Cerium anomaly

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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). [1] 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. [1]

Contents

Cerium oxidation states

Cerium is a rare-earth element (lanthanide) characterized by two different redox states: III and IV. Contrary to other lanthanide elements, which are only trivalent (with the notable exception of Eu2+), Ce3+ can be oxidized by atmospheric oxygen (O2) to Ce4+ under alkaline conditions. [2]

The cerium anomaly relates to the decrease in solubility, which accompanies the oxidation of Ce(III) to Ce(IV). Under reducing conditions, Ce3+ is relatively soluble, while under oxidizing conditions CeO2 precipitates. [1] Sediments deposited under oxic or anoxic conditions can preserve on the long term the geochemical signature of Ce3+ or Ce4+ upon reserve that no early diagenetic transformation altered it. [1]

Cerium anomalies in zircon

Crystal structure of Ceria-zirconia. Ce has the same charge and similar ionic radius as Ze resulting in elemental substitution and therefore a positive cerium anomaly. Fluorite-like crystal structure of ceria and cubic zirconia.png
Crystal structure of Ceria-zirconia. Ce has the same charge and similar ionic radius as Ze resulting in elemental substitution and therefore a positive cerium anomaly.

Zircon (ZrSiO4) is commonly found in felsic igneous rock. [3] Because both Ce3+ and Ce4+ can substitute for zirconium, Zircon often has a positive Ce anomaly. [3] Ce4+ substitutes with Zr much more easily than Ce3+ because Ce4+ (ionic radius 0.97Å) has the same charge and a similar ionic radius as Zr4+ (ionic radius 0.84Å). [1] Therefore, the oxidation state of the magma is what determines the Ce anomaly in Zircon. [3] If the oxygen fugacity is high, more Ce3+ will oxidize to Ce4+ and create a larger positive Ce anomaly in the zircon structure. At lower levels of oxygen fugacity, the level of Ce anomaly will also be lower. [3]

Cerium anomalies in coal

Negative cerium anomalies

Cerium in coal is typically weakly negative, meaning that it is present at slightly lower concentrations than the other rare-earth elements. [2] Cerium anomalies in coal are influenced by the sediment source region. [2] Coal mined from mafic regions dominated by basalts, such as the location of the Xinde Mine in China, does not have a Ce-anomaly. [2] In contrast, coal mined in felsic rock regions, such as Guxu Coalfield in China, does have weakly negative Ce-anomalies. [2] Negative Ce-anomalies can also be attributed to the weathering and oxidation of the coal-mining region. [2] During oxidation, Ce3+ precipitates out as CeO2, leaving less Ce in the coal. [1]

Positive cerium anomalies

While cerium anomalies in coal are usually negative, they can rarely be positive as well. [4] This can occur during volcanic eruptions when volcanic ash is weathered into mafic tuffs with positive Ce-anomalies. [1] The Pavlovka deposit in Far East Russia has large positive Ce-anomalies in its Fe-Mn oxyhydroxide ores. [4] Because cerium is one of only two REEs that can obtain an oxidation number of +4, Ce4+ is absorbed into Mn(IV) oxides instead of other REEs and this results in a positive Ce-anomaly. [4]

See also

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Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lanthanide, as it can be dented with a fingernail and easily cut with a knife. When oxidation is removed a shiny-white metal is visible. Europium was isolated in 1901 and is named after the continent of Europe. Being a typical member of the lanthanide series, europium usually assumes the oxidation state +3, but the oxidation state +2 is also common. All europium compounds with oxidation state +2 are slightly reducing. Europium has no significant biological role and is relatively non-toxic as compared to other heavy metals. Most applications of europium exploit the phosphorescence of europium compounds. Europium is one of the rarest of the rare-earth elements on Earth.

<span class="mw-page-title-main">Lanthanum</span> Chemical element, symbol La and atomic number 57

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 lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. Lanthanum is traditionally counted among the rare earth elements. Like most other rare earth elements, the usual oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.

The lanthanide or lanthanoid series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare-earth elements or rare-earth metals.

<span class="mw-page-title-main">Neodymium</span> Chemical element, symbol Nd and atomic number 60

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<span class="mw-page-title-main">Promethium</span> Chemical element, symbol Pm and atomic number 61

Promethium is a chemical element with the symbol Pm and atomic number 61. All of its isotopes are radioactive; it is extremely rare, with only about 500–600 grams naturally occurring in Earth's crust at any given time. Promethium is one of only two radioactive elements that are followed in the periodic table by elements with stable forms, the other being technetium. Chemically, promethium is a lanthanide. Promethium shows only one stable oxidation state of +3.

<span class="mw-page-title-main">Terbium</span> Chemical element, symbol Tb and atomic number 65

Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white, rare earth metal that is malleable, and ductile. The ninth member of the lanthanide series, terbium is a fairly electropositive metal that reacts with water, evolving hydrogen gas. Terbium is never found in nature as a free element, but it is contained in many minerals, including cerite, gadolinite, monazite, xenotime and euxenite.

<span class="mw-page-title-main">Zircon</span> Zirconium silicate, a mineral belonging to the group of nesosilicates

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<span class="mw-page-title-main">Rare-earth element</span> Any of the fifteen lanthanides plus scandium and yttrium

The rare-earth elements (REE), also called the rare-earth metals or in context rare-earth oxides, and sometimes the lanthanides, are a set of 17 nearly-indistinguishable lustrous silvery-white soft heavy metals. Compounds containing rare earths have diverse applications in electrical and electronic components, lasers, glass, magnetic materials, and industrial processes.

<span class="mw-page-title-main">Monazite</span> Mineral containing rare-earth elements

Monazite is a primarily reddish-brown phosphate mineral that contains rare-earth elements. Due to variability in composition, monazite is considered a group of minerals. The most common species of the group is monazite-(Ce), that is, the cerium-dominant member of the group. It occurs usually in small isolated crystals. It has a hardness of 5.0 to 5.5 on the Mohs scale of mineral hardness and is relatively dense, about 4.6 to 5.7 g/cm3. There are five different most common species of monazite, depending on the relative amounts of the rare earth elements in the mineral:

<span class="mw-page-title-main">Bastnäsite</span>

The mineral bastnäsite (or bastnaesite) is one of a family of three carbonate-fluoride minerals, which includes bastnäsite-(Ce) with a formula of (Ce, La)CO3F, bastnäsite-(La) with a formula of (La, Ce)CO3F, and bastnäsite-(Y) with a formula of (Y, Ce)CO3F. Some of the bastnäsites contain OH instead of F and receive the name of hydroxylbastnasite. Most bastnäsite is bastnäsite-(Ce), and cerium is by far the most common of the rare earths in this class of minerals. Bastnäsite and the phosphate mineral monazite are the two largest sources of cerium and other rare-earth elements.

<span class="mw-page-title-main">Praseodymium</span> Chemical element, symbol Pr and atomic number 59

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<span class="mw-page-title-main">Cerium(IV) oxide</span> Chemical compound

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<span class="mw-page-title-main">Europium anomaly</span> Relative europium concentration in a mineral is either enriched or depleted

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<span class="mw-page-title-main">Mineral redox buffer</span>

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.

<span class="mw-page-title-main">Yttrium</span> Chemical element, symbol Y and atomic number 39

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<span class="mw-page-title-main">Cerium</span> Chemical element, symbol Ce and atomic number 58

Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the oxidation state of +3 characteristic of the series, it also has a stable +4 state that does not oxidize water. It is also considered one of the rare-earth elements. Cerium has no known biological role in humans but is not particularly toxic, except with intense or continued exposure.

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Cerimetry or cerimetric titration, also known as cerate oximetry, is a method of volumetric chemical analysis developed by Ion Atanasiu. It is a redox titration in which an iron(II)–1,10-phenanthroline complex (ferroin) color change indicates the end point. Ferroin can be reversibly discolored in its oxidized form upon titration with a Ce4+ solution. The use of cerium(IV) salts as reagents for volumetric analysis was first proposed in the middle of 19th century, but systematic studies did not start until about 70 years later. Standard solutions can be prepared from different Ce4+ salts, but often cerium sulfate is chosen.

<span class="mw-page-title-main">Pyrosilicate</span> Chemical compound

A pyrosilicate is a type of chemical compound; either an ionic compound that contains the pyrosilicate anionSi
2
O6−
7
, or an organic compound with the hexavalent ≡O
3
Si
-O-SiO
3
≡ group. The anion is also called disilicate or diorthosilicate.

Cerium compounds are compounds containing the element cerium (Ce), a lanthanide. Cerium exists in two main oxidation states, Ce(III) and Ce(IV). This pair of adjacent oxidation states dominates several aspects of the chemistry of this element. Cerium(IV) aqueous solutions may be prepared by reacting cerium(III) solutions with the strong oxidizing agents peroxodisulfate or bismuthate. The value of E(Ce4+/Ce3+) varies widely depending on conditions due to the relative ease of complexation and hydrolysis with various anions, although +1.72 V is representative. Cerium is the only lanthanide which has important aqueous and coordination chemistry in the +4 oxidation state.

References

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