Copper
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{{Infobox copper}}'''Copper''' ({{pronEng|ˈkɒpɚ}}) is a [[chemical element]] with the symbol '''Cu''' ({{lang-la|cuprum}}) and [[atomic number]] 29.
It is a [[ductile]] [[metal]] with excellent [[electrical conductivity]] and is rather supple in its pure state and has a pinkish luster which is (beside [[gold]]) unusual for metals which are normally silvery white. It finds use as a heat conductor, an electrical conductor, as a building material, and as a constituent of various metal [[alloy]]s.
Copper is an essential trace nutrient to all high plants and animals. In animals, including humans, it is found primarily in the [[bloodstream]], as a [[Cofactor (biochemistry)|co-factor]] in various [[enzymes]], and in copper-based [[pigments]]. However, in sufficient amounts, copper can be poisonous and even fatal to organisms.
Copper has played a significant part in the history of mankind, which has used the easily accessible uncompounded metal for thousands of years. Several early civilizations have early evidence of using copper. During the [[Roman Empire]], copper was principally mined on [[Cyprus]], hence the origin of the name of the metal as Cyprium, "metal of Cyprus", later shortened to Cuprum.
A number of countries, such as [[Chile]] and the [[United States]], still have sizable reserves of the metal which are extracted through large open pit mines, however like [[tin]] there may be insufficient reserves to sustain current rates of consumption.<ref>{{cite web |url=http://www.livescience.com/strangenews/060119_scarce_metals.html |title=Earth's Limited Supply of Metals Raises Concern |accessdate=2008-03-16}}</ref> High demand relative to supply has caused a price spike in the 2000s<ref>{{cite web |url=http://www.lme.co.uk/copper.asp|title=Copper Grade A Prices on The London Metal Exchange|accessdate=2008-05-29}}</ref>.
Copper also has a significant presence as a decorative metal art. It can also be used as an anti-germ surface that can add to the anti-bacterial and antimicrobial features of buildings such as hospitals. <ref>{{cite news |title=Regulators Stamp Copper as a Germ Killer |author=Barnaby J. Feder |date=[[March 26]], [[2008]] |url=http://www.nytimes.com/2008/03/26/business/26microbes.html?_r=1&scp=2&sq=copper&st=nyt&oref=slogin |publisher=New York Times}}</ref>
== History ==
===Copper Age===
Copper, as [[native copper]], is one of the few metals to naturally occur as an uncompounded mineral. Copper was known to some of the oldest civilizations on record, and has a history of use that is at least 10,000 years old. No one knows exactly when copper was first discovered, but earliest estimates place this event around 9000 BC in the [[Middle East]].<ref name=discovery>[http://www.csa.com/discoveryguides/copper/overview.php CSA - Discovery Guides, A Brief History of Copper<!-- Bot generated title -->]</ref> A copper pendant was found in what is now northern [[Iraq]] that dates to 8700 BC.{{Fact|date=July 2008}} It is probable that gold and iron were the only metals used by humans before copper.<ref>http://elements.vanderkrogt.net/elem/cu.html</ref> By 5000 BC, there are signs of copper [[smelting]]: the refining of copper from simple copper compounds such as [[malachite]] or [[azurite]]. Among archaeological sites in Anatolia, [[Çatal Höyük]] (~6000 BC) features native copper artifacts and smelted lead beads, but no smelted copper. [[Can Hasan]] (~5000 BC) had access to smelted copper; but the oldest smelted copper artifact found has pre-dated [[Can Hasan]] by 500 years. A copper chisel from the chalcolithic site of [[Prokuplje]] in Serbia. The smelting facilities in the Balkans appear to be more advanced than the Turkish forges found at a later date, so it is quite probable that copper smelting originated in the [[Balkans]]. [[Investment casting]] was realized in 4500-4000 BCE in Southeast Asia.<ref name=discovery/>
[[Image:Copper Ingot Crete.jpg|left|thumb|200px|Ancient Copper [[ingot]] from [[Zakros]], [[Crete]] is shaped in the form of an animal skin typical for that era.]]
Copper smelting appears to have been developed independently in several parts of the world. In addition to its development in the Balkans by 5,500 BC, it was developed in China before 2800 BC, in the Andes around 2000 BC, in Central America around 600 AD, and in West Africa around 900 AD.<ref>Richard Cowen, [http://www.geology.ucdavis.edu/~cowen/~GEL115/115CH3.html ''Essays on Geology, History, and People'', Chapter 3: "Fire and Metals: Copper"].</ref> Copper is found extensively in the [[Indus Valley Civilization]] by the 3rd millennium BC.<ref>[http://web.archive.org/web/20070519194706/http://www.harappa.com harappa.com] (Web archive)</ref> In Europe, [[Ötzi the Iceman]], a well-preserved male dated to 3300-3200 BC, was found with an axe tipped with copper that was 99.7% pure. High levels of [[arsenic]]<!-- or copper? --> in his hair suggest he was involved in copper smelting. Over the course of centuries, experience with copper has assisted the development of other metals; for example, knowledge of copper smelting led to the discovery of [[iron smelting]].
In the Americas production in the [[Old Copper Complex]], located in present day Michigan and Wisconsin, was dated back to between 6000 to 3000 BC.<ref>{{cite web |url=http://www.uwfox.uwc.edu/academics/depts/tpleger/oldcopper.html |title=The Old Copper Complex of the Western Great Lakes |author=Thomas C. Pleger |publisher=UW-Fox Valley Anthropology |year=2000 |accessdate=2007-08-15}}</ref>
===Bronze Age===
Alloying to make brass or bronze was realized soon after the discovery of copper itself. There exist copper and [[bronze]] artifacts from [[Sumer]]ian cities that date to 3000 BC, and [[Ancient Egypt|Egyptian]] artifacts of copper and copper-[[tin]] alloys nearly as old. In one pyramid, a copper plumbing system was found that is 5000 years old. The Egyptians found that adding a small amount of tin made the metal easier to cast, so copper-tin ([[bronze]]) alloys were found in Egypt almost as soon as copper was found. Very important sources of copper in the Levant were located in [[Timna valley]] (Palestine) and Faynan (biblical [[Punon]], Jordan).<ref>{{cite journal
| author = J.M. Tebes | url = http://dialnet.unirioja.es/servlet/articulo?codigo=2314512 | title = A Land whose Stones are Iron, and out of whose Hills You can Dig Copper: The Exploitation and Circulation of Copper in the Iron Age Negev and Edom | journal = DavarLogos | volume = 6 | issue =1 | year = 2007}}</ref>
By 2000 BC, Europe was using bronze. The use of [[bronze]] became so pervasive in a certain era of civilization (approximately 2500 BC to 600 BC in Europe) that it has been named the [[Bronze Age]]. The transitional period in certain regions between the preceding [[Neolithic]] period and the Bronze Age is termed the [[Chalcolithic]] ("copper-stone"), with some high-purity copper tools being used alongside stone tools. [[Brass]] (copper-zinc) was known to the Greeks, but only became a significant supplement to bronze during the Roman empire.[[Image:Venus symbol.svg|left|thumb|100px|In [[alchemy]] the symbol for copper, perhaps a stylized mirror, was also the symbol for the goddess and planet [[Venus (planet)|Venus]].]]
During the Bronze Age, one copper mine at [[Great Orme]] in North Wales, extended for a depth of 70 metres.<ref>{{cite book |author=O’Brien, W. |title=Bronze Age Copper Mining in Britain and Ireland |publisher=Shire Publications Ltd |year=1997 |isbn=0747803218}}</ref> At [[Alderley Edge]] in [[Cheshire]], carbon dates have established mining at around 2280 to 1890 BC (at 95% probability).<ref>Timberlake and Prag, 2005</ref>
===Antiquity and Middle Ages===
In Greek the metal was known by the name ''chalkos'' (χαλκός). Copper was a very important resource for the Romans, Greeks and other ancient peoples. In Roman times, it became known as ''aes Cyprium'' (''aes'' being the generic Latin term for copper alloys such as [[bronze]] and other metals, and ''Cyprium'' because so much of it was mined in [[Cyprus]]). From this, the phrase was simplified to ''cuprum'' and then eventually Anglicized into the English ''copper''. Copper was associated with the goddess [[Aphrodite]]/[[Venus (goddess)|Venus]] in mythology and [[alchemy]], owing to its lustrous beauty, its ancient use in producing mirrors, and its association with [[Cyprus]], which was sacred to the goddess. In astrology alchemy the seven heavenly bodies known to the ancients were associated with seven metals also known in antiquity, and [[Venus]] was assigned to copper.<ref>{{cite journal
| title = The Nomenclature of Copper and its Alloys.
| author = T. A. Rickard
| journal = The Journal of the Royal Anthropological Institute of Great Britain and Ireland
| volume = 62
| year = 1932
| pages = 281–290
| url = http://www.jstor.org/pss/2843960}}</ref>
[[Image:westmine.jpg|right|thumb|West Mine at Alderley Edge]]
Britain's first use of brass occurred some time around the 3rd - 2nd century B.C. In north America, copper mining began with marginal workings by Native Americans. Native copper is known to have been extracted from sites on [[Isle Royale]] with primitive stone tools between 800 and 1600.<ref>{{cite journal
| title = The State of Our Knowledge About Ancient Copper Mining in Michigan
| journal = The Michigan Archaeologist
| volume = 41
| issue 2-3
| pages = 119–138
| author = Susan R. Martin
| year = 1995
| url = http://www.ramtops.co.uk/copper.html }}</ref><!-- Drier and Du Temples book from 1961 ''Prehistoric Copper Mining in the Lake Superior Region'' states different things, but the story seems controversial http://copperculture.homestead.com/ -->
Copper metallurgy was flourishing in South America, particularly in Peru around the beginning of the first millennium AD. Copper technology proceeded at a much slower rate on other continents. Africa's major location for copper reserves is Zambia. Copper burial ornamentals dated from the 15th century have been uncovered, but the metal's commercial production did not start until the early 1900s. Australian copper artifacts exist, but they appear only after the arrival of the Europeans; the aboriginal culture apparently did not develop their own metallurgical skills.
Crucial in the metallurgical and technological worlds, copper has also played an important cultural role, particularly in currency. [[Romans]] in the 6th through 3rd centuries B.C. used copper lumps as money. At first, just the copper itself was valued, but gradually the shape and look of the copper became more important. Julius Caesar had his own coins, made from a copper-zinc alloy, while [[Octavianus Augustus Caesar]]'s) coins were made from Cu-Pb-Sn alloys.
The gates of the [[Temple of Jerusalem]] used [[Corinthian]] bronze made by depletion gilding. Corinthian bronze was most prevalent in Alexandria, where alchemy is thought to have begun. In ancient India (before 1000 B.C.), copper was used in the [[holistic]] medical science [[Ayurveda]] for surgical instruments and other medical equipment. Ancient Egyptians (~2400 B.C.) used copper for sterilizing wounds and drinking water, and as time passed, (~1500 B.C.) for headaches, burns, and itching. [[Hippocrates]] (~400 B.C.) used copper to treat leg ulcers associated with varicose veins. Ancient Aztecs fought sore throats by gargling with copper mixtures.
Copper is also the part of many rich stories and legends, such as that of Iraq's "Baghdad Battery." Copper cylinders soldered to lead, which date back to 248 B.C. to 226 A.D, resemble a galvanic cell, leading people to believe this may have been the first battery. This claim has so far not been substantiated.
The Bible also refers to the importance of copper: "Men know how to mine silver and refine gold, to dig iron from the earth and melt copper from stone" (Job. 28:1-2).
===Modern period===
[[Image:TamarackMiners CopperCountryMI sepia.jpg|thumb|Miners at the [[Tamarack Mine]] in [[Copper Country]], Michigan, USA in 1905.]]
Throughout history, copper's use in art has extended far beyond currency. [[Vannoccio Biringuccio]], [[Giorgio Vasari]] and [[Benvenuto Cellini]] are three [[Renaissance]] [[sculptors]] from the mid 1500s, notable for their work with bronze. From about 1560 to about 1775, thin sheets of copper were commonly used as a canvas for paintings. Silver plated copper was used in the pre-photograph known as the [[daguerreotype]]. The [[Statue of Liberty]], dedicated on October 28, 1886, was constructed of copper thought to have come from French-owned mines in Norway.
The [[Norddeutsche Affinerie]] in [[Hamburg]] was the first modern [[electroplating]] plant.
Plating was a technology that began started in the mid 1600s in some areas. One common use for [[copper plating]], widespread in the 1700s, was the sheathing of ships' hulls. [[Copper sheathing]] could be used to protect wooden hulled ships from algae, and from the shipworm "toredo". The ships of Christopher Columbus were among the earliest to have this protection.
In the early 1800s, it was discovered that copper [[wire]] could be used as an insulator, but it wasn't until 1990 that copper, in oxide form, was discovered for use as a [[superconducting material]]. The German scientist [[Osann]] invented [[powder metallurgy]] of copper in 1830 while determining the metal's atomic weight. Around then it was also discovered that the amount and type of alloying element (e.g. tin) would affect the tones of bells, allowing for a variety of rich sounds, leading to bell casting, another common use for copper and its alloys.
[[Flash smelting]], which is still used today, was developed in Europe in order to make the smelting process more energy efficient. In 1908, in Outokumpu, Finland, a large deposit of copper ore was discovered, which eventually led to the development of flash smelting.
Copper has been pivotal in the economic and sociological worlds, notably disputes involving copper mines. The 1906 Cananea Strike in Mexico dealt with issues of work organization. The Teniente copper mine (1904-1951) raised political issues about capitalism and class structure. Japan's largest copper mine, the Ashio mine, was the site of a riot in 1907. The Arizona miners' strike of 1938 dealt with American labor issues including the "right to strike".
==Characteristics==
[[Image:029-Cu.jpg|thumb|left|150px|Copper just above its melting point keeps its pink luster color when enough light outshines the orange incandescence color.]]
[[Image:Metallic bond Cu.svg|thumb|right|150px|Copper exists as a [[metallic bond|metallically bonded]] substance, allowing it to have a wide variety of metallic properties.]]
<!-- color -->
Copper is a reddish-colored [[metal]]; it has its characteristic color because of its [[band structure]]. In its liquefied state, a pure copper surface without ambient light appears somewhat greenish, a characteristic shared with gold. When liquid copper is in bright ambient light, it retains some of its pinkish luster.
<!-- group 11 -->
Copper occupies the same family of the periodic table as [[silver]] and [[gold]], since they each have one s-orbital electron on top of a filled [[electron shell]]. This similarity in electron structure makes them similar in many characteristics. All have very high thermal and electrical conductivity, and all are malleable metals.<!-- more! --> Among pure metals at [[room temperature]], copper has the second highest [[electrical conductivity|electrical]] and [[thermal conductivity]], after [[silver]].<ref name="LANL">[http://periodic.lanl.gov/elements/29.html Los Alamos National Laboratory - Copper]</ref>
===Corrosion===
'''Pure water and air'''<br>
Copper is a metal that does not react with water (H<sub>2</sub>O), but the oxygen of the air will react slowly at room temperature to form a layer of brown-black copper oxide on copper metal.
[[Image:Copper in water pourbiax diagram.png|thumb|right|150px|The [[Pourbaix diagram]] for copper in pure water, perchloric acid or sodium It can be seen that copper in "pure" water is more noble than hydrogen. As a result it does not corrode in oxygen free water and the corrosion rate in oxygenated water is low.
hydroxide<ref name="medusa">Ignasi Puigdomenech, ''Hydra/Medusa Chemical Equilibrium Database and Plotting Software'' (2004) KTH Royal Institute of Technology, freely downloadable software at [http://www.kemi.kth.se/medusa/]</ref>]]
It is important to note that in contrast to the oxidation of iron by wet air that the layer formed by the reaction of air with copper has a protective effect against further corrosion. On old copper roofs a green layer of copper carbonate, called [[verdigris]] or [[patina]], can often be seen. Another notable example of this is on the [[Statue of Liberty]].
'''In contact with other metals'''
{{main|Galvanic corrosion}}
Copper should not be in only mechanical contact with metals of different [[Galvanic series|electropotential]] (for example, a copper pipe joined to an [[iron]] pipe), especially in the presence of moisture, as the completion of an electrical circuit (as through the common earth ground) will cause the juncture to act as an [[electrochemical cell]] (as is a single cell of a [[battery (electricity)|battery]]). The weak electrical currents themseves are harmless but the electrochemical reaction will cause the conversion of the iron to other compounds, eventually destroying the functionality of the union. This problem is usually solved in [[plumbing]] by separating copper pipe from iron pipe with some non-conducting segment (usually plastic or rubber).
'''Sulfide media'''
Copper metal does react with [[hydrogen sulfide]]- and [[sulfide]]-containing solutions. A series of different copper sulfides can form on the surface of the copper metal.
[[Image:Copper in sulphide media pourbiax diagram.png|thumb|left|150px|The [[Pourbaix diagram]] for copper in a sulfide containing aqueous medium<ref name="medusa">Ignasi Puigdomenech, ''Hydra/Medusa Chemical Equilibrium Database and Plotting Software'' (2004) KTH Royal Institute of Technology, freely downloadable software at [http://www.kemi.kth.se/medusa/]</ref>]]
Note that the copper sulfide area of the plot is very complex due to the existence of many different sulfides, a close up is also provided to make the graph more clear. It is clear that the copper is now able to corrode even without the need for oxygen as the copper is now less noble than [[hydrogen]]. This can be observed in every day life when copper metal surfaces [[tarnish]] after exposure to air which contains sulfur compounds.
[[Image:Close up of copper sulphide pourbiax diagram.png|thumb|right|150px|The [[Pourbaix diagram]] for copper in a sulfide containing aqueous medium<ref name="medusa">Ignasi Puigdomenech, ''Hydra/Medusa Chemical Equilibrium Database and Plotting Software'' (2004) KTH Royal Institute of Technology, freely downloadable software at [http://www.kemi.kth.se/medusa/]</ref>]]
'''Ammonia media'''
Copper does react with oxygen-containing ammonia solutions because the ammonia forms water-soluble copper complexes. The formation of these complexes causes the corrosion to become more thermodynamically favored than the corrosion of copper in an identical solution that does not contain the ammonia.
[[Image:Copper in 10M ammonia pourbiax diagram.png|thumb|left|150px|The [[Pourbaix diagram]] for copper in 10 M ammonia solution<ref name="medusa">Ignasi Puigdomenech, ''Hydra/Medusa Chemical Equilibrium Database and Plotting Software'' (2004) KTH Royal Institute of Technology, freely downloadable software at [http://www.kemi.kth.se/medusa/]</ref>]]
'''Chloride media'''
Copper does react with a combination of oxygen and hydrochloric acid to form a series of copper chlorides. It is interesting to note that if copper(II) chloride (green/blue) is boiled with copper metal (with little or no oxygen present) then white copper(I) chloride will be formed.
[[Image:Copper in chloride media more copper pourbiax.png|thumb|right|150px|The [[Pourbaix diagram]] for copper in a chloride solution<ref name="medusa">Ignasi Puigdomenech, ''Hydra/Medusa Chemical Equilibrium Database and Plotting Software'' (2004) KTH Royal Institute of Technology, freely downloadable software at [http://www.kemi.kth.se/medusa/]</ref>]]
===Mechanical properties===
A single crystal copper consists of a few micrometres of small crystals. In this form of crystal (c), the yield stress is high and crystal undergoes a large amount of elastic deformation before going into the plastic deformation region. The plastic deformation region has an unpredictable outcome. The stress level decreases significantly as necking begins to occur.
[[Polycrystal copper]] has many crystal of different geometries combined. The plastic deformation of polycrystal is similar to mild steel. Copper has a high ductility and will continue to elongate as stress is applied. It is very useful in copper wire drawing.
Numerous [[copper alloys]] exist, many with important historical and contemporary uses. [[Speculum metal]] and [[bronze]] are alloys of copper and [[tin]]. [[Brass]] is an alloy of copper and [[zinc]]. [[Monel]] metal, also called [[cupronickel]], is an alloy of copper and [[nickel]]. While the metal "bronze" usually refers to copper-tin alloys, it also is a generic term for any alloy of copper, such as [[aluminium bronze]], silicon bronze, and manganese bronze.
===Germicidal effect===
Copper is germicidal, via the [[oligodynamic effect]]. For example, brass doorknobs disinfect themselves of many bacteria within a period of eight hours.<ref>{{cite web |url=http://members.vol.at/schmiede/MsgverSSt.html |title=Doorknobs: A Source of Nosocomial Infection? |author=Phyllis J. Kuhn, Ph.D. |year=1983 |accessdate=2007-08-15}}</ref> [[Antimicrobial]] properties of copper are effective against [[MRSA]],<ref name="pmid16650507">{{cite journal |author=Noyce JO, Michels H, Keevil CW |title=Potential use of copper surfaces to reduce survival of epidemic meticillin-resistant Staphylococcus aureus in the healthcare environment |journal=J. Hosp. Infect. |volume=63 |issue=3 |pages=289–97 |year=2006 |pmid=16650507 |doi=10.1016/j.jhin.2005.12.008}}</ref> [[Escherichia coli]]<ref name="pmid16751537">{{cite journal |author=Noyce JO, Michels H, Keevil CW |title=Use of copper cast alloys to control Escherichia coli O157 cross-contamination during food processing |journal=Appl. Environ. Microbiol. |volume=72 |issue=6 |pages=4239–44 |year=2006 |pmid=16751537 |doi=10.1128/AEM.02532-05}}</ref> and other [[pathogen]]s.<ref name="pmid18069086">{{cite journal |author=Mehtar S, Wiid I, Todorov SD |title=The antimicrobial activity of copper and copper alloys against nosocomial pathogens and Mycobacterium tuberculosis isolated from healthcare facilities in the Western Cape: an in-vitro study |journal=J. Hosp. Infect. |volume=68 |issue=1 |pages=45–51 |year=2008 |pmid=18069086 |doi=10.1016/j.jhin.2007.10.009}}</ref><ref name="pmid17567632">{{cite journal |author=Gant VA, Wren MW, Rollins MS, Jeanes A, Hickok SS, Hall TJ |title=Three novel highly charged copper-based biocides: safety and efficacy against healthcare-associated organisms |journal=J. Antimicrob. Chemother. |volume=60 |issue=2 |pages=294–9 |year=2007 |pmid=17567632 |doi=10.1093/jac/dkm201}}</ref><ref name="pmid17259354">{{cite journal |author=Noyce JO, Michels H, Keevil CW |title=Inactivation of influenza A virus on copper versus stainless steel surfaces |journal=Appl. Environ. Microbiol. |volume=73 |issue=8 |pages=2748–50 |year=2007 |pmid=17259354 |doi=10.1128/AEM.01139-06}}</ref> In colder temperature, longer time is required to kill bacteria.
===Isotopes===
{{main|Isotopes of copper}}
Copper has 29 distinct [[isotope]]s ranging in [[atomic mass]] from 52 to 80. Two of these, <sup>63</sup>Cu and <sup>65</sup>Cu, are stable and occur naturally, with <sup>63</sup>Cu comprising approximately 69% of naturally occurring copper. <ref name="nubase">{{cite journal|title=Nubase2003 Evaluation of Nuclear and Decay Properties|journal=Nuclear Physics A|volume=729|pages=3–128|publisher=Atomic Mass Data Center|date=2003|doi=10.1016/j.nuclphysa.2003.11.001|author=Audi, G}}</ref>
The other 27 isotopes are [[radioactivity|radioactive]] and do not occur naturally. The most stable of these is <sup>67</sup>Cu with a [[half-life]] of 61.83 hours. The least stable is <sup>54</sup>Cu with a half-life of approximately 75 ns. Unstable copper isotopes with atomic masses below 63 tend to undergo [[Positron emission|β<sup>+</sup> decay]], while isotopes with atomic masses above 65 tend to undergo [[Beta decay|β<sup>−</sup> decay]]. <sup>64</sup>Cu decays by both β<sup>+</sup> and β<sup>−</sup>.<ref name="nubase"/>
<sup>68</sup>Cu, <sup>69</sup>Cu, <sup>71</sup>Cu, <sup>72</sup>Cu, and <sup>76</sup>Cu each have one [[metastable isomer]]. <sup>70</sup>Cu has two isomers, making a total of 7 distinct isomers. The most stable of these is <sup>68m</sup>Cu with a half-life of 3.75 minutes. The least stable is <sup>69m</sup>Cu with a half-life of 360 ns.<ref name="nubase"/>
=== Occurrence ===
[[Image:Coppernuggets.jpg|200px|right|thumb|Native Copper Placer Nuggets]]
[[Image:CopperMineralUSGOV.jpg|200px|right|thumb|Native copper]]
Copper can be found as [[native copper]] in [[mineral]] form. Minerals such as the [[sulfide]]s: [[chalcopyrite]] (CuFeS<sub>2</sub>), [[bornite]] (Cu<sub>5</sub>FeS<sub>4</sub>), [[covellite]] (CuS), [[chalcocite]] (Cu<sub>2</sub>S) are sources of copper, as are the [[carbonate]]s: [[azurite]] (Cu<sub>3</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub>) and [[malachite]] (Cu<sub>2</sub>CO<sub>3</sub>(OH)<sub>2</sub>) and the oxide: [[cuprite]] (Cu<sub>2</sub>O).
==Production==
[[Image:Chuquicamata-002.jpg|200px|left|thumb|[[Chuquicamata]] ([[Chile]]). The largest [[open-pit mining|open pit]] copper [[mining|mines]] in the world.]]
[[Image:2005copper (mined).PNG|thumb|200px|left|Copper output in 2005]]
[[Image:Copper - world production trend.svg|200px|thumb|left|World production trend]]
[[Image:Historical copper price.png|200px|thumb|right|Evolution of the historical copper price<br>source : [http://minerals.usgs.gov/ds/2005/140/copper.xls minerals.usgs.gov] (XLS)<br> Current price is at least four times higher than the 2002 value.]]
[[Image:Copper Price History USD.png|200px|left|thumb|Copper Prices 2003 - 2008 in USD]]
{{see|Peak copper}}
In 2005, Chile was the top mine producer of copper with at least one-third world share followed by the USA, Indonesia and Peru, reports the [[British Geological Survey]].
Most copper ore is mined or [[copper extraction|extracted]] as copper sulfides from large [[open pit mine]]s in [[porphyry copper]] deposits that contain 0.4 to 1.0 percent copper. Examples include: [[Chuquicamata]] in [[Chile]] and [[El Chino Mine]] in [[New Mexico]]. The average abundance of copper found within [[crustal rocks]] is approximately 68 [[parts per million|ppm]] by mass, and 22 [[parts per million|ppm]] by [[atoms]].
The [[Intergovernmental Council of Copper Exporting Countries]] (CIPEC), defunct since 1992, once tried to play a similar role for copper as [[OPEC]] does for [[Petroleum|oil]], but never achieved the same influence, not least because the second-largest producer, the [[United States]], was never a member. Formed in 1967, its principal members were [[Chile]], [[Peru]], [[Zaire]], and [[Zambia]].
The copper price has quintupled from the 60-year low in 1999, rising from [[us dollar|US$]]0.60 per [[Pound (mass)|pound]] ([[us dollar|US$]]1.32/[[kg]]) in June 1999 to US$3.75 per [[Pound (mass)|pound]] ([[us dollar|US$]]8.27/[[kg]]) in May 2006, where it dropped to [[us dollar|US$]]2.40 ([[us dollar|US$]]5.29/[[kg]]) in February 2007 then rebounded to [[us dollar|US$]]3.50 ([[us dollar|US$]]7.71/[[kg]] =
[[pound sterling|£]]3.89 = [[euro|€]]5.00) in April 2007.<ref>[http://metalspotprice.com/copper-trends/ Copper Trends: Live Metal Spot Prices], MetalSpotPrice.com</ref>
The Earth has an estimated 61 years of copper reserves remaining.<ref> New Scientist. May 26, 2007.</ref> Environmental analyst, [[Lester Brown]], however, has suggested copper might run out within 25 years based on a reasonable extrapolation of 2% growth per year.<ref name="Brown">{{cite book|author=Brown, Lester|title=Plan B 2.0: Rescuing a Planet Under Stress and a Civilization in Trouble|publisher=New York: W.W. Norton|date=2006|page=109|isbn=0393328317}}</ref>
Copper has been in use at least 10,000 years, but more than 95 percent of all copper ever mined and smelted has been extracted since 1900. And as India and China race to catch up with the West, copper supplies are getting tight.<ref name=Leonard2006>{{cite web
|url=http://www.salon.com/tech/htww/2006/03/02/peak_copper/index.html
|title=Peak copper?
|publisher=Salon - How the World Works
|author=Andrew Leonard
|date=2006-03-02
|language=English
|accessdate=2008-03-23
}}</ref> Copper is among the most important industrial metals. Like fossil fuels, copper is a finite resource. [[Peak copper]] is the point in time at which the maximum global [[copper]] production rate is reached, according to [[Hubbert peak theory]], the rate of production enters its terminal decline.
{{further|[[Copper extraction techniques]]}}
== Applications ==
[[Image:Native Copper Macro Digon3.jpg|thumb|right|225px|Native copper specimen (~ 4 cm in size)]]
[[Image:Cu pipe leonard.jpg|thumb|right|200px|Copper piping system with [[intumescent]] [[firestop]] being installed by an insulator in [[Vancouver]], [[Canada]]]]
Copper is [[malleable]] and [[ductile]], a good [[conductor of heat]] and, when very pure, a good [[conductor of electricity]].
The purity of copper is expressed as 4N for 99.99% pure or 7N for 99.99999% pure. The numeral gives the number of nines after the decimal point when expressed as a decimal (e.g. 4N means 0.9999, or 99.99%). Copper is often too soft for its applications, so it is incorporated in numerous [[alloys]]. For example, [[brass]] is a copper-zinc alloy , and [[bronze]] is a copper-tin alloy.<ref name=Applications for Copper>{{cite web| title = Copper| publisher = American Elements| date = 2008| url = http://www.americanelements.com/cu.html| accessdate = 2008-07-12}}</ref>
It is used extensively, in products such as:
=== [[Piping]] ===
* including [[water]] supply.
=== Electronics ===
* [[Copper wire]].
* [[Electromagnet]]s.
* [[Printed circuit board]]s.
* [[Lead]] free [[solder]], alloyed with [[tin]].
* [[Electrical machine]]s, especially electromagnetic motors, generators and transformers.
* Electrical [[relay]]s, electrical [[busbar]]s and electrical [[switch]]es.
* [[Vacuum tube]]s, [[cathode ray tube]]s, and the [[magnetron]]s in [[microwave oven]]s.
* [[Waveguide|Wave guide]]s for microwave radiation.
* [[Integrated circuit]]s, increasingly replacing [[aluminium]] because of its superior electrical conductivity.
* As a material in the manufacture of computer [[heat sink]]s, as a result of its superior heat dissipation capacity to [[aluminium]].
[[Image:Minneapolis City Hall.jpg|thumb|right|200px|Copper roof on the [[Minneapolis City Hall]], coated with [[Patina]]]]
=== Architecture / Industry ===
* Copper has been used as water-proof [[Metal roof|roofing]] material since ancient times, giving many old buildings their greenish roofs and domes. Initially [[copper oxide]] forms, replaced by [[Copper sulfide|cuprous and cupric sulfide]], and finally by [[Copper(II) carbonate|copper carbonate]]. The final [[carbonate]] [[patina]] is highly resistant to [[corrosion]].<ref>{{cite web | last = Berg | first = Jan | title = Why did we paint the library's roof? | url = http://www.deforest.lib.wi.us/FAQS.htm | accessdate = 2007-09-20}}</ref>
* [[Statue|Statuary]]: The [[Statue of Liberty]], for example, contains 179,220 pounds (81.3 [[tonne]]s) of copper.
* Alloyed with [[nickel]], e.g. [[cupronickel]] and [[Monel]], used as corrosive assistant materials in [[shipbuilding]].
* [[James Watt|Watt]]'s [[steam engine]] firebox due to superior heat dissipation.
* Copper [[nails]] were used in making [[oast]] [[cowl (oast)|cowls]].
* Copper compounds in liquid form are used as a preservative, particularly in treating original portion of structures during restoration of damage due to [[dry rot]].
* Copper wires may be placed over non-conductive roofing materials to discourage the growth of [[moss]]. ([[Zinc]] may also be used for this purpose.)
[[Image:CopperC.jpg|thumb|right|200px|Old copper utensils in a Jerusalem restaurant]]
=== Household products ===
* Copper [[plumbing]] fittings and compression tubes.
* Doorknobs and other fixtures in houses.
* [[Roofing]], guttering, and rainspouts on buildings.
* In [[cookware]], such as [[frying pan]]s.
* Most [[flatware]] ([[knife|knives]], [[fork]]s, [[spoon]]s) contains some copper ([[nickel silver]]).
* [[Sterling silver]], if it is to be used in dinnerware, must contain a few percent copper.
* Copper water heating cylinders
* Copper Range Hoods
* Copper Bath Tubs
* Copper Counters
* Copper Sinks
* Copper [[slug tape]]
=== Coinage ===
* As a component of [[coin]]s, often as [[cupronickel]] alloy.
* Coins in the following countries all contain copper: European Union ([[Euro]]),<ref name=CDAUK>{{cite web| title = The Euro - Born out of Copper| publisher = Copper Development Association| url = http://www.cda.org.uk/news/euro.htm| accessdate = 2008-07-12}}</ref> United States,<ref name=US_mint>{{cite web| title = Coin Specifications| publisher = United States Mint| date = 2008| url = http://www.usmint.gov/about_the_mint/index.cfm?flash=yes&action=coin_specifications| accessdate = 2008-07-12}}</ref> United Kingdom ([[Pound sterling|sterling]]),<ref name=Royal_mint>{{cite web| title = Demonetisation| publisher = The Royal Mint| date = 2008-07-01| url = http://www.royalmint.com/Corporate/BritishCoinage/Demonetisation.aspx| accessdate = 2008-07-13}}</ref> Australia<ref name=Royal_Aus_mint>{{cite web| title = Circulating Coin Designs| publisher = Royal Australian Mint| url = http://www.ramint.gov.au/making_coins/default.cfm?DefaultPage=coin_designs.cfm| accessdate = 2008-07-13}}</ref> and New Zealand.<ref
name=The_Reserve_Bank_of_New_Zealand>{{cite web| title = Questions and answers| work = Change for the Better| publisher = Reserve Bank of New Zealand| url = http://www.newcoins.govt.nz/1570749.html| accessdate = 2008-07-13}}</ref>
* [[Nickel (United States coin)|U.S. Nickels]] are 75.0% copper by weight and only 25.0% [[nickel]].<ref name=US_mint/>
=== Biomedical applications ===
* As a [[biostatic]] surface in hospitals, and to line parts of [[ship]]s to protect against [[barnacle]]s and [[mussel]]s, originally used pure, but superseded by [[Muntz Metal]]. [[Bacteria]] will not grow on a copper surface because it is biostatic. Copper [[doorknob]]s are used by [[hospital]]s to reduce the transfer of disease, and [[Legionellosis|Legionnaires' disease]] is suppressed by copper tubing in [[air-conditioning]] systems.
* [[Copper(II) sulfate]] is used as a [[fungicide]] and as algae control in domestic lakes and ponds. It is used in gardening powders and sprays to kill [[mildew]].
* [[Copper-62-PTSM]], a complex containing radioactive [[copper-62]], is used as a [[Positron emission tomography]] radiotracer for heart blood flow measurements.
* [[Copper-64]] can be used as a [[Positron emission tomography]] radiotracer for [[medical imaging]]. When complexed with a [[chelate]] it can be used to treat cancer through [[radiation therapy]].
=== Chemical applications ===
* Compounds, such as [[Fehling's solution]], have applications in chemistry.
* As a component in [[ceramic glaze]]s, and to colour [[glass]].
=== Other ===
* [[Musical instrument]]s, especially [[brass instrument]]s and [[cymbals]].
* [[Class D Fire Extinguisher]], used in powder form to extinguish lithium fires by covering the burning metal and performing similar to a heat sink.
* Textile fibers to create [[antimicrobial]] protective fabrics.<ref>{{cite web| title = Antimicrobial Products that Shield Against Bacteria and Fungi| publisher = Cupron, Inc. | date = 2008| url = http://www.cupron.com/| accessdate = 2008-07-13}}</ref>
* Small arms [[Cartridge (firearms)| ammunition]] commonly uses copper as a jacketing material around the bullet core.
* Copper is also commonly used as a case material, in the form of brass.
* Copper is frequently used in [[electroplating]] with Zinc and other metals.
== Compounds ==
Common [[oxidation state]]s of copper include the less stable copper(I) state, Cu<sup>+</sup>; and the more stable copper(II) state, Cu<sup>2+</sup>, which forms blue or blue-green salts and solutions. Under unusual conditions, a 3+ state and even an extremely rare 4+ state can be obtained. Using old nomenclature for the naming of salts, copper(I) is called ''cuprous'', and copper(II) is ''cupric''. In [[oxidation]] copper is mildly [[Base (chemistry)|basic]].
[[Copper(II) carbonate]] is green from which arises the unique appearance of copper-clad roofs or domes on some buildings. [[Copper(II) sulfate]] forms a blue crystalline penta[[hydrate]] which is perhaps the most familiar copper compound in the laboratory. It is used as a [[fungicide]], known as Bordeaux mixture.
There are two stable copper oxides, [[copper(II) oxide]] (CuO) and [[copper(I) oxide]] (Cu<sub>2</sub>O). Copper oxides are used to make [[yttrium]] [[barium]] copper oxide (YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7-δ</sub>) or [[YBCO]] which forms the basis of many [[unconventional superconductors]].
*'''Copper(I) compounds''': [[copper(I) chloride]], [[copper(I) bromide]], [[copper(I) iodide]], [[copper(I) oxide]].
*'''Copper(II) compounds''': [[copper(II) acetate]], [[copper(II) carbonate]], [[copper(II) chloride]], [[copper(II) hydroxide]], [[copper(II) nitrate]], [[copper(II) oxide]], [[copper(II) sulfate]], [[copper(II) sulfide]], [[copper(II) tetrafluoroborate]], [[copper(II) triflate]].
*'''Copper(III) compounds''', rare: [[potassium hexafluorocuprate]] (K<sub>3</sub>CuF<sub>6</sub>)
*'''Copper(IV) compounds''', extremely rare: [[caesium hexafluorocuprate]] (Cs<sub>2</sub>CuF<sub>6</sub>)
{{seealso|Category:Copper compounds}}
==== Tests for copper(II) ion ====
Add aqueous [[sodium hydroxide]]. A blue precipitate of [[copper(II) hydroxide]] should form.
Ionic equation:
:Cu<sup>2+</sup>(aq) + 2OH<sup>−</sup>(aq) → Cu(OH)<sub>2</sub>(s)
The full equation shows that the reaction is due to hydroxide ions deprotonating the hexaaquacopper (II) complex:
:[Cu(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup>(aq) + 2 OH<sup>−</sup>(aq) → Cu(H<sub>2</sub>O)<sub>4</sub>(OH)<sub>2</sub>(s) + 2 H<sub>2</sub>O (l)
Adding [[ammonium hydroxide]] (aqueous ammonia) causes the same precipitate to form. It then dissolves upon adding excess ammonia, to form a deep blue ammonia complex, tetraamminecopper(II).
Ionic equation:
:Cu(H<sub>2</sub>O)<sub>4</sub>(OH)<sub>2</sub>(s) + 4 NH<sub>3</sub>(aq) → [Cu(H<sub>2</sub>O)<sub>2</sub>(NH<sub>3</sub>)<sub>4</sub>]<sup>2+</sup>(aq) + 2H<sub>2</sub>O(l) + 2 OH<sup>−</sup>(aq)
A more delicate test than ammonia is [[potassium ferrocyanide]], which gives a brown precipitate with copper salts.
== Biological role ==
[[Image:ARS copper rich foods.jpg|right|thumb|Rich sources of [[copper]] include oysters, beef or lamb liver, Brazil nuts, blackstrap molasses, cocoa, and black pepper. Good sources include lobster, nuts and sunflower seeds, green olives, avocados and wheat bran.]]
Copper is essential in all plants and animals. Copper is carried mostly in the bloodstream on a [[plasma protein]] called [[ceruloplasmin]]. When copper is first absorbed in the gut it is transported to the [[liver]] bound to [[serum albumin|albumin]]. Copper is found in a variety of [[enzyme]]s, including the copper centers of [[cytochrome c oxidase]] and the enzyme [[superoxide dismutase]] (containing copper and zinc). In addition to its enzymatic roles, copper is used for biological electron transport. The blue copper proteins that participate in electron transport include [[azurin]] and [[plastocyanin]]. The name "blue copper" comes from their intense blue color arising from a ligand-to-metal charge transfer (LMCT) absorption band around 600 nm.
Most [[mollusc]]s and some [[arthropod]]s such as the [[horseshoe crab]] use the copper-containing pigment [[hemocyanin]] rather than [[iron]]-containing [[hemoglobin]] for oxygen transport, so their blood is blue when oxygenated rather than red.<ref name=NOAA>{{cite web| title = Fun Facts|work = Horseshoe Crab| publisher = University of Delaware| url = http://www.ocean.udel.edu/horseshoecrab/funFacts.html| accessdate = 2008-07-13}}</ref>
It is believed that [[zinc]] and copper compete for absorption in the digestive tract so that a diet that is excessive in one of these minerals may result in a deficiency in the other. The [[Recommended Dietary Allowance|RDA]] for copper in normal healthy adults is 0.9 [[milligram|mg]]/day. On the other hand, professional research on the subject recommends 3.0 [[milligram|mg]]/day.<ref>National Research Council. Copper. In: Recommended Dietary Allowances. Washington, D.C.: Food Nutrition Board, NRC/NAS, 1980: 151-154.</ref> Because of its role in facilitating iron uptake, [[copper deficiency]] can often produce [[anemia]]-like symptoms. In humans, the symptoms of [[Wilson's disease]] are caused by an accumulation of copper in body tissues.
Chronic copper depletion leads to abnormalities in metabolism of fats, high triglycerides, non-alcoholic steatohepatitis (NASH), fatty liver disease and poor melanin and dopamine sythesis causing depression and sunburn. Food rich in copper should be eaten away from any milk or egg proteins as they block absorption.
=== Toxicity ===
{{Unreferenced|date=March 2008}}
{{Expand|date=March 2008}}
Toxicity can occur from eating acid food that had been cooked in Copper cookware. Cirrhosis of the liver in children (Indian Childhood Cirrhosis) has been linked to boiling milk in copper cookware. The Merck Manual states that recent studies suggest that a genetic defect is associated with this cirrhosis, but this should not be regarded as an endorsement of the practice since other toxicity besides cirrhosis can occur as in adults. see: http://www.merck.com/mmpe/sec01/ch005/ch005c.html?qt=copper%20and%20milk&alt=sh
With an [[LD50|LD<sub>50</sub>]] of 30 mg/kg in rats, "gram quantities" of [[copper sulfate]] are potentially [[lethal]] in humans.<ref>{{cite web| title = Pesticide Information Profile for Copper Sulfate| url = http://pmep.cce.cornell.edu/profiles/extoxnet/carbaryl-dicrotophos/copper-sulfate-ext.html | publisher = Cornell University | accessdate=2008-07-10}}</ref> The suggested safe level of copper in [[drinking water]] for humans varies depending on the source, but tends to be pegged at 1.5 to 2 mg/L{{Fact|date=March 2008}}. The [[Dietary Reference Intake|DRI]] Tolerable Upper Intake Level for adults of dietary copper from all sources is 10 mg/day{{Fact|date=March 2008}}. In toxicity, copper can inhibit the [[enzyme]] [[dihydrophil hydratase]], an enzyme involved in [[haemopoiesis]]{{Facts|date=November 2007}}.
Symptoms of copper [[poison]]ing are very similar to those produced by [[arsenic]]. Fatal cases are generally terminated by convulsions, palsy, and insensibility.{{Facts|date=November 2007}}
In cases of suspected copper poisoning, [[Ovalbumin]] is to be administered in either of its forms which can be most readily obtained, as milk or [[egg white|whites of eggs]]. Vinegar should not be given. The inflammatory symptoms are to be treated on general principles, and so are the nervous.{{Facts|date=November 2007}}
A significant portion of the toxicity of copper comes from its ability to accept and donate single electrons as it changes oxidation state. This catalyzes the production of very reactive radical ions such as [[hydroxyl radical]] in a manner similar to [[Fenton's reagent|Fenton chemistry]].<ref name=PubMed>{{cite journal
| url = http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=8619019&dopt=Abstract | journal = Radiat Res. | author = Held KD ''et al.'' | date = May 1996 | volume = 145 | issue = 5 |pages = 542–53 | title = Role of Fenton chemistry in thiol-induced toxicity and apoptosis | doi = 10.2307/3579272
}}</ref> This catalytic activity of copper is used by the enzymes that it is associated with and is thus only toxic when unsequestered and unmediated. This increase in unmediated reactive radicals is generally termed [[oxidative stress]] and is an active area of research in a variety of diseases where copper may play an important but more subtle role than in acute toxicity.
[[Image:Kayser-Fleischer ring.jpg|right|thumb|A [[Kayser-Fleischer ring]]. Copper deposits are found in the iris. This is an indication that the body is not metabolizing copper properly.]]
An inherited condition called [[Wilson's disease]] causes the body to retain copper, since it is not excreted by the [[liver]] into the [[bile]]. This disease, if untreated, can lead to [[brain]] and [[liver]] damage. In addition, studies have found that people with mental illnesses such as [[schizophrenia]] had heightened levels of copper in their systems. However it is unknown at this stage whether the copper contributes to the mental illness, whether the body attempts to store more copper in response to the illness, or whether the high levels of copper are the result of the mental illness.{{Facts|date=November 2007}}
Too much copper in water has also been found to damage marine life. The observed effect of these higher concentrations on fish and other creatures is damage to gills, liver, kidneys, and the nervous system. It also interferes with the sense of smell in fish, thus preventing them from choosing good mates or finding their way to mating areas.{{Facts|date=November 2007}}
=== Miscellaneous hazards ===
The metal, when powdered, is a [[fire hazard]]. At concentrations higher than 1 mg/L, copper can stain clothes and items washed in water.
==See also==
<div class="references-small" style="-moz-column-count:3; column-count:3;">
*[[Acierage]]
*[[Anaconda Copper]]
*[[Antofagasta PLC]]
*[[Codelco]]
*[[Cold Water Pitting of Copper Tube]]
*[[Copper extraction techniques]]
*[[Erosion Corrosion of Copper Water Tubes]]
*[[Metal theft]]
*[[Native Copper]]
*[[Operation Tremor]]
*[[Peak copper]]
*[[Smelter]]
</div>
==References==
{{reflist}}
==Further reading==
*{{cite web |title=''Copper: Technology & Competitiveness (Summary)'' Chapter 6: Copper Production Technology |publisher=Office of Technology Assessment |year=2005 |url=http://www.wws.princeton.edu/ota/ns20/alpha_f.html}}
*Current Medicinal Chemistry, Volume 12, Number 10, May 2005, pp. 1161-1208(48) Metals, Toxicity and Oxidative Stress
*{{cite book |title=Materials Science and Engineering: an Introduction, 6th Ed. |author=William D. Callister |publisher=Wiley, New York |year=2003 |isbn=0471736961 |location=Table 6.1 p137. }}
*[http://www.memsnet.org/material/coppercubulk/ Material: Copper (Cu), bulk], MEMS and Nanotechnology Clearinghouse.
*{{cite journal |author=Kim BE, Nevitt T, Thiele DJ |title=Mechanisms for copper acquisition, distribution and regulation |journal=[[Nat. Chem. Biol.]] |volume=4 |issue=3 |pages=176–85 |year=2008 |pmid=18277979 |doi=10.1038/nchembio.72 |url=http://www.nature.com/nchembio/journal/v4/n3/abs/nchembio.72.html}}
==External links==
{{Commons|Copper}}
{{wiktionary|copper}}
*[http://www.npi.gov.au/database/substance-info/profiles/27.html National Pollutant Inventory - Copper and compounds fact sheet]
*[http://www.weldaloy.com/resource_center.php Copper Resource Page.] Includes 12 PDF files detailing the material properties of various kinds of copper, as well as various guides and tools for the copper industry.
*[http://www.copper.org The Copper Development Association] has an extensive site of properties and uses of copper; it also maintains a [http://www.brass.org web site dedicated to [[brass]], a copper alloy].
* [http://www.3rd1000.com/elements/Copper.htm The Third Millennium Online page on Copper]
* [http://www.webelements.com/webelements/elements/text/Cu/index.html The WebElements page on Copper]
*[http://www.pniok.de/cu.htm Picture in the Element collection from Heinrich Pniok]
*[http://mathildasanthropologyblog.wordpress.com/2008/05/27/the-worlds-oldest-forged-copper-object/]
{{clear}}
{{compact periodic table}}
{{Jewellery Materials}}
[[Category:Copper| ]]
[[Category:Chemical elements]]
[[Category:Dietary minerals]]
[[Category:Electrical conductors]]
[[Category:Noble metals]]
[[Category:Recyclable materials]]
[[Category:Symbols of Utah]]
[[Category:Transition metals]]
{{Link FA|es}}
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