Rare-earth element

Rare-earth elements
The rare-earth elements (REE), also called the rare-earth in the periodic table
metals or rare earths or, in context, rare-earth oxides, and
sometimes the lanthanides (although yttrium and scandium, which
do not belong to this series, are usually included as rare earths),[1]
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 deposits as the
lanthanides and exhibit similar chemical properties, but have
different electronic and magnetic properties.[2][3] The term 'rare-
earth' is a misnomer because they are not actually scarce,
although historically it took a long time to isolate these
elements.[4][5] Rare-earth ore (shown with a 19 mm
diameter US 1 cent coin for size
These metals tarnish slowly in air at room temperature and react comparison)
slowly with cold water to form hydroxides, liberating hydrogen.
They react with steam to form oxides and ignite spontaneously at
a temperature of 400 °C (752 °F). These elements and their
compounds have no biological function other than in several
specialized enzymes, such as in lanthanide-dependent methanol
dehydrogenases in bacteria.[6] The water-soluble compounds are
mildly to moderately toxic, but the insoluble ones are not.[7] All
isotopes of promethium are radioactive, and it does not occur
naturally in the earth's crust, except for a trace amount generated Refined rare-earth oxides are heavy,
by spontaneous fission of uranium-238. They are often found in gritty powders usually brown or black,
minerals with thorium, and less commonly uranium. but can be lighter colors as shown
here.
Though rare-earth elements are technically relatively plentiful in Legend:
the entire Earth's crust (cerium being the 25th-most-abundant gadolinium · praseodymium · cerium
samarium · lanthanum
element at 68 parts per million, more abundant than copper), in neodymium
practice this is spread thin across trace impurities, so to obtain
rare earths at usable purity requires processing enormous
amounts of raw ore at great expense, thus the name "rare" earths.

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 are
sparse.[8] 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 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.
 Overview of rare-earth metal properties

Abundance[9][10]
Z Symbol Name Etymology Selected applications
(ppm[a])
Light aluminium-scandium alloys for
from Latin aerospace components, additive in
21 Sc Scandium Scandia metal-halide lamps and mercury-vapor 22
(Scandinavia). lamps,[11] radioactive tracing agent in
oil refineries

Yttrium aluminium garnet (YAG) laser,

yttrium vanadate (YVO4) as host for
europium in television red phosphor,
YBCO high-temperature
superconductors, yttria-stabilized
zirconia (YSZ) (used in tooth crowns;
as refractory material - in metal alloys
used in jet engines, and coatings of
engines and industrial gas turbines;
electroceramics - for measuring
oxygen and pH of hot water solutions,
after the village i.e. in fuel cells; ceramic electrolyte -
of Ytterby, used in solid oxide fuel cell; jewelry -
Sweden, where for its hardness and optical properties;
39 Y Yttrium do-it-yourself high temperature 33
the first rare-
earth ore was ceramics and cements based on
discovered. water), yttrium iron garnet (YIG)
microwave filters,[11] energy-efficient
light bulbs (part of triphosphor white
phosphor coating in fluorescent tubes,
CFLs and CCFLs, and yellow phosphor
coating in white LEDs),[12] spark plugs,
gas mantles, additive to steel,
aluminium and magnesium alloys,
cancer treatments, camera and
refractive telescope lenses (due to high
refractive index and very low thermal
expansion), battery cathodes (LYP)

High refractive index and alkali-

from the Greek resistant glass, flint, hydrogen storage,
"lanthanein", battery-electrodes, camera and
57 La Lanthanum 39
meaning to be refractive telescope lenses, fluid
hidden. catalytic cracking catalyst for oil
refineries
Chemical oxidizing agent, polishing
after the dwarf powder, yellow colors in glass and
planet Ceres, ceramics, catalyst for self-cleaning
named after ovens, fluid catalytic cracking catalyst
58 Ce Cerium 66.5
the Roman for oil refineries, ferrocerium flints for
goddess of lighters, robust intrinsically hydrophobic
agriculture.
coatings for turbine blades[13]

Rare-earth magnets, lasers, core

from the Greek material for carbon arc lighting,
"prasios", colorant in glasses and enamels,
meaning leek- additive in didymium glass used in
59 Pr Praseodymium 9.2
green, and welding goggles,[11] ferrocerium
"didymos", firesteel (flint) products, single-mode
meaning twin. fiber optical amplifiers (as a dopant of
fluoride glass)
 Abundance[9][10]
Z Symbol Name Etymology Selected applications
(ppm[a])
from the Greek
Rare-earth magnets, lasers, violet
"neos",
colors in glass and ceramics, didymium
60 Nd Neodymium meaning new, 41.5
glass, ceramic capacitors, electric
and "didymos",
motors in electric automobiles
meaning twin.

after the Titan

Prometheus,
61 Pm Promethium Nuclear batteries, luminous paint 1 × 10−15 [14][b]
who brought
fire to mortals.
after mine
Rare-earth magnets, lasers, neutron
official, Vasili
62 Sm Samarium capture, masers, control rods of 7.05
Samarsky-
nuclear reactors
Bykhovets.

after the Red and blue phosphors, lasers,

63 Eu Europium continent of mercury-vapor lamps, fluorescent 2
Europe. lamps, NMR relaxation agent
High refractive index glass or garnets,
lasers, X-ray tubes, computer bubble
memories, neutron capture, MRI
contrast agent, NMR relaxation agent,
steel and chromium alloys additive,
after Johan
magnetic refrigeration (using significant
Gadolin (1760–
magnetocaloric effect), positron
1852), to honor
64 Gd Gadolinium emission tomography scintillator 6.2
his
detectors, a substrate for magneto-
investigation of
optical films, high performance high-
rare earths.
temperature superconductors, ceramic
electrolyte used in solid oxide fuel
cells, oxygen detectors, possibly in
catalytic conversion of automobile
fumes.

Additive in Neodymium based

magnets, green phosphors, lasers,
after the village fluorescent lamps (as part of the white
65 Tb Terbium of Ytterby, triband phosphor coating), 1.2
Sweden. magnetostrictive alloys such as
terfenol-D, naval sonar systems,
stabilizer of fuel cells

from the Greek Additive in Neodymium based

"dysprositos", magnets, lasers, magnetostrictive
66 Dy Dysprosium 5.2
meaning hard alloys such as terfenol-D, hard disk
to get. drives
after Stockholm
(in Latin,
Lasers, wavelength calibration
"Holmia"), the
67 Ho Holmium standards for optical 1.3
native city of
spectrophotometers, magnets
one of its
discoverers.

after the village

Infrared lasers, vanadium steel, fiber-
68 Er Erbium of Ytterby, 3.5
optic technology
Sweden.

69 Tm Thulium after the Portable X-ray machines, metal-halide 0.52

mythological lamps, lasers
 Abundance[9][10]
Z Symbol Name Etymology Selected applications
(ppm[a])
northern land
of Thule.

Infrared lasers, chemical reducing

after the village
agent, decoy flares, stainless steel,
70 Yb Ytterbium of Ytterby, 3.2
strain gauges, nuclear medicine,
Sweden.
earthquake monitoring
Positron emission tomography – PET
after Lutetia,
scan detectors, high-refractive-index
the city that
71 Lu Lutetium glass, lutetium tantalate hosts for 0.8
later became
phosphors, catalyst used in refineries,
Paris.
LED light bulb

a. Parts per million in earth's crust, e.g. Pb=13 ppm

b. Promethium has no stable isotopes or primordial radioisotopes; trace quantities occur in nature as
fission products.

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".[15]

Discovery and early history

Rare earths were mainly discovered as components of minerals. Ytterbium was found in the
"ytterbite" (renamed to gadolinite in 1800) discovered by Lieutenant Carl Axel Arrhenius in 1787 at a
quarry in the village of Ytterby, Sweden[16] and termed "rare" because it had never yet been seen.[17]
Arrhenius's "ytterbite" reached Johan Gadolin, a Royal Academy of Turku professor, and his analysis
yielded an unknown oxide ("earth" in the geological parlance of the day[17]), which he called yttria.
Anders Gustav Ekeberg isolated beryllium 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–tungsten mineral, was re-examined by Jöns Jacob Berzelius and Wilhelm
Hisinger. In 1803 they obtained a white oxide and called it ceria. Martin Heinrich Klaproth
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. 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.

In 1842 the number of known rare-earth elements had reached six: yttrium, cerium, lanthanum,
didymium, erbium, and terbium.

Nils Johan Berlin 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 of Delafontaine. Due to the difficulty in separating the metals (and determining the
separation is complete), the total number of false discoveries was dozens,[18][19] with some putting the
total number of discoveries at over a hundred.[20]

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, Paul Émile
Lecoq de Boisbaudran isolated the new element samarium from the mineral samarskite.

The samaria earth was further separated by Lecoq de Boisbaudran in 1886, and a similar result was
obtained by Jean Charles Galissard de Marignac by direct isolation from samarskite. They named the
element gadolinium after Johan Gadolin, and its oxide was named "gadolinia".

Further spectroscopic analysis between 1886 and 1901 of samaria, yttria, and samarskite by William
Crookes, Lecoq de Boisbaudran and Eugène-Anatole Demarçay yielded several new spectral 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 called
uranotantalum (now called "samarskite") an oxide of a mixture of elements such as yttrium,
ytterbium, iron, uranium, thorium, calcium, niobium, and tantalum. This mineral from Miass in the
southern Ural Mountains was documented by Gustav Rose. 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 and
niobium (columbium) 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) 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, but that element 61 had not yet been discovered. (This is
promethium, a radioactive element whose most stable isotope has a half-life of just 18 years.)

Using these facts about atomic numbers from X-ray crystallography, Moseley also showed that
hafnium (element 72) would not be a rare-earth element. Moseley was killed in World War I in 1915,
years before hafnium was discovered. Hence, the claim of Georges Urbain that he had discovered
element 72 was untrue. Hafnium is an element that lies in the periodic table immediately below
zirconium, and hafnium and zirconium have very similar chemical and physical properties.

Sources and purification

During the 1940s, Frank Spedding and others in the United States (during the Manhattan Project)
developed chemical ion-exchange procedures for separating and purifying rare-earth elements. This
method was first applied to the actinides for separating plutonium-239 and neptunium from uranium,
thorium, actinium, and the other actinides in the materials produced in nuclear reactors. Plutonium-
239 was very desirable because it is a fissile material.
The principal sources of rare-earth elements are the minerals bastnäsite (RCO3F, where R is a mixture
of rare-earth elements), monazite (XPO4, where X is a mixture of rare-earth elements and sometimes
thorium), and loparite ((Ce,Na,Ca)(Ti,Nb)O3), and the lateritic ion-adsorption clays. Despite their
high relative abundance, rare-earth minerals are more difficult to mine and extract than equivalent
sources of transition metals (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, fractional crystallization, and liquid–liquid
extraction during the late 1950s and early 1960s.[21]

Some ilmenite concentrates contain small amounts of scandium and other rare-earth elements, which
could be analysed by XRF.[22]

Classification
Before the time that ion exchange methods and elution were available, the separation of the rare
earths was primarily achieved by repeated precipitation 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 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.[23] 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.[24] 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.[25] The most common
distinction between rare-earth elements is made by atomic numbers; 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).[26] 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.[27] Increasing atomic numbers between light and heavy rare-
earth elements and decreasing atomic radii throughout the series causes chemical variations.[27]
Europium is exempt of this classification as it has two valence states: Eu2+ and Eu3+.[27] Yttrium is
grouped as heavy rare-earth element due to chemical similarities.[28] The break between the two
groups is sometimes put elsewhere, such as between elements 63 (europium) and 64 (gadolinium).[29]
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 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 and dating fossils.

Compounds
Rare-earth elements occur in nature in combination with phosphate (monazite), carbonate-fluoride
(bastnäsite), and oxygen anions.

In their oxides, most rare-earth elements only have a valence of 3 and form sesquioxides (cerium
forms CeO2). Five different crystal structures are known, depending on the element and the
temperature. The X-phase and the H-phase are only stable above 2000 K. At lower temperatures,
there are the hexagonal A-phase, the monoclinic B-phase, and the cubic C-phase, which is the stable
form at room temperature for most of the elements. The C-phase was once thought to be in space
group I213 (no. 199),[30] but is now known to be in space group Ia3 (no. 206). The structure is similar
to that of fluorite or cerium dioxide (in which the cations form a face-centred cubic lattice and the
anions sit inside the tetrahedra of cations), except that one-quarter of the anions (oxygen) are missing.
The unit cell of these sesquioxides corresponds to eight unit cells of fluorite or cerium dioxide, with 32
cations instead of 4. This is called the bixbyite structure, as it occurs in a mineral of that name
((Mn,Fe)2O3).[31]

Geological distribution
As seen in the chart, rare-earth elements are found on earth at similar concentrations to many
common transition metals. The most abundant rare-earth element is cerium, 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).[32] 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).

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.[33] 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.[33] REE are chemically very similar and have always been difficult to separate, but the
gradual decrease in ionic radius
from light REE (LREE) to heavy
REE (HREE), called the lanthanide
contraction, 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. [33][34] The result is that all
magma formed from partial
melting will always have greater
concentrations of LREE than
HREE, and individual minerals Abundance of elements in Earth's crust per million Si atoms (y axis is
may be dominated by either HREE logarithmic)
or LREE, depending on which
range of ionic radii best fits the
crystal lattice.[33]

Among the anhydrous rare-earth phosphates, it is the tetragonal mineral xenotime that incorporates
yttrium and the HREE, whereas the monoclinic monazite 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 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.[35]

Well-known minerals containing yttrium, and other HREE, include gadolinite, xenotime, samarskite,
euxenite, fergusonite, yttrotantalite, yttrotungstite, yttrofluorite (a variety of fluorite), thalenite, and
yttrialite. Small amounts occur in zircon, which derives its typical yellow fluorescence from some of
the accompanying HREE. The zirconium mineral eudialyte, such as is found in southern Greenland,
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 (which typically contains a few percent of yttrium). Uranium ores from
Ontario have occasionally yielded yttrium as a byproduct.[35]

Well-known minerals containing cerium, and other LREE, include bastnäsite, monazite, allanite,
loparite, ancylite, parisite, lanthanite, chevkinite, cerite, stillwellite, britholite, fluocerite, and
cerianite. Monazite (marine sands from Brazil, India, or Australia; rock from South Africa), bastnäsite
(from Mountain Pass rare earth mine, or several localities in China), and loparite (Kola Peninsula,
Russia) have been the principal ores of cerium and the light lanthanides.[35]
Enriched deposits of rare-earth elements at the surface of the Earth, carbonatites 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.[34] In a rift setting, the alkaline magma is produced
by very small degrees of partial melting (<1%) of garnet peridotite in the upper mantle (200 to
600 km depth).[34] 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, along pre-existing fractures, and can be emplaced deep in the crust, or erupted at the
surface. Typical REE enriched deposits types forming in rift settings are carbonatites, and A- and M-
Type granitoids.[33][34] 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 CO2 and
water), with high concentrations of alkaline elements, and high element mobility that the rare earths
are strongly partitioned into.[33] 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.[33][34]

Alkaline magmas enriched with rare-earth elements include carbonatites, peralkaline granites
(pegmatites), and nepheline syenite. Carbonatites crystallize from CO2-rich fluids, which can be
produced by partial melting of hydrous-carbonated lherzolite to produce a CO2-rich primary magma,
by fractional crystallization of an alkaline primary magma, or by separation of a CO2-rich immiscible
liquid from.[33][34] These liquids are most commonly forming in association with very deep
Precambrian cratons, like the ones found in Africa and the Canadian Shield.[33] Ferrocarbonatites are
the most common type of carbonatite to be enriched in REE, and are often emplaced as late-stage,
brecciated 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.[33][34]
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.[34] 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.[33][34] These fluids have very low
viscosities and high element mobility, which allows for the 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.[34] 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.[34] Nepheline syenite (M-Type granitoids) deposits are 90%
feldspar and feldspathoid minerals. They are deposited in small, circular massifs and contain high
concentrations of rare-earth-bearing accessory minerals.[33][34] For the most part, these deposits are
small but important examples include Illimaussaq-Kvanefeld in Greenland, and Lovozera in
Russia.[34]

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 be extracted from placer deposits if the sedimentary parent lithology contains REE-bearing,
heavy resistate minerals.[34]

In 2011, Yasuhiro Kato, a geologist at the University of Tokyo 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 "[h]ot plumes from hydrothermal vents pull[ing] these
materials out of seawater and deposit[ing] them 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." "I
believe that rare[-]earth resources undersea are much more promising than on-land resources," said
Kato. "[C]oncentrations 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."[35][36]

Notes on rare-earth elements geochemistry

The REE geochemical classification is usually done on the basis of their atomic weight. One of the
most common classifications divides REE into 3 groups: light rare earths (LREE - from 57La to 60Nd),
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. 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. Sc, Y, and Lu can be electronically distinguished
from the other rare earths because they do not have f valence electrons, whereas the others do, but the
chemical behaviour is almost the same.

A distinguishing factor in the geochemical behaviour of the REE is linked to the so-called "lanthanide
contraction" 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 towards the
nuclear charge due to the progressive filling of the 4f orbital which acts against the electrons of the 6s
and 5d 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[37]) 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, sedimentary and metamorphic 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 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 the initial abundances of the element. Normalization also removes the pronounced
'zig-zag' pattern caused by the differences in abundance between even and odd atomic numbers.
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:

where n indicates the normalized concentration, the analytical concentration of the

element measured in the sample, and the concentration of the same element in the
reference material.[38]

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.[26]

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:

where is the normalized concentration of the element whose anomaly has to be calculated,
and 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.[26] Fractionation is in turn a function of the partition coefficients of each element.
Partition coefficients are responsible for the fractionation of 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 if it preferentially partitions
into the melt phase it is described as ‘incompatible’.[26] 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 feldspars. Hornblende, controls the enrichment of MREE
compared to LREE and HREE. Depletion of LREE relative to HREE may be due to the crystallization
of olivine, orthopyroxene, and clinopyroxene. On the other hand, the depletion of HREE relative to
LREE may be due to the presence of garnet, as garnet preferentially incorporates HREE into its crystal
structure. The presence of zircon may also cause a similar effect.[26]

In sedimentary rocks, rare-earth elements in clastic sediments are a representation of 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
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.[26]

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;[26] this is important in the investigation of ocean mixing
and circulation.[28]

Rare-earth elements are also useful for dating rocks, as some radioactive isotopes display long half-
lives. Of particular interest are the 138La-138Ce, 147Sm-143Nd, and 176Lu-176Hf systems.[28]

Production
Until 1948, most of the world's rare earths were
sourced from placer sand deposits in India and
Brazil. Through the 1950s, South Africa was the
world's rare earth source, from a monazite-rich
reef at the Steenkampskraal mine in Western Cape
province.[39] 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
were dwarfed by the scale of Chinese production.
Global production 1950–2000
In 2017, China produced 81% of the world's rare-
earth supply, mostly in Inner Mongolia,[8][40]
although it had only 36.7% of reserves. Australia was the second and only other major producer with
15% of world production.[41] All of the world's heavy rare earths (such as dysprosium) come from
Chinese rare-earth sources such as the polymetallic Bayan Obo deposit.[40][42] The Browns Range
mine, located 160 km south east of Halls Creek in northern Western Australia, is currently under
development and is positioned to become the first significant dysprosium producer outside of
China.[43]

Increased demand has strained supply, and there is growing concern that the world may soon face a
shortage of the rare earths.[44] 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.[45]
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.[46] 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.[47]

China

These concerns have intensified due to the actions of China, the predominant supplier.[48]
Specifically, China has announced regulations on exports and a crackdown on smuggling.[49] 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.[50] On October 19, 2010, China
Daily, 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."[51] 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.[52] 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.[53] 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.[54] 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.[55][56] In August 2012, China announced a further 20% reduction
in production.[57] 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.[56]

In response to the opening of new mines in other countries (Lynas in Australia and Molycorp in the
United States), prices of rare earths dropped.[58] The price of dysprosium oxide was 994 USD/kg in
2011, but dropped to US$265/kg by 2014.[59]

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 licenses will still be required.[60]

In 2019, China supplied between 85% and 95% of the global demand for the 17 rare-earth powders,
half of them sourced from Myanmar.[61] 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 electric vehicle manufacturing and high-tech military
applications.[62]

Myanmar (Burma)

Kachin State in Myanmar is the world's largest source of rare earths.[63] In 2021, China imported
US$200 million of rare earths from Myanmar in December 2021, exceeding 20,000 tonnes.[64] Rare
earths were discovered near Pangwa in Chipwi Township along the China–Myanmar border in the late
2010s.[65] As China has shut down domestic mines due to the detrimental environmental impact, it
has largely outsourced rare-earth mining to Kachin State.[64] Chinese companies and miners illegally
set up operations in Kachin State without government permits, and instead circumvent the central
government by working with a Border Guard Force militia under the Tatmadaw, formerly known as
the New Democratic Army – Kachin, which has profited from this extractive industry.[64][66] As of
March 2022, 2,700 mining collection pools scattered across 300 separate locations were found in
Kachin State, encompassing the area of Singapore, and an exponential increase from 2016.[64] Land
has also been seized from locals to conduct mining operations.[64]

Other countries

As a result of the increased demand and tightening restrictions on exports of the metals from China,
some countries are stockpiling rare-earth resources.[67] Searches for alternative sources in Australia,
Brazil, Canada, South Africa, Tanzania, Greenland, and the United States are ongoing.[68] 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.[49][69] 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.[70] Over
80% of the infrastructure is already complete.[71] Other mines include the Nolans Project in Central
Australia, the Bokan Mountain project in Alaska, the remote Hoidas Lake project in northern
Canada,[72] and the Mount Weld project in Australia.[40][69][73] The Hoidas Lake project has the
potential to supply about 10% of the $1 billion of REE consumption that occurs in North America
every year.[74] Vietnam signed an agreement in October 2010 to supply Japan with rare earths[75]
from its northwestern Lai Châu Province,[76] however the deal was never realized due to
disagreements.[77]

The largest rare-earth deposit in the U.S. is at Mountain Pass, California, sixty miles south of Las
Vegas. Originally opened by Molycorp, the deposit has been mined, off and on, since 1951.[40][78] A
second large deposit of REEs at Elk Creek in southeast Nebraska[79] is under consideration by
NioCorp Development Ltd [80] who hopes to open a niobium, scandium, and titanium mine there.[81]
That mine may be able to produce as much as 7200 tonnes of ferro niobium and 95 tonnes of
scandium trioxide annually,[82] although, as of 2022, financing is still in the works.[79]

In the UK, Pensana has 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.[83][84] 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.[85][86]
Also under consideration for mining are sites such as Thor Lake in the Northwest Territories, and
various locations in Vietnam.[40][45][87] Additionally, in 2010, a large deposit of rare-earth minerals
was discovered in Kvanefjeld in southern Greenland.[88] Pre-feasibility drilling at this site has
confirmed significant quantities of black lujavrite, which contains about 1% rare-earth oxides
(REO).[89] The European Union has urged Greenland to restrict Chinese development of rare-earth
projects there, but as of early 2013, the government of Greenland has said that it has no plans to
impose such restrictions.[90] 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.[91]

In central Spain, 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.[92]

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.[93]

North Korea has been reported to have exported rare-earth ore to China, about US$1.88 million worth
during May and June 2014.[94][95]

In May 2012, researchers from two universities in Japan announced that they had discovered rare
earths in Ehime Prefecture, Japan.[96]

On 12 January 2023, Swedish state-owned mining company LKAB announced that it had discovered a
deposit of over 1 million tonnes of rare earths in the country's Kiruna area, which would make it the
largest such deposit in Europe.[97]

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.
The plant would refine ore — lanthanides concentrate from the Mount Weld mine in Australia. The
ore would be trucked to Fremantle and transported by container ship 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.[98] 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.[99][100] In mid-2011, after protests, Malaysian government restrictions on the Lynas plant
were announced. At that time, citing subscription-only Dow Jones Newswire 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."[101] 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.[102]

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.[103]

Other sources

Mine tailings

Significant quantities of rare-earth oxides are found in tailings accumulated from 50 years of uranium
ore, shale, and loparite mining at Sillamäe, Estonia.[104] 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.[105] Similar resources are
suspected in the western United States, where gold rush-era mines are believed to have discarded
large amounts of rare earths, because they had no value at the time.[106]

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 250 kilometres (160 mi)
south of the island of Minami-Tori-Shima.[107] 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.[108][109]

Waste

Another recently developed source of rare earths is electronic waste and other wastes that have
significant rare-earth components.[110] Advances in recycling technology have made the extraction of
rare earths from these materials less expensive.[111] Recycling plants operate in Japan, where an
estimated 300,000 tons of rare earths are found in unused electronics.[112] In France, the Rhodia
group is setting up two factories, in La Rochelle and Saint-Fons, that will produce 200 tons of rare
earths a year from used fluorescent lamps, magnets, and batteries.[113][114] 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.[115]

Methods

One study mixed fly ash with carbon black and then sent a 1-second current pulse through the
mixture, heating it to 3,000 °C (5,430 °F). The fly ash contains microscopic bits of glass that
encapsulate the metals. The heat shatters the glass, exposing the rare earths. Flash heating also
converts phosphates 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.[116]

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.[2] For example, "the rare-earth elements praseodymium
(Pr) and neodymium (Nd) can both be embedded inside glass and they completely cut out the glare
from the flame when one is doing glass-blowing."[2]

Uses
The uses, applications, and demand for rare-earth elements have
expanded over the years. Globally, most REEs are used for catalysts
and magnets.[117] In the USA, more than half of REEs are used for
catalysts; ceramics, glass, and polishing are also main uses.[118]

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 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 some wind turbines, hard disc drives,
portable electronics, microphones, and speakers. Global REE consumption,
2015[117]
Ce, La, and Nd are important in alloy making, and in the production
Catalysts, 24% (24%)
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 Magnets, 23% (23%)
plasma screens, fiber optics, and lasers,[119] and in medical imaging. Polishing, 12% (12%)
Additional uses for rare-earth elements are as tracers in medical "other", 9% (9%)
applications, fertilizers, and in water treatment.[28] Metallurgy, 8% (8%)
Batteries, 8% (8%)
REEs have been used in agriculture to increase plant growth, Glass, 7% (7%)
productivity, and stress resistance seemingly without negative effects Ceramics, 6% (6%)
for human and animal consumption. REEs are used in agriculture Phosphors and pigments,
through REE-enriched fertilizers which is a widely used practice in 3% (3%)
China.[120] 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
bioaccumulation within livestock and has impacted vegetation and algae growth in these agricultural
areas.[121] 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.[120][122]

Environmental considerations
REEs are naturally found in very low concentrations 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.[123][124]
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, groundwater, 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.[125] Furthermore, strong acids are used during the
extraction process of REEs, which can then leach out into the
environment and be transported through water bodies and result in US consumption of REE,
the acidification of aquatic environments. Another additive of REE 2018[118]
mining that contributes to REE environmental contamination is
cerium oxide (CeO2), which is produced during the combustion of Catalysts, 60% (60%)
diesel and released as exhaust, contributing heavily to soil and water Ceramics and glass, 15%
contamination.[121] (15%)
Polishing, 10% (10%)
Mining, refining, and recycling of rare earths have serious "other", 5% (5%)
environmental consequences if not properly managed. Low-level Metallurgy, 10% (10%)
radioactive tailings resulting from the occurrence of thorium and
uranium in rare-earth ores present a potential hazard[126] 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,[127] where mines – commonly small,
rural, and illegal operations – are particularly prone to releasing
toxic waste into the general water supply.[40][128] However, even
the major operation in Baotou, in Inner Mongolia, where much of
the world's rare-earth supply is refined, has caused major False-color satellite image of the
Bayan Obo Mining District, 2006
environmental damage.[129] China's Ministry of Industry and
Information Technology estimated that cleanup costs in Jiangxi
province at $5.5 billion.[124]

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.[130][131][132]

Recycling and reusing REEs

Potential methods

The rare-earth elements (REEs) are vital to modern technologies and society and are amongst the
most critical elements. Despite this, typically only around 1% of REEs are recycled from end-products,
with the rest deporting to waste and being removed from the materials cycle.[133] Recycling and
reusing REEs play an important role in high technology fields and manufacturing environmentally
friendly products all around the world.[134]
REE recycling and reuse have been increasingly focused on in recent years. The main concerns include
environmental pollution during REE recycling and increasing recycling efficiency. 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.[135] A study
published in 2014 suggests a method to recycle REEs from waste nickel-metal hydride batteries,
demonstrating a recovery rate of 95.16%.[136] 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.[137][138] 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."[139] In most of the
reported studies reviewed by a scientific review, "secondary waste is subjected to chemical and or
bioleaching followed by solvent extraction processes for clean separation of REEs."[140]

Currently, people take two essential resources into consideration for the secure supply of REEs: one is
to extract REEs from primary resources like mines harboring REE-bearing ores, regolith-hosted clay
deposits,[141] ocean bed sediments, coal fly ash,[142] etc. A work developed a green system for recovery
of REEs from coal fly ash by using citrate and oxalate who are strong organic ligand and capable of
complexing or precipItating with REE.[143] The other one is from secondary resources such as
electronic, industrial waste and municipal waste. E-waste contains a significant concentration of
REEs, and thus is the primary option for REE recycling now. According to a study, approximately 50
million metric tons of electronic waste are dumped in landfills worldwide each year. Despite the fact
that e-waste contains a significant amount of rare-earth elements (REE), only 12.5% of e-waste is
currently being recycled for all metals.[144][145]

Challenges

For now, there are some obstacles during REE recycling and reuse. One big challenge is REE
separation chemistry. Specifically, the process of isolating and refining individual rare earth elements
(REE) presents a difficulty due to their similar chemical properties. In order to reduce the
environmental pollution released during REE isolation and also diversify their sources, there is a clear
necessity for the development of novel separation technologies that can lower the cost of large-scale
REE separation and recycling.[146] In this condition, the Critical Materials Institute (CMI) under the
Department of Energy has devised a technique that involves utilizing Gluconobacter bacteria to
metabolize sugars, producing acids that can dissolve and separate rare-earth elements (REE) from
shredded electronic waste.[147]

Impact of REE contamination

On vegetation

The mining of REEs has caused the 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.[121] 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 of 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.[148] 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.[125] 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 (Eichhornia crassipes) in China, where the water was contaminated due to
a REE-enriched fertilizer being used in a nearby agricultural area. The aquatic environment became
contaminated with cerium and resulted in the water hyacinth becoming three times more
concentrated in cerium than its surrounding water.[148]

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.[149] 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.[150][151] 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.[46] 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
risk and toxicity as some of these are harmless while others pose a risk.[149][151][150]

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.[152][121] 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.[150][151] 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.[153]

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 the air near REE mines is higher than the limit value from WHO, which can affect the surrounding
environment and become a risk to those who live or work nearby.[154]

Residents blamed a rare-earth refinery at Bukit Merah for birth defects and eight leukemia 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 [grown with the fertilizer] all died."[155] 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.[156]

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.[157]
REEs have been added to feed in livestock to increase their body mass and increase milk
production.[157] 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.[157] 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.[157] 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 REE-contaminated areas have been diagnosed with organ or system
problems.[121] REEs have been used in freshwater fish farming because it protects the fish from
possible diseases.[157] 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.[158]

Remediation after pollution

After the 1982 Bukit Merah radioactive pollution, the mine in Malaysia 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."[100]

In May 2011, after the Fukushima 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."[155]
Construction of the facility has been halted until an independent United Nations IAEA panel
investigation is completed, which is expected by the end of June 2011.[159] New restrictions were
announced by the Malaysian government in late June.[101]

An IAEA panel investigation was completed and no construction has been halted. Lynas is on budget
and on schedule to start producing in 2011. The IAEA concluded in a report issued in June 2011 that it
did not find any instance of "any non-compliance with international radiation safety standards" in the
project.[160]

If the proper safety standards are followed, REE mining is relatively low impact. Molycorp (before
going bankrupt) often exceeded environmental regulations to improve its public image.[161]
In Greenland, there is a significant dispute on whether to start a new rare-earth mine in Kvanefjeld
due to environmental concerns.[162]

Geopolitical considerations
China has officially cited resource depletion and environmental
concerns as the reasons for a nationwide crackdown on its rare-
earth mineral production sector.[54] However, non-environmental
motives have also been imputed to China's rare-earth policy.[129]
According to The Economist, "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."[163] Furthermore, China currently has
an effective monopoly on the world's REE Value Chain.[164] (All of Global rare-earth-oxide production
the refineries and processing plants that transform the raw ore trends, 1956-2008 (USGS)
into valuable elements.[165]) 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."[166]

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[167]
(China's export quota only applies to the metal but not products made from these metals such as
magnets).

It was reported,[168] but officially denied,[169] 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.[170][56] 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."[171][56]

The United States Department of Energy in its 2010 Critical Materials Strategy report identified
dysprosium as the element that was most critical in terms of import reliance.[172]

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 [metric tons] during the period from 2009 to 2015. The export
quota for rare-earth products may be about 35,000 [metric tons] and the Government may allow 20
domestic rare-earth producers and traders to export rare earths."[173]
The United States Geological Survey is actively surveying southern Afghanistan 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 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.[174]

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.[175][176] 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
criticized for failing to recognize that most wind turbines have gears and do not use permanent
magnets.[176]

Rare Earth Elements in popular culture

The plot of Eric Ambler's now-classic 1967 international crime-thriller Dirty Story (aka This Gun for
Hire, but not to be confused with the movie This Gun for Hire (1942)) features a struggle between two
rival mining cartels to control a plot of land in a fictional African country, which contains rich minable
rare-earth ore deposits.[177]

Prices
The Institute of Rare Earths Elements and Strategic Metals is an informal network in the international
raw metal market. The main interest of the institute's customers is the database, which is available on
a subscription basis with daily updated prices: In addition to the eponymous rare-earth elements,
900 pure metals and 4,500 other metallic products are listed there. The company's headquarters are
located in Lucerne, Switzerland.

See also
Geology portal

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

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External links
Media related to Rare earth elements at Wikimedia Commons
Rare-earth element (https://www.britannica.com/EBchecked/topic/491579) at the Encyclopædia
Britannica
External media
Audio
"Rare Earths: The Hidden Cost
to Their Magic" (https://www.science
history.org/distillations/podcast/rare-
earths-the-hidden-cost-to-their-magi
c), Distillations Podcast and
transcript, Episode 242, June 25,
2019, Science History Institute
Video
"10 ways rare earth elements
make life better" (https://www.scienc
ehistory.org/rare-earth-elements-pro
ject), animation, Science History
Institute
"Rare-Earth Elements: The
Intersection of Science and Society"
(https://www.youtube.com/watch?v=
aglMNj4hld0), presentation and
discussion led by Ira Flatow,
Science History Institute, September
24, 2019

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