far from those of the FMQ (fayalite-magnetite-quartz) redox buffer. Nonetheless, there are systematic differences that correlate with tectonic setting. Igneous rock emplaced and erupted in island arcs typically record oxygen fugacities 1 or more log units more oxidizing than those of the NiNiO buffer. In contrast, basalt and gabbro in non-arc settings typically record oxygen fugacities from about those of the FMQ buffer to a log unit or so more reducing than that buffer.
Oxidizing conditions are common in some environments of deposition and diagenesis of sedimentary rocks. The fugacity of oxygen at the MH buffer (magnetite-hematite) is only about 10−70 at 25 °C, but it is about 0.2 atmospheres in the Earth's atmosphere, so some sedimentary environments are far more oxidizing than those in magmas. Other sedimentary environments, such as the environments for formation of black shale, are relatively reducing.
Oxygen fugacities during metamorphism extend to higher values than those in magmatic environments, because of the more oxidizing compositions inherited from some sedimentary rocks. Nearly pure hematite is present in some metamorphosed banded iron formations. In contrast, native nickel-iron is present in some serpentinites.
Within meteorites, the iron-wüstite redox buffer may be more appropriate for describing the oxygen fugacity of these extraterrestrial systems.
Sulfide minerals such as pyrite (FeS2) and pyrrhotite (Fe1−xS) occur in many ore deposits. Pyrite and its polymorph marcasite also are important in many coal deposits and shales. These sulfide minerals form in environments more reducing than that of the Earth's surface. When in contact with oxidizing surface waters, sulfides react: sulfate (SO42−) forms, and the water becomes acidic and charged with a variety of elements, some potentially toxic. Consequences can be environmentally harmful, as discussed in the entry for acid mine drainage.
Sulfur oxidation to sulfate or sulfur dioxide also is important in generating sulfur-rich volcanic eruptions, like those of Pinatubo [3] in 1991 and El Chichon in 1982. These eruptions contributed unusually large quantities of sulfur dioxide to the Earth's atmosphere, with consequent effects on atmospheric quality and on climate. The magmas were unusually oxidizing, almost two log units more so than the NiNiO buffer. The calcium sulfate, anhydrite, was present as phenocrysts in the erupted tephra. In contrast, sulfides contain most of the sulfur in magmas more reducing than the FMQ buffer.
Redox is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. The oxidation and reduction processes occur simultaneously in the chemical reaction.
Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With the exception of extremely rare native iron deposits, it is the most magnetic of all the naturally occurring minerals on Earth. Naturally magnetized pieces of magnetite, called lodestone, will attract small pieces of iron, which is how ancient peoples first discovered the property of magnetism.
Wüstite is a mineral form of mostly iron(II) oxide found with meteorites and native iron. It has a grey colour with a greenish tint in reflected light. Wüstite crystallizes in the isometric-hexoctahedral crystal system in opaque to translucent metallic grains. It has a Mohs hardness of 5 to 5.5 and a specific gravity of 5.88. Wüstite is a typical example of a non-stoichiometric compound.
Forsterite (Mg2SiO4; commonly abbreviated as Fo; also known as white olivine) is the magnesium-rich end-member of the olivine solid solution series. It is isomorphous with the iron-rich end-member, fayalite. Forsterite crystallizes in the orthorhombic system (space group Pbnm) with cell parameters a 4.75 Å (0.475 nm), b 10.20 Å (1.020 nm) and c 5.98 Å (0.598 nm).
The pedosphere is the outermost layer of the Earth that is composed of soil and subject to soil formation processes. It exists at the interface of the lithosphere, atmosphere, hydrosphere and biosphere. The pedosphere is the skin of the Earth and only develops when there is a dynamic interaction between the atmosphere, biosphere, lithosphere and the hydrosphere. The pedosphere is the foundation of terrestrial life on Earth.
Fayalite is the iron-rich end-member of the olivine solid-solution series. In common with all minerals in the olivine group, fayalite crystallizes in the orthorhombic system with cell parameters a 4.82 Å, b 10.48 Å and c 6.09 Å.
Serpentinization is a hydration and metamorphic transformation of ferromagnesian minerals, such as olivine and pyroxene, in mafic and ultramafic rock to produce serpentinite. Minerals formed by serpentinization include the serpentine group minerals, brucite, talc, Ni-Fe alloys, and magnetite. The mineral alteration is particularly important at the sea floor at tectonic plate boundaries.
The iron cycle (Fe) is the biogeochemical cycle of iron through the atmosphere, hydrosphere, biosphere and lithosphere. While Fe is highly abundant in the Earth's crust, it is less common in oxygenated surface waters. Iron is a key micronutrient in primary productivity, and a limiting nutrient in the Southern ocean, eastern equatorial Pacific, and the subarctic Pacific referred to as High-Nutrient, Low-Chlorophyll (HNLC) regions of the ocean.
Rubredoxins are a class of low-molecular-weight iron-containing proteins found in sulfur-metabolizing bacteria and archaea. Sometimes rubredoxins are classified as iron-sulfur proteins; however, in contrast to iron-sulfur proteins, rubredoxins do not contain inorganic sulfide. Like cytochromes, ferredoxins and Rieske proteins, rubredoxins are thought to participate in electron transfer in biological systems. Recent work in bacteria and algae have led to the hypothesis that some rubredoxins may instead have a role in delivering iron to metalloproteins.
The tholeiitic magma series is one of two main magma series in subalkaline igneous rocks, the other being the calc-alkaline series. A magma series is a chemically distinct range of magma compositions that describes the evolution of a mafic magma into a more evolved, silica rich end member. Rock types of the tholeiitic magma series include tholeiitic basalt, ferro-basalt, tholeiitic basaltic andesite, tholeiitic andesite, dacite and rhyolite. The variety of basalt in the series was originally called tholeiite but the International Union of Geological Sciences recommends that tholeiitic basalt be used in preference to that term.
Ulvöspinel or ulvite is an iron titanium oxide mineral with formula: Fe2TiO4 or TiFe2+2O4. It forms brown to black metallic isometric crystals with a Mohs hardness of 5.5 to 6. It belongs to the spinel group of minerals, as does magnetite, Fe3O4.
Normative mineralogy is a calculation of the composition of a rock sample that estimates the idealised mineralogy of a rock based on a quantitative chemical analysis according to the principles of geochemistry.
Fractional crystallization, or crystal fractionation, is one of the most important geochemical and physical processes operating within crust and mantle of a rocky planetary body, such as the Earth. It is important in the formation of igneous rocks because it is one of the main processes of magmatic differentiation. Fractional crystallization is also important in the formation of sedimentary evaporite rocks or simply fractional crystallization is the removal of early formed crystals from an Original homogeneous magma so that the crystals are prevented from further reaction with the residual melt.
The calc-alkaline magma series is one of two main subdivisions of the subalkaline magma series, the other subalkaline magma series being the tholeiitic series. A magma series is a series of compositions that describes the evolution of a mafic magma, which is high in magnesium and iron and produces basalt or gabbro, as it fractionally crystallizes to become a felsic magma, which is low in magnesium and iron and produces rhyolite or granite. Calc-alkaline rocks are rich in alkaline earths and alkali metals and make up a major part of the crust of the continents.
The surface color of the planet Mars appears reddish from a distance because of rusty atmospheric dust. From close up, it looks more of a butterscotch, and other common surface colors include golden, brown, tan, and greenish, depending on minerals.
The cerium anomaly, in geochemistry, is the phenomenon whereby cerium (Ce) concentration is either depleted or enriched in a rock relative to the other rare-earth elements (REEs). A Ce anomaly is said to be "negative" if Ce is depleted relative to the other REEs and is said to be "positive" if Ce is enriched relative to the other REEs.
The Schikorr reaction formally describes the conversion of the iron(II) hydroxide (Fe(OH)2) into iron(II,III) oxide (Fe3O4). This transformation reaction was first studied by Gerhard Schikorr. The global reaction follows:
Magnetic mineralogy is the study of the magnetic properties of minerals. The contribution of a mineral to the total magnetism of a rock depends strongly on the type of magnetic order or disorder. Magnetically disordered minerals contribute a weak magnetism and have no remanence. The more important minerals for rock magnetism are the minerals that can be magnetically ordered, at least at some temperatures. These are the ferromagnets, ferrimagnets and certain kinds of antiferromagnets. These minerals have a much stronger response to the field and can have a remanence.
Iron-rich sedimentary rocks are sedimentary rocks which contain 15 wt.% or more iron. However, most sedimentary rocks contain iron in varying degrees. The majority of these rocks were deposited during specific geologic time periods: The Precambrian, the early Paleozoic, and the middle to late Mesozoic. Overall, they make up a very small portion of the total sedimentary record.
Mantle oxidation state (redox state) applies the concept of oxidation state in chemistry to the study of the Earth's mantle. The chemical concept of oxidation state mainly refers to the valence state of one element, while mantle oxidation state provides the degree of decreasing of increasing valence states of all polyvalent elements in mantle materials confined in a closed system. The mantle oxidation state is controlled by oxygen fugacity and can be benchmarked by specific groups of redox buffers.