Copper is a chemical element with symbol Cu (from ) 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 reddish-orange color. Copper is used as a conductor of heat and electricity, as 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 occur in nature in directly usable metallic form ( native metals) as opposed to needing extraction from an ore. This led to very early human use, from c. 8000 BC. It was the first metal to be smelted from its ore, c. 5000 BC, the first metal to be cast into a shape in a mold, c. 4000 BC and the first metal to be purposefully alloyed with another metal, tin, to create bronze, c. 3500 BC. In the Roman era, copper was principally mined on Cyprus, the origin of the name of the metal, from aes сyprium (metal of Cyprus), later corrupted to сuprum, from which the words copper (English), cuivre (French), Koper (Dutch) and Kupfer (German) are all derived.Encyclopaedia Britannica, 11th ed., vol. 7, p. 102. The 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 a green verdigris (or patina). 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 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.
Physical; etched to reveal crystallites.]] color.]] 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 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 (59.6×106 S/m) and high thermal conductivity, second highest (second only to silver) among pure metals at room temperature. This 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 permissible current density of copper in open air is approximately 3.1×106 A/m2 of cross-sectional area, above which it begins to heat excessively. Copper is one of a few metallic elements with a natural color other than gray or silver. Pure copper is orange-red and acquires a reddish tarnish when exposed to air. The characteristic color of copper results from the electronic transitions between the filled 3d and half-empty 4s atomic shells – the energy difference between these shells corresponds to orange light. As with other metals, if copper is put in contact with another metal, galvanic corrosion will occur.
Chemical. The contrast between the refurbished copper installed in 2010 and the green color of the original 1894 copper is clearly seen.]] Copper does not react with water, but it does slowly react with atmospheric oxygen to form 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.
IsotopesThere are 29 isotopes of copper. 63Cu and 65Cu are stable, with 63Cu comprising approximately 69% of naturally occurring copper; both have a spin of . The other isotopes are radioactive, with the most stable being 67Cu with a half-life of 61.83 hours. Seven metastable isotopes have been characterized; 68mCu 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+. 64Cu, which has a half-life of 12.7 hours, decays both ways. 62Cu and 64Cu have significant applications. 62Cu is used in 62Cu-PTSM as a radioactive tracer for positron emission tomography.
OccurrenceCopper is produced in massive stars and is present in the Earth's crust in a proportion of about 50 parts per million (ppm). It occurs as native copper, in the copper sulfides chalcopyrite and chalcocite, in the copper carbonates azurite and malachite, and in the copper(I) oxide mineral cuprite. The largest mass of elemental copper discovered weighed 420 tonnes and 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.
Productionin Chile is one of the world's largest open pit copper mines.]] 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 the British Geological Survey in 2005, Chile was the top producer of copper with at least one-third 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.
ReservesCopper has been in use at least 10,000 years, but more than 95% of all copper ever mined and smelted has been extracted since 1900, and more than half was extracted the last 24 years. As with many natural resources, the total amount of copper on Earth is vast, with around 1014 tons in 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 years to 60 years, depending on core assumptions such as the growth rate. Recycling is a major source of copper in the modern world. Because of these and other factors, the future of copper production and supply is the subject of much debate, including the concept of peak copper, analogous to peak oil. The price of copper has historically been unstable, and it sextupled from the 60-year low of US$0.60/lb (US$1.32/kg) in June 1999 to US$3.75 per pound (US$8.27/kg) in May 2006. It dropped to US$2.40/lb (US$5.29/kg) in February 2007, then rebounded to US$3.50/lb (US$7.71/kg) in April 2007. In February 2009, weakening global demand and a steep fall in commodity prices since the previous year's highs left copper prices at US$1.51/lb (US$3.32/kg).
MethodsThe concentration of copper in ores averages only 0.6%, and most commercial ores are sulfides, especially chalcopyrite (CuFeS2) and to a lesser extent chalcocite (Cu2S). These minerals are concentrated from crushed ores to the level of 10–15% copper by froth flotation or bioleaching. Heating this material with silica in flash smelting removes much of the iron as slag. The process exploits the greater ease of converting iron sulfides into oxides, which in turn react with the silica to form the silicate slag that floats on top of the heated mass. The resulting copper matte, consisting of Cu2S, is roasted to convert all sulfides into oxides: 2 Cu2S + 3 O2 → 2 Cu2O + 2 SO2 The cuprous oxide is converted to blister copper upon heating: 2 Cu2O → 4 Cu + O2 The Sudbury matte process converted only half the sulfide to oxide and then used this oxide to remove the rest of the sulfur as oxide. It was then electrolytically refined and the anode mud exploited for the platinum and gold it contained. This step exploits the relatively easy reduction of copper oxides to copper metal. Natural gas is blown across the blister to remove most of the remaining oxygen and electrorefining is performed on the resulting material to produce pure copper: Cu2+ + 2 e− → Cu S. J. Lippard, J. M. Berg "Principles of bioinorganic chemistry" University Science Books: Mill Valley, CA; 1994. . The biological role for copper commenced with the appearance of oxygen in earth's atmosphere. Copper is essential in the aerobic respiration of all eukaryotes. In mitochondria, it is found in cytochrome c oxidase, which is the last protein in oxidative phosphorylation. Cytochrome c oxidase is the protein that binds the O2 between a copper and an iron; the protein transfers 8 electrons to the O2 molecule to reduce it to two molecules of water. Copper is also found in many superoxide dismutases, proteins that catalyze the decomposition of superoxides by converting it (by disproportionation) to oxygen and hydrogen peroxide: 2 HO2 → H2O2 + O2 The protein hemocyanin is the oxygen carrier in most mollusks and some arthropods such as the horseshoe crab (Limulus polyphemus). Because hemocyanin is blue, these organisms have blue blood rather than the red blood of iron-based hemoglobin. Structurally related to hemocyanin are the laccases and tyrosinases. Instead of reversibly binding oxygen, these proteins hydroxylate substrates, illustrated by their role in the formation of lacquers. Several copper proteins, such as the "blue copper proteins", do not interact directly with substrates, hence they are not enzymes. These proteins relay electrons by the process called electron transfer. . A central link in this chain is plastocyanin, a blue copper protein.]] A unique tetranuclear copper center has been found in nitrous-oxide reductase.
Dietary needsCopper is an essential trace element in plants and animals, but not all microorganisms. The human body contains copper at a level of about 1.4 to 2.1 mg per kg of body mass. Copper is absorbed in the gut, then transported to the liver bound to albumin. After processing in the liver, copper is distributed to other tissues in a second phase, which involves the protein ceruloplasmin, carrying the majority of copper in blood. Ceruloplasmin also carries the copper that is excreted in milk, and is particularly well-absorbed as a copper source. Copper in the body normally undergoes enterohepatic circulation (about 5 mg a day, vs. about 1 mg per day absorbed in the diet and excreted from the body), and the body is able to excrete some excess copper, if needed, via bile, which carries some copper out of the liver that is not then reabsorbed by the intestine.
Dietary recommendationsThe U.S. Institute of Medicine (IOM) updated the estimated average requirements (EARs) and recommended dietary allowances (RDAs) for copper in 2001. If there is not sufficient information to establish EARs and RDAs, an estimate designated Adequate Intake (AI) is used instead. The current EAR for copper for people age 14 and older is 0.7 mg/day. The RDA is 0.9 mg/day. RDAs are higher than EARs so as to identify amounts that will cover people with higher than average requirements. The RDA for pregnancy is 1.0 mg/day. RDA for lactation is 1.3 mg/day. For infants up to 12 months, AI is 0.22 mg/day. For children age 1–13 years the RDA increases with age from 0.34 to 0.7 mg/day. As for safety, the IOM also sets Tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of copper the UL is set at 10 mg/day. Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes.Copper. IN: Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Copper. National Academy Press. 2001, PP. 224–257. The European Food Safety Authority (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR. AI and UL defined the same as in United States. For women and men ages 18 and older the AIs are set at 1.3 and 1.6 mg/day, respectively. AIs for pregnancy and lactation is 1.5 mg/day. For children ages 1–17 years the AIs increase with age from 0.7 tp 1.3 mg/day. These AIs are higher than the U.S. RDAs. The European Food Safety Authority reviewed the same safety question and set its UL at 5 mg/day, which is half the U.S. value. For U.S. food and dietary supplement labeling purposes the amount in a serving is expressed as a percent of Daily Value (%DV). For copper labeling purposes 100% of the Daily Value was 2.0 mg, but as of May 27, 2016 it was revised to 0.9 mg to bring it into agreement with the RDA. A table of the old and new adult Daily Values is provided at Reference Daily Intake. The original deadline to be in compliance was July 28, 2018, but on September 29, 2017 the FDA released a proposed rule that extended the deadline to January 1, 2020 for large companies and January 1, 2021 for small companies. "Changes to the Nutrition Facts Panel - Compliance Date"
Copper-based disordersBecause of its role in facilitating iron uptake, copper deficiency can produce anemia-like symptoms, neutropenia, bone abnormalities, hypopigmentation, impaired growth, increased incidence of infections, osteoporosis, hyperthyroidism, and abnormalities in glucose and cholesterol metabolism. Conversely, Wilson's disease causes an accumulation of copper in body tissues. Severe deficiency can be found by testing for low plasma or serum copper levels, low ceruloplasmin, and low red blood cell superoxide dismutase levels; these are not sensitive to marginal copper status. The "cytochrome c oxidase activity of leucocytes and platelets" has been stated as another factor in deficiency, but the results have not been confirmed by replication. Gram quantities of various copper salts have been taken in suicide attempts and produced acute copper toxicity in humans, possibly due to redox cycling and the generation of reactive oxygen species that damage DNA. Corresponding amounts of copper salts (30 mg/kg) are toxic in animals. A minimum dietary value for healthy growth in rabbits has been reported to be at least 3 ppm in the diet. However, higher concentrations of copper (100 ppm, 200 ppm, or 500 ppm) in the diet of rabbits may favorably influence feed conversion efficiency, growth rates, and carcass dressing percentages. Chronic copper toxicity does not normally occur in humans because of transport systems that regulate absorption and excretion. Autosomal recessive mutations in copper transport proteins can disable these systems, leading to Wilson's disease with copper accumulation and cirrhosis of the liver in persons who have inherited two defective genes. Elevated copper levels have also been linked to worsening symptoms of Alzheimer's disease.
Human exposureIn the US, the Occupational Safety and Health Administration (OSHA) has designated a permissible exposure limit (PEL) for copper dust and fumes in the workplace as a time-weighted average (TWA) of 1 mg/m3. The National Institute for Occupational Safety and Health (NIOSH) has set a Recommended exposure limit (REL) of 1 mg/m3, time-weighted average. The IDLH (immediately dangerous to life and health) value is 100 mg/m3. Copper is a constituent of tobacco smoke. OEHHA Copper The tobacco plant readily absorbs and accumulates heavy metals, such as copper from the surrounding soil into its leaves. These are readily absorbed into the user's body following smoke inhalation.Alireza Pourkhabbaz, Hamidreza Pourkhabbaz Investigation of Toxic Metals in the Tobacco of Different Iranian Cigarette Brands and Related Health Issues, Iran J Basic Med Sci. 2012 Jan-Feb; 15(1): 636–644. The health implications are not clear.David Bernhard, Andrea Rossmann, and Georg Wick Metals in Cigarette Smoke, IUBMB Life, 57(12): 805–809, December 2005
- Copper nanoparticle
- Erosion corrosion of copper water tubes
- * Cold water pitting of copper tube
- List of countries by copper production
- Metal theft
- * Operation Tremor
- Peak copper
- * Anaconda Copper
- * Antofagasta PLC
- * Bingham Canyon Mine
- * Codelco
- * Grasberg mine
- * El Boleo mine
- Current Medicinal Chemistry, Volume 12, Number 10, May 2005, pp. 1161–1208(48) Metals, Toxicity and Oxidative Stress
- Material: Copper (Cu), bulk, MEMS and Nanotechnology Clearinghouse.
- Copper transport disorders: an Instant insight from the Royal Society of Chemistry
- Copper at The Periodic Table of Videos (University of Nottingham)
- Copper and compounds fact sheet from the National Pollutant Inventory of Australia
- CDC–NIOSH Pocket Guide to Chemical Hazards – Copper (dusts and mists) from the Centers for Disease Control and Prevention's National Institute for Occupational Safety and Health
- CDC–NIOSH Pocket Guide to Chemical Hazards – Copper fume from the Centers for Disease Control and Prevention's National Institute for Occupational Safety and Health
- Copper.org - official website of the Copper Development Association with an extensive site of properties and uses of copper
- * Brass.org - also operated by the Copper Development Association; dedicated to brass, a copper alloy.
- Price history of copper, according to the IMF