Rare earth elements
   HOME

TheInfoList



OR:

The rare-earth elements (REE), also called the rare-earth metals or (in context) rare-earth oxides or sometimes the lanthanides (
yttrium Yttrium is a chemical element with the symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a " rare-earth element". Yttrium is almost always found in co ...
and scandium are usually included as rare earths), 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. Scandium and yttrium are considered rare-earth elements because they tend to occur in the same
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 Apr ...
deposits as the lanthanides and exhibit similar chemical properties, but have different electronic and magnetic properties. These metals tarnish slowly in air at room temperature and react slowly with cold water to form hydroxides, liberating hydrogen. They react with steam to form oxides, and at elevated temperature (400°C) ignite spontaneously. These elements and their compounds have no biological function other than in several specialized enzymes, such as in lanthanide-dependent methanol dehydrogenases in bacteria. The water-soluble compounds are mildly to moderately toxic, but the insoluble ones are not. Despite their name, rare-earth elements are relatively plentiful in Earth's crust, with
cerium 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 +3 ...
being the 25th most abundant element at 68 parts per million, more abundant than
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
. All isotopes of promethium are radioactive, and it does not occur naturally in the earth's crust, except for a trace amount generated by spontaneous fission of Uranium-238. They are often found in minerals with
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
, and less commonly
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
. Because of their geochemical properties, rare-earth elements are typically dispersed and not often found concentrated in rare-earth minerals. Consequently, economically exploitable
ore deposits Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 April ...
are sparse (i.e. "rare"). The first rare-earth mineral discovered (1787) was gadolinite, a black mineral composed of cerium, yttrium, iron, silicon, and other elements. This mineral was extracted from a mine in the village of Ytterby in Sweden; four of the rare-earth elements bear names derived from this single location.


List

A table listing the 17 rare-earth elements, their
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
and symbol, the etymology of their names, and their main uses (see also Applications of lanthanides) is provided here. Some of the rare-earth elements are named after the scientists who discovered them, or elucidated their elemental properties, and some after the geographical locations where discovered. A mnemonic for the names of the sixth-row elements in order is "Lately college parties never produce sexy European girls that drink heavily even though you look".


Discovery and early history

Rare earths were mainly discovered as components of minerals. Ytterbium was found in the "ytterbite" (renamed to gadolinite in 1800). It was discovered by Lieutenant
Carl Axel Arrhenius Carl Axel Arrhenius (29 March 1757 – 20 November 1824) was an officer in the Swedish army as well as an amateur geologist and chemist. He is best known for his discovery of the mineral ytterbite (later called gadolinite) in 1787. The disc ...
in 1787 at a quarry in the village of Ytterby, Sweden. Arrhenius's "ytterbite" reached
Johan Gadolin Johan Gadolin (5 June 176015 August 1852) was a Finnish chemist, physicist and mineralogist. Gadolin discovered a " new earth" containing the first rare-earth compound yttrium, which was later determined to be a chemical element. He is also ...
, a
Royal Academy of Turku The Royal Academy of Turku or the Royal Academy of Åbo ( sv, Kungliga Akademin i Åbo or ; la, Regia Academia Aboensis; fi, Turun akatemia) was the first university in Finland, and the only Finnish university that was founded when the country ...
professor, and his analysis yielded an unknown oxide ("earth"), which he called yttria. Anders Gustav Ekeberg isolated
beryllium Beryllium is a chemical element with the symbol Be and atomic number 4. It is a steel-gray, strong, lightweight and brittle alkaline earth metal. It is a divalent element that occurs naturally only in combination with other elements to form m ...
from the gadolinite but failed to recognize other elements in the ore. After this discovery in 1794, a mineral from Bastnäs near Riddarhyttan, Sweden, which was believed to be an
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
mineral, was re-examined by Jöns Jacob Berzelius and
Wilhelm Hisinger Wilhelm Hisinger (23 December 1766 – 28 June 1852) was a Swedish physicist and chemist who in 1807, working in coordination with Jöns Jakob Berzelius, noted that in electrolysis any given substance always went to the same pole, and that substan ...
. In 1803 they obtained a white oxide and called it ceria.
Martin Heinrich Klaproth Martin Heinrich Klaproth (1 December 1743 – 1 January 1817) was a German chemist. He trained and worked for much of his life as an apothecary, moving in later life to the university. His shop became the second-largest apothecary in Berlin, and ...
independently discovered the same oxide and called it ''ochroia''. It took another 30 years for researchers to determine that other elements were contained in the two ores ceria and yttria (the similarity of the rare-earth metals' chemical properties made their separation difficult). In 1839 Carl Gustav Mosander, an assistant of Berzelius, separated ceria by heating the nitrate and dissolving the product in
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
. He called the oxide of the soluble salt ''lanthana''. It took him three more years to separate the lanthana further into ''didymia'' and pure lanthana. Didymia, although not further separable by Mosander's techniques, was in fact still a mixture of oxides. In 1842 Mosander also separated the yttria into three oxides: pure yttria, terbia and erbia (all the names are derived from the town name "Ytterby"). The earth giving pink salts he called ''terbium''; the one that yielded yellow peroxide he called ''erbium''. So in 1842 the number of known rare-earth elements had reached six: yttrium, cerium, lanthanum, didymium, erbium and terbium.
Nils Johan Berlin Nils Johan Berlin (Nils Johannes Berlin) (18 February 1812 – 27 December 1891) was a Swedish chemist and physician, who held various professorships at the University of Lund from 1843 to 1864. Berlin was the first chemist who took the initiativ ...
and Marc Delafontaine tried also to separate the crude yttria and found the same substances that Mosander obtained, but Berlin named (1860) the substance giving pink salts ''erbium'', and Delafontaine named the substance with the yellow peroxide ''terbium''. This confusion led to several false claims of new elements, such as the ''mosandrium'' of J. Lawrence Smith, or the ''philippium'' and ''
decipium Decipium was the proposed name for a new chemical element isolated by Marc Delafontaine from the mineral samarskite. He published his discovery in 1878 and later published a follow-up paper in 1881. Decipium was considered to be in the cerium gro ...
'' of Delafontaine. Due to the difficulty in separating the metals (and determining the separation is complete), the total number of false discoveries was dozens, with some putting the total number of discoveries at over a hundred.


Spectroscopic identification

There were no further discoveries for 30 years, and the element didymium was listed in the periodic table of elements with a molecular mass of 138. In 1879 Delafontaine used the new physical process of optical flame spectroscopy and found several new spectral lines in didymia. Also in 1879, the new element ''
samarium Samarium is a chemical element with symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of samar ...
'' was isolated by
Paul Émile Lecoq de Boisbaudran Paul may refer to: *Paul (given name), a given name (includes a list of people with that name) * Paul (surname), a list of people People Christianity *Paul the Apostle (AD c.5–c.64/65), also known as Saul of Tarsus or Saint Paul, early Chri ...
from the mineral
samarskite Samarskite is a radioactive rare earth mineral series which includes samarskite-(Y), with the chemical formula and samarskite-(Yb), with the chemical formula . The formula for samarskite-(Y) is also given as . Samarskite crystallizes in the orth ...
. The samaria earth was further separated by Lecoq de Boisbaudran in 1886, and a similar result was obtained by
Jean Charles Galissard de Marignac Jean Charles Galissard de Marignac (24 April 1817 – 15 April 1894) was a Swiss chemist whose work with atomic weights suggested the possibility of isotopes and the packing fraction of nuclei. His study of the rare earth elements led to h ...
by direct isolation from samarskite. They named the element ''
gadolinium Gadolinium is a chemical element with the symbol Gd and atomic number 64. Gadolinium is a silvery-white metal when oxidation is removed. It is only slightly malleable and is a ductile rare-earth element. Gadolinium reacts with atmospheric oxygen ...
'' after
Johan Gadolin Johan Gadolin (5 June 176015 August 1852) was a Finnish chemist, physicist and mineralogist. Gadolin discovered a " new earth" containing the first rare-earth compound yttrium, which was later determined to be a chemical element. He is also ...
, and its oxide was named " gadolinia". Further spectroscopic analysis between 1886 and 1901 of samaria, yttria, and samarskite by
William Crookes Sir William Crookes (; 17 June 1832 – 4 April 1919) was a British chemist and physicist who attended the Royal College of Chemistry, now part of Imperial College London, and worked on spectroscopy. He was a pioneer of vacuum tubes, inventing t ...
, Lecoq de Boisbaudran and Eugène-Anatole Demarçay yielded several new spectroscopic lines that indicated the existence of an unknown element. The fractional crystallization of the oxides then yielded '' europium'' in 1901. In 1839 the third source for rare earths became available. This is a mineral similar to gadolinite, ''uranotantalum'' (now called "samarskite"). This mineral from
Miass Miass ( rus, Миа́сс, p=mʲɪˈas) is a city in Chelyabinsk Oblast, Russia, located west of Chelyabinsk, on the eastern slope of the Southern Ural Mountains, on the bank of the river Miass. Population: Name The name Miass is taken from ...
in the southern
Ural Mountains The Ural Mountains ( ; rus, Ура́льские го́ры, r=Uralskiye gory, p=ʊˈralʲskʲɪjə ˈɡorɨ; ba, Урал тауҙары) or simply the Urals, are a mountain range that runs approximately from north to south through western ...
was documented by
Gustav Rose Prof Gustavus ("Gustav") Rose FRSFor HFRSE (18 March 1798 – 15 July 1873) was a German mineralogist who was a native of Berlin. He was President of the German Geological Society from 1863 to 1873. Life He was born in Berlin the son of pharmaco ...
. The Russian chemist R. Harmann proposed that a new element he called " ilmenium" should be present in this mineral, but later, Christian Wilhelm Blomstrand, Galissard de Marignac, and Heinrich Rose found only
tantalum Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that ...
and niobium (
columbium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
) in it. The exact number of rare-earth elements that existed was highly unclear, and a maximum number of 25 was estimated. The use of X-ray spectra (obtained by
X-ray crystallography X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
) by Henry Gwyn Jeffreys Moseley made it possible to assign atomic numbers to the elements. Moseley found that the exact number of lanthanides had to be 15, and that element 61 had yet to be discovered. Using these facts about atomic numbers from X-ray crystallography, Moseley also showed that
hafnium Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...
(element 72) would not be a rare-earth element. Moseley was killed in
World War I World War I (28 July 1914 11 November 1918), often abbreviated as WWI, was one of the deadliest global conflicts in history. Belligerents included much of Europe, the Russian Empire, the United States, and the Ottoman Empire, with fightin ...
in 1915, years before hafnium was discovered. Hence, the claim of
Georges Urbain Georges Urbain (12 April 1872 – 5 November 1938) was a French chemist, a professor of the Sorbonne, a member of the Institut de France, and director of the Institute of Chemistry in Paris. Much of his work focused on the rare earths, isolating a ...
that he had discovered element 72 was untrue. Hafnium is an element that lies in the periodic table immediately below
zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
, and hafnium and zirconium are very similar in their chemical and physical properties. During the 1940s, Frank Spedding and others in the United States (during the
Manhattan Project The Manhattan Project was a research and development undertaking during World War II that produced the first nuclear weapons. It was led by the United States with the support of the United Kingdom and Canada. From 1942 to 1946, the project w ...
) developed chemical ion-exchange procedures for separating and purifying the rare-earth elements. This method was first applied to the
actinide The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The info ...
s for separating
plutonium-239 Plutonium-239 (239Pu or Pu-239) is an isotope of plutonium. Plutonium-239 is the primary fissile isotope used for the production of nuclear weapons, although uranium-235 is also used for that purpose. Plutonium-239 is also one of the three mai ...
and
neptunium Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to it bein ...
from
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
,
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
,
actinium Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated by Friedrich Oskar Giesel in 1902, who gave it the name ''emanium''; the element got its name by being wrongly identified with a substance An ...
, and the other actinides in the materials produced in
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat fr ...
s. Plutonium-239 was very desirable because it is a fissile material. The principal sources of rare-earth elements are the minerals
bastnäsite 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 formul ...
,
monazite 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 ceriu ...
, and
loparite Loparite-(Ce) is a granular, brittle oxide mineral of the perovskite class. It is black to dark grey and may appear grey to white in reflected light on polished thin section with reddish brown internal reflections.Loparite-(Ce) oWebmineral/ref> It ...
and the lateritic ion-adsorption
clay Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
s. Despite their high relative abundance, rare-earth minerals are more difficult to mine and extract than equivalent sources of
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that ca ...
s (due in part to their similar chemical properties), making the rare-earth elements relatively expensive. Their industrial use was very limited until efficient separation techniques were developed, such as
ion exchange Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, ...
, fractional crystallization and liquid–liquid extraction during the late 1950s and early 1960s. Some ilmenite concentrates contain small amounts of scandium and other rare-earth elements, which could be analysed by XRF.


Early classification

Before the time that ion-exchange methods and
elution In analytical and organic chemistry, elution is the process of extracting one material from another by washing with a solvent; as in washing of loaded ion-exchange resins to remove captured ions. In a liquid chromatography experiment, for exam ...
were available, the separation of the rare earths was primarily achieved by repeated
precipitation In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls under gravitational pull from clouds. The main forms of precipitation include drizzle, rain, sleet, snow, ice pellets, graupel and hail. ...
or crystallization. In those days, the first separation was into two main groups, the cerium earths (scandium, lanthanum, cerium, praseodymium, neodymium, and samarium) and the yttrium earths (yttrium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). Europium, gadolinium, and terbium were either considered as a separate group of rare-earth elements (the terbium group), or europium was included in the cerium group, and gadolinium and terbium were included in the yttrium group. The reason for this division arose from the difference in
solubility In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solub ...
of rare-earth double sulfates with sodium and potassium. The sodium double sulfates of the cerium group are poorly soluble, those of the terbium group slightly, and those of the yttrium group are very soluble. Sometimes, the yttrium group was further split into the erbium group (dysprosium, holmium, erbium, and thulium) and the ytterbium group (ytterbium and lutetium), but today the main grouping is between the cerium and the yttrium groups. Today, the rare-earth elements are classified as light or heavy rare-earth elements, rather than in cerium and yttrium groups.


Light versus heavy classification

The classification of rare-earth elements is inconsistent between authors. The most common distinction between rare-earth elements is made by
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
s; those with low atomic numbers are referred to as light rare-earth elements (LREE), those with high atomic numbers are the heavy rare-earth elements (HREE), and those that fall in between are typically referred to as the middle rare-earth elements (MREE). Commonly, rare-earth elements with atomic numbers 57 to 61 (lanthanum to promethium) are classified as light and those with atomic numbers 62 and greater are classified as heavy-rare earth elements. Increasing atomic numbers between light and heavy rare-earth elements and decreasing atomic radii throughout the series causes chemical variations. Europium is exempt of this classification as it has two valence states: Eu and Eu. Yttrium is grouped as heavy rare-earth element due to chemical similarities. The break between the two groups is sometimes put elsewhere, such as between elements 63 (europium) and 64 (gadolinium). The actual metallic densities of these two groups overlap, with the "light" group having densities from 6.145 (lanthanum) to 7.26 (promethium) or 7.52 (samarium) g/cc, and the "heavy" group from 6.965 (ytterbium) to 9.32 (thulium), as well as including yttrium at 4.47. Europium has a density of 5.24.


Origin

Rare-earth elements, except scandium, are heavier than
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
and thus are produced by supernova nucleosynthesis or by the s-process in asymptotic giant branch stars. In nature, spontaneous fission of uranium-238 produces trace amounts of radioactive promethium, but most promethium is synthetically produced in nuclear reactors. Due to their chemical similarity, the concentrations of rare earths in rocks are only slowly changed by geochemical processes, making their proportions useful for
geochronology Geochronology is the science of determining the age of rocks, fossils, and sediments using signatures inherent in the rocks themselves. Absolute geochronology can be accomplished through radioactive isotopes, whereas relative geochronology is ...
and dating fossils.


Geological distribution

As seen in the chart to the right, rare-earth elements are found on earth at similar concentrations to many common transition metals. The most abundant rare-earth element is
cerium 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 +3 ...
, which is actually the 25th most abundant element in Earth's crust, having 68 parts per million (about as common as copper). The exception is the highly unstable and radioactive promethium "rare earth" is quite scarce. The longest-lived isotope of promethium has a half-life of 17.7 years, so the element exists in nature in only negligible amounts (approximately 572 g in the entire Earth's crust). Promethium is one of the two elements that do not have stable (non-radioactive) isotopes and are followed by (i.e. with higher atomic number) stable elements (the other being
technetium Technetium is a chemical element with the symbol Tc and atomic number 43. It is the lightest element whose isotopes are all radioactive. All available technetium is produced as a synthetic element. Naturally occurring technetium is a spontaneous ...
). The rare-earth elements are often found together. During the sequential accretion of the Earth, the dense rare-earth elements were incorporated into the deeper portions of the planet. Early differentiation of molten material largely incorporated the rare-earths into mantle rocks. The high field strength and large ionic radii of rare-earths make them incompatible with the crystal lattices of most rock-forming minerals, so REE will undergo strong partitioning into a melt phase if one is present. REE are chemically very similar and have always been difficult to separate, but a gradual decrease in ionic radius from light REE (LREE) to heavy REE (HREE), called
lanthanide contraction The lanthanide contraction is the greater-than-expected decrease in atomic radii/ionic radii of the elements in the lanthanide series from atomic number 57, lanthanum, to 71, lutetium, which results in smaller than otherwise expected atomic radii ...
, can produce a broad separation between light and heavy REE. The larger ionic radii of LREE make them generally more incompatible than HREE in rock-forming minerals, and will partition more strongly into a melt phase, while HREE may prefer to remain in the crystalline residue, particularly if it contains HREE-compatible minerals like
garnet Garnets () are a group of silicate minerals that have been used since the Bronze Age as gemstones and abrasives. All species of garnets possess similar physical properties and crystal forms, but differ in chemical composition. The different s ...
. The result is that all magma formed from partial melting will always have greater concentrations of LREE than HREE, and individual minerals may be dominated by either HREE or LREE, depending on which range of ionic radii best fits the crystal lattice. Among the anhydrous rare-earth phosphates, it is the tetragonal mineral xenotime that incorporates yttrium and the HREE, whereas the monoclinic
monazite 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 ceriu ...
phase incorporates cerium and the LREE preferentially. The smaller size of the HREE allows greater solid solubility in the rock-forming minerals that make up Earth's mantle, and thus yttrium and the HREE show less enrichment in Earth's crust relative to
chondritic A chondrite is a stony (non-metallic) meteorite that has not been modified, by either melting or differentiation of the parent body. They are formed when various types of dust and small grains in the early Solar System accreted to form pri ...
abundance than does cerium and the LREE. This has economic consequences: large ore bodies of LREE are known around the world and are being exploited. Ore bodies for HREE are more rare, smaller, and less concentrated. Most of the current supply of HREE originates in the "ion-absorption clay" ores of Southern China. Some versions provide concentrates containing about 65% yttrium oxide, with the HREE being present in ratios reflecting the Oddo–Harkins rule: even-numbered REE at abundances of about 5% each, and odd-numbered REE at abundances of about 1% each. Similar compositions are found in xenotime or gadolinite. Well-known minerals containing yttrium, and other HREE, include gadolinite, xenotime,
samarskite Samarskite is a radioactive rare earth mineral series which includes samarskite-(Y), with the chemical formula and samarskite-(Yb), with the chemical formula . The formula for samarskite-(Y) is also given as . Samarskite crystallizes in the orth ...
, euxenite, fergusonite, yttrotantalite, yttrotungstite, yttrofluorite (a variety of
fluorite Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon. The Mohs sca ...
), thalenite,
yttrialite Yttrialite or Yttrialite-(Y) is a rare yttrium thorium sorosilicate mineral with formula: ( Y, Th)2 Si2 O7. It forms green to orange yellow masses with conchoidal fracture. It crystallizes in the monoclinic-prismatic crystal system. It has a Mohs h ...
. Small amounts occur in
zircon Zircon () is a mineral belonging to the group of nesosilicates and is a source of the metal zirconium. Its chemical name is zirconium(IV) silicate, and its corresponding chemical formula is Zr SiO4. An empirical formula showing some of t ...
, which derives its typical yellow fluorescence from some of the accompanying HREE. The
zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
mineral
eudialyte Eudialyte, whose name derives from the Greek phrase , , meaning "well decomposable", is a somewhat rare, nine member ring cyclosilicate mineral, which forms in alkaline igneous rocks, such as nepheline syenites. Its name alludes to its ready ...
, such as is found in southern
Greenland Greenland ( kl, Kalaallit Nunaat, ; da, Grønland, ) is an island country in North America that is part of the Kingdom of Denmark. It is located between the Arctic and Atlantic oceans, east of the Canadian Arctic Archipelago. Greenland i ...
, contains small but potentially useful amounts of yttrium. Of the above yttrium minerals, most played a part in providing research quantities of lanthanides during the discovery days. Xenotime is occasionally recovered as a byproduct of heavy-sand processing, but is not as abundant as the similarly recovered
monazite 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 ceriu ...
(which typically contains a few percent of yttrium). Uranium ores from Ontario have occasionally yielded yttrium as a byproduct. Well-known minerals containing cerium, and other LREE, include
bastnäsite 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 formul ...
,
monazite 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 ceriu ...
, allanite,
loparite Loparite-(Ce) is a granular, brittle oxide mineral of the perovskite class. It is black to dark grey and may appear grey to white in reflected light on polished thin section with reddish brown internal reflections.Loparite-(Ce) oWebmineral/ref> It ...
, ancylite,
parisite Parisite is a rare mineral consisting of cerium, lanthanum and calcium fluoro-carbonate, . Parisite is mostly parisite-(Ce), but when neodymium is present in the structure the mineral becomes parisite-(Nd). It is found only as crystals, which bel ...
,
lanthanite Lanthanites are a group of isostructural rare earth element (REE) carbonate minerals. This group comprises the minerals lanthanite-(La), lanthanite-(Ce), and lanthanite-(Nd). This mineral group has the general chemical formula of (''REE'')2(CO3)3 ...
, chevkinite, cerite, stillwellite, britholite, fluocerite, and cerianite. Monazite (marine sands from
Brazil Brazil ( pt, Brasil; ), officially the Federative Republic of Brazil (Portuguese: ), is the largest country in both South America and Latin America. At and with over 217 million people, Brazil is the world's fifth-largest country by area ...
,
India India, officially the Republic of India (Hindi: ), is a country in South Asia. It is the seventh-largest country by area, the second-most populous country, and the most populous democracy in the world. Bounded by the Indian Ocean on the so ...
, or Australia; rock from
South Africa South Africa, officially the Republic of South Africa (RSA), is the Southern Africa, southernmost country in Africa. It is bounded to the south by of coastline that stretch along the Atlantic Ocean, South Atlantic and Indian Oceans; to the ...
), bastnäsite (from Mountain Pass rare earth mine, or several localities in China), and
loparite Loparite-(Ce) is a granular, brittle oxide mineral of the perovskite class. It is black to dark grey and may appear grey to white in reflected light on polished thin section with reddish brown internal reflections.Loparite-(Ce) oWebmineral/ref> It ...
(
Kola Peninsula sjd, Куэлнэгк нёа̄ррк , image_name= Kola peninsula.png , image_caption= Kola Peninsula as a part of Murmansk Oblast , image_size= 300px , image_alt= , map_image= Murmansk in Russia.svg , map_caption = Location of Murmansk Oblas ...
,
Russia Russia (, , ), or the Russian Federation, is a transcontinental country spanning Eastern Europe and Northern Asia. It is the largest country in the world, with its internationally recognised territory covering , and encompassing one-eig ...
) have been the principal ores of cerium and the light lanthanides. Enriched deposits of rare-earth elements at the surface of the Earth,
carbonatite Carbonatite () is a type of intrusive or extrusive igneous rock defined by mineralogic composition consisting of greater than 50% carbonate minerals. Carbonatites may be confused with marble and may require geochemical verification. Carbonati ...
s and pegmatites, are related to alkaline plutonism, an uncommon kind of magmatism that occurs in tectonic settings where there is rifting or that are near subduction zones. In a rift setting, the alkaline magma is produced by very small degrees of partial melting (<1%) of garnet peridotite in the
upper mantle The upper mantle of Earth is a very thick layer of rock inside the planet, which begins just beneath the crust (at about under the oceans and about under the continents) and ends at the top of the lower mantle at . Temperatures range from appr ...
(200 to 600 km depth). This melt becomes enriched in incompatible elements, like the rare-earth elements, by leaching them out of the crystalline residue. The resultant magma rises as a diapir, or
diatreme A diatreme, sometimes known as a maar-diatreme volcano, is a volcanic pipe formed by a gaseous explosion. When magma rises up through a crack in Earth's crust and makes contact with a shallow body of groundwater, rapid expansion of heated wate ...
, along pre-existing fractures, and can be emplaced deep in
the crust ''The Crust'' is a British television series about a pizza parlour which was originally shown by CBBC. It was produced by Darrall Macqueen Darrall Macqueen is an independent children's television production company based in London, United ...
, or erupted at the surface. Typical REE enriched deposits types forming in rift settings are carbonatites, and A- and M-Type granitoids. Near subduction zones, partial melting of the subducting plate within the asthenosphere (80 to 200 km depth) produces a volatile-rich magma (high concentrations of and water), with high concentrations of alkaline elements, and high element mobility that the rare-earths are strongly partitioned into. This melt may also rise along pre-existing fractures, and be emplaced in the crust above the subducting slab or erupted at the surface. REE enriched deposits forming from these melts are typically S-Type granitoids. Alkaline magmas enriched with rare-earth elements include carbonatites, peralkaline granites (pegmatites), and nepheline syenite.
Carbonatite Carbonatite () is a type of intrusive or extrusive igneous rock defined by mineralogic composition consisting of greater than 50% carbonate minerals. Carbonatites may be confused with marble and may require geochemical verification. Carbonati ...
s crystallize from -rich fluids, which can be produced by partial melting of hydrous-carbonated lherzolite to produce a CO-rich primary magma, by fractional crystallization of an alkaline primary magma, or by separation of a -rich immiscible liquid from. These liquids are most commonly forming in association with very deep Precambrian
Craton A craton (, , or ; from grc-gre, κράτος "strength") is an old and stable part of the continental lithosphere, which consists of Earth's two topmost layers, the crust and the uppermost mantle. Having often survived cycles of merging an ...
s, like the ones found in Africa and the Canadian Shield. Ferrocarbonatites are the most common type of carbonatite to be enriched in REE, and are often emplaced as late-stage,
breccia Breccia () is a rock composed of large angular broken fragments of minerals or rocks cemented together by a fine-grained matrix. The word has its origins in the Italian language, in which it means "rubble". A breccia may have a variety of ...
ted pipes at the core of igneous complexes; they consist of fine-grained calcite and hematite, sometimes with significant concentrations of ankerite and minor concentrations of siderite. Large carbonatite deposits enriched in rare-earth elements include Mount Weld in Australia, Thor Lake in Canada, Zandkopsdrift in South Africa, and Mountain Pass in the USA. Peralkaline granites (A-Type granitoids) have very high concentrations of alkaline elements and very low concentrations of phosphorus; they are deposited at moderate depths in extensional zones, often as igneous ring complexes, or as pipes, massive bodies, and lenses. These fluids have very low viscosities and high element mobility, which allows for crystallization of large grains, despite a relatively short crystallization time upon emplacement; their large grain size is why these deposits are commonly referred to as pegmatites. Economically viable pegmatites are divided into Lithium-Cesium-Tantalum (LCT) and Niobium-Yttrium-Fluorine (NYF) types; NYF types are enriched in rare-earth minerals. Examples of rare-earth pegmatite deposits include Strange Lake in Canada, and Khaladean-Buregtey in Mongolia. Nepheline syenite (M-Type granitoids) deposits are 90% feldspar and feldspathoid minerals, and are deposited in small, circular massifs. They contain high concentrations of rare-earth-bearing accessory minerals. For the most part these deposits are small but important examples include Illimaussaq-Kvanefeld in Greenland, and Lovozera in Russia. Rare-earth elements can also be enriched in deposits by secondary alteration either by interactions with hydrothermal fluids or meteoric water or by erosion and transport of resistate REE-bearing minerals. Argillization of primary minerals enriches insoluble elements by leaching out silica and other soluble elements, recrystallizing feldspar into clay minerals such kaolinite, halloysite and montmorillonite. In tropical regions where precipitation is high, weathering forms a thick argillized regolith, this process is called supergene enrichment and produces laterite deposits; heavy rare-earth elements are incorporated into the residual clay by absorption. This kind of deposit is only mined for REE in Southern China, where the majority of global heavy rare-earth element production occurs. REE-laterites do form elsewhere, including over the carbonatite at Mount Weld in Australia. REE may also by extracted from placer deposits if the sedimentary parent lithology contained REE-bearing, heavy resistate minerals. In 2011, Yasuhiro Kato, a geologist at the
University of Tokyo , abbreviated as or UTokyo, is a public research university located in Bunkyō, Tokyo, Japan. Established in 1877, the university was the first Imperial University and is currently a Top Type university of the Top Global University Project b ...
who led a study of Pacific Ocean seabed mud, published results indicating the mud could hold rich concentrations of rare-earth minerals. The deposits, studied at 78 sites, came from " t plumes from hydrothermal vents pull ngthese materials out of seawater and deposit ngthem on the seafloor, bit by bit, over tens of millions of years. One square patch of metal-rich mud 2.3 kilometers wide might contain enough rare earths to meet most of the global demand for a year, Japanese geologists report in ''
Nature Geoscience ''Nature Geoscience'' is a monthly peer-reviewed scientific journal published by the Nature Publishing Group. The Chief Editor is Tamara Goldin, who took over from Heike Langenberg in February 2020. It was established in January 2008. Scope The ...
''." "I believe that rare arth resources undersea are much more promising than on-land resources," said Kato. " ncentrations of rare earths were comparable to those found in clays mined in China. Some deposits contained twice as much heavy rare earths such as dysprosium, a component of magnets in hybrid car motors."Powell, Devin
"Rare earth elements plentiful in ocean sediments"
'' ScienceNews'', 3 July 2011. Via Kurt Brouwer'
Fundmastery Blog
''MarketWatch'', 2011-07-05. Retrieved 2011-07-05.


Notes on rare-earth elements geochemistry

The REE geochemical classification is usually done on the basis of their
atomic weight Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity defined as the ratio of the average mass of atoms of a chemical element in a giv ...
. One of the most common classifications divides REE into 3 groups: light rare earths (LREE - from 57La to 64Nd), intermediate (MREE - from 62Sm to 67Ho) and heavy (HREE - from 68Er to 71Lu). REE usually appear as trivalent ions, except for Ce and Eu which can take the form of Ce4+ and Eu2+ depending on the redox conditions of the system. Unlike Y, the lanthanides are characterized by the progressive filling of the 4''f'' orbital. The latter is not the outermost orbital and therefore the electrons contained in it are not part of the
valence electrons In chemistry and physics, a valence electron is an electron in the outer shell associated with an atom, and that can participate in the formation of a chemical bond if the outer shell is not closed. In a single covalent bond, a shared pair forms ...
, which are instead represented by the 2 electrons in the 6''s'' orbital and by the single electron in the 5''d'' orbital. This electron behaviour is highlighted by the
radial distribution function In statistical mechanics, the radial distribution function, (or pair correlation function) g(r) in a system of particles (atoms, molecules, colloids, etc.), describes how density varies as a function of distance from a reference particle. If ...
of the electrons around the nucleus of the lanthanides for the various external orbitals, from which it can be deduced that the function relative to the 4''f'' orbital is closer to the nucleus of the element than those of the 6''s'' and 5''d'' orbitals. This does not apply to the Y since it does not have electrons in the 4''f'' orbitals. Therefore, the external electron configuration is the same for all lanthanides, being efn6s25d1 in the neutral form and efn6s05d0 in the ionic form. Consequentially, REE are characterized by a substantial identity in their chemical reactivity, which results in a serial behaviour during geochemical processes rather than being characteristic of a single element of the series. A distinguishing factor in the geochemical behaviour of the REE is linked to the so-called "
lanthanide contraction The lanthanide contraction is the greater-than-expected decrease in atomic radii/ionic radii of the elements in the lanthanide series from atomic number 57, lanthanum, to 71, lutetium, which results in smaller than otherwise expected atomic radii ...
" which represents a higher-than-expected decrease in the atomic/ionic radius of the elements along the series. This is determined by the variation of the
shielding effect In chemistry, the shielding effect sometimes referred to as atomic shielding or electron shielding describes the attraction between an electron and the nucleus in any atom with more than one electron. The shielding effect can be defined as a re ...
towards the nuclear charge due to the progressive filling of the 4''f'' orbital which acts against the electrons of the 6''s'' and 5''d'' orbitals.The lanthanide contraction has a direct effect on the geochemistry of the lanthanides, which show a different behaviour depending on the systems and processes in which they are involved. The effect of the lanthanide contraction can be observed in the REE behaviour both in a CHARAC-type geochemical system (CHArge-and-RAdius-Controlled) where elements with similar charge and radius should show coherent geochemical behaviour, and in non-CHARAC systems, such as aqueous solutions, where the electron structure is also an important parameter to consider as the lanthanide contraction affects the ionic potential. A direct consequence is that, during the formation of coordination bonds, the REE behaviour gradually changes along the series. Furthermore, the lanthanide contraction causes the ionic radius of Ho3+ (0.901 Å) to be almost identical to that of Y3+ (0.9 Å), justifying the inclusion of the latter among the REE.


Geochemistry applications

The application of rare-earth elements to geology is important to understanding the petrological processes of
igneous Igneous rock (derived from the Latin word ''ignis'' meaning fire), or magmatic rock, is one of the three main rock types, the others being sedimentary and metamorphic. Igneous rock is formed through the cooling and solidification of magma or ...
,
sedimentary Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles ...
and
metamorphic Metamorphic rocks arise from the transformation of existing rock to new types of rock in a process called metamorphism. The original rock (protolith) is subjected to temperatures greater than and, often, elevated pressure of or more, causi ...
rock formation. In geochemistry, rare-earth elements can be used to infer the petrological mechanisms that have affected a rock due to the subtle atomic size differences between the elements, which causes preferential
fractionation Fractionation is a separation process in which a certain quantity of a mixture (of gases, solids, liquids, enzymes, or isotopes, or a suspension) is divided during a phase transition, into a number of smaller quantities (fractions) in which the ...
of some rare earths relative to others depending on the processes at work. The geochemical study of the REE is not carried out on absolute concentrations – as it is usually done with other chemical elements – but on normalized concentrations in order to observe their serial behaviour. In geochemistry, rare-earth elements are typically presented in normalized "spider" diagrams, in which concentration of rare-earth elements are normalized to a reference standard and are then expressed as the logarithm to the base 10 of the value. Commonly, the rare-earth elements are normalized to chondritic meteorites, as these are believed to be the closest representation of unfractionated solar system material. However, other normalizing standards can be applied depending on the purpose of the study. Normalization to a standard reference value, especially of a material believed to be unfractionated, allows the observed abundances to be compared to initial abundances of the element. Normalization also removes the pronounced 'zig-zag' pattern caused by the differences in abundance between even and odd
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
s. Normalization is carried out by dividing the analytical concentrations of each element of the series by the concentration of the same element in a given standard, according to the equation: text_in = \frac where ''n'' indicates the normalized concentration, the analytical concentration of element measured in the sample, and the concentration of the same element in the reference material. It is possible to observe the serial trend of the REE by reporting their normalized concentrations against the atomic number. The trends that are observed in "spider" diagrams are typically referred to as "patterns", which may be diagnostic of petrological processes that have affected the material of interest. According to the general shape of the patterns or thanks to the presence (or absence) of so-called "anomalies", information regarding the system under examination and the occurring geochemical processes can be obtained. The anomalies represent enrichment (positive anomalies) or depletion (negative anomalies) of specific elements along the series and are graphically recognizable as positive or negative “peaks” along the REE patterns. The anomalies can be numerically quantified as the ratio between the normalized concentration of the element showing the anomaly and the predictable one based on the average of the normalized concentrations of the two elements in the previous and next position in the series, according to the equation: \frac = \frac where text_in is the normalized concentration of the element whose anomaly has to be calculated, text_n and text_n the normalized concentrations of the respectively previous and next elements along the series. The rare-earth elements patterns observed in igneous rocks are primarily a function of the chemistry of the source where the rock came from, as well as the fractionation history the rock has undergone. Fractionation is in turn a function of the
partition coefficient In the physical sciences, a partition coefficient (''P'') or distribution coefficient (''D'') is the ratio of concentrations of a compound in a mixture of two immiscible solvents at equilibrium. This ratio is therefore a comparison of the solub ...
s of each element. Partition coefficients are responsible for the fractionation of a trace elements (including rare-earth elements) into the liquid phase (the melt/magma) into the solid phase (the mineral). If an element preferentially remains in the solid phase it is termed ‘compatible’, and it preferentially partitions into the melt phase it is described as ‘incompatible’. Each element has a different partition coefficient, and therefore fractionates into solid and liquid phases distinctly. These concepts are also applicable to metamorphic and sedimentary petrology. In igneous rocks, particularly in felsic melts, the following observations apply: anomalies in europium are dominated by the crystallization of
feldspar Feldspars are a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagioclase'' (sodium-calcium) felds ...
s.
Hornblende Hornblende is a complex inosilicate series of minerals. It is not a recognized mineral in its own right, but the name is used as a general or field term, to refer to a dark amphibole. Hornblende minerals are common in igneous and metamorphic rock ...
, controls the enrichment of MREE compared to LREE and HREE. Depletion of LREE relative to HREE may be due to the crystallization of
olivine The mineral olivine () is a magnesium iron silicate with the chemical formula . It is a type of nesosilicate or orthosilicate. The primary component of the Earth's upper mantle, it is a common mineral in Earth's subsurface, but weathers quickl ...
, orthopyroxene, and
clinopyroxene The pyroxenes (commonly abbreviated to ''Px'') are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents calcium (Ca), sodium (Na), iron (Fe I ...
. On the other hand, depletion of HREE relative to LREE may be due to the presence of
garnet Garnets () are a group of silicate minerals that have been used since the Bronze Age as gemstones and abrasives. All species of garnets possess similar physical properties and crystal forms, but differ in chemical composition. The different s ...
, as garnet preferentially incorporates HREE into its crystal structure. The presence of
zircon Zircon () is a mineral belonging to the group of nesosilicates and is a source of the metal zirconium. Its chemical name is zirconium(IV) silicate, and its corresponding chemical formula is Zr SiO4. An empirical formula showing some of t ...
may also cause a similar effect. In sedimentary rocks, rare-earth elements in clastic sediments are a representation provenance. The rare-earth element concentrations are not typically affected by sea and river waters, as rare-earth elements are insoluble and thus have very low concentrations in these fluids. As a result, when a sediment is transported, rare-earth element concentrations are unaffected by the fluid and instead the rock retains the rare-earth element concentration from its source. Sea and river waters typically have low rare-earth element concentrations. However, aqueous geochemistry is still very important. In oceans, rare-earth elements reflect input from rivers, hydrothermal vents, and aeolian sources; this is important in the investigation of ocean mixing and circulation. Rare-earth elements are also useful for dating rocks, as some
radioactive isotopes A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferr ...
display long half-lives. Of particular interest are the La-Ce, Sm-Nd, and Lu-Hf systems.


Production

Until 1948, most of the world's rare earths were sourced from placer sand deposits in
India India, officially the Republic of India (Hindi: ), is a country in South Asia. It is the seventh-largest country by area, the second-most populous country, and the most populous democracy in the world. Bounded by the Indian Ocean on the so ...
and
Brazil Brazil ( pt, Brasil; ), officially the Federative Republic of Brazil (Portuguese: ), is the largest country in both South America and Latin America. At and with over 217 million people, Brazil is the world's fifth-largest country by area ...
. Through the 1950s, South Africa was the world's rare-earth source, from a monazite-rich reef at the Steenkampskraal mine in
Western Cape The Western Cape is a province of South Africa, situated on the south-western coast of the country. It is the fourth largest of the nine provinces with an area of , and the third most populous, with an estimated 7 million inhabitants in 2020 ...
province. Through the 1960s until the 1980s, the Mountain Pass rare earth mine in California made the United States the leading producer. Today, the Indian and South African deposits still produce some rare-earth concentrates, but they are dwarfed by the scale of Chinese production. In 2017, China produced 81% of the world's rare-earth supply, mostly in
Inner Mongolia Inner Mongolia, officially the Inner Mongolia Autonomous Region, is an autonomous region of the People's Republic of China. Its border includes most of the length of China's border with the country of Mongolia. Inner Mongolia also accounts for a ...
, China's Rare Earth Dominance, Wikinvest. Retrieved on 11 Aug 2010. although it had only 36.7% of reserves. Australia was the second and only other major producer with 15% of world production. All of the world's heavy rare earths (such as dysprosium) come from Chinese rare-earth sources such as the polymetallic
Bayan Obo Bayan'obo Mining District, ( Mongolian: ''Bayan Oboɣ-a Aɣurqai-yin toɣoriɣ'', Баян-Овоо Уурхайн тойрог ( mn, italic=yes, "rich" + ovoo); ), or Baiyun-Obo or Baiyun'ebo, is a mining town in the west of Inner Mongolia, ...
deposit. The Browns Range mine, located 160 km south east of
Halls Creek Halls is a plural of the word hall. Halls may also refer to: People * Walter Halls (1871–1953), British trade unionist and politician * Ethel May Halls (1882–1967), American actress * Julian Halls (born 1967), British field hockey player * ...
in northern
Western Australia Western Australia (commonly abbreviated as WA) is a state of Australia occupying the western percent of the land area of Australia excluding external territories. It is bounded by the Indian Ocean to the north and west, the Southern Ocean to th ...
, is currently under development and is positioned to become the first significant dysprosium producer outside of China. Increased demand has strained supply, and there is growing concern that the world may soon face a shortage of the rare earths. In several years from 2009 worldwide demand for rare-earth elements is expected to exceed supply by 40,000 tonnes annually unless major new sources are developed."As hybrid cars gobble rare metals, shortage looms"
Reuters. August 31, 2009. Retrieved Aug 31, 2009.
In 2013, it was stated that the demand for REEs would increase due to the dependence of the EU on these elements, the fact that rare earth elements cannot be substituted by other elements and that REEs have a low recycling rate. Furthermore, due to the increased demand and low supply, future prices are expected to increase and there is a chance that countries other than China will open REE mines. REE is increasing in demand due to the fact that they are essential for new and innovative technology that is being created. These new products that need REEs to be produced are high technology equipment such as smart phones, digital cameras, computer parts, semiconductors, etc. In addition, these elements are more prevalent in the following industries: renewable energy technology, military equipment, glass making, and metallurgy.


China

These concerns have intensified due to the actions of China, the predominant supplier. Specifically, China has announced regulations on exports and a crackdown on smuggling. On September 1, 2009, China announced plans to reduce its export quota to 35,000 tons per year in 2010–2015 to conserve scarce resources and protect the environment. On October 19, 2010, ''
China Daily ''China Daily'' () is an English-language daily newspaper owned by the Central Propaganda Department of the Chinese Communist Party. Overview ''China Daily'' has the widest print circulation of any English-language newspaper in China. T ...
'', citing an unnamed Ministry of Commerce official, reported that China will "further reduce quotas for rare-earth exports by 30 percent at most next year to protect the precious metals from over-exploitation." The government in Beijing further increased its control by forcing smaller, independent miners to merge into state-owned corporations or face closure. At the end of 2010, China announced that the first round of export quotas in 2011 for rare earths would be 14,446 tons, which was a 35% decrease from the previous first round of quotas in 2010. China announced further export quotas on 14 July 2011 for the second half of the year with total allocation at 30,184 tons with total production capped at 93,800 tonnes. In September 2011, China announced the halt in production of three of its eight major rare-earth mines, responsible for almost 40% of China's total rare-earth production. In March 2012, the US, EU, and Japan confronted China at WTO about these export and production restrictions. China responded with claims that the restrictions had environmental protection in mind. In August 2012, China announced a further 20% reduction in production. The United States, Japan, and the European Union filed a joint lawsuit with the World Trade Organization in 2012 against China, arguing that China should not be able to deny such important exports. In response to the opening of new mines in other countries ( Lynas in Australia and
Molycorp Molycorp Inc. was an American mining corporation headquartered in Greenwood Village, Colorado. The corporation, which was formerly traded on the New York Stock Exchange, owned the Mountain Pass rare earth mine in California. It filed for bankrup ...
in the United States), prices of rare earths dropped. The price of dysprosium oxide was 994 
USD The United States dollar (symbol: $; code: USD; also abbreviated US$ or U.S. Dollar, to distinguish it from other dollar-denominated currencies; referred to as the dollar, U.S. dollar, American dollar, or colloquially buck) is the official ...
/kg in 2011, but dropped to US$265/kg by 2014. On August 29, 2014, the WTO ruled that China had broken free-trade agreements, and the WTO said in the summary of key findings that "the overall effect of the foreign and domestic restrictions is to encourage domestic extraction and secure preferential use of those materials by Chinese manufacturers." China declared that it would implement the ruling on September 26, 2014, but would need some time to do so. By January 5, 2015, China had lifted all quotas from the export of rare earths, but export licences will still be required. In 2019, China supplied between 85% and 95% of the global demand for the 17 rare earth powders, half of them sourced from
Myanmar Myanmar, ; UK pronunciations: US pronunciations incl. . Note: Wikipedia's IPA conventions require indicating /r/ even in British English although only some British English speakers pronounce r at the end of syllables. As John Wells explai ...
. After the 2021 military coup in that country, future supplies of critical ores were possibly constrained. Additionally, it was speculated that the PRC could again reduce rare earth exports to counter-act economic sanctions imposed by the US and EU countries. Rare earth metals serve as crucial materials for EV-manufacturing and high-tech military applications.


Outside China

As a result of the increased demand and tightening restrictions on exports of the metals from China, some countries are stockpiling rare-earth resources. Searches for alternative sources in Australia,
Brazil Brazil ( pt, Brasil; ), officially the Federative Republic of Brazil (Portuguese: ), is the largest country in both South America and Latin America. At and with over 217 million people, Brazil is the world's fifth-largest country by area ...
,
Canada Canada is a country in North America. Its ten provinces and three territories extend from the Atlantic Ocean to the Pacific Ocean and northward into the Arctic Ocean, covering over , making it the world's second-largest country by tot ...
,
South Africa South Africa, officially the Republic of South Africa (RSA), is the Southern Africa, southernmost country in Africa. It is bounded to the south by of coastline that stretch along the Atlantic Ocean, South Atlantic and Indian Oceans; to the ...
,
Tanzania Tanzania (; ), officially the United Republic of Tanzania ( sw, Jamhuri ya Muungano wa Tanzania), is a country in East Africa within the African Great Lakes region. It borders Uganda to the north; Kenya to the northeast; Comoro Islands ...
,
Greenland Greenland ( kl, Kalaallit Nunaat, ; da, Grønland, ) is an island country in North America that is part of the Kingdom of Denmark. It is located between the Arctic and Atlantic oceans, east of the Canadian Arctic Archipelago. Greenland i ...
, and the
United States The United States of America (U.S.A. or USA), commonly known as the United States (U.S. or US) or America, is a country primarily located in North America. It consists of 50 states, a federal district, five major unincorporated territori ...
are ongoing. Mines in these countries were closed when China undercut world prices in the 1990s, and it will take a few years to restart production as there are many barriers to entry. Significant sites under development outside China include Steenkampskraal in South Africa, the world's highest grade rare earths and thorium mine, closed in 1963, but has been gearing to go back into production. Over 80% of the infrastructure is already complete. Other mines include the Nolans Project in Central Australia, the Bokan Mountain project in Alaska, the remote
Hoidas Lake Hoidas Lake is a remote northern Canadian lake which lies approximately 50 kilometers north of Uranium City, Saskatchewan. Named in honor of Irvin Frank Hoidas, a Royal Canadian Air Force pilot officer killed in action during the Second World War ...
project in northern Canada, and the
Mount Weld Mount Weld mine is a rare earth mine in Western Australia, located about south of Laverton and east of Leonora. It ranks as one of the richest major rare-earth deposits in the world. Rare earths are contained in secondary phosphates and a ...
project in Australia. The
Hoidas Lake Hoidas Lake is a remote northern Canadian lake which lies approximately 50 kilometers north of Uranium City, Saskatchewan. Named in honor of Irvin Frank Hoidas, a Royal Canadian Air Force pilot officer killed in action during the Second World War ...
project has the potential to supply about 10% of the $1 billion of REE consumption that occurs in North America every year.
Vietnam Vietnam or Viet Nam ( vi, Việt Nam, ), officially the Socialist Republic of Vietnam,., group="n" is a country in Southeast Asia, at the eastern edge of mainland Southeast Asia, with an area of and population of 96 million, making i ...
signed an agreement in October 2010 to supply Japan with rare earths from its northwestern Lai Châu Province, however the deal was never realized due to disagreements. The largest rare earth deposit in the U.S. is at Mountain Pass, California, sixty miles south of
Las Vegas Las Vegas (; Spanish for "The Meadows"), often known simply as Vegas, is the 25th-most populous city in the United States, the most populous city in the state of Nevada, and the county seat of Clark County. The city anchors the Las Vegas ...
. Originally opened by
Molycorp Molycorp Inc. was an American mining corporation headquartered in Greenwood Village, Colorado. The corporation, which was formerly traded on the New York Stock Exchange, owned the Mountain Pass rare earth mine in California. It filed for bankrup ...
, the deposit has been mined, off and on, since 1951. A second large deposit of REEs at Elk Creek in southeast
Nebraska Nebraska () is a state in the Midwestern region of the United States. It is bordered by South Dakota to the north; Iowa to the east and Missouri to the southeast, both across the Missouri River; Kansas to the south; Colorado to the sout ...
is under consideration by NioCorp Development Ltd who hopes to open a niobium, scandium, and titanium mine there. That mine may be able to produce as much as 7200 tonnes of ferro niobium and 95 tonnes of scandium trioxide annually, although, as of 2022, financing is still in the works. In the UK, Pensana have begun construction of their US$195 million rare earth processing plant which secured funding from the UK government's Automotive Transformation Fund. The plant will process ore from the Longonjo mine in Angola and other sources as they become available. The company are targeting production in late 2023, before ramping up to full capacity in 2024. Pensana aim to produce 12,500 metric tons of separated rare earths, including 4,500 tons of magnet metal rare earths. Also under consideration for mining are sites such as Thor Lake in the Northwest Territories, and various locations in
Vietnam Vietnam or Viet Nam ( vi, Việt Nam, ), officially the Socialist Republic of Vietnam,., group="n" is a country in Southeast Asia, at the eastern edge of mainland Southeast Asia, with an area of and population of 96 million, making i ...
. Additionally, in 2010, a large deposit of rare-earth minerals was discovered in Kvanefjeld in southern
Greenland Greenland ( kl, Kalaallit Nunaat, ; da, Grønland, ) is an island country in North America that is part of the Kingdom of Denmark. It is located between the Arctic and Atlantic oceans, east of the Canadian Arctic Archipelago. Greenland i ...
. Pre-feasibility drilling at this site has confirmed significant quantities of black lujavrite, which contains about 1% rare-earth oxides (REO). The
European Union The European Union (EU) is a supranational political and economic union of member states that are located primarily in Europe. The union has a total area of and an estimated total population of about 447million. The EU has often been de ...
has urged Greenland to restrict Chinese development of rare-earth projects there, but as of early 2013, the
government of Greenland Naalakkersuisut ( en, Cabinet of Greenland, da, Grønlands Regering), is the chief executive body and the government of Greenland since the island became self-governing in 1979. An "autonomous territory" ( da, land) of the Kingdom of Denmark, tak ...
has said that it has no plans to impose such restrictions. Many Danish politicians have expressed concerns that other nations, including China, could gain influence in thinly populated Greenland, given the number of foreign workers and investment that could come from Chinese companies in the near future because of the law passed December 2012. In central
Spain , image_flag = Bandera de España.svg , image_coat = Escudo de España (mazonado).svg , national_motto = ''Plus ultra'' (Latin)(English: "Further Beyond") , national_anthem = (English: "Royal March") , i ...
, Ciudad Real Province, the proposed rare-earth mining project 'Matamulas' may provide, according to its developers, up to 2,100 Tn/year (33% of the annual UE demand). However, this project has been suspended by regional authorities due to social and environmental concerns. Adding to potential mine sites, ASX listed Peak Resources announced in February 2012, that their Tanzanian-based Ngualla project contained not only the 6th largest deposit by tonnage outside of China, but also the highest grade of rare-earth elements of the 6.
North Korea North Korea, officially the Democratic People's Republic of Korea (DPRK), is a country in East Asia. It constitutes the northern half of the Korean Peninsula and shares borders with China and Russia to the north, at the Yalu (Amnok) and T ...
has been reported to have exported rare-earth ore to China, about US$1.88 million worth during May and June 2014. In May 2012, researchers from two universities in Japan announced that they had discovered rare earths in
Ehime Prefecture is a prefecture of Japan located on the island of Shikoku. Ehime Prefecture has a population of 1,342,011 (1 June 2019) and has a geographic area of 5,676 km2 (2,191 sq mi). Ehime Prefecture borders Kagawa Prefecture to the northeast, Tok ...
, Japan.


Malaysian refining plans

In early 2011, Australian mining company Lynas was reported to be "hurrying to finish" a US$230 million rare-earth refinery on the eastern coast of Peninsular Malaysia's industrial port of
Kuantan Kuantan ( Jawi: ) is a city and the state capital of Pahang, Malaysia. It is located near the mouth of the Kuantan River. Kuantan is the 18th largest city in Malaysia based on 2010 population, and the largest city in the East Coast of Peni ...
. The plant would refine ore — lanthanides concentrate from the
Mount Weld Mount Weld mine is a rare earth mine in Western Australia, located about south of Laverton and east of Leonora. It ranks as one of the richest major rare-earth deposits in the world. Rare earths are contained in secondary phosphates and a ...
mine in Australia. The ore would be trucked to Fremantle and transported by
container ship A container ship (also called boxship or spelled containership) is a cargo ship that carries all of its load in truck-size intermodal containers, in a technique called containerization. Container ships are a common means of commercial intermoda ...
to Kuantan. Within two years, Lynas was said to expect the refinery to be able to meet nearly a third of the world's demand for rare-earth materials, not counting China. The Kuantan development brought renewed attention to the Malaysian town of Bukit Merah in Perak, where a rare-earth mine operated by a Mitsubishi Chemical subsidiary, Asian Rare Earth, closed in 1994 and left continuing environmental and health concerns. In mid-2011, after protests, Malaysian government restrictions on the Lynas plant were announced. At that time, citing subscription-only ''
Dow Jones Newswire Dow Jones & Company, Inc. is an American publishing firm owned by News Corp and led by CEO Almar Latour. The company publishes ''The Wall Street Journal'', '' Barron's'', ''MarketWatch'', ''Mansion Global'', ''Financial News'' and ''Private E ...
'' reports, a '' Barrons'' report said the Lynas investment was $730 million, and the projected share of the global market it would fill put at "about a sixth." An independent review initiated by the Malaysian Government, and conducted by the International Atomic Energy Agency (IAEA) in 2011 to address concerns of radioactive hazards, found no non-compliance with international radiation safety standards. However, the Malaysian authorities confirmed that as of October 2011, Lynas was not given any permit to import any rare-earth ore into Malaysia. On February 2, 2012, the Malaysian AELB (Atomic Energy Licensing Board) recommended that Lynas be issued a temporary operating license subject to meeting a number of conditions. On 2 September 2014, Lynas was issued a 2-year full operating stage license by the AELB.


Other sources


Mine tailings

Significant quantities of rare-earth oxides are found in tailings accumulated from 50 years of
uranium ore Uranium ore deposits are economically recoverable concentrations of uranium within the Earth's crust. Uranium is one of the more common elements in the Earth's crust, being 40 times more common than silver and 500 times more common than gold. It ...
, shale and
loparite Loparite-(Ce) is a granular, brittle oxide mineral of the perovskite class. It is black to dark grey and may appear grey to white in reflected light on polished thin section with reddish brown internal reflections.Loparite-(Ce) oWebmineral/ref> It ...
mining at
Sillamäe Sillamäe (Estonian for 'Bridge Hill'; also known by the Germanised names of ''Sillamäggi'' or ''Sillamägi'') is a town in Ida-Viru County in the northern part of Estonia, on the southern coast of the Gulf of Finland. It has a population of ...
,
Estonia Estonia, formally the Republic of Estonia, is a country by the Baltic Sea in Northern Europe. It is bordered to the north by the Gulf of Finland across from Finland, to the west by the sea across from Sweden, to the south by Latvia, a ...
. Due to the rising prices of rare earths, extraction of these oxides has become economically viable. The country currently exports around 3,000 tonnes per year, representing around 2% of world production. Similar resources are suspected in the western United States, where
gold rush A gold rush or gold fever is a discovery of gold—sometimes accompanied by other precious metals and rare-earth minerals—that brings an onrush of miners seeking their fortune. Major gold rushes took place in the 19th century in Australia, New ...
-era mines are believed to have discarded large amounts of rare earths, because they had no value at the time.


Ocean mining

In January 2013 a Japanese deep-sea research vessel obtained seven deep-sea mud core samples from the Pacific Ocean seafloor at 5,600 to 5,800 meters depth, approximately south of the island of Minami-Tori-Shima. The research team found a mud layer 2 to 4 meters beneath the seabed with concentrations of up to 0.66% rare-earth oxides. A potential deposit might compare in grade with the ion-absorption-type deposits in southern China that provide the bulk of Chinese REO mine production, which grade in the range of 0.05% to 0.5% REO.


Waste

Another recently developed source of rare earths is
electronic waste Electronic waste or e-waste describes discarded electrical or electronic devices. Used electronics which are destined for refurbishment, reuse, resale, salvage recycling through material recovery, or disposal are also considered e-waste. Inform ...
and other
waste Waste (or wastes) are unwanted or unusable materials. Waste is any substance discarded after primary use, or is worthless, defective and of no use. A by-product, by contrast is a joint product of relatively minor economic value. A waste prod ...
s that have significant rare-earth components. Advances in recycling technology have made extraction of rare earths from these materials less expensive. Recycling plants operate in Japan, where an estimated 300,000 tons of rare earths are found in unused electronics. In
France France (), officially the French Republic ( ), is a country primarily located in Western Europe. It also comprises of overseas regions and territories in the Americas and the Atlantic, Pacific and Indian Oceans. Its metropolitan area ...
, the Rhodia group is setting up two factories, in
La Rochelle La Rochelle (, , ; Poitevin-Saintongeais: ''La Rochéle''; oc, La Rochèla ) is a city on the west coast of France and a seaport on the Bay of Biscay, a part of the Atlantic Ocean. It is the capital of the Charente-Maritime department. Wi ...
and Saint-Fons, that will produce 200 tons of rare earths a year from used
fluorescent lamp A fluorescent lamp, or fluorescent tube, is a low-pressure mercury-vapor gas-discharge lamp that uses fluorescence to produce visible light. An electric current in the gas excites mercury vapor, which produces short-wave ultraviolet ligh ...
s, magnets and batteries. Coal and coal by-products are a potential source of critical elements including rare earth elements (REE) with estimated amounts in the range of 50 million metric tons.


Methods

One study mixed fly ash with carbon black and then sent a 1-second current pulse through the mixture, heating it to . The fly ash contains microscopic bits of glass that encapsulate the metals. The heats shatters the glass, exposing the rare earths. Flash heating also converts
phosphates In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phosph ...
into oxides, which are more soluble and extractable. Using hydrochloric acid at concentrations less than 1% of conventional methods, the process extracted twice as much material.


Properties

According to chemistry professor Andrea Sella, rare-earth elements differ from other elements, in that when looked at analytically, they are virtually inseparable, having almost the same chemical properties. However, in terms of their electronic and magnetic properties, each one occupies a unique technological niche that nothing else can.Professor of Chemistry at
University College London , mottoeng = Let all come who by merit deserve the most reward , established = , type = Public research university , endowment = £143 million (2020) , budget = ...
, Andrea Sella, , Interview on TRT World / Oct 2016, minutes 4:40 - ff.
For example, "the rare-earth elements
praseodymium Praseodymium is a chemical element with the symbol Pr and the atomic number 59. It is the third member of the lanthanide series and is considered to be one of the rare-earth metals. It is a soft, silvery, malleable and ductile metal, valued for i ...
(Pr) and
neodymium Neodymium is a chemical element with the symbol Nd and atomic number 60. It is the fourth member of the lanthanide series and is considered to be one of the rare-earth metals. It is a hard, slightly malleable, silvery metal that quickly tarnishe ...
(Nd) can both be embedded inside glass and they completely cut out the glare from the flame when one is doing glass-blowing."


Uses

The uses, applications, and demand for rare-earth elements has expanded over the years. Globally, most REEs are used for
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s and magnets. In USA, more than half of REEs are used for catalysts, and ceramics, glass and polishing are also main uses. Other important uses of rare-earth elements are applicable to the production of high-performance magnets, alloys, glasses, and electronics. Ce and La are important as catalysts, and are used for
petroleum refining An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into useful products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefi ...
and as diesel additives. Nd is important in magnet production in traditional and low-carbon technologies. Rare-earth elements in this category are used in the electric motors of hybrid and electric vehicles, generators in
wind turbine A wind turbine is a device that converts the kinetic energy of wind into electrical energy. Hundreds of thousands of large turbines, in installations known as wind farms, now generate over 650 gigawatts of power, with 60 GW added each yea ...
s, hard disc drives, portable electronics, microphones, speakers. Ce, La and Nd are important in alloy making, and in the production of fuel cells and nickel-metal hydride batteries. Ce, Ga and Nd are important in electronics and are used in the production of LCD and plasma screens, fiber optics, lasers, as well as in medical imaging. Additional uses for rare-earth elements are as tracers in medical applications, fertilizers, and in water treatment. REEs have been used in agriculture to increase plant growth, productivity, and stress resistance seemingly without negative effects for human and animal consumption. REEs are used in agriculture through REE-enriched fertilizers which is a widely used practice in China. In addition, REEs are feed additives for livestock which has resulted in increased production such as larger animals and a higher production of eggs and dairy products. However, this practice has resulted in REE bio-accumulation within livestock and has impacted vegetation and algae growth in these agricultural areas. Additionally while no ill effects have been observed at current low concentrations the effects over the long term and with accumulation over time are unknown prompting some calls for more research into their possible effects. Given the limited supply, industries directly compete with each other for resources, e.g. the electronics sector is in direct competition with renewable energy use in windfarms, solar panels and batteries.


Environmental considerations

REEs are naturally found in very low concentration in the environment. Mines are often in countries where environmental and social standards are very low, leading to human rights violations, deforestation and contamination of land and water. Near mining and industrial sites, the concentrations of REEs can rise to many times the normal background levels. Once in the environment, REEs can leach into the soil where their transport is determined by numerous factors such as erosion, weathering, pH, precipitation, ground water, etc. Acting much like metals, they can speciate depending on the soil condition being either motile or adsorbed to soil particles. Depending on their bio-availability, REEs can be absorbed into plants and later consumed by humans and animals. The mining of REEs, use of REE-enriched fertilizers, and the production of phosphorus fertilizers all contribute to REE contamination. Furthermore, strong acids are used during the extraction process of REEs, which can then leach out in to the environment and be transported through water bodies and result in the acidification of aquatic environments. Another additive of REE mining that contributes to REE environmental contamination is cerium oxide (), which is produced during the combustion of diesel and released as exhaust, contributing heavily to soil and water contamination. Mining, refining, and recycling of rare earths have serious environmental consequences if not properly managed. Low-level radioactive
tailings In mining, tailings are the materials left over after the process of separating the valuable fraction from the uneconomic fraction (gangue) of an ore. Tailings are different to overburden, which is the waste rock or other material that overli ...
resulting from the occurrence of
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
and
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
in rare-earth element ores present a potential hazard and improper handling of these substances can result in extensive environmental damage. In May 2010, China announced a major, five-month crackdown on illegal mining in order to protect the environment and its resources. This campaign is expected to be concentrated in the South, where mines – commonly small, rural, and illegal operations – are particularly prone to releasing toxic waste into the general water supply. However, even the major operation in Baotou, in Inner Mongolia, where much of the world's rare-earth supply is refined, has caused major environmental damage. China's Ministry of Industry and Information Technology estimated that cleanup costs in Jiangxi province at $5.5 billion. It is, however, possible to filter out and recover any rare earth elements that flow out with the wastewater from mining facilities. However, such filtering and recovery equipment may not always be present on the outlets carrying the wastewater.


Recycling and reusing REEs

Literature published in 2004 suggests that, along with previously established pollution mitigation, a more circular supply chain would help mitigate some of the pollution at the extraction point. This means recycling and reusing REEs that are already in use or reaching the end of their life cycle. A study published in 2014 suggests a method to recycle REEs from waste nickel-metal hydride batteries, demonstrating a recovery rate of 95.16%. Rare-earth elements could also be recovered from industrial wastes with practical potential to reduce environmental and health impacts from mining, waste-generation and imports if known and experimental processes are scaled up. A study suggests that "fulfillment of the circular economy approach could reduce up to 200 times the impact in the climate change category and up to 70 times the cost due to the REE mining." In most of the reported studies reviewed by a
scientific review A review article is an article that summarizes the current state of understanding on a topic within a certain discipline. A review article is generally considered a secondary source since it may analyze and discuss the method and conclusions i ...
, "secondary waste is subjected to chemical and or bioleaching followed by solvent extraction processes for clean separation of REEs."


Impact of REE contamination


On vegetation

The mining of REEs has caused the
contamination Contamination is the presence of a constituent, impurity, or some other undesirable element that spoils, corrupts, infects, makes unfit, or makes inferior a material, physical body, natural environment, workplace, etc. Types of contamination ...
of soil and water around production areas, which has impacted vegetation in these areas by decreasing chlorophyll production which affects photosynthesis and inhibits the growth of the plants. However, the impact of REE contamination on vegetation is dependent on the plants present in the contaminated environment: some plants retain and absorb REEs and some don't. Also, the ability for the vegetation to intake the REE is dependent on the type of REE present in the soil, hence there are a multitude of factors that influence this process. Agricultural plants are the main type of vegetation affected by REE contamination in the environment, the two plants with a higher chance of absorbing and storing REEs being apples and beets. Furthermore, there is a possibility that REEs can leach out into aquatic environments and be absorbed by aquatic vegetation, which can then bio-accumulate and potentially enter the human food-chain if livestock or humans choose to eat the vegetation. An example of this situation was the case of the
water hyacinth ''Pontederia crassipes'' (formerly ''Eichhornia crassipes''), commonly known as common water hyacinth is an aquatic plant native to South America, naturalized throughout the world, and often invasive outside its native range.cerium 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 +3 ...
and resulted in the water hyacinth becoming three times more concentrated in cerium than its surrounding water.


On human health

REEs are a large group with many different properties and levels in the environment. Because of this, and limited research, it has been difficult to determine safe levels of exposure for humans. A number of studies have focused on risk assessment based on routes of exposure and divergence from background levels related to nearby agriculture, mining, and industry. It has been demonstrated that numerous REEs have toxic properties and are present in the environment or in work places. Exposure to these can lead to a wide range of negative health outcomes such as cancer, respiratory issues, dental loss, and even death. However REEs are numerous and present in many different forms and at different levels of toxicity, making it difficult to give blanket warnings on
cancer Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
risk and toxicity as some of these are harmless while others pose a risk. What toxicity is shown appears to be at very high levels of exposure through ingestion of contaminated food and water, through inhalation of dust/smoke particles either as an occupational hazard or due to proximity to contaminated sites such as mines and cities. Therefore, the main issues that these residents would face is bioaccumulation of REEs and the impact on their respiratory system but overall, there can be other possible short term and long-term health effects. It was found that people living near mines in China had many times the levels of REEs in their blood, urine, bone and hair compared to controls far from mining sites. This higher level was related to the high levels of REEs present in the vegetables they cultivated, the soil, and the water from the wells, indicating that the high levels were caused by the nearby mine. While REE levels varied between men and women, the group most at risk were children because REEs can impact the neurological development of children, affecting their IQ and potentially causing memory loss. The rare earth mining and smelting process can release airborne fluoride which will associate with total suspended particles (TSP) to form aerosols that can enter human respiratory systems and cause damage and respiratory diseases. Research from Baotou, China shows that the fluoride concentration in air near REE mines is higher than the limit value from WHO, which can affect the surrounding environment and become a risk to those that live or work nearby. Residents blamed a rare-earth refinery at Bukit Merah for
birth defects A birth defect, also known as a congenital disorder, is an abnormal condition that is present at birth regardless of its cause. Birth defects may result in disabilities that may be physical, intellectual, or developmental. The disabilities can ...
and eight
leukemia Leukemia ( also spelled leukaemia and pronounced ) is a group of blood cancers that usually begin in the bone marrow and result in high numbers of abnormal blood cells. These blood cells are not fully developed and are called ''blasts'' or ...
cases within five years in a community of 11,000 — after many years with no leukemia cases. Seven of the leukemia victims died. Osamu Shimizu, a director of Asian Rare Earth, said "the company might have sold a few bags of calcium phosphate fertilizer on a trial basis as it sought to market byproducts; calcium phosphate is not radioactive or dangerous" in reply to a former resident of Bukit Merah who said that "The cows that ate the grass rown with the fertilizerall died." Malaysia's Supreme Court ruled on 23 December 1993 that there was no evidence that the local chemical joint venture Asian Rare Earth was contaminating the local environment.


On animal health

Experiments exposing rats to various cerium compounds have found accumulation primarily in the lungs and liver. This resulted in various negative health outcomes associated with those organs. REEs have been added to feed in livestock to increase their body mass and increase milk production. They are most commonly used to increase the body mass of pigs, and it was discovered that REEs increase the digestibility and nutrient use of pigs' digestive systems. Studies point to a dose response when considering toxicity versus positive effects. While small doses from the environment or with proper administration seem to have no ill effects, larger doses have been shown to have negative effects specifically in the organs where they accumulate. The process of mining REEs in China has resulted in soil and water contamination in certain areas, which when transported into aquatic bodies could potentially bio-accumulate within aquatic biota. Furthermore, in some cases animals that live in the REE-contaminated areas have been diagnosed with organ or system problems. REEs have been used in freshwater fish farming because it protects the fish from possible diseases. One main reason why they have been avidly used in animal livestock feeding is that they have had better results than inorganic livestock feed enhancers.


Remediation after pollution

After the 1982 Bukit Merah radioactive pollution, the mine in
Malaysia Malaysia ( ; ) is a country in Southeast Asia. The federation, federal constitutional monarchy consists of States and federal territories of Malaysia, thirteen states and three federal territories, separated by the South China Sea into two r ...
has been the focus of a US$100 million cleanup that is proceeding in 2011. After having accomplished the hilltop entombment of 11,000 truckloads of radioactively contaminated material, the project is expected to entail in summer, 2011, the removal of "more than 80,000 steel barrels of radioactive waste to the hilltop repository." In May 2011, after the Fukushima Daiichi nuclear disaster, widespread protests took place in Kuantan over the Lynas refinery and radioactive waste from it. The ore to be processed has very low levels of thorium, and Lynas founder and chief executive Nicholas Curtis said "There is absolutely no risk to public health." T. Jayabalan, a doctor who says he has been monitoring and treating patients affected by the Mitsubishi plant, "is wary of Lynas's assurances. The argument that low levels of thorium in the ore make it safer doesn't make sense, he says, because radiation exposure is cumulative."Lee, Yoolim
"Malaysia Rare Earths in Largest Would-Be Refinery Incite Protest"
'' Bloomberg Markets Magazine'', May 31, 2011 5:00 PM ET.
Construction of the facility has been halted until an independent
United Nations The United Nations (UN) is an intergovernmental organization whose stated purposes are to maintain international peace and security, develop friendly relations among nations, achieve international cooperation, and be a centre for harmoniz ...
IAEA panel investigation is completed, which is expected by the end of June 2011. New restrictions were announced by the Malaysian government in late June. IAEA panel investigation is completed and no construction has been halted. Lynas is on budget and on schedule to start producing 2011. The IAEA report has concluded in a report issued on Thursday June 2011 said it did not find any instance of "any non-compliance with international radiation safety standards" in the project. If the proper safety standards are followed, REE mining is relatively low impact. Molycorp (before going bankrupt) often exceeded environmental regulations to improve public image. In Greenland there is a significant dispute on whether to start a new rare earth mine in Kvanefjeld due to environmental concerns.


Geo-political considerations

China has officially cited
resource depletion Resource depletion is the consumption of a resource faster than it can be replenished. Natural resources are commonly divided between renewable resources and non-renewable resources (see also mineral resource classification). Use of either ...
and environmental concerns as the reasons for a nationwide crackdown on its rare-earth mineral production sector. However, non-environmental motives have also been imputed to China's rare-earth policy. According to ''
The Economist ''The Economist'' is a British weekly newspaper printed in demitab format and published digitally. It focuses on current affairs, international business, politics, technology, and culture. Based in London, the newspaper is owned by The Eco ...
'', "Slashing their exports of rare-earth metals… is all about moving Chinese manufacturers up the supply chain, so they can sell valuable finished goods to the world rather than lowly raw materials." Furthermore, China currently has an effective monopoly on the world's REE Value Chain. (all the refineries and processing plants that transform the raw ore into valuable elements). In the words of Deng Xiaoping, a Chinese politician from the late 1970s to the late 1980s, "The Middle East has oil; we have rare earths ... it is of extremely important strategic significance; we must be sure to handle the rare earth issue properly and make the fullest use of our country's advantage in rare earth resources." One possible example of market control is the division of General Motors that deals with miniaturized magnet research, which shut down its US office and moved its entire staff to China in 2006 (China's export quota only applies to the metal but not products made from these metals such as magnets). It was reported, but officially denied, that China instituted an export ban on shipments of rare-earth oxides (but not alloys) to Japan on 22 September 2010, in response to the detainment of a Chinese fishing boat captain by the Japanese Coast Guard. On September 2, 2010, a few days before the fishing boat incident, ''The Economist'' reported that "China...in July announced the latest in a series of annual export reductions, this time by 40% to precisely 30,258 tonnes." The
United States Department of Energy The United States Department of Energy (DOE) is an executive department of the U.S. federal government that oversees U.S. national energy policy and manages the research and development of nuclear power and nuclear weapons in the United Stat ...
in its 2010 Critical Materials Strategy report identified dysprosium as the element that was most critical in terms of import reliance. A 2011 report "China's Rare-Earth Industry", issued by the US Geological Survey and US Department of the Interior, outlines industry trends within China and examines national policies that may guide the future of the country's production. The report notes that China's lead in the production of rare-earth minerals has accelerated over the past two decades. In 1990, China accounted for only 27% of such minerals. In 2009, world production was 132,000 metric tons; China produced 129,000 of those tons. According to the report, recent patterns suggest that China will slow the export of such materials to the world: "Owing to the increase in domestic demand, the Government has gradually reduced the export quota during the past several years." In 2006, China allowed 47 domestic rare-earth producers and traders and 12 Sino-foreign rare-earth producers to export. Controls have since tightened annually; by 2011, only 22 domestic rare-earth producers and traders and 9 Sino-foreign rare-earth producers were authorized. The government's future policies will likely keep in place strict controls: "According to China's draft rare-earth development plan, annual rare-earth production may be limited to between 130,000 and 140,000 etric tonsduring the period from 2009 to 2015. The export quota for rare-earth products may be about 35,000 etric tonsand the Government may allow 20 domestic rare-earth producers and traders to export rare earths." The United States Geological Survey is actively surveying southern
Afghanistan Afghanistan, officially the Islamic Emirate of Afghanistan,; prs, امارت اسلامی افغانستان is a landlocked country located at the crossroads of Central Asia and South Asia. Referred to as the Heart of Asia, it is bordere ...
for rare-earth deposits under the protection of United States military forces. Since 2009 the USGS has conducted remote sensing surveys as well as fieldwork to verify Soviet claims that volcanic rocks containing rare-earth metals exist in
Helmand Province Helmand (Pashto/Dari: ; ), also known as Hillmand, in ancient times, as Hermand and Hethumand, is one of the 34 provinces of Afghanistan, in the south of the country. It is the largest province by area, covering area. The province contains 13 ...
near the village of Khanashin. The USGS study team has located a sizable area of rocks in the center of an extinct volcano containing light rare-earth elements including cerium and neodymium. It has mapped 1.3 million metric tons of desirable rock, or about ten years of supply at current demand levels. The Pentagon has estimated its value at about $7.4 billion. It has been argued that the geopolitical importance of rare earths has been exaggerated in the literature on the geopolitics of renewable energy, underestimating the power of economic incentives for expanded production. This especially concerns neodymium. Due to its role in permanent magnets used for wind turbines, it has been argued that neodymium will be one of the main objects of geopolitical competition in a world running on renewable energy. But this perspective has been criticised for failing to recognise that most wind turbines have gears and do not use permanent magnets.


Prices

The Institute of Rare Earths Elements and Strategic Metals is an informal network in the international ''raw metall market''. The main interest of the institut's customers is the database, which is available on a subscription base with daily updatet prices: In addition with the eponymous ''rare-earth elements'', 900 pure metalls and 4,500 other metall products are listed there. The company's headquartesr are located in Lucerne, Switzerland.


See also

* Rare-earth mineral * Rare-earth magnet * List of elements facing shortage * Material passport: lists used materials in products * Digital Product Passport: renewed in function of the Circular Economy Action Plan * Pensana Salt End


References


External links

* * {{Authority control Sets of chemical elements Metallic elements