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121-424: The mines north of the town are the largest deposits of rare-earth elements yet found and, as of 2005, responsible for 45% of global rare-earth element production. In the satellite image at right, vegetation appears red, grassland is light brown, rocks are black, and water surfaces are green. Two circular open-pit mines are visible, as well as a number of tailings ponds and tailings piles. Bayan Obo Mining District

242-573: A Gilman reagent . These can undergo substitution with alkyl halides to form coupling products ; as such, they are important in the field of organic synthesis . Copper(I) acetylide is highly shock-sensitive but is an intermediate in reactions such as the Cadiot–Chodkiewicz coupling and the Sonogashira coupling . Conjugate addition to enones and carbocupration of alkynes can also be achieved with organocopper compounds. Copper(I) forms

363-485: A building material , and as a constituent of various metal alloys , such as sterling silver used in jewelry , cupronickel used to make marine hardware and coins , and constantan used in strain gauges and thermocouples for temperature measurement. Copper is one of the few metals that can occur in nature in a directly usable metallic form ( native metals ). This led to very early human use in several regions, from c.  8000 BC . Thousands of years later, it

484-696: A covalent character and are relatively weak. This observation explains the low hardness and high ductility of single crystals of copper. At the macroscopic scale, introduction of extended defects to the crystal lattice , such as grain boundaries, hinders flow of the material under applied stress, thereby increasing its hardness. For this reason, copper is usually supplied in a fine-grained polycrystalline form, which has greater strength than monocrystalline forms. The softness of copper partly explains its high electrical conductivity ( 59.6 × 10   S /m ) and high thermal conductivity, second highest (second only to silver) among pure metals at room temperature. This

605-549: A fissile material . The principal sources of rare-earth elements are the minerals bastnäsite ( RCO 3 F , where R is a mixture of rare-earth elements), monazite ( XPO 4 , where X is a mixture of rare-earth elements and sometimes thorium), and loparite ( (Ce,Na,Ca)(Ti,Nb)O 3 ), 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

726-636: A nickel ) consists of 75% copper and 25% nickel in homogeneous composition. Prior to the introduction of cupronickel, which was widely adopted by countries in the latter half of the 20th century, alloys of copper and silver were also used, with the United States using an alloy of 90% silver and 10% copper until 1965, when circulating silver was removed from all coins with the exception of the half dollar—these were debased to an alloy of 40% silver and 60% copper between 1965 and 1970. The alloy of 90% copper and 10% nickel, remarkable for its resistance to corrosion,

847-425: A spin of 3 ⁄ 2 . The other isotopes are radioactive , with the most stable being Cu with a half-life of 61.83 hours. Seven metastable isomers have been characterized; Cu is the longest-lived with a half-life of 3.8 minutes. Isotopes with a mass number above 64 decay by β , whereas those with a mass number below 64 decay by β . Cu , which has

968-595: A CO 2 -rich primary magma, by fractional crystallization of an alkaline primary magma, or by separation of a CO 2 -rich immiscible liquid from. These liquids are most commonly forming in association with very deep Precambrian cratons , 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, brecciated pipes at

1089-399: A blast furnace. A potential source of copper is polymetallic nodules, which have an estimated concentration 1.3%. Like aluminium , copper is recyclable without any loss of quality, both from raw state and from manufactured products. In volume, copper is the third most recycled metal after iron and aluminium. An estimated 80% of all copper ever mined is still in use today. According to

1210-459: A blue crystalline penta hydrate , the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture . Polyols , compounds containing more than one alcohol functional group , generally interact with cupric salts. For example, copper salts are used to test for reducing sugars . Specifically, using Benedict's reagent and Fehling's solution the presence of

1331-532: A component of magnets in hybrid car motors." The global demand for rare-earth elements (REEs) is expected to increase more than fivefold by 2030. 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 57 La to 60 Nd), intermediate (MREE - from 62 Sm to 67 Ho) and heavy (HREE - from 68 Er to 71 Lu). REE usually appear as trivalent ions, except for Ce and Eu which can take

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1452-657: 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 , 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

1573-457: A green patina of compounds called verdigris . Copper is sometimes used in decorative art , both in its elemental metal form and in compounds as pigments. Copper compounds are used as bacteriostatic agents , fungicides , and wood preservatives . Copper is essential to all living organisms as a trace dietary mineral because it is a key constituent of the respiratory enzyme complex cytochrome c oxidase . In molluscs and crustaceans , copper

1694-495: A half-life of 12.7 hours, decays both ways. Cu and Cu have significant applications. Cu is used in Cu Cu-PTSM as a radioactive tracer for positron emission tomography . Copper is produced in massive stars and is present in the Earth's crust in a proportion of about 50 parts per million (ppm). In nature, copper occurs in

1815-683: A layer of brown-black copper oxide which, unlike the rust that forms on iron in moist air, protects the underlying metal from further corrosion ( passivation ). A green layer of verdigris (copper carbonate) can often be seen on old copper structures, such as the roofing of many older buildings and the Statue of Liberty . Copper tarnishes when exposed to some sulfur compounds, with which it reacts to form various copper sulfides . There are 29 isotopes of copper. Cu and Cu are stable, with Cu comprising approximately 69% of naturally occurring copper; both have

1936-544: 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

2057-432: A melt phase if one is present. 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

2178-404: A melt phase, while HREE may prefer to remain in the crystalline residue, particularly if it contains HREE-compatible minerals like garnet . 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

2299-532: A natural color other than gray or silver. Pure copper is orange-red and acquires a reddish tarnish when exposed to air. This is due to the low plasma frequency of the metal, which lies in the red part of the visible spectrum, causing it to absorb the higher-frequency green and blue colors. As with other metals, if copper is put in contact with another metal in the presence of an electrolyte , galvanic corrosion will occur. Copper does not react with water, but it does slowly react with atmospheric oxygen to form

2420-451: 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. During the 1940s, Frank Spedding and others in

2541-407: A red-brown precipitate with copper(II) salts. Compounds that contain a carbon-copper bond are known as organocopper compounds. They are very reactive towards oxygen to form copper(I) oxide and have many uses in chemistry . They are synthesized by treating copper(I) compounds with Grignard reagents , terminal alkynes or organolithium reagents ; in particular, the last reaction described produces

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2662-451: A rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric , respectively. Copper compounds promote or catalyse numerous chemical and biological processes. As with other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements, the principal examples being oxides, sulfides, and halides . Both cuprous and cupric oxides are known. Among

2783-404: 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. In the latter case, the f-block elements are split into half: the first half (La–Eu) form the cerium group, and the second half (Gd–Yb) together with group 3 (Sc, Y, Lu) form the yttrium group. The reason for this division arose from

2904-494: 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 electrical and magnetic properties . The term 'rare-earth'

3025-420: A similar effect. 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

3146-520: A ton of radioactive waste residue are also produced. Very large rare-earth elements (REE) Fe-Nb deposit (Bayan-Obo type), discovered as an iron deposit in 1927. REE minerals were discovered in 1936, and niobium -bearing ores in the late 1950s. Reserves are estimated at more than 40 million tons of REE minerals grading at 3–5.4% REE (70% of world's known REE reserves), 1 million tons of Nb 2 O 5 and 470 million tons of iron. The deposit also contains an estimated 130 million tons of fluorite . Bayan'obo

3267-457: A valence of 3 and form sesquioxides (cerium forms CeO 2 ). 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

3388-424: A variety of minerals, including native copper , copper sulfides such as chalcopyrite , bornite , digenite , covellite , and chalcocite , copper sulfosalts such as tetrahedite-tennantite , and enargite , copper carbonates such as azurite and malachite , and as copper(I) or copper(II) oxides such as cuprite and tenorite , respectively. The largest mass of elemental copper discovered weighed 420 tonnes and

3509-436: A variety of weak complexes with alkenes and carbon monoxide , especially in the presence of amine ligands. Copper(III) is most often found in oxides. A simple example is potassium cuprate , KCuO 2 , a blue-black solid. The most extensively studied copper(III) compounds are the cuprate superconductors . Yttrium barium copper oxide (YBa 2 Cu 3 O 7 ) consists of both Cu(II) and Cu(III) centres. Like oxide, fluoride

3630-604: Is a misnomer because they are not actually scarce, although historically it took a long time to isolate these elements. 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 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. The water-soluble compounds are mildly to moderately toxic, but

3751-579: Is a constituent of the blood pigment hemocyanin , replaced by the iron-complexed hemoglobin in fish and other vertebrates . In humans, copper is found mainly in the liver, muscle, and bone. The adult body contains between 1.4 and 2.1 mg of copper per kilogram of body weight. In the Roman era , copper was mined principally on Cyprus , the origin of the name of the metal, from aes cyprium (metal of Cyprus), later corrupted to cuprum (Latin). Coper ( Old English ) and copper were derived from this,

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3872-405: Is a highly basic anion and is known to stabilize metal ions in high oxidation states. Both copper(III) and even copper(IV) fluorides are known, K 3 CuF 6 and Cs 2 CuF 6 , respectively. Some copper proteins form oxo complexes , which, in extensively studied synthetic analog systems, feature copper(III). With tetrapeptides , purple-colored copper(III) complexes are stabilized by

3993-401: Is because the resistivity to electron transport in metals at room temperature originates primarily from scattering of electrons on thermal vibrations of the lattice, which are relatively weak in a soft metal. The maximum possible current density of copper in open air is approximately 3.1 × 10  A/m , above which it begins to heat excessively. Copper is one of a few metallic elements with

4114-461: Is called the bixbyite structure, as it occurs in a mineral of that name ( (Mn,Fe) 2 O 3 ). 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

4235-599: 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

4356-543: Is made up of 2 subdistricts . China produced about 81,000 tons of rare-earth metals in 2001; the number jumped to about 120,000 by 2006. According to the Chinese Society of Rare Earths, 9,600 to 12,000 cubic metres (340,000 to 420,000 cubic feet) of waste gas—containing dust concentrate, hydrofluoric acid, sulfur dioxide, and sulfuric acid—are released with every ton of rare metals that are mined. Approximately 75 m (2,600 cu ft) of acidic wastewater, plus about

4477-529: Is melted in a furnace and then reduced and cast into billets and ingots ; lower-purity scrap is refined by electroplating in a bath of sulfuric acid . The environmental cost of copper mining was estimated at 3.7 kg CO2eq per kg of copper in 2019. Codelco, a major producer in Chile, reported that in 2020 the company emitted 2.8t CO2eq per ton (2.8 kg CO2eq per kg) of fine copper. Greenhouse gas emissions primarily arise from electricity consumed by

4598-444: Is one of the most important constituents of silver and karat gold solders used in the jewelry industry, modifying the color, hardness and melting point of the resulting alloys. Some lead-free solders consist of tin alloyed with a small proportion of copper and other metals. The alloy of copper and nickel , called cupronickel , is used in low-denomination coins, often for the outer cladding. The US five-cent coin (currently called

4719-445: 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

4840-443: 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". Rare earths were mainly discovered as components of minerals. Ytterbium

4961-437: Is recovered from mine tailings and heaps. A variety of methods are used including leaching with sulfuric acid, ammonia, ferric chloride. Biological methods are also used. A significant source of copper is from recycling. Recycling is facilitated because copper is usually deployed in its metallic state. In 2001, a typical automobile contained 20–30 kg of copper. Recycling usually begins with some melting process using

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5082-438: 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. The first rare-earth mineral discovered (1787)

5203-443: 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. 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

5324-517: 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 ). The rare-earth elements are often found together. During

5445-563: Is the world's largest known REE deposit. The fluorite content of the ores also makes it the world's largest fluorite deposit. The deposit occurs in an east–west trending Mesoproterozoic rift zone along the northern margin of the Sino-Korean Craton . Host strata are quartzite, slate, limestone, and dolomite. Dolomite is the main host rock. The orebodies are stratiform and lenticular, with masses, bands, layers, veins, and disseminations. Besides clear features of hydrothermal mineralization,

5566-411: Is used for various objects exposed to seawater, though it is vulnerable to the sulfides sometimes found in polluted harbors and estuaries. Alloys of copper with aluminium (about 7%) have a golden color and are used in decorations. Shakudō is a Japanese decorative alloy of copper containing a low percentage of gold, typically 4–10%, that can be patinated to a dark blue or black color. Copper forms

5687-675: The British Geological Survey , in 2005, Chile was the top producer of copper with at least one-third of the world share followed by the United States, Indonesia and Peru. Copper can also be recovered through the in-situ leach process. Several sites in the state of Arizona are considered prime candidates for this method. The amount of copper in use is increasing and the quantity available is barely sufficient to allow all countries to reach developed world levels of usage. An alternative source of copper for collection currently being researched are polymetallic nodules , which are located at

5808-588: The Great Lakes may have also been mining copper during this time, making it one of the oldest known examples of copper extraction in the world. There is evidence from prehistoric lead pollution from lakes in Michigan that people in the region began mining copper c.  6000 BC . Evidence suggests that utilitarian copper objects fell increasingly out of use in the Old Copper Complex of North America during

5929-536: The International Resource Panel 's Metal Stocks in Society report , the global per capita stock of copper in use in society is 35–55 kg. Much of this is in more-developed countries (140–300 kg per capita) rather than less-developed countries (30–40 kg per capita). The process of recycling copper is roughly the same as is used to extract copper but requires fewer steps. High-purity scrap copper

6050-699: The Neolithic period and the Bronze Age was formerly termed the Chalcolithic period (copper-stone), when copper tools were used with stone tools. The term has gradually fallen out of favor because in some parts of the world, the Chalcolithic and Neolithic are coterminous at both ends. Brass, an alloy of copper and zinc, is of much more recent origin. It was known to the Greeks, but became a significant supplement to bronze during

6171-563: 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 , 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

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6292-521: The Vinča culture date to 4500 BC. Sumerian and Egyptian artifacts of copper and bronze alloys date to 3000 BC. Egyptian Blue , or cuprorivaite (calcium copper silicate) is a synthetic pigment that contains copper and started being used in ancient Egypt around 3250 BC. The manufacturing process of Egyptian blue was known to the Romans, but by the fourth century AD the pigment fell out of use and

6413-486: The upper mantle (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 , 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. Near subduction zones, partial melting of

6534-428: 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. 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

6655-568: 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

6776-539: The 9th or 10th century AD. Carbon dating has established mining at Alderley Edge in Cheshire , UK, at 2280 to 1890 BC. Ötzi the Iceman , a male dated from 3300 to 3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest an involvement in copper smelting. Experience with copper has assisted the development of other metals; in particular, copper smelting likely led to

6897-512: The Bronze Age and a shift towards an increased production of ornamental copper objects occurred. Natural bronze, a type of copper made from ores rich in silicon, arsenic, and (rarely) tin, came into general use in the Balkans around 5500 BC. Alloying copper with tin to make bronze was first practiced about 4000 years after the discovery of copper smelting, and about 2000 years after "natural bronze" had come into general use. Bronze artifacts from

7018-498: 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

7139-535: The Middle East; a copper pendant was found in northern Iraq that dates to 8700 BC. Evidence suggests that gold and meteoric iron (but not smelted iron) were the only metals used by humans before copper. The history of copper metallurgy is thought to follow this sequence: first, cold working of native copper, then annealing , smelting , and, finally, lost-wax casting . In southeastern Anatolia , all four of these techniques appear more or less simultaneously at

7260-459: 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

7381-449: 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

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7502-521: The affected areas is highly acidic, with a pH range of 2.1–4.9, and shows elevated electrical conductivity levels between 280 and 1561 mS/cm. These changes in water chemistry make the environment inhospitable for fish, essentially rendering the water uninhabitable for aquatic life. Numerous copper alloys have been formulated, many with important uses. Brass is an alloy of copper and zinc . Bronze usually refers to copper- tin alloys, but can refer to any alloy of copper such as aluminium bronze . Copper

7623-448: 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

7744-531: The atmosphere; 150 mg/kg in soil; 30 mg/kg in vegetation; 2 μg/L in freshwater and 0.5 μg/L in seawater. Most copper is mined or extracted as copper sulfides from large open pit mines in porphyry copper deposits that contain 0.4 to 1.0% copper. Sites include Chuquicamata , in Chile, Bingham Canyon Mine , in Utah, United States, and El Chino Mine , in New Mexico, United States. According to

7865-734: The beginning of the Neolithic c.  7500 BC . Copper smelting was independently invented in different places. The earliest evidence of lost-wax casting copper comes from an amulet found in Mehrgarh , Pakistan, and is dated to 4000 BC. Investment casting was invented in 4500–4000 BC in Southeast Asia Smelting was probably discovered in China before 2800 BC, in Central America around 600 AD, and in West Africa about

7986-527: The company, especially when sourced from fossil fuels, and from engines required for copper extraction and refinement. Companies that mine land often mismanage waste, rendering the area sterile for life. Additionally, nearby rivers and forests are also negatively impacted. The Philippines is an example of a region where land is overexploited by mining companies. Copper mining waste in Valea Şesei, Romania, has significantly altered nearby water properties. The water in

8107-858: 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

8228-408: 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

8349-735: 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. 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. They are deposited in small, circular massifs and contain high concentrations of rare-earth-bearing accessory minerals . For

8470-513: The deposit also exhibits Mg, Fe, Na and F metasomatism . Sm-Nd monazite isochron age for bastnaesite and riebeckite is 1200 to 1300 Ma, whereas Th-Pb and Sm-Nd age of Ba-REE-F carbonates and aeschynite is 474 to 402 Ma. Rare-earth metal The rare-earth elements ( REE ), also called the rare-earth metals or rare earths , and sometimes the lanthanides or lanthanoids (although scandium and yttrium , which do not belong to this series, are usually included as rare earths), are

8591-522: The deprotonated amide ligands. Complexes of copper(III) are also found as intermediates in reactions of organocopper compounds, for example in the Kharasch–Sosnovsky reaction . A timeline of copper illustrates how this metal has advanced human civilization for the past 11,000 years. Copper occurs naturally as native metallic copper and was known to some of the oldest civilizations on record. The history of copper use dates to 9000 BC in

8712-454: The depths of the Pacific Ocean approximately 3000–6500 meters below sea level. These nodules contain other valuable metals such as cobalt and nickel . Copper has been in use for at least 10,000 years, but more than 95% of all copper ever mined and smelted has been extracted since 1900. As with many natural resources, the total amount of copper on Earth is vast, with around 10 tons in

8833-413: 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. 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

8954-550: The discovery of iron smelting . Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6500 and 3000 BC. A copper spearpoint found in Wisconsin has been dated to 6500 BC. Copper usage by the indigenous peoples of the Old Copper Complex from the Great Lakes region of North America has been radiometrically dated to as far back as 7500 BC. Indigenous peoples of North America around

9075-409: 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 Ho (0.901 Å) to be almost identical to that of Y (0.9 Å), justifying the inclusion of

9196-651: 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 [ REE i ] n {\displaystyle [{\text{REE}}_{i}]_{n}} is the normalized concentration of the element whose anomaly has to be calculated, [ REE i − 1 ] n {\displaystyle [{\text{REE}}_{i-1}]_{n}} and [ REE i + 1 ] n {\displaystyle [{\text{REE}}_{i+1}]_{n}}

9317-417: 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

9438-545: The fastest water exchange rate (speed of water ligands attaching and detaching) for any transition metal aquo complex . Adding aqueous sodium hydroxide causes the precipitation of light blue solid copper(II) hydroxide . A simplified equation is: Aqueous ammonia results in the same precipitate. Upon adding excess ammonia, the precipitate dissolves, forming tetraamminecopper(II) : Many other oxyanions form complexes; these include copper(II) acetate , copper(II) nitrate , and copper(II) carbonate . Copper(II) sulfate forms

9559-511: 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

9680-433: The form of Ce and Eu 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

9801-566: 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'. 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,

9922-573: 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

10043-448: 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

10164-502: The insoluble ones are not. 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 , and less commonly uranium . Though rare-earth elements are technically relatively plentiful in the entire Earth's crust ( cerium being the 25th-most-abundant element at 68 parts per million, more abundant than copper ), in practice this

10285-511: The later spelling first used around 1530. Copper, silver , and gold are in group 11 of the periodic table; these three metals have one s-orbital electron on top of a filled d- electron shell and are characterized by high ductility , and electrical and thermal conductivity. The filled d-shells in these elements contribute little to interatomic interactions, which are dominated by the s-electrons through metallic bonds . Unlike metals with incomplete d-shells, metallic bonds in copper are lacking

10406-470: The latter among the REE. 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

10527-419: The level of <1% Cu. Concentration of the ore is required, which begins with comminution followed by froth flotation . The remaining concentrate is the smelted, which can be described with two simplified equations: Cuprous oxide reacts with cuprous sulfide to convert to blister copper upon heating This roasting gives matte copper, roughly 50% Cu by weight, which is purified by electrolysis. Depending on

10648-418: 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

10769-472: 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. The classification of rare-earth elements is inconsistent between authors. 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

10890-522: 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. 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

11011-472: The modern world. The price of copper is volatile . After a peak in 2022 the price unexpectedly fell. The global market for copper is one of the most commodified and financialized of the commodity markets , and has been so for decades. The great majority of copper ores are sulfides. Common ores are the sulfides chalcopyrite (CuFeS 2 ), bornite (Cu 5 FeS 4 ) and, to a lesser extent, covellite (CuS) and chalcocite (Cu 2 S). These ores occur at

11132-688: 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

11253-560: 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

11374-424: The normalized concentration, [ REE i ] sam {\displaystyle {[{\text{REE}}_{i}]_{\text{sam}}}} the analytical concentration of the element measured in the sample, and [ REE i ] ref {\displaystyle {[{\text{REE}}_{i}]_{\text{ref}}}} the concentration of the same element in the reference material. It

11495-427: 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 coefficients of each element. Partition coefficients are responsible for

11616-516: The numerous copper sulfides , important examples include copper(I) sulfide ( Cu 2 S ) and copper monosulfide ( CuS ). Cuprous halides with fluorine , chlorine , bromine , and iodine are known, as are cupric halides with fluorine , chlorine , and bromine . Attempts to prepare copper(II) iodide yield only copper(I) iodide and iodine. Copper forms coordination complexes with ligands . In aqueous solution, copper(II) exists as [Cu(H 2 O) 6 ] . This complex exhibits

11737-432: 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

11858-428: The ore, sometimes other metals are obtained during the electrolysis including platinum and gold. Aside from sulfides, another family of ores are oxides. Approximately 15% of the world's copper supply derives from these oxides. The beneficiation process for oxides involves extraction with sulfuric acid solutions followed by electrolysis. In parallel with the above method for "concentrated" sulfide and oxide ores, copper

11979-414: 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

12100-446: The principal ores of cerium and the light lanthanides. 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. In a rift setting, the alkaline magma is produced by very small degrees of partial melting (<1%) of garnet peridotite in

12221-440: 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

12342-421: 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. Some ilmenite concentrates contain small amounts of scandium and other rare-earth elements, which could be analysed by X-ray fluorescence (XRF). Before

12463-434: The rock retains the rare-earth element concentration from its source. Copper Copper is a chemical element ; it has symbol Cu (from Latin 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 pinkish-orange color . Copper is used as a conductor of heat and electricity, as

12584-576: 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,

12705-715: The secret to its manufacturing process became lost. The Romans said the blue pigment was made from copper, silica, lime and natron and was known to them as caeruleum . The Bronze Age began in Southeastern Europe around 3700–3300 BC, in Northwestern Europe about 2500 BC. It ended with the beginning of the Iron Age, 2000–1000 BC in the Near East, and 600 BC in Northern Europe. The transition between

12826-487: The sedimentary parent lithology contains REE-bearing, heavy resistate minerals. 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

12947-419: 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

13068-497: 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

13189-401: 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

13310-766: The subducting plate within the asthenosphere (80 to 200 km depth) produces a volatile-rich magma (high concentrations of CO 2 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 . Carbonatites crystallize from CO 2 -rich fluids, which can be produced by partial melting of hydrous-carbonated lherzolite to produce

13431-438: The sugar is signaled by a color change from blue Cu(II) to reddish copper(I) oxide. Schweizer's reagent and related complexes with ethylenediamine and other amines dissolve cellulose . Amino acids such as cystine form very stable chelate complexes with copper(II) including in the form of metal-organic biohybrids (MOBs). Many wet-chemical tests for copper ions exist, one involving potassium ferricyanide , which gives

13552-399: 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

13673-479: 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 (lanthanum, cerium, praseodymium, neodymium, and samarium) and the yttrium earths (scandium, yttrium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). Europium, gadolinium, and terbium were either considered as

13794-399: The top kilometer of Earth's crust, which is about 5 million years' worth at the current rate of extraction. However, only a tiny fraction of these reserves is economically viable with present-day prices and technologies. Estimates of copper reserves available for mining vary from 25 to 60 years, depending on core assumptions such as the growth rate. Recycling is a major source of copper in

13915-484: 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,

14036-474: 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. 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 )

14157-468: Was found in 1857 on the Keweenaw Peninsula in Michigan, US. Native copper is a polycrystal , with the largest single crystal ever described measuring 4.4 × 3.2 × 3.2 cm . Copper is the 26th most abundant element in Earth's crust , representing 50 ppm compared with 75 ppm for zinc , and 14 ppm for lead . Typical background concentrations of copper do not exceed 1 ng/m in

14278-478: 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 and termed "rare" because it had never yet been seen. 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 ), which he called yttria . Anders Gustav Ekeberg isolated beryllium from

14399-492: 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

14520-494: Was once thought to be in space group I 2 1 3 (no. 199), but is now known to be in space group Ia 3 (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

14641-547: Was the first metal to be smelted from sulfide ores, c.  5000 BC ; the first metal to be cast into a shape in a mold, c.  4000 BC ; and the first metal to be purposely alloyed with another metal, tin , to create bronze , c.  3500 BC . Commonly encountered compounds are copper(II) salts, which often impart blue or green colors to such minerals as azurite , malachite , and turquoise , and have been used widely and historically as pigments. Copper used in buildings, usually for roofing, oxidizes to form

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