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Wikipedia

Zinc

February 08, 2023

This article is about the chemical element. For other uses, see Zinc (disambiguation).

Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic table. In some respects, zinc is chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and the Zn2+ and Mg2+ ions are of similar size.[note 1] Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined by froth flotation of the ore, roasting, and final extraction using electricity (electrowinning).

Zinc, 30Zn
Zinc
Appearancesilver-gray
Standard atomic weight Ar°(Zn)
  • 65.38±0.02
  • 65.38±0.02 (abridged)[1]
Zinc in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
–
↑
Zn
↓
Cd
copper ← zinc → gallium
Atomic number (Z)30
Groupgroup 12
Periodperiod 4
Block  d-block
Electron configuration[Ar] 3d10 4s2
Electrons per shell2, 8, 18, 2
Physical properties
Phase at STPsolid
Melting point692.68 K ​(419.53 °C, ​787.15 °F)
Boiling point1180 K ​(907 °C, ​1665 °F)
Density (near r.t.)7.14 g/cm3
when liquid (at m.p.)6.57 g/cm3
Heat of fusion7.32 kJ/mol
Heat of vaporization115 kJ/mol
Molar heat capacity25.470 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 610 670 750 852 990 1179
Atomic properties
Oxidation states−2, 0, +1, +2 (an amphoteric oxide)
ElectronegativityPauling scale: 1.65
Ionization energies
  • 1st: 906.4 kJ/mol
  • 2nd: 1733.3 kJ/mol
  • 3rd: 3833 kJ/mol
  • (more)
Atomic radiusempirical: 134 pm
Covalent radius122±4 pm
Van der Waals radius139 pm
Spectral lines of zinc
Other properties
Natural occurrenceprimordial
Crystal structure ​hexagonal close-packed (hcp)
Speed of sound thin rod3850 m/s (at r.t.) (rolled)
Thermal expansion30.2 µm/(m⋅K) (at 25 °C)
Thermal conductivity116 W/(m⋅K)
Electrical resistivity59.0 nΩ⋅m (at 20 °C)
Magnetic orderingdiamagnetic
Molar magnetic susceptibility−11.4×10−6 cm3/mol (298 K)[2]
Young's modulus108 GPa
Shear modulus43 GPa
Bulk modulus70 GPa
Poisson ratio0.25
Mohs hardness2.5
Brinell hardness327–412 MPa
CAS Number7440-66-6
History
DiscoveryIndian metallurgists (before 1000 BCE)
First isolationAndreas Sigismund Marggraf (1746)
Recognized as a unique metal byRasaratna Samuccaya (1300)
Main isotopes of zinc
Iso­tope Decay
abun­dance half-life (t1/2) mode pro­duct
64Zn 49.2% stable
65Zn syn 244 d ε 65Cu
γ –
66Zn 27.7% stable
67Zn 4.0% stable
68Zn 18.5% stable
69Zn syn 56 min β− 69Ga
69mZn syn 13.8 h β− 69Ga
70Zn 0.6% stable
71Zn syn 2.4 min β− 71Ga
71mZn syn 4 h β− 71Ga
72Zn syn 46.5 h β− 72Ga
 Category: Zinc
| references

Zinc is an essential trace element for humans,[3][4][5] animals,[6] plants[7] and for microorganisms[8] and is necessary for prenatal and postnatal development.[9] It is the second most abundant trace metal in humans after iron and it is the only metal which appears in all enzyme classes.[7][5] Zinc is also an essential nutrient element for coral growth as it is an important cofactor for many enzymes.[10]

Zinc deficiency affects about two billion people in the developing world and is associated with many diseases.[11] In children, deficiency causes growth retardation, delayed sexual maturation, infection susceptibility, and diarrhea.[9] Enzymes with a zinc atom in the reactive center are widespread in biochemistry, such as alcohol dehydrogenase in humans.[12] Consumption of excess zinc may cause ataxia, lethargy, and copper deficiency.

Brass, an alloy of copper and zinc in various proportions, was used as early as the third millennium BC in the Aegean area and the region which currently includes Iraq, the United Arab Emirates, Kalmykia, Turkmenistan and Georgia. In the second millennium BC it was used in the regions currently including West India, Uzbekistan, Iran, Syria, Iraq, and Israel.[13][14][15] Zinc metal was not produced on a large scale until the 12th century in India, though it was known to the ancient Romans and Greeks.[16] The mines of Rajasthan have given definite evidence of zinc production going back to the 6th century BC.[17] To date, the oldest evidence of pure zinc comes from Zawar, in Rajasthan, as early as the 9th century AD when a distillation process was employed to make pure zinc.[18] Alchemists burned zinc in air to form what they called "philosopher's wool" or "white snow".

The element was probably named by the alchemist Paracelsus after the German word Zinke (prong, tooth). German chemist Andreas Sigismund Marggraf is credited with discovering pure metallic zinc in 1746. Work by Luigi Galvani and Alessandro Volta uncovered the electrochemical properties of zinc by 1800. Corrosion-resistant zinc plating of iron (hot-dip galvanizing) is the major application for zinc. Other applications are in electrical batteries, small non-structural castings, and alloys such as brass. A variety of zinc compounds are commonly used, such as zinc carbonate and zinc gluconate (as dietary supplements), zinc chloride (in deodorants), zinc pyrithione (anti-dandruff shampoos), zinc sulfide (in luminescent paints), and dimethylzinc or diethylzinc in the organic laboratory.

Characteristics

Physical properties

Zinc is a bluish-white, lustrous, diamagnetic metal,[19] though most common commercial grades of the metal have a dull finish.[20] It is somewhat less dense than iron and has a hexagonal crystal structure, with a distorted form of hexagonal close packing, in which each atom has six nearest neighbors (at 265.9 pm) in its own plane and six others at a greater distance of 290.6 pm.[21] The metal is hard and brittle at most temperatures but becomes malleable between 100 and 150 °C.[19][20] Above 210 °C, the metal becomes brittle again and can be pulverized by beating.[22] Zinc is a fair conductor of electricity.[19] For a metal, zinc has relatively low melting (419.5 °C) and boiling point (907 °C).[23] The melting point is the lowest of all the d-block metals aside from mercury and cadmium; for this reason among others, zinc, cadmium, and mercury are often not considered to be transition metals like the rest of the d-block metals.[23]

Many alloys contain zinc, including brass. Other metals long known to form binary alloys with zinc are aluminium, antimony, bismuth, gold, iron, lead, mercury, silver, tin, magnesium, cobalt, nickel, tellurium, and sodium.[24] Although neither zinc nor zirconium is ferromagnetic, their alloy, ZrZn
2, exhibits ferromagnetism below 35 K.[19]

Occurrence

See also: Zinc minerals

Zinc makes up about 75 ppm (0.0075%) of Earth's crust, making it the 24th most abundant element. Typical background concentrations of zinc do not exceed 1 μg/m3 in the atmosphere; 300 mg/kg in soil; 100 mg/kg in vegetation; 20 μg/L in freshwater and 5 μg/L in seawater.[25] The element is normally found in association with other base metals such as copper and lead in ores.[26] Zinc is a chalcophile, meaning the element is more likely to be found in minerals together with sulfur and other heavy chalcogens, rather than with the light chalcogen oxygen or with non-chalcogen electronegative elements such as the halogens. Sulfides formed as the crust solidified under the reducing conditions of the early Earth's atmosphere.[27] Sphalerite, which is a form of zinc sulfide, is the most heavily mined zinc-containing ore because its concentrate contains 60–62% zinc.[26]

Other source minerals for zinc include smithsonite (zinc carbonate), hemimorphite (zinc silicate), wurtzite (another zinc sulfide), and sometimes hydrozincite (basic zinc carbonate).[28] With the exception of wurtzite, all these other minerals were formed by weathering of the primordial zinc sulfides.[27]

Identified world zinc resources total about 1.9–2.8 billion tonnes.[29][30] Large deposits are in Australia, Canada and the United States, with the largest reserves in Iran.[27][31][32] The most recent estimate of reserve base for zinc (meets specified minimum physical criteria related to current mining and production practices) was made in 2009 and calculated to be roughly 480 Mt.[33] Zinc reserves, on the other hand, are geologically identified ore bodies whose suitability for recovery is economically based (location, grade, quality, and quantity) at the time of determination. Since exploration and mine development is an ongoing process, the amount of zinc reserves is not a fixed number and sustainability of zinc ore supplies cannot be judged by simply extrapolating the combined mine life of today's zinc mines. This concept is well supported by data from the United States Geological Survey (USGS), which illustrates that although refined zinc production increased 80% between 1990 and 2010, the reserve lifetime for zinc has remained unchanged. About 346 million tonnes have been extracted throughout history to 2002, and scholars have estimated that about 109–305 million tonnes are in use.[34][35][36]

 
Sphalerite (ZnS)

Isotopes

Main article: Isotopes of zinc

Five stable isotopes of zinc occur in nature, with 64Zn being the most abundant isotope (49.17% natural abundance).[37][38] The other isotopes found in nature are 66
Zn (27.73%), 67
Zn (4.04%), 68
Zn (18.45%), and 70
Zn (0.61%).[38]

Several dozen radioisotopes have been characterized. 65
Zn, which has a half-life of 243.66 days, is the least active radioisotope, followed by 72
Zn with a half-life of 46.5 hours.[37] Zinc has 10 nuclear isomers, of which 69mZn has the longest half-life, 13.76 h.[37] The superscript m indicates a metastable isotope. The nucleus of a metastable isotope is in an excited state and will return to the ground state by emitting a photon in the form of a gamma ray. 61
Zn has three excited metastable states and 73
Zn has two.[39] The isotopes 65
Zn, 71
Zn, 77
Zn and 78
Zn each have only one excited metastable state.[37]

The most common decay mode of a radioisotope of zinc with a mass number lower than 66 is electron capture. The decay product resulting from electron capture is an isotope of copper.[37]

n
30Zn
 +
e−
 → n
29Cu

The most common decay mode of a radioisotope of zinc with mass number higher than 66 is beta decay (β−), which produces an isotope of gallium.[37]

n
30Zn
 → n
31Ga
 +
e−
 +
ν
e

Compounds and chemistry

Main article: Compounds of zinc

Reactivity

See also: Clemmensen reduction

Zinc has an electron configuration of [Ar]3d104s2 and is a member of the group 12 of the periodic table. It is a moderately reactive metal and strong reducing agent.[40] The surface of the pure metal tarnishes quickly, eventually forming a protective passivating layer of the basic zinc carbonate, Zn
5(OH)
6(CO3)
2, by reaction with atmospheric carbon dioxide.[41]

Zinc burns in air with a bright bluish-green flame, giving off fumes of zinc oxide.[42] Zinc reacts readily with acids, alkalis and other non-metals.[43] Extremely pure zinc reacts only slowly at room temperature with acids.[42] Strong acids, such as hydrochloric or sulfuric acid, can remove the passivating layer and the subsequent reaction with the acid releases hydrogen gas.[42]

The chemistry of zinc is dominated by the +2 oxidation state. When compounds in this oxidation state are formed, the outer shell s electrons are lost, yielding a bare zinc ion with the electronic configuration [Ar]3d10.[44] In aqueous solution an octahedral complex, [Zn(H
2O)6]2+
 is the predominant species.[45] The volatilization of zinc in combination with zinc chloride at temperatures above 285 °C indicates the formation of Zn
2Cl
2, a zinc compound with a +1 oxidation state.[42] No compounds of zinc in positive oxidation states other than +1 or +2 are known.[46] Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist.[47] Zn(III) is predicted to exist in the presence of strongly electronegative trianions;[48] however, there exists some doubt around this possibility.[49] But in 2021 another compound was reported with more evidence that had the oxidation state of +3 with the formula ZnBeB11(CN)12.[50]

Zinc chemistry is similar to the chemistry of the late first-row transition metals, nickel and copper, though it has a filled d-shell and compounds are diamagnetic and mostly colorless.[51] The ionic radii of zinc and magnesium happen to be nearly identical. Because of this some of the equivalent salts have the same crystal structure,[52] and in other circumstances where ionic radius is a determining factor, the chemistry of zinc has much in common with that of magnesium.[42] In other respects, there is little similarity with the late first-row transition metals. Zinc tends to form bonds with a greater degree of covalency and much more stable complexes with N- and S- donors.[51] Complexes of zinc are mostly 4- or 6- coordinate, although 5-coordinate complexes are known.[42]

Zinc(I) compounds

Zinc(I) compounds are very rare. The [Zn2]2+ ion is implicated by the formation of a yellow diamagnetic glass by dissolving metallic zinc in molten ZnCl2.[53] The [Zn2]2+ core would be analogous to the [Hg2]2+ cation present in mercury(I) compounds. The diamagnetic nature of the ion confirms its dimeric structure. The first zinc(I) compound containing the Zn–Zn bond, (η5-C5Me5)2Zn2.

Zinc(II) compounds

 
Zinc acetate
 
Zinc chloride

Binary compounds of zinc are known for most of the metalloids and all the nonmetals except the noble gases. The oxide ZnO is a white powder that is nearly insoluble in neutral aqueous solutions, but is amphoteric, dissolving in both strong basic and acidic solutions.[42] The other chalcogenides (ZnS, ZnSe, and ZnTe) have varied applications in electronics and optics.[54] Pnictogenides (Zn
3N
2, Zn
3P
2, Zn
3As
2 and Zn
3Sb
2),[55][56] the peroxide (ZnO
2), the hydride (ZnH
2), and the carbide (ZnC
2) are also known.[57] Of the four halides, ZnF
2 has the most ionic character, while the others (ZnCl
2, ZnBr
2, and ZnI
2) have relatively low melting points and are considered to have more covalent character.[58]

In weak basic solutions containing Zn2+
 ions, the hydroxide Zn(OH)
2 forms as a white precipitate. In stronger alkaline solutions, this hydroxide is dissolved to form zincates ([Zn(OH)4]2−
).[42] The nitrate Zn(NO3)
2, chlorate Zn(ClO3)
2, sulfate ZnSO
4, phosphate Zn
3(PO4)
2, molybdate ZnMoO
4, cyanide Zn(CN)
2, arsenite Zn(AsO2)
2, arsenate Zn(AsO4)
2·8H
2O and the chromate ZnCrO
4 (one of the few colored zinc compounds) are a few examples of other common inorganic compounds of zinc.[59][60]

Organozinc compounds are those that contain zinc–carbon covalent bonds. Diethylzinc ((C
2H5)
2Zn) is a reagent in synthetic chemistry. It was first reported in 1848 from the reaction of zinc and ethyl iodide, and was the first compound known to contain a metal–carbon sigma bond.[61]

Test for zinc

Cobalticyanide paper (Rinnmann's test for Zn) can be used as a chemical indicator for zinc. 4 g of K3Co(CN)6 and 1 g of KClO3 is dissolved on 100 ml of water. Paper is dipped in the solution and dried at 100 °C. One drop of the sample is dropped onto the dry paper and heated. A green disc indicates the presence of zinc.[62]

History

Ancient use

The Charaka Samhita, thought to have been written between 300 and 500 AD,[63] mentions a metal which, when oxidized, produces pushpanjan, thought to be zinc oxide.[64] Zinc mines at Zawar, near Udaipur in India, have been active since the Mauryan period (c.  322 and 187 BCE). The smelting of metallic zinc here, however, appears to have begun around the 12th century AD.[65][66] One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries.[28] Another estimate gives a total production of 60,000 tonnes of metallic zinc over this period.[65] The Rasaratna Samuccaya, written in approximately the 13th century AD, mentions two types of zinc-containing ores: one used for metal extraction and another used for medicinal purposes.[66]

 
Late Roman brass bucket – the Hemmoorer Eimer from Warstade, Germany, second to third century AD

Various isolated examples of the use of impure zinc in ancient times have been discovered. Zinc ores were used to make the zinc–copper alloy brass thousands of years prior to the discovery of zinc as a separate element. Judean brass from the 14th to 10th centuries BC contains 23% zinc.[14]

Knowledge of how to produce brass spread to Ancient Greece by the 7th century BC, but few varieties were made.[15] Ornaments made of alloys containing 80–90% zinc, with lead, iron, antimony, and other metals making up the remainder, have been found that are 2,500 years old.[26] A possibly prehistoric statuette containing 87.5% zinc was found in a Dacian archaeological site.[67]

The oldest known pills were made of the zinc carbonates hydrozincite and smithsonite. The pills were used for sore eyes and were found aboard the Roman ship Relitto del Pozzino, wrecked in 140 BC.[68][69]

The manufacture of brass was known to the Romans by about 30 BC.[70] They made brass by heating powdered calamine (zinc silicate or carbonate), charcoal and copper together in a crucible.[70] The resulting calamine brass was then either cast or hammered into shape for use in weaponry.[71] Some coins struck by Romans in the Christian era are made of what is probably calamine brass.[72]

Strabo writing in the 1st century BC (but quoting a now lost work of the 4th century BC historian Theopompus) mentions "drops of false silver" which when mixed with copper make brass. This may refer to small quantities of zinc that is a by-product of smelting sulfide ores.[73] Zinc in such remnants in smelting ovens was usually discarded as it was thought to be worthless.[74]

The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly zinc.[75]

Early studies and naming

Zinc was distinctly recognized as a metal under the designation of Yasada or Jasada in the medical Lexicon ascribed to the Hindu king Madanapala (of Taka dynasty) and written about the year 1374.[76] Smelting and extraction of impure zinc by reducing calamine with wool and other organic substances was accomplished in the 13th century in India.[19][77] The Chinese did not learn of the technique until the 17th century.[77]

 
Various alchemical symbols for the element zinc

Alchemists burned zinc metal in air and collected the resulting zinc oxide on a condenser. Some alchemists called this zinc oxide lana philosophica, Latin for "philosopher's wool", because it collected in wooly tufts, whereas others thought it looked like white snow and named it nix album.[78]

The name of the metal was probably first documented by Paracelsus, a Swiss-born German alchemist, who referred to the metal as "zincum" or "zinken" in his book Liber Mineralium II, in the 16th century.[77][79] The word is probably derived from the German zinke, and supposedly meant "tooth-like, pointed or jagged" (metallic zinc crystals have a needle-like appearance).[80] Zink could also imply "tin-like" because of its relation to German zinn meaning tin.[81] Yet another possibility is that the word is derived from the Persian word سنگ seng meaning stone.[82] The metal was also called Indian tin, tutanego, calamine, and spinter.[26]

German metallurgist Andreas Libavius received a quantity of what he called "calay" of Malabar from a cargo ship captured from the Portuguese in the year 1596.[83] Libavius described the properties of the sample, which may have been zinc. Zinc was regularly imported to Europe from the Orient in the 17th and early 18th centuries,[77] but was at times very expensive.[note 2]

Isolation

 
Andreas Sigismund Marggraf is given credit for first isolating pure zinc

Metallic zinc was isolated in India by 1300 AD,[84][85][86] much earlier than in the West. Before it was isolated in Europe, it was imported from India in about 1600 CE.[87] Postlewayt's Universal Dictionary, a contemporary source giving technological information in Europe, did not mention zinc before 1751 but the element was studied before then.[66][88]

Flemish metallurgist and alchemist P. M. de Respour reported that he had extracted metallic zinc from zinc oxide in 1668.[28] By the start of the 18th century, Étienne François Geoffroy described how zinc oxide condenses as yellow crystals on bars of iron placed above zinc ore that is being smelted.[28] In Britain, John Lane is said to have carried out experiments to smelt zinc, probably at Landore, prior to his bankruptcy in 1726.[89]

In 1738 in Great Britain, William Champion patented a process to extract zinc from calamine in a vertical retort-style smelter.[90] His technique resembled that used at Zawar zinc mines in Rajasthan, but no evidence suggests he visited the Orient.[87] Champion's process was used through 1851.[77]

German chemist Andreas Marggraf normally gets credit for discovering pure metallic zinc, even though Swedish chemist Anton von Swab had distilled zinc from calamine four years previously.[77] In his 1746 experiment, Marggraf heated a mixture of calamine and charcoal in a closed vessel without copper to obtain a metal.[91][74] This procedure became commercially practical by 1752.[92]

Later work

 
Galvanization was named after Luigi Galvani.

William Champion's brother, John, patented a process in 1758 for calcining zinc sulfide into an oxide usable in the retort process.[26] Prior to this, only calamine could be used to produce zinc. In 1798, Johann Christian Ruberg improved on the smelting process by building the first horizontal retort smelter.[93] Jean-Jacques Daniel Dony built a different kind of horizontal zinc smelter in Belgium that processed even more zinc.[77] Italian doctor Luigi Galvani discovered in 1780 that connecting the spinal cord of a freshly dissected frog to an iron rail attached by a brass hook caused the frog's leg to twitch.[94] He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect "animal electricity".[95] The galvanic cell and the process of galvanization were both named for Luigi Galvani, and his discoveries paved the way for electrical batteries, galvanization, and cathodic protection.[95]

Galvani's friend, Alessandro Volta, continued researching the effect and invented the Voltaic pile in 1800.[94] Volta's pile consisted of a stack of simplified galvanic cells, each being one plate of copper and one of zinc connected by an electrolyte. By stacking these units in series, the Voltaic pile (or "battery") as a whole had a higher voltage, which could be used more easily than single cells. Electricity is produced because the Volta potential between the two metal plates makes electrons flow from the zinc to the copper and corrode the zinc.[94]

The non-magnetic character of zinc and its lack of color in solution delayed discovery of its importance to biochemistry and nutrition.[96] This changed in 1940 when carbonic anhydrase, an enzyme that scrubs carbon dioxide from blood, was shown to have zinc in its active site.[96] The digestive enzyme carboxypeptidase became the second known zinc-containing enzyme in 1955.[96]

Production

Mining and processing

Top zinc mine production output (by countries) 2019[29]
Rank Country Tonnes
1 China 4,210,000
2 Peru 1,400,000
3 Australia 1,330,000
5 United States 753,000
4 India 720,000
6 Mexico 677,000
Main articles: Zinc mining and Zinc smelting
See also: List of countries by zinc production
 
Price of Zinc
 
Percentage of zinc output in 2006 by countries[97]
 
World production trend
 
Zinc Mine Rosh Pinah, Namibia
27°57′17″S 016°46′00″E / 27.95472°S 16.76667°E / -27.95472; 16.76667 (Rosh Pinah)

Zinc is the fourth most common metal in use, trailing only iron, aluminium, and copper with an annual production of about 13 million tonnes.[29] The world's largest zinc producer is Nyrstar, a merger of the Australian OZ Minerals and the Belgian Umicore.[98] About 70% of the world's zinc originates from mining, while the remaining 30% comes from recycling secondary zinc.[99]

Commercially pure zinc is known as Special High Grade, often abbreviated SHG, and is 99.995% pure.[100]

Worldwide, 95% of new zinc is mined from sulfidic ore deposits, in which sphalerite (ZnS) is nearly always mixed with the sulfides of copper, lead and iron.[101]: 6  Zinc mines are scattered throughout the world, with the main areas being China, Australia, and Peru. China produced 38% of the global zinc output in 2014.[29]

Zinc metal is produced using extractive metallurgy.[102]: 7  The ore is finely ground, then put through froth flotation to separate minerals from gangue (on the property of hydrophobicity), to get a zinc sulfide ore concentrate[102]: 16  consisting of about 50% zinc, 32% sulfur, 13% iron, and 5% SiO
2.[102]: 16 

Roasting converts the zinc sulfide concentrate to zinc oxide:[101]

 

The sulfur dioxide is used for the production of sulfuric acid, which is necessary for the leaching process. If deposits of zinc carbonate, zinc silicate, or zinc-spinel (like the Skorpion Deposit in Namibia) are used for zinc production, the roasting can be omitted.[103]

For further processing two basic methods are used: pyrometallurgy or electrowinning. Pyrometallurgy reduces zinc oxide with carbon or carbon monoxide at 950 °C (1,740 °F) into the metal, which is distilled as zinc vapor to separate it from other metals, which are not volatile at those temperatures.[104] The zinc vapor is collected in a condenser.[101] The equations below describe this process:[101]

 
 

In electrowinning, zinc is leached from the ore concentrate by sulfuric acid and impurities are precipitated:[105]

 

Finally, the zinc is reduced by electrolysis.[101]

 

The sulfuric acid is regenerated and recycled to the leaching step.

When galvanised feedstock is fed to an electric arc furnace, the zinc is recovered from the dust by a number of processes, predominantly the Waelz process (90% as of 2014).[106]

Environmental impact

Refinement of sulfidic zinc ores produces large volumes of sulfur dioxide and cadmium vapor. Smelter slag and other residues contain significant quantities of metals. About 1.1 million tonnes of metallic zinc and 130 thousand tonnes of lead were mined and smelted in the Belgian towns of La Calamine and Plombières between 1806 and 1882.[107] The dumps of the past mining operations leach zinc and cadmium, and the sediments of the Geul River contain non-trivial amounts of metals.[107] About two thousand years ago, emissions of zinc from mining and smelting totaled 10 thousand tonnes a year. After increasing 10-fold from 1850, zinc emissions peaked at 3.4 million tonnes per year in the 1980s and declined to 2.7 million tonnes in the 1990s, although a 2005 study of the Arctic troposphere found that the concentrations there did not reflect the decline. Man-made and natural emissions occur at a ratio of 20 to 1.[7]

Zinc in rivers flowing through industrial and mining areas can be as high as 20 ppm.[108] Effective sewage treatment greatly reduces this; treatment along the Rhine, for example, has decreased zinc levels to 50 ppb.[108] Concentrations of zinc as low as 2 ppm adversely affects the amount of oxygen that fish can carry in their blood.[109]

 
Historically responsible for high metal levels in the Derwent River,[110] the zinc works at Lutana is the largest exporter in Tasmania, generating 2.5% of the state's GDP, and producing more than 250,000 tonnes of zinc per year.[111]

Soils contaminated with zinc from mining, refining, or fertilizing with zinc-bearing sludge can contain several grams of zinc per kilogram of dry soil. Levels of zinc in excess of 500 ppm in soil interfere with the ability of plants to absorb other essential metals, such as iron and manganese. Zinc levels of 2000 ppm to 180,000 ppm (18%) have been recorded in some soil samples.[108]

Applications

Major applications of zinc include (numbers are given for the US)[112]

  1. Galvanizing (55%)
  2. Brass and bronze (16%)
  3. Other alloys (21%)
  4. Miscellaneous (8%)

Anti-corrosion and batteries

 
Hot-dip handrail galvanized crystalline surface

Zinc is most commonly used as an anti-corrosion agent,[113] and galvanization (coating of iron or steel) is the most familiar form. In 2009 in the United States, 55% or 893,000 tons of the zinc metal was used for galvanization.[112]

Zinc is more reactive than iron or steel and thus will attract almost all local oxidation until it completely corrodes away.[114] A protective surface layer of oxide and carbonate (Zn
5(OH)
6(CO
3)
2) forms as the zinc corrodes.[115] This protection lasts even after the zinc layer is scratched but degrades through time as the zinc corrodes away.[115] The zinc is applied electrochemically or as molten zinc by hot-dip galvanizing or spraying. Galvanization is used on chain-link fencing, guard rails, suspension bridges, lightposts, metal roofs, heat exchangers, and car bodies.[116]

The relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient sacrificial anode in cathodic protection (CP). For example, cathodic protection of a buried pipeline can be achieved by connecting anodes made from zinc to the pipe.[115] Zinc acts as the anode (negative terminus) by slowly corroding away as it passes electric current to the steel pipeline.[115][note 3] Zinc is also used to cathodically protect metals that are exposed to sea water.[117] A zinc disc attached to a ship's iron rudder will slowly corrode while the rudder stays intact.[114] Similarly, a zinc plug attached to a propeller or the metal protective guard for the keel of the ship provides temporary protection.

With a standard electrode potential (SEP) of −0.76 volts, zinc is used as an anode material for batteries. (More reactive lithium (SEP −3.04 V) is used for anodes in lithium batteries ). Powdered zinc is used in this way in alkaline batteries and the case (which also serves as the anode) of zinc–carbon batteries is formed from sheet zinc.[118][119] Zinc is used as the anode or fuel of the zinc–air battery/fuel cell.[120][121][122] The zinc-cerium redox flow battery also relies on a zinc-based negative half-cell.[123]

Alloys

A widely used zinc alloy is brass, in which copper is alloyed with anywhere from 3% to 45% zinc, depending upon the type of brass.[115] Brass is generally more ductile and stronger than copper, and has superior corrosion resistance.[115] These properties make it useful in communication equipment, hardware, musical instruments, and water valves.[115]

 
Cast brass microstructure at magnification 400x

Other widely used zinc alloys include nickel silver, typewriter metal, soft and aluminium solder, and commercial bronze.[19] Zinc is also used in contemporary pipe organs as a substitute for the traditional lead/tin alloy in pipes.[124] Alloys of 85–88% zinc, 4–10% copper, and 2–8% aluminium find limited use in certain types of machine bearings. Zinc has been the primary metal in American one cent coins (pennies) since 1982.[125] The zinc core is coated with a thin layer of copper to give the appearance of a copper coin. In 1994, 33,200 tonnes (36,600 short tons) of zinc were used to produce 13.6 billion pennies in the United States.[126]

Alloys of zinc with small amounts of copper, aluminium, and magnesium are useful in die casting as well as spin casting, especially in the automotive, electrical, and hardware industries.[19] These alloys are marketed under the name Zamak.[127] An example of this is zinc aluminium. The low melting point together with the low viscosity of the alloy makes possible the production of small and intricate shapes. The low working temperature leads to rapid cooling of the cast products and fast production for assembly.[19][128] Another alloy, marketed under the brand name Prestal, contains 78% zinc and 22% aluminium, and is reported to be nearly as strong as steel but as malleable as plastic.[19][129] This superplasticity of the alloy allows it to be molded using die casts made of ceramics and cement.[19]

Similar alloys with the addition of a small amount of lead can be cold-rolled into sheets. An alloy of 96% zinc and 4% aluminium is used to make stamping dies for low production run applications for which ferrous metal dies would be too expensive.[130] For building facades, roofing, and other applications for sheet metal formed by deep drawing, roll forming, or bending, zinc alloys with titanium and copper are used.[131] Unalloyed zinc is too brittle for these manufacturing processes.[131]

As a dense, inexpensive, easily worked material, zinc is used as a lead replacement. In the wake of lead concerns, zinc appears in weights for various applications ranging from fishing[132] to tire balances and flywheels.[133]

Cadmium zinc telluride (CZT) is a semiconductive alloy that can be divided into an array of small sensing devices.[134] These devices are similar to an integrated circuit and can detect the energy of incoming gamma ray photons.[134] When behind an absorbing mask, the CZT sensor array can determine the direction of the rays.[134]

Other industrial uses

 
Zinc oxide is used as a white pigment in paints.

Roughly one quarter of all zinc output in the United States in 2009 was consumed in zinc compounds;[112] a variety of which are used industrially. Zinc oxide is widely used as a white pigment in paints and as a catalyst in the manufacture of rubber to disperse heat. Zinc oxide is used to protect rubber polymers and plastics from ultraviolet radiation (UV).[116] The semiconductor properties of zinc oxide make it useful in varistors and photocopying products.[135] The zinc zinc-oxide cycle is a two step thermochemical process based on zinc and zinc oxide for hydrogen production.[136]

Zinc chloride is often added to lumber as a fire retardant[137] and sometimes as a wood preservative.[138] It is used in the manufacture of other chemicals.[137] Zinc methyl (Zn(CH3)
2) is used in a number of organic syntheses.[139] Zinc sulfide (ZnS) is used in luminescent pigments such as on the hands of clocks, X-ray and television screens, and luminous paints.[140] Crystals of ZnS are used in lasers that operate in the mid-infrared part of the spectrum.[141] Zinc sulfate is a chemical in dyes and pigments.[137] Zinc pyrithione is used in antifouling paints.[142]

Zinc powder is sometimes used as a propellant in model rockets.[143] When a compressed mixture of 70% zinc and 30% sulfur powder is ignited there is a violent chemical reaction.[143] This produces zinc sulfide, together with large amounts of hot gas, heat, and light.[143]

Zinc sheet metal is used as a durable covering for roofs, walls, and countertops, the last often seen in bistros and oyster bars, and is known for the rustic look imparted by its surface oxidation in use to a blue-gray patina and susceptibility to scratching.[144][145][146][147]

64
Zn, the most abundant isotope of zinc, is very susceptible to neutron activation, being transmuted into the highly radioactive 65
Zn, which has a half-life of 244 days and produces intense gamma radiation. Because of this, zinc oxide used in nuclear reactors as an anti-corrosion agent is depleted of 64
Zn before use, this is called depleted zinc oxide. For the same reason, zinc has been proposed as a salting material for nuclear weapons (cobalt is another, better-known salting material).[148] A jacket of isotopically enriched 64
Zn would be irradiated by the intense high-energy neutron flux from an exploding thermonuclear weapon, forming a large amount of 65
Zn significantly increasing the radioactivity of the weapon's fallout.[148] Such a weapon is not known to have ever been built, tested, or used.[148]

65
Zn is used as a tracer to study how alloys that contain zinc wear out, or the path and the role of zinc in organisms.[149]

Zinc dithiocarbamate complexes are used as agricultural fungicides; these include Zineb, Metiram, Propineb and Ziram.[150] Zinc naphthenate is used as wood preservative.[151] Zinc in the form of ZDDP, is used as an anti-wear additive for metal parts in engine oil.[152]

Organic chemistry

 
Addition of diphenylzinc to an aldehyde

Organozinc chemistry is the science of compounds that contain carbon-zinc bonds, describing the physical properties, synthesis, and chemical reactions. Many organozinc compounds are important.[153][154][155][156] Among important applications are

  • The Frankland-Duppa Reaction in which an oxalate ester (ROCOCOOR) reacts with an alkyl halide R'X, zinc and hydrochloric acid to form the α-hydroxycarboxylic esters RR'COHCOOR[157][158]
  • On the downside, organozincs are much less nucleophilic than Grignards, and they are expensive and difficult to handle. Commercially available diorganozinc compounds are dimethylzinc, diethylzinc and diphenylzinc. In one study,[159][160] the active organozinc compound is obtained from much cheaper organobromine precursors.

Zinc has found many uses as a catalyst in organic synthesis including asymmetric synthesis, being cheap and easily available alternative to precious metal complexes. The results (yield and enantiomeric excess) obtained with chiral zinc catalysts are comparable to those achieved with palladium, ruthenium, iridium and others, and zinc becomes a metal catalyst of choice.[161]

Dietary supplement

 
GNC zinc 50 mg tablets. The amount exceeds what is deemed the safe upper limit in the United States (40 mg) and European Union (25 mg)
 
Zinc gluconate is one compound used for the delivery of zinc as a dietary supplement.
See also: Zinc sulfate (medical use) and Zinc gluconate

In most single-tablet, over-the-counter, daily vitamin and mineral supplements, zinc is included in such forms as zinc oxide, zinc acetate, zinc gluconate, or zinc amino acid chelate.[162][163]

Generally, zinc supplement is recommended where there is high risk of zinc deficiency (such as low and middle income countries) as a preventive measure.[164] Although zinc sulfate is a commonly used zinc form, zinc citrate, gluconate and picolinate may be valid options as well. These forms are better absorbed than zinc oxide.[165]

Gastroenteritis

Zinc is an inexpensive and effective part of treatment of diarrhea among children in the developing world. Zinc becomes depleted in the body during diarrhea and replenishing zinc with a 10- to 14-day course of treatment can reduce the duration and severity of diarrheal episodes and may also prevent future episodes for as long as three months.[166] Gastroenteritis is strongly attenuated by ingestion of zinc, possibly by direct antimicrobial action of the ions in the gastrointestinal tract, or by the absorption of the zinc and re-release from immune cells (all granulocytes secrete zinc), or both.[167][168]

Common cold

This section is an excerpt from Zinc and the common cold.[edit]

Zinc supplements (frequently zinc acetate or zinc gluconate lozenges) are a group of dietary supplements that are commonly used for the treatment of the common cold.[169] The use of zinc supplements at doses in excess of 75 mg/day within 24 hours of the onset of symptoms has been shown to reduce the duration of cold symptoms by about 1 day in adults.[169][170] Adverse effects with zinc supplements by mouth include bad taste and nausea.[169][170] The intranasal use of zinc-containing nasal sprays has been associated with the loss of the sense of smell;[169] consequently, in June 2009, the United States Food and Drug Administration (USFDA) warned consumers to stop using intranasal zinc.[169]

The human rhinovirus – the most common viral pathogen in humans – is the predominant cause of the common cold.[171] The hypothesized mechanism of action by which zinc reduces the severity and/or duration of cold symptoms is the suppression of nasal inflammation and the direct inhibition of rhinoviral receptor binding and rhinoviral replication in the nasal mucosa.[169]

Weight gain

See also: Zinc deficiency § Appetite

Zinc deficiency may lead to loss of appetite.[172] The use of zinc in the treatment of anorexia has been advocated since 1979. At least 15 clinical trials have shown that zinc improved weight gain in anorexia. A 1994 trial showed that zinc doubled the rate of body mass increase in the treatment of anorexia nervosa. Deficiency of other nutrients such as tyrosine, tryptophan and thiamine could contribute to this phenomenon of "malnutrition-induced malnutrition".[173] A meta-analysis of 33 prospective intervention trials regarding zinc supplementation and its effects on the growth of children in many countries showed that zinc supplementation alone had a statistically significant effect on linear growth and body weight gain, indicating that other deficiencies that may have been present were not responsible for growth retardation.[174]

Other

A Cochrane review stated that people taking zinc supplement may be less likely to progress to age-related macular degeneration.[175] Zinc supplement is an effective treatment for acrodermatitis enteropathica, a genetic disorder affecting zinc absorption that was previously fatal to affected infants.[70] Zinc deficiency has been associated with major depressive disorder (MDD), and zinc supplements may be an effective treatment.[176] Zinc may help individuals sleep more.[5]

Topical use

Further information: Zinc oxide § Medicine

Topical preparations of zinc include those used on the skin, often in the form of zinc oxide. Zinc oxide is generally recognised by the FDA as safe and effective[177] and is considered a very photo-stable.[178] Zinc oxide is one of the most common active ingredients formulated into a sunscreen to mitigate sunburn.[70] Applied thinly to a baby's diaper area (perineum) with each diaper change, it can protect against diaper rash.[70]

Chelated zinc is used in toothpastes and mouthwashes to prevent bad breath; zinc citrate helps reduce the build-up of calculus (tartar).[179][180]

Zinc pyrithione is widely included in shampoos to prevent dandruff.[181]

Topical zinc has also been shown to effectively treat, as well as prolong remission in genital herpes.[182]

Biological role

Main article: Zinc in biology

Zinc is an essential trace element for humans[3][4][5] and other animals,[6] for plants[7] and for microorganisms.[8] Zinc is required for the function of over 300 enzymes and 1000 transcription factors,[5] and is stored and transferred in metallothioneins.[183][184] It is the second most abundant trace metal in humans after iron and it is the only metal which appears in all enzyme classes.[7][5]

In proteins, zinc ions are often coordinated to the amino acid side chains of aspartic acid, glutamic acid, cysteine and histidine. The theoretical and computational description of this zinc binding in proteins (as well as that of other transition metals) is difficult.[185]

Roughly 2–4 grams of zinc[186] are distributed throughout the human body. Most zinc is in the brain, muscle, bones, kidney, and liver, with the highest concentrations in the prostate and parts of the eye.[187] Semen is particularly rich in zinc, a key factor in prostate gland function and reproductive organ growth.[188]

Zinc homeostasis of the body is mainly controlled by the intestine. Here, ZIP4 and especially TRPM7 were linked to intestinal zinc uptake essential for postnatal survival.[189][190]

In humans, the biological roles of zinc are ubiquitous.[9][4] It interacts with "a wide range of organic ligands",[9] and has roles in the metabolism of RNA and DNA, signal transduction, and gene expression. It also regulates apoptosis. A review from 2015 indicated that about 10% of human proteins (~3000) bind zinc,[191] in addition to hundreds more that transport and traffic zinc; a similar in silico study in the plant Arabidopsis thaliana found 2367 zinc-related proteins.[7]

In the brain, zinc is stored in specific synaptic vesicles by glutamatergic neurons and can modulate neuronal excitability.[4][5][192] It plays a key role in synaptic plasticity and so in learning.[4][193] Zinc homeostasis also plays a critical role in the functional regulation of the central nervous system.[4][192][5] Dysregulation of zinc homeostasis in the central nervous system that results in excessive synaptic zinc concentrations is believed to induce neurotoxicity through mitochondrial oxidative stress (e.g., by disrupting certain enzymes involved in the electron transport chain, including complex I, complex III, and α-ketoglutarate dehydrogenase), the dysregulation of calcium homeostasis, glutamatergic neuronal excitotoxicity, and interference with intraneuronal signal transduction.[4][194] L- and D-histidine facilitate brain zinc uptake.[195] SLC30A3 is the primary zinc transporter involved in cerebral zinc homeostasis.[4]

Enzymes

 
Ribbon diagram of human carbonic anhydrase II, with zinc atom visible in the center
 
Zinc fingers help read DNA sequences.

Zinc is an efficient Lewis acid, making it a useful catalytic agent in hydroxylation and other enzymatic reactions.[196] The metal also has a flexible coordination geometry, which allows proteins using it to rapidly shift conformations to perform biological reactions.[197] Two examples of zinc-containing enzymes are carbonic anhydrase and carboxypeptidase, which are vital to the processes of carbon dioxide (CO
2) regulation and digestion of proteins, respectively.[198]

In vertebrate blood, carbonic anhydrase converts CO
2 into bicarbonate and the same enzyme transforms the bicarbonate back into CO
2 for exhalation through the lungs.[199] Without this enzyme, this conversion would occur about one million times slower[200] at the normal blood pH of 7 or would require a pH of 10 or more.[201] The non-related β-carbonic anhydrase is required in plants for leaf formation, the synthesis of indole acetic acid (auxin) and alcoholic fermentation.[202]

Carboxypeptidase cleaves peptide linkages during digestion of proteins. A coordinate covalent bond is formed between the terminal peptide and a C=O group attached to zinc, which gives the carbon a positive charge. This helps to create a hydrophobic pocket on the enzyme near the zinc, which attracts the non-polar part of the protein being digested.[198]

Signalling

Zinc has been recognized as a messenger, able to activate signalling pathways. Many of these pathways provide the driving force in aberrant cancer growth. They can be targeted through ZIP transporters.[203]

Other proteins

Zinc serves a purely structural role in zinc fingers, twists and clusters.[204] Zinc fingers form parts of some transcription factors, which are proteins that recognize DNA base sequences during the replication and transcription of DNA. Each of the nine or ten Zn2+
 ions in a zinc finger helps maintain the finger's structure by coordinately binding to four amino acids in the transcription factor.[200]

In blood plasma, zinc is bound to and transported by albumin (60%, low-affinity) and transferrin (10%).[186] Because transferrin also transports iron, excessive iron reduces zinc absorption, and vice versa. A similar antagonism exists with copper.[205] The concentration of zinc in blood plasma stays relatively constant regardless of zinc intake.[196] Cells in the salivary gland, prostate, immune system, and intestine use zinc signaling to communicate with other cells.[206]

Zinc may be held in metallothionein reserves within microorganisms or in the intestines or liver of animals.[207] Metallothionein in intestinal cells is capable of adjusting absorption of zinc by 15–40%.[208] However, inadequate or excessive zinc intake can be harmful; excess zinc particularly impairs copper absorption because metallothionein absorbs both metals.[209]

The human dopamine transporter contains a high affinity extracellular zinc binding site which, upon zinc binding, inhibits dopamine reuptake and amplifies amphetamine-induced dopamine efflux in vitro.[210][211][212] The human serotonin transporter and norepinephrine transporter do not contain zinc binding sites.[212] Some EF-hand calcium binding proteins such as S100 or NCS-1 are also able to bind zinc ions.[213]

Nutrition

Dietary recommendations

The U.S. Institute of Medicine (IOM) updated Estimated Average Requirements (EARs) and Recommended Dietary Allowances (RDAs) for zinc in 2001. The current EARs for zinc for women and men ages 14 and up is 6.8 and 9.4 mg/day, respectively. The RDAs are 8 and 11 mg/day. RDAs are higher than EARs so as to identify amounts that will cover people with higher than average requirements. RDA for pregnancy is 11 mg/day. RDA for lactation is 12 mg/day. For infants up to 12 months the RDA is 3 mg/day. For children ages 1–13 years the RDA increases with age from 3 to 8 mg/day. As for safety, the IOM sets Tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of zinc the adult UL is 40 mg/day (lower for children). Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes (DRIs).[196]

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 are defined the same as in the United States. For people ages 18 and older the PRI calculations are complex, as the EFSA has set higher and higher values as the phytate content of the diet increases. For women, PRIs increase from 7.5 to 12.7 mg/day as phytate intake increases from 300 to 1200 mg/day; for men the range is 9.4 to 16.3 mg/day. These PRIs are higher than the U.S. RDAs.[214] The EFSA reviewed the same safety question and set its UL at 25 mg/day, which is much lower than the U.S. value.[215]

For U.S. food and dietary supplement labeling purposes the amount in a serving is expressed as a percent of Daily Value (%DV). For zinc labeling purposes 100% of the Daily Value was 15 mg, but on May 27, 2016, it was revised to 11 mg.[216][217] A table of the old and new adult daily values is provided at Reference Daily Intake.

Dietary intake

 
Foods and spices containing zinc

Animal products such as meat, fish, shellfish, fowl, eggs, and dairy contain zinc. The concentration of zinc in plants varies with the level in the soil. With adequate zinc in the soil, the food plants that contain the most zinc are wheat (germ and bran) and various seeds, including sesame, poppy, alfalfa, celery, and mustard.[218] Zinc is also found in beans, nuts, almonds, whole grains, pumpkin seeds, sunflower seeds, and blackcurrant.[219]

Other sources include fortified food and dietary supplements in various forms. A 1998 review concluded that zinc oxide, one of the most common supplements in the United States, and zinc carbonate are nearly insoluble and poorly absorbed in the body.[220] This review cited studies that found lower plasma zinc concentrations in the subjects who consumed zinc oxide and zinc carbonate than in those who took zinc acetate and sulfate salts.[220] For fortification, however, a 2003 review recommended cereals (containing zinc oxide) as a cheap, stable source that is as easily absorbed as the more expensive forms.[221] A 2005 study found that various compounds of zinc, including oxide and sulfate, did not show statistically significant differences in absorption when added as fortificants to maize tortillas.[222]

Deficiency

Main article: Zinc deficiency

Nearly two billion people in the developing world are deficient in zinc. Groups at risk include children in developing countries and elderly with chronic illnesses.[11] In children, it causes an increase in infection and diarrhea and contributes to the death of about 800,000 children worldwide per year.[9] The World Health Organization advocates zinc supplementation for severe malnutrition and diarrhea.[223] Zinc supplements help prevent disease and reduce mortality, especially among children with low birth weight or stunted growth.[223] However, zinc supplements should not be administered alone, because many in the developing world have several deficiencies, and zinc interacts with other micronutrients.[224] While zinc deficiency is usually due to insufficient dietary intake, it can be associated with malabsorption, acrodermatitis enteropathica, chronic liver disease, chronic renal disease, sickle cell disease, diabetes, malignancy, and other chronic illnesses.[11]

In the United States, a federal survey of food consumption determined that for women and men over the age of 19, average consumption was 9.7 and 14.2 mg/day, respectively. For women, 17% consumed less than the EAR, for men 11%. The percentages below EAR increased with age.[225] The most recent published update of the survey (NHANES 2013–2014) reported lower averages – 9.3 and 13.2 mg/day – again with intake decreasing with age.[226]

Symptoms of mild zinc deficiency are diverse.[196] Clinical outcomes include depressed growth, diarrhea, impotence and delayed sexual maturation, alopecia, eye and skin lesions, impaired appetite, altered cognition, impaired immune functions, defects in carbohydrate utilization, and reproductive teratogenesis.[196] Zinc deficiency depresses immunity,[227] but excessive zinc does also.[186]

Despite some concerns,[228] western vegetarians and vegans do not suffer any more from overt zinc deficiency than meat-eaters.[229] Major plant sources of zinc include cooked dried beans, sea vegetables, fortified cereals, soy foods, nuts, peas, and seeds.[228] However, phytates in many whole-grains and fibers may interfere with zinc absorption and marginal zinc intake has poorly understood effects. The zinc chelator phytate, found in seeds and cereal bran, can contribute to zinc malabsorption.[11] Some evidence suggests that more than the US RDA (8 mg/day for adult women; 11 mg/day for adult men) may be needed in those whose diet is high in phytates, such as some vegetarians.[228] The European Food Safety Authority (EFSA) guidelines attempt to compensate for this by recommending higher zinc intake when dietary phytate intake is greater.[214] These considerations must be balanced against the paucity of adequate zinc biomarkers, and the most widely used indicator, plasma zinc, has poor sensitivity and specificity.[230]

Soil remediation

Species of Calluna, Erica and Vaccinium can grow in zinc-metalliferous soils, because translocation of toxic ions is prevented by the action of ericoid mycorrhizal fungi.[231]

Agriculture

Zinc deficiency appears to be the most common micronutrient deficiency in crop plants; it is particularly common in high-pH soils.[232] Zinc-deficient soil is cultivated in the cropland of about half of Turkey and India, a third of China, and most of Western Australia. Substantial responses to zinc fertilization have been reported in these areas.[7] Plants that grow in soils that are zinc-deficient are more susceptible to disease. Zinc is added to the soil primarily through the weathering of rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate fertilizers, pesticide (zinc phosphide), limestone, manure, sewage sludge, and particles from galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less widespread.[7]

Precautions

Main article: Zinc toxicity

Toxicity

Although zinc is an essential requirement for good health, excess zinc can be harmful. Excessive absorption of zinc suppresses copper and iron absorption.[209] The free zinc ion in solution is highly toxic to plants, invertebrates, and even vertebrate fish.[233] The Free Ion Activity Model is well-established in the literature, and shows that just micromolar amounts of the free ion kills some organisms. A recent example showed 6 micromolar killing 93% of all Daphnia in water.[234]

The free zinc ion is a powerful Lewis acid up to the point of being corrosive. Stomach acid contains hydrochloric acid, in which metallic zinc dissolves readily to give corrosive zinc chloride. Swallowing a post-1982 American one cent piece (97.5% zinc) can cause damage to the stomach lining through the high solubility of the zinc ion in the acidic stomach.[235]

Evidence shows that people taking 100–300 mg of zinc daily may suffer induced copper deficiency. A 2007 trial observed that elderly men taking 80 mg daily were hospitalized for urinary complications more often than those taking a placebo.[236] Levels of 100–300 mg may interfere with the utilization of copper and iron or adversely affect cholesterol.[209] Zinc in excess of 500 ppm in soil interferes with the plant absorption of other essential metals, such as iron and manganese.[108] A condition called the zinc shakes or "zinc chills" can be induced by inhalation of zinc fumes while brazing or welding galvanized materials.[140] Zinc is a common ingredient of denture cream which may contain between 17 and 38 mg of zinc per gram. Disability and even deaths from excessive use of these products have been claimed.[237]

The U.S. Food and Drug Administration (FDA) states that zinc damages nerve receptors in the nose, causing anosmia. Reports of anosmia were also observed in the 1930s when zinc preparations were used in a failed attempt to prevent polio infections.[238] On June 16, 2009, the FDA ordered removal of zinc-based intranasal cold products from store shelves. The FDA said the loss of smell can be life-threatening because people with impaired smell cannot detect leaking gas or smoke, and cannot tell if food has spoiled before they eat it.[239]

Recent research suggests that the topical antimicrobial zinc pyrithione is a potent heat shock response inducer that may impair genomic integrity with induction of PARP-dependent energy crisis in cultured human keratinocytes and melanocytes.[240]

Poisoning

In 1982, the US Mint began minting pennies coated in copper but containing primarily zinc. Zinc pennies pose a risk of zinc toxicosis, which can be fatal. One reported case of chronic ingestion of 425 pennies (over 1 kg of zinc) resulted in death due to gastrointestinal bacterial and fungal sepsis. Another patient who ingested 12 grams of zinc showed only lethargy and ataxia (gross lack of coordination of muscle movements).[241] Several other cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins.[242][243]

Pennies and other small coins are sometimes ingested by dogs, requiring veterinary removal of the foreign objects. The zinc content of some coins can cause zinc toxicity, commonly fatal in dogs through severe hemolytic anemia and liver or kidney damage; vomiting and diarrhea are possible symptoms.[244] Zinc is highly toxic in parrots and poisoning can often be fatal.[245] The consumption of fruit juices stored in galvanized cans has resulted in mass parrot poisonings with zinc.[70]

See also

Notes

  1. ^ The elements are from different metal groups. See periodic table.
  2. ^ An East India Company ship carrying a cargo of nearly pure zinc metal from the Orient sank off the coast Sweden in 1745.(Emsley 2001, p. 502)
  3. ^ Electric current will naturally flow between zinc and steel but in some circumstances inert anodes are used with an external DC source.

Citations

  1. ^ "Standard Atomic Weights: Zinc". CIAAW. 2007.
  2. ^ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
  3. ^ a b Maret, Wolfgang (2013). "Chapter 12. Zinc and Human Disease". In Astrid Sigel; Helmut Sigel; Roland K. O. Sigel (eds.). Interrelations between Essential Metal Ions and Human Diseases. Metal Ions in Life Sciences. Vol. 13. Springer. pp. 389–414. doi:10.1007/978-94-007-7500-8_12. ISBN 978-94-007-7499-5. PMID 24470098.
  4. ^ a b c d e f g h Prakash A, Bharti K, Majeed AB (April 2015). "Zinc: indications in brain disorders". Fundam Clin Pharmacol. 29 (2): 131–149. doi:10.1111/fcp.12110. PMID 25659970. S2CID 21141511.
  5. ^ a b c d e f g h Cherasse Y, Urade Y (November 2017). "Dietary Zinc Acts as a Sleep Modulator". International Journal of Molecular Sciences. 18 (11): 2334. doi:10.3390/ijms18112334. PMC 5713303. PMID 29113075. Zinc is the second most abundant trace metal in the human body, and is essential for many biological processes.  ... The trace metal zinc is an essential cofactor for more than 300 enzymes and 1000 transcription factors [16]. ... In the central nervous system, zinc is the second most abundant trace metal and is involved in many processes. In addition to its role in enzymatic activity, it also plays a major role in cell signaling and modulation of neuronal activity.
  6. ^ a b Prasad A. S. (2008). "Zinc in Human Health: Effect of Zinc on Immune Cells". Mol. Med. 14 (5–6): 353–7. doi:10.2119/2008-00033.Prasad. PMC 2277319. PMID 18385818.
  7. ^ a b c d e f g h Broadley, M. R.; White, P. J.; Hammond, J. P.; Zelko I.; Lux A. (2007). "Zinc in plants". New Phytologist. 173 (4): 677–702. doi:10.1111/j.1469-8137.2007.01996.x. PMID 17286818.
  8. ^ a b Zinc's role in microorganisms is particularly reviewed in: Sugarman B (1983). "Zinc and infection". Reviews of Infectious Diseases. 5 (1): 137–47. doi:10.1093/clinids/5.1.137. PMID 6338570.
  9. ^ a b c d e Hambidge, K. M. & Krebs, N. F. (2007). "Zinc deficiency: a special challenge". J. Nutr. 137 (4): 1101–5. doi:10.1093/jn/137.4.1101. PMID 17374687.
  10. ^ Xiao, Hangfang; Deng, Wenfeng; Wei, Gangjian; Chen, Jiubin; Zheng, Xinqing; Shi, Tuo; Chen, Xuefei; Wang, Chenying; Liu, Xi (October 30, 2020). "A Pilot Study on Zinc Isotopic Compositions in Shallow-Water Coral Skeletons". Geochemistry, Geophysics, Geosystems. 21 (11). Bibcode:2020GGG....2109430X. doi:10.1029/2020GC009430. S2CID 228975484.
  11. ^ a b c d Prasad, AS (2003). "Zinc deficiency : Has been known of for 40 years but ignored by global health organisations". British Medical Journal. 326 (7386): 409–410. doi:10.1136/bmj.326.7386.409. PMC 1125304. PMID 12595353.
  12. ^ Maret, Wolfgang (2013). "Chapter 14 Zinc and the Zinc Proteome". In Banci, Lucia (ed.). Metallomics and the Cell. Metal Ions in Life Sciences. Vol. 12. Springer. pp. 479–501. doi:10.1007/978-94-007-5561-1_14. ISBN 978-94-007-5561-1. PMID 23595681.
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February 08, 2023
zinc, this, article, about, chemical, element, other, uses, disambiguation, chemical, element, with, symbol, atomic, number, slightly, brittle, metal, room, temperature, shiny, greyish, appearance, when, oxidation, removed, first, element, group, periodic, tab. This article is about the chemical element For other uses see Zinc disambiguation Zinc is a chemical element with the symbol Zn and atomic number 30 Zinc is a slightly brittle metal at room temperature and has a shiny greyish appearance when oxidation is removed It is the first element in group 12 IIB of the periodic table In some respects zinc is chemically similar to magnesium both elements exhibit only one normal oxidation state 2 and the Zn2 and Mg2 ions are of similar size note 1 Zinc is the 24th most abundant element in Earth s crust and has five stable isotopes The most common zinc ore is sphalerite zinc blende a zinc sulfide mineral The largest workable lodes are in Australia Asia and the United States Zinc is refined by froth flotation of the ore roasting and final extraction using electricity electrowinning Zinc 30ZnZincAppearancesilver grayStandard atomic weight Ar Zn 65 38 0 0265 38 0 02 abridged 1 Zinc in the periodic tableHydrogen HeliumLithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine NeonSodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine ArgonPotassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine KryptonRubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine XenonCaesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury element Thallium Lead Bismuth Polonium Astatine RadonFrancium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson Zn Cdcopper zinc galliumAtomic number Z 30Groupgroup 12Periodperiod 4Block d blockElectron configuration Ar 3d10 4s2Electrons per shell2 8 18 2Physical propertiesPhase at STPsolidMelting point692 68 K 419 53 C 787 15 F Boiling point1180 K 907 C 1665 F Density near r t 7 14 g cm3when liquid at m p 6 57 g cm3Heat of fusion7 32 kJ molHeat of vaporization115 kJ molMolar heat capacity25 470 J mol K Vapor pressureP Pa 1 10 100 1 k 10 k 100 kat T K 610 670 750 852 990 1179Atomic propertiesOxidation states 2 0 1 2 an amphoteric oxide ElectronegativityPauling scale 1 65Ionization energies1st 906 4 kJ mol2nd 1733 3 kJ mol3rd 3833 kJ mol more Atomic radiusempirical 134 pmCovalent radius122 4 pmVan der Waals radius139 pmSpectral lines of zincOther propertiesNatural occurrenceprimordialCrystal structure hexagonal close packed hcp Speed of sound thin rod3850 m s at r t rolled Thermal expansion30 2 µm m K at 25 C Thermal conductivity116 W m K Electrical resistivity59 0 nW m at 20 C Magnetic orderingdiamagneticMolar magnetic susceptibility 11 4 10 6 cm3 mol 298 K 2 Young s modulus108 GPaShear modulus43 GPaBulk modulus70 GPaPoisson ratio0 25Mohs hardness2 5Brinell hardness327 412 MPaCAS Number7440 66 6HistoryDiscoveryIndian metallurgists before 1000 BCE First isolationAndreas Sigismund Marggraf 1746 Recognized as a unique metal byRasaratna Samuccaya 1300 Main isotopes of zincveIso tope Decayabun dance half life t1 2 mode pro duct64Zn 49 2 stable65Zn syn 244 d e 65Cug 66Zn 27 7 stable67Zn 4 0 stable68Zn 18 5 stable69Zn syn 56 min b 69Ga69mZn syn 13 8 h b 69Ga70Zn 0 6 stable71Zn syn 2 4 min b 71Ga71mZn syn 4 h b 71Ga72Zn syn 46 5 h b 72Ga Category Zincviewtalkedit referencesZinc is an essential trace element for humans 3 4 5 animals 6 plants 7 and for microorganisms 8 and is necessary for prenatal and postnatal development 9 It is the second most abundant trace metal in humans after iron and it is the only metal which appears in all enzyme classes 7 5 Zinc is also an essential nutrient element for coral growth as it is an important cofactor for many enzymes 10 Zinc deficiency affects about two billion people in the developing world and is associated with many diseases 11 In children deficiency causes growth retardation delayed sexual maturation infection susceptibility and diarrhea 9 Enzymes with a zinc atom in the reactive center are widespread in biochemistry such as alcohol dehydrogenase in humans 12 Consumption of excess zinc may cause ataxia lethargy and copper deficiency Brass an alloy of copper and zinc in various proportions was used as early as the third millennium BC in the Aegean area and the region which currently includes Iraq the United Arab Emirates Kalmykia Turkmenistan and Georgia In the second millennium BC it was used in the regions currently including West India Uzbekistan Iran Syria Iraq and Israel 13 14 15 Zinc metal was not produced on a large scale until the 12th century in India though it was known to the ancient Romans and Greeks 16 The mines of Rajasthan have given definite evidence of zinc production going back to the 6th century BC 17 To date the oldest evidence of pure zinc comes from Zawar in Rajasthan as early as the 9th century AD when a distillation process was employed to make pure zinc 18 Alchemists burned zinc in air to form what they called philosopher s wool or white snow The element was probably named by the alchemist Paracelsus after the German word Zinke prong tooth German chemist Andreas Sigismund Marggraf is credited with discovering pure metallic zinc in 1746 Work by Luigi Galvani and Alessandro Volta uncovered the electrochemical properties of zinc by 1800 Corrosion resistant zinc plating of iron hot dip galvanizing is the major application for zinc Other applications are in electrical batteries small non structural castings and alloys such as brass A variety of zinc compounds are commonly used such as zinc carbonate and zinc gluconate as dietary supplements zinc chloride in deodorants zinc pyrithione anti dandruff shampoos zinc sulfide in luminescent paints and dimethylzinc or diethylzinc in the organic laboratory Contents 1 Characteristics 1 1 Physical properties 1 2 Occurrence 1 3 Isotopes 2 Compounds and chemistry 2 1 Reactivity 2 2 Zinc I compounds 2 3 Zinc II compounds 2 4 Test for zinc 3 History 3 1 Ancient use 3 2 Early studies and naming 3 3 Isolation 3 4 Later work 4 Production 4 1 Mining and processing 4 2 Environmental impact 5 Applications 5 1 Anti corrosion and batteries 5 2 Alloys 5 3 Other industrial uses 5 4 Organic chemistry 5 5 Dietary supplement 5 5 1 Gastroenteritis 5 5 2 Common cold 5 5 3 Weight gain 5 5 4 Other 5 6 Topical use 6 Biological role 6 1 Enzymes 6 2 Signalling 6 3 Other proteins 6 4 Nutrition 6 4 1 Dietary recommendations 6 4 2 Dietary intake 6 5 Deficiency 6 6 Soil remediation 6 7 Agriculture 7 Precautions 7 1 Toxicity 7 2 Poisoning 8 See also 9 Notes 10 Citations 11 Bibliography 12 External linksCharacteristics EditPhysical properties Edit Zinc is a bluish white lustrous diamagnetic metal 19 though most common commercial grades of the metal have a dull finish 20 It is somewhat less dense than iron and has a hexagonal crystal structure with a distorted form of hexagonal close packing in which each atom has six nearest neighbors at 265 9 pm in its own plane and six others at a greater distance of 290 6 pm 21 The metal is hard and brittle at most temperatures but becomes malleable between 100 and 150 C 19 20 Above 210 C the metal becomes brittle again and can be pulverized by beating 22 Zinc is a fair conductor of electricity 19 For a metal zinc has relatively low melting 419 5 C and boiling point 907 C 23 The melting point is the lowest of all the d block metals aside from mercury and cadmium for this reason among others zinc cadmium and mercury are often not considered to be transition metals like the rest of the d block metals 23 Many alloys contain zinc including brass Other metals long known to form binary alloys with zinc are aluminium antimony bismuth gold iron lead mercury silver tin magnesium cobalt nickel tellurium and sodium 24 Although neither zinc nor zirconium is ferromagnetic their alloy ZrZn2 exhibits ferromagnetism below 35 K 19 Occurrence Edit See also Zinc minerals Zinc makes up about 75 ppm 0 0075 of Earth s crust making it the 24th most abundant element Typical background concentrations of zinc do not exceed 1 mg m3 in the atmosphere 300 mg kg in soil 100 mg kg in vegetation 20 mg L in freshwater and 5 mg L in seawater 25 The element is normally found in association with other base metals such as copper and lead in ores 26 Zinc is a chalcophile meaning the element is more likely to be found in minerals together with sulfur and other heavy chalcogens rather than with the light chalcogen oxygen or with non chalcogen electronegative elements such as the halogens Sulfides formed as the crust solidified under the reducing conditions of the early Earth s atmosphere 27 Sphalerite which is a form of zinc sulfide is the most heavily mined zinc containing ore because its concentrate contains 60 62 zinc 26 Other source minerals for zinc include smithsonite zinc carbonate hemimorphite zinc silicate wurtzite another zinc sulfide and sometimes hydrozincite basic zinc carbonate 28 With the exception of wurtzite all these other minerals were formed by weathering of the primordial zinc sulfides 27 Identified world zinc resources total about 1 9 2 8 billion tonnes 29 30 Large deposits are in Australia Canada and the United States with the largest reserves in Iran 27 31 32 The most recent estimate of reserve base for zinc meets specified minimum physical criteria related to current mining and production practices was made in 2009 and calculated to be roughly 480 Mt 33 Zinc reserves on the other hand are geologically identified ore bodies whose suitability for recovery is economically based location grade quality and quantity at the time of determination Since exploration and mine development is an ongoing process the amount of zinc reserves is not a fixed number and sustainability of zinc ore supplies cannot be judged by simply extrapolating the combined mine life of today s zinc mines This concept is well supported by data from the United States Geological Survey USGS which illustrates that although refined zinc production increased 80 between 1990 and 2010 the reserve lifetime for zinc has remained unchanged About 346 million tonnes have been extracted throughout history to 2002 and scholars have estimated that about 109 305 million tonnes are in use 34 35 36 Sphalerite ZnS Isotopes Edit Main article Isotopes of zinc Five stable isotopes of zinc occur in nature with 64Zn being the most abundant isotope 49 17 natural abundance 37 38 The other isotopes found in nature are 66 Zn 27 73 67 Zn 4 04 68 Zn 18 45 and 70 Zn 0 61 38 Several dozen radioisotopes have been characterized 65 Zn which has a half life of 243 66 days is the least active radioisotope followed by 72 Zn with a half life of 46 5 hours 37 Zinc has 10 nuclear isomers of which 69mZn has the longest half life 13 76 h 37 The superscript m indicates a metastable isotope The nucleus of a metastable isotope is in an excited state and will return to the ground state by emitting a photon in the form of a gamma ray 61 Zn has three excited metastable states and 73 Zn has two 39 The isotopes 65 Zn 71 Zn 77 Zn and 78 Zn each have only one excited metastable state 37 The most common decay mode of a radioisotope of zinc with a mass number lower than 66 is electron capture The decay product resulting from electron capture is an isotope of copper 37 n30 Zn e n29 CuThe most common decay mode of a radioisotope of zinc with mass number higher than 66 is beta decay b which produces an isotope of gallium 37 n30 Zn n31 Ga e n eCompounds and chemistry EditMain article Compounds of zinc Reactivity Edit See also Clemmensen reduction Zinc has an electron configuration of Ar 3d104s2 and is a member of the group 12 of the periodic table It is a moderately reactive metal and strong reducing agent 40 The surface of the pure metal tarnishes quickly eventually forming a protective passivating layer of the basic zinc carbonate Zn5 OH 6 CO3 2 by reaction with atmospheric carbon dioxide 41 Zinc burns in air with a bright bluish green flame giving off fumes of zinc oxide 42 Zinc reacts readily with acids alkalis and other non metals 43 Extremely pure zinc reacts only slowly at room temperature with acids 42 Strong acids such as hydrochloric or sulfuric acid can remove the passivating layer and the subsequent reaction with the acid releases hydrogen gas 42 The chemistry of zinc is dominated by the 2 oxidation state When compounds in this oxidation state are formed the outer shell s electrons are lost yielding a bare zinc ion with the electronic configuration Ar 3d10 44 In aqueous solution an octahedral complex Zn H2 O 6 2 is the predominant species 45 The volatilization of zinc in combination with zinc chloride at temperatures above 285 C indicates the formation of Zn2 Cl2 a zinc compound with a 1 oxidation state 42 No compounds of zinc in positive oxidation states other than 1 or 2 are known 46 Calculations indicate that a zinc compound with the oxidation state of 4 is unlikely to exist 47 Zn III is predicted to exist in the presence of strongly electronegative trianions 48 however there exists some doubt around this possibility 49 But in 2021 another compound was reported with more evidence that had the oxidation state of 3 with the formula ZnBeB11 CN 12 50 Zinc chemistry is similar to the chemistry of the late first row transition metals nickel and copper though it has a filled d shell and compounds are diamagnetic and mostly colorless 51 The ionic radii of zinc and magnesium happen to be nearly identical Because of this some of the equivalent salts have the same crystal structure 52 and in other circumstances where ionic radius is a determining factor the chemistry of zinc has much in common with that of magnesium 42 In other respects there is little similarity with the late first row transition metals Zinc tends to form bonds with a greater degree of covalency and much more stable complexes with N and S donors 51 Complexes of zinc are mostly 4 or 6 coordinate although 5 coordinate complexes are known 42 Zinc I compounds Edit Zinc I compounds are very rare The Zn2 2 ion is implicated by the formation of a yellow diamagnetic glass by dissolving metallic zinc in molten ZnCl2 53 The Zn2 2 core would be analogous to the Hg2 2 cation present in mercury I compounds The diamagnetic nature of the ion confirms its dimeric structure The first zinc I compound containing the Zn Zn bond h5 C5Me5 2Zn2 Zinc II compounds Edit Zinc acetate Zinc chloride Binary compounds of zinc are known for most of the metalloids and all the nonmetals except the noble gases The oxide ZnO is a white powder that is nearly insoluble in neutral aqueous solutions but is amphoteric dissolving in both strong basic and acidic solutions 42 The other chalcogenides ZnS ZnSe and ZnTe have varied applications in electronics and optics 54 Pnictogenides Zn3 N2 Zn3 P2 Zn3 As2 and Zn3 Sb2 55 56 the peroxide ZnO2 the hydride ZnH2 and the carbide ZnC2 are also known 57 Of the four halides ZnF2 has the most ionic character while the others ZnCl2 ZnBr2 and ZnI2 have relatively low melting points and are considered to have more covalent character 58 In weak basic solutions containing Zn2 ions the hydroxide Zn OH 2 forms as a white precipitate In stronger alkaline solutions this hydroxide is dissolved to form zincates Zn OH 4 2 42 The nitrate Zn NO3 2 chlorate Zn ClO3 2 sulfate ZnSO4 phosphate Zn3 PO4 2 molybdate ZnMoO4 cyanide Zn CN 2 arsenite Zn AsO2 2 arsenate Zn AsO4 2 8H2 O and the chromate ZnCrO4 one of the few colored zinc compounds are a few examples of other common inorganic compounds of zinc 59 60 Organozinc compounds are those that contain zinc carbon covalent bonds Diethylzinc C2 H5 2 Zn is a reagent in synthetic chemistry It was first reported in 1848 from the reaction of zinc and ethyl iodide and was the first compound known to contain a metal carbon sigma bond 61 Test for zinc Edit Cobalticyanide paper Rinnmann s test for Zn can be used as a chemical indicator for zinc 4 g of K3Co CN 6 and 1 g of KClO3 is dissolved on 100 ml of water Paper is dipped in the solution and dried at 100 C One drop of the sample is dropped onto the dry paper and heated A green disc indicates the presence of zinc 62 History EditAncient use Edit The Charaka Samhita thought to have been written between 300 and 500 AD 63 mentions a metal which when oxidized produces pushpanjan thought to be zinc oxide 64 Zinc mines at Zawar near Udaipur in India have been active since the Mauryan period c 322 and 187 BCE The smelting of metallic zinc here however appears to have begun around the 12th century AD 65 66 One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries 28 Another estimate gives a total production of 60 000 tonnes of metallic zinc over this period 65 The Rasaratna Samuccaya written in approximately the 13th century AD mentions two types of zinc containing ores one used for metal extraction and another used for medicinal purposes 66 Late Roman brass bucket the Hemmoorer Eimer from Warstade Germany second to third century AD Various isolated examples of the use of impure zinc in ancient times have been discovered Zinc ores were used to make the zinc copper alloy brass thousands of years prior to the discovery of zinc as a separate element Judean brass from the 14th to 10th centuries BC contains 23 zinc 14 Knowledge of how to produce brass spread to Ancient Greece by the 7th century BC but few varieties were made 15 Ornaments made of alloys containing 80 90 zinc with lead iron antimony and other metals making up the remainder have been found that are 2 500 years old 26 A possibly prehistoric statuette containing 87 5 zinc was found in a Dacian archaeological site 67 The oldest known pills were made of the zinc carbonates hydrozincite and smithsonite The pills were used for sore eyes and were found aboard the Roman ship Relitto del Pozzino wrecked in 140 BC 68 69 The manufacture of brass was known to the Romans by about 30 BC 70 They made brass by heating powdered calamine zinc silicate or carbonate charcoal and copper together in a crucible 70 The resulting calamine brass was then either cast or hammered into shape for use in weaponry 71 Some coins struck by Romans in the Christian era are made of what is probably calamine brass 72 Strabo writing in the 1st century BC but quoting a now lost work of the 4th century BC historian Theopompus mentions drops of false silver which when mixed with copper make brass This may refer to small quantities of zinc that is a by product of smelting sulfide ores 73 Zinc in such remnants in smelting ovens was usually discarded as it was thought to be worthless 74 The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly zinc 75 Early studies and naming Edit Zinc was distinctly recognized as a metal under the designation of Yasada or Jasada in the medical Lexicon ascribed to the Hindu king Madanapala of Taka dynasty and written about the year 1374 76 Smelting and extraction of impure zinc by reducing calamine with wool and other organic substances was accomplished in the 13th century in India 19 77 The Chinese did not learn of the technique until the 17th century 77 Various alchemical symbols for the element zinc Alchemists burned zinc metal in air and collected the resulting zinc oxide on a condenser Some alchemists called this zinc oxide lana philosophica Latin for philosopher s wool because it collected in wooly tufts whereas others thought it looked like white snow and named it nix album 78 The name of the metal was probably first documented by Paracelsus a Swiss born German alchemist who referred to the metal as zincum or zinken in his book Liber Mineralium II in the 16th century 77 79 The word is probably derived from the German zinke and supposedly meant tooth like pointed or jagged metallic zinc crystals have a needle like appearance 80 Zink could also imply tin like because of its relation to German zinn meaning tin 81 Yet another possibility is that the word is derived from the Persian word سنگ seng meaning stone 82 The metal was also called Indian tin tutanego calamine and spinter 26 German metallurgist Andreas Libavius received a quantity of what he called calay of Malabar from a cargo ship captured from the Portuguese in the year 1596 83 Libavius described the properties of the sample which may have been zinc Zinc was regularly imported to Europe from the Orient in the 17th and early 18th centuries 77 but was at times very expensive note 2 Isolation Edit Andreas Sigismund Marggraf is given credit for first isolating pure zinc Metallic zinc was isolated in India by 1300 AD 84 85 86 much earlier than in the West Before it was isolated in Europe it was imported from India in about 1600 CE 87 Postlewayt s Universal Dictionary a contemporary source giving technological information in Europe did not mention zinc before 1751 but the element was studied before then 66 88 Flemish metallurgist and alchemist P M de Respour reported that he had extracted metallic zinc from zinc oxide in 1668 28 By the start of the 18th century Etienne Francois Geoffroy described how zinc oxide condenses as yellow crystals on bars of iron placed above zinc ore that is being smelted 28 In Britain John Lane is said to have carried out experiments to smelt zinc probably at Landore prior to his bankruptcy in 1726 89 In 1738 in Great Britain William Champion patented a process to extract zinc from calamine in a vertical retort style smelter 90 His technique resembled that used at Zawar zinc mines in Rajasthan but no evidence suggests he visited the Orient 87 Champion s process was used through 1851 77 German chemist Andreas Marggraf normally gets credit for discovering pure metallic zinc even though Swedish chemist Anton von Swab had distilled zinc from calamine four years previously 77 In his 1746 experiment Marggraf heated a mixture of calamine and charcoal in a closed vessel without copper to obtain a metal 91 74 This procedure became commercially practical by 1752 92 Later work Edit Galvanization was named after Luigi Galvani William Champion s brother John patented a process in 1758 for calcining zinc sulfide into an oxide usable in the retort process 26 Prior to this only calamine could be used to produce zinc In 1798 Johann Christian Ruberg improved on the smelting process by building the first horizontal retort smelter 93 Jean Jacques Daniel Dony built a different kind of horizontal zinc smelter in Belgium that processed even more zinc 77 Italian doctor Luigi Galvani discovered in 1780 that connecting the spinal cord of a freshly dissected frog to an iron rail attached by a brass hook caused the frog s leg to twitch 94 He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect animal electricity 95 The galvanic cell and the process of galvanization were both named for Luigi Galvani and his discoveries paved the way for electrical batteries galvanization and cathodic protection 95 Galvani s friend Alessandro Volta continued researching the effect and invented the Voltaic pile in 1800 94 Volta s pile consisted of a stack of simplified galvanic cells each being one plate of copper and one of zinc connected by an electrolyte By stacking these units in series the Voltaic pile or battery as a whole had a higher voltage which could be used more easily than single cells Electricity is produced because the Volta potential between the two metal plates makes electrons flow from the zinc to the copper and corrode the zinc 94 The non magnetic character of zinc and its lack of color in solution delayed discovery of its importance to biochemistry and nutrition 96 This changed in 1940 when carbonic anhydrase an enzyme that scrubs carbon dioxide from blood was shown to have zinc in its active site 96 The digestive enzyme carboxypeptidase became the second known zinc containing enzyme in 1955 96 Production EditMining and processing Edit Top zinc mine production output by countries 2019 29 Rank Country Tonnes1 China 4 210 0002 Peru 1 400 0003 Australia 1 330 0005 United States 753 0004 India 720 0006 Mexico 677 000Main articles Zinc mining and Zinc smelting See also List of countries by zinc production Price of Zinc Percentage of zinc output in 2006 by countries 97 World production trend Zinc Mine Rosh Pinah Namibia27 57 17 S 016 46 00 E 27 95472 S 16 76667 E 27 95472 16 76667 Rosh Pinah Zinc Mine Skorpion Namibia27 49 09 S 016 36 28 E 27 81917 S 16 60778 E 27 81917 16 60778 Skorpion Zinc is the fourth most common metal in use trailing only iron aluminium and copper with an annual production of about 13 million tonnes 29 The world s largest zinc producer is Nyrstar a merger of the Australian OZ Minerals and the Belgian Umicore 98 About 70 of the world s zinc originates from mining while the remaining 30 comes from recycling secondary zinc 99 Commercially pure zinc is known as Special High Grade often abbreviated SHG and is 99 995 pure 100 Worldwide 95 of new zinc is mined from sulfidic ore deposits in which sphalerite ZnS is nearly always mixed with the sulfides of copper lead and iron 101 6 Zinc mines are scattered throughout the world with the main areas being China Australia and Peru China produced 38 of the global zinc output in 2014 29 Zinc metal is produced using extractive metallurgy 102 7 The ore is finely ground then put through froth flotation to separate minerals from gangue on the property of hydrophobicity to get a zinc sulfide ore concentrate 102 16 consisting of about 50 zinc 32 sulfur 13 iron and 5 SiO2 102 16 Roasting converts the zinc sulfide concentrate to zinc oxide 101 2 ZnS 3 O 2 t o 2 ZnO 2 SO 2 displaystyle ce 2ZnS 3O2 gt t o 2ZnO 2SO2 The sulfur dioxide is used for the production of sulfuric acid which is necessary for the leaching process If deposits of zinc carbonate zinc silicate or zinc spinel like the Skorpion Deposit in Namibia are used for zinc production the roasting can be omitted 103 For further processing two basic methods are used pyrometallurgy or electrowinning Pyrometallurgy reduces zinc oxide with carbon or carbon monoxide at 950 C 1 740 F into the metal which is distilled as zinc vapor to separate it from other metals which are not volatile at those temperatures 104 The zinc vapor is collected in a condenser 101 The equations below describe this process 101 ZnO C 950 o C Zn CO displaystyle ce ZnO C gt 950 oC Zn CO ZnO CO 950 o C Zn CO 2 displaystyle ce ZnO CO gt 950 oC Zn CO2 In electrowinning zinc is leached from the ore concentrate by sulfuric acid and impurities are precipitated 105 ZnO H 2 SO 4 ZnSO 4 H 2 O displaystyle ce ZnO H2SO4 gt ZnSO4 H2O Finally the zinc is reduced by electrolysis 101 2 ZnSO 4 2 H 2 O 2 Zn O 2 2 H 2 SO 4 displaystyle ce 2ZnSO4 2H2O gt 2Zn O2 2H2SO4 The sulfuric acid is regenerated and recycled to the leaching step When galvanised feedstock is fed to an electric arc furnace the zinc is recovered from the dust by a number of processes predominantly the Waelz process 90 as of 2014 106 Environmental impact Edit Refinement of sulfidic zinc ores produces large volumes of sulfur dioxide and cadmium vapor Smelter slag and other residues contain significant quantities of metals About 1 1 million tonnes of metallic zinc and 130 thousand tonnes of lead were mined and smelted in the Belgian towns of La Calamine and Plombieres between 1806 and 1882 107 The dumps of the past mining operations leach zinc and cadmium and the sediments of the Geul River contain non trivial amounts of metals 107 About two thousand years ago emissions of zinc from mining and smelting totaled 10 thousand tonnes a year After increasing 10 fold from 1850 zinc emissions peaked at 3 4 million tonnes per year in the 1980s and declined to 2 7 million tonnes in the 1990s although a 2005 study of the Arctic troposphere found that the concentrations there did not reflect the decline Man made and natural emissions occur at a ratio of 20 to 1 7 Zinc in rivers flowing through industrial and mining areas can be as high as 20 ppm 108 Effective sewage treatment greatly reduces this treatment along the Rhine for example has decreased zinc levels to 50 ppb 108 Concentrations of zinc as low as 2 ppm adversely affects the amount of oxygen that fish can carry in their blood 109 Historically responsible for high metal levels in the Derwent River 110 the zinc works at Lutana is the largest exporter in Tasmania generating 2 5 of the state s GDP and producing more than 250 000 tonnes of zinc per year 111 Soils contaminated with zinc from mining refining or fertilizing with zinc bearing sludge can contain several grams of zinc per kilogram of dry soil Levels of zinc in excess of 500 ppm in soil interfere with the ability of plants to absorb other essential metals such as iron and manganese Zinc levels of 2000 ppm to 180 000 ppm 18 have been recorded in some soil samples 108 Applications EditMajor applications of zinc include numbers are given for the US 112 Galvanizing 55 Brass and bronze 16 Other alloys 21 Miscellaneous 8 Anti corrosion and batteries Edit Hot dip handrail galvanized crystalline surface Zinc is most commonly used as an anti corrosion agent 113 and galvanization coating of iron or steel is the most familiar form In 2009 in the United States 55 or 893 000 tons of the zinc metal was used for galvanization 112 Zinc is more reactive than iron or steel and thus will attract almost all local oxidation until it completely corrodes away 114 A protective surface layer of oxide and carbonate Zn5 OH 6 CO3 2 forms as the zinc corrodes 115 This protection lasts even after the zinc layer is scratched but degrades through time as the zinc corrodes away 115 The zinc is applied electrochemically or as molten zinc by hot dip galvanizing or spraying Galvanization is used on chain link fencing guard rails suspension bridges lightposts metal roofs heat exchangers and car bodies 116 The relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient sacrificial anode in cathodic protection CP For example cathodic protection of a buried pipeline can be achieved by connecting anodes made from zinc to the pipe 115 Zinc acts as the anode negative terminus by slowly corroding away as it passes electric current to the steel pipeline 115 note 3 Zinc is also used to cathodically protect metals that are exposed to sea water 117 A zinc disc attached to a ship s iron rudder will slowly corrode while the rudder stays intact 114 Similarly a zinc plug attached to a propeller or the metal protective guard for the keel of the ship provides temporary protection With a standard electrode potential SEP of 0 76 volts zinc is used as an anode material for batteries More reactive lithium SEP 3 04 V is used for anodes in lithium batteries Powdered zinc is used in this way in alkaline batteries and the case which also serves as the anode of zinc carbon batteries is formed from sheet zinc 118 119 Zinc is used as the anode or fuel of the zinc air battery fuel cell 120 121 122 The zinc cerium redox flow battery also relies on a zinc based negative half cell 123 Alloys Edit A widely used zinc alloy is brass in which copper is alloyed with anywhere from 3 to 45 zinc depending upon the type of brass 115 Brass is generally more ductile and stronger than copper and has superior corrosion resistance 115 These properties make it useful in communication equipment hardware musical instruments and water valves 115 Cast brass microstructure at magnification 400x Other widely used zinc alloys include nickel silver typewriter metal soft and aluminium solder and commercial bronze 19 Zinc is also used in contemporary pipe organs as a substitute for the traditional lead tin alloy in pipes 124 Alloys of 85 88 zinc 4 10 copper and 2 8 aluminium find limited use in certain types of machine bearings Zinc has been the primary metal in American one cent coins pennies since 1982 125 The zinc core is coated with a thin layer of copper to give the appearance of a copper coin In 1994 33 200 tonnes 36 600 short tons of zinc were used to produce 13 6 billion pennies in the United States 126 Alloys of zinc with small amounts of copper aluminium and magnesium are useful in die casting as well as spin casting especially in the automotive electrical and hardware industries 19 These alloys are marketed under the name Zamak 127 An example of this is zinc aluminium The low melting point together with the low viscosity of the alloy makes possible the production of small and intricate shapes The low working temperature leads to rapid cooling of the cast products and fast production for assembly 19 128 Another alloy marketed under the brand name Prestal contains 78 zinc and 22 aluminium and is reported to be nearly as strong as steel but as malleable as plastic 19 129 This superplasticity of the alloy allows it to be molded using die casts made of ceramics and cement 19 Similar alloys with the addition of a small amount of lead can be cold rolled into sheets An alloy of 96 zinc and 4 aluminium is used to make stamping dies for low production run applications for which ferrous metal dies would be too expensive 130 For building facades roofing and other applications for sheet metal formed by deep drawing roll forming or bending zinc alloys with titanium and copper are used 131 Unalloyed zinc is too brittle for these manufacturing processes 131 As a dense inexpensive easily worked material zinc is used as a lead replacement In the wake of lead concerns zinc appears in weights for various applications ranging from fishing 132 to tire balances and flywheels 133 Cadmium zinc telluride CZT is a semiconductive alloy that can be divided into an array of small sensing devices 134 These devices are similar to an integrated circuit and can detect the energy of incoming gamma ray photons 134 When behind an absorbing mask the CZT sensor array can determine the direction of the rays 134 Other industrial uses Edit Zinc oxide is used as a white pigment in paints Roughly one quarter of all zinc output in the United States in 2009 was consumed in zinc compounds 112 a variety of which are used industrially Zinc oxide is widely used as a white pigment in paints and as a catalyst in the manufacture of rubber to disperse heat Zinc oxide is used to protect rubber polymers and plastics from ultraviolet radiation UV 116 The semiconductor properties of zinc oxide make it useful in varistors and photocopying products 135 The zinc zinc oxide cycle is a two step thermochemical process based on zinc and zinc oxide for hydrogen production 136 Zinc chloride is often added to lumber as a fire retardant 137 and sometimes as a wood preservative 138 It is used in the manufacture of other chemicals 137 Zinc methyl Zn CH3 2 is used in a number of organic syntheses 139 Zinc sulfide ZnS is used in luminescent pigments such as on the hands of clocks X ray and television screens and luminous paints 140 Crystals of ZnS are used in lasers that operate in the mid infrared part of the spectrum 141 Zinc sulfate is a chemical in dyes and pigments 137 Zinc pyrithione is used in antifouling paints 142 Zinc powder is sometimes used as a propellant in model rockets 143 When a compressed mixture of 70 zinc and 30 sulfur powder is ignited there is a violent chemical reaction 143 This produces zinc sulfide together with large amounts of hot gas heat and light 143 Zinc sheet metal is used as a durable covering for roofs walls and countertops the last often seen in bistros and oyster bars and is known for the rustic look imparted by its surface oxidation in use to a blue gray patina and susceptibility to scratching 144 145 146 147 64 Zn the most abundant isotope of zinc is very susceptible to neutron activation being transmuted into the highly radioactive 65 Zn which has a half life of 244 days and produces intense gamma radiation Because of this zinc oxide used in nuclear reactors as an anti corrosion agent is depleted of 64 Zn before use this is called depleted zinc oxide For the same reason zinc has been proposed as a salting material for nuclear weapons cobalt is another better known salting material 148 A jacket of isotopically enriched 64 Zn would be irradiated by the intense high energy neutron flux from an exploding thermonuclear weapon forming a large amount of 65 Zn significantly increasing the radioactivity of the weapon s fallout 148 Such a weapon is not known to have ever been built tested or used 148 65 Zn is used as a tracer to study how alloys that contain zinc wear out or the path and the role of zinc in organisms 149 Zinc dithiocarbamate complexes are used as agricultural fungicides these include Zineb Metiram Propineb and Ziram 150 Zinc naphthenate is used as wood preservative 151 Zinc in the form of ZDDP is used as an anti wear additive for metal parts in engine oil 152 Organic chemistry Edit Addition of diphenylzinc to an aldehyde Organozinc chemistry is the science of compounds that contain carbon zinc bonds describing the physical properties synthesis and chemical reactions Many organozinc compounds are important 153 154 155 156 Among important applications are The Frankland Duppa Reaction in which an oxalate ester ROCOCOOR reacts with an alkyl halide R X zinc and hydrochloric acid to form the a hydroxycarboxylic esters RR COHCOOR 157 158 On the downside organozincs are much less nucleophilic than Grignards and they are expensive and difficult to handle Commercially available diorganozinc compounds are dimethylzinc diethylzinc and diphenylzinc In one study 159 160 the active organozinc compound is obtained from much cheaper organobromine precursors Zinc has found many uses as a catalyst in organic synthesis including asymmetric synthesis being cheap and easily available alternative to precious metal complexes The results yield and enantiomeric excess obtained with chiral zinc catalysts are comparable to those achieved with palladium ruthenium iridium and others and zinc becomes a metal catalyst of choice 161 Dietary supplement Edit GNC zinc 50 mg tablets The amount exceeds what is deemed the safe upper limit in the United States 40 mg and European Union 25 mg Zinc gluconate is one compound used for the delivery of zinc as a dietary supplement See also Zinc sulfate medical use and Zinc gluconate In most single tablet over the counter daily vitamin and mineral supplements zinc is included in such forms as zinc oxide zinc acetate zinc gluconate or zinc amino acid chelate 162 163 Generally zinc supplement is recommended where there is high risk of zinc deficiency such as low and middle income countries as a preventive measure 164 Although zinc sulfate is a commonly used zinc form zinc citrate gluconate and picolinate may be valid options as well These forms are better absorbed than zinc oxide 165 Gastroenteritis Edit Zinc is an inexpensive and effective part of treatment of diarrhea among children in the developing world Zinc becomes depleted in the body during diarrhea and replenishing zinc with a 10 to 14 day course of treatment can reduce the duration and severity of diarrheal episodes and may also prevent future episodes for as long as three months 166 Gastroenteritis is strongly attenuated by ingestion of zinc possibly by direct antimicrobial action of the ions in the gastrointestinal tract or by the absorption of the zinc and re release from immune cells all granulocytes secrete zinc or both 167 168 Common cold Edit This section is an excerpt from Zinc and the common cold edit Zinc supplements frequently zinc acetate or zinc gluconate lozenges are a group of dietary supplements that are commonly used for the treatment of the common cold 169 The use of zinc supplements at doses in excess of 75 mg day within 24 hours of the onset of symptoms has been shown to reduce the duration of cold symptoms by about 1 day in adults 169 170 Adverse effects with zinc supplements by mouth include bad taste and nausea 169 170 The intranasal use of zinc containing nasal sprays has been associated with the loss of the sense of smell 169 consequently in June 2009 the United States Food and Drug Administration USFDA warned consumers to stop using intranasal zinc 169 The human rhinovirus the most common viral pathogen in humans is the predominant cause of the common cold 171 The hypothesized mechanism of action by which zinc reduces the severity and or duration of cold symptoms is the suppression of nasal inflammation and the direct inhibition of rhinoviral receptor binding and rhinoviral replication in the nasal mucosa 169 Weight gain Edit See also Zinc deficiency Appetite Zinc deficiency may lead to loss of appetite 172 The use of zinc in the treatment of anorexia has been advocated since 1979 At least 15 clinical trials have shown that zinc improved weight gain in anorexia A 1994 trial showed that zinc doubled the rate of body mass increase in the treatment of anorexia nervosa Deficiency of other nutrients such as tyrosine tryptophan and thiamine could contribute to this phenomenon of malnutrition induced malnutrition 173 A meta analysis of 33 prospective intervention trials regarding zinc supplementation and its effects on the growth of children in many countries showed that zinc supplementation alone had a statistically significant effect on linear growth and body weight gain indicating that other deficiencies that may have been present were not responsible for growth retardation 174 Other Edit A Cochrane review stated that people taking zinc supplement may be less likely to progress to age related macular degeneration 175 Zinc supplement is an effective treatment for acrodermatitis enteropathica a genetic disorder affecting zinc absorption that was previously fatal to affected infants 70 Zinc deficiency has been associated with major depressive disorder MDD and zinc supplements may be an effective treatment 176 Zinc may help individuals sleep more 5 Topical use Edit Further information Zinc oxide Medicine Topical preparations of zinc include those used on the skin often in the form of zinc oxide Zinc oxide is generally recognised by the FDA as safe and effective 177 and is considered a very photo stable 178 Zinc oxide is one of the most common active ingredients formulated into a sunscreen to mitigate sunburn 70 Applied thinly to a baby s diaper area perineum with each diaper change it can protect against diaper rash 70 Chelated zinc is used in toothpastes and mouthwashes to prevent bad breath zinc citrate helps reduce the build up of calculus tartar 179 180 Zinc pyrithione is widely included in shampoos to prevent dandruff 181 Topical zinc has also been shown to effectively treat as well as prolong remission in genital herpes 182 Biological role EditMain article Zinc in biology Zinc is an essential trace element for humans 3 4 5 and other animals 6 for plants 7 and for microorganisms 8 Zinc is required for the function of over 300 enzymes and 1000 transcription factors 5 and is stored and transferred in metallothioneins 183 184 It is the second most abundant trace metal in humans after iron and it is the only metal which appears in all enzyme classes 7 5 In proteins zinc ions are often coordinated to the amino acid side chains of aspartic acid glutamic acid cysteine and histidine The theoretical and computational description of this zinc binding in proteins as well as that of other transition metals is difficult 185 Roughly 2 4 grams of zinc 186 are distributed throughout the human body Most zinc is in the brain muscle bones kidney and liver with the highest concentrations in the prostate and parts of the eye 187 Semen is particularly rich in zinc a key factor in prostate gland function and reproductive organ growth 188 Zinc homeostasis of the body is mainly controlled by the intestine Here ZIP4 and especially TRPM7 were linked to intestinal zinc uptake essential for postnatal survival 189 190 In humans the biological roles of zinc are ubiquitous 9 4 It interacts with a wide range of organic ligands 9 and has roles in the metabolism of RNA and DNA signal transduction and gene expression It also regulates apoptosis A review from 2015 indicated that about 10 of human proteins 3000 bind zinc 191 in addition to hundreds more that transport and traffic zinc a similar in silico study in the plant Arabidopsis thaliana found 2367 zinc related proteins 7 In the brain zinc is stored in specific synaptic vesicles by glutamatergic neurons and can modulate neuronal excitability 4 5 192 It plays a key role in synaptic plasticity and so in learning 4 193 Zinc homeostasis also plays a critical role in the functional regulation of the central nervous system 4 192 5 Dysregulation of zinc homeostasis in the central nervous system that results in excessive synaptic zinc concentrations is believed to induce neurotoxicity through mitochondrial oxidative stress e g by disrupting certain enzymes involved in the electron transport chain including complex I complex III and a ketoglutarate dehydrogenase the dysregulation of calcium homeostasis glutamatergic neuronal excitotoxicity and interference with intraneuronal signal transduction 4 194 L and D histidine facilitate brain zinc uptake 195 SLC30A3 is the primary zinc transporter involved in cerebral zinc homeostasis 4 Enzymes Edit Ribbon diagram of human carbonic anhydrase II with zinc atom visible in the center Zinc fingers help read DNA sequences Zinc is an efficient Lewis acid making it a useful catalytic agent in hydroxylation and other enzymatic reactions 196 The metal also has a flexible coordination geometry which allows proteins using it to rapidly shift conformations to perform biological reactions 197 Two examples of zinc containing enzymes are carbonic anhydrase and carboxypeptidase which are vital to the processes of carbon dioxide CO2 regulation and digestion of proteins respectively 198 In vertebrate blood carbonic anhydrase converts CO2 into bicarbonate and the same enzyme transforms the bicarbonate back into CO2 for exhalation through the lungs 199 Without this enzyme this conversion would occur about one million times slower 200 at the normal blood pH of 7 or would require a pH of 10 or more 201 The non related b carbonic anhydrase is required in plants for leaf formation the synthesis of indole acetic acid auxin and alcoholic fermentation 202 Carboxypeptidase cleaves peptide linkages during digestion of proteins A coordinate covalent bond is formed between the terminal peptide and a C O group attached to zinc which gives the carbon a positive charge This helps to create a hydrophobic pocket on the enzyme near the zinc which attracts the non polar part of the protein being digested 198 Signalling Edit Zinc has been recognized as a messenger able to activate signalling pathways Many of these pathways provide the driving force in aberrant cancer growth They can be targeted through ZIP transporters 203 Other proteins Edit Zinc serves a purely structural role in zinc fingers twists and clusters 204 Zinc fingers form parts of some transcription factors which are proteins that recognize DNA base sequences during the replication and transcription of DNA Each of the nine or ten Zn2 ions in a zinc finger helps maintain the finger s structure by coordinately binding to four amino acids in the transcription factor 200 In blood plasma zinc is bound to and transported by albumin 60 low affinity and transferrin 10 186 Because transferrin also transports iron excessive iron reduces zinc absorption and vice versa A similar antagonism exists with copper 205 The concentration of zinc in blood plasma stays relatively constant regardless of zinc intake 196 Cells in the salivary gland prostate immune system and intestine use zinc signaling to communicate with other cells 206 Zinc may be held in metallothionein reserves within microorganisms or in the intestines or liver of animals 207 Metallothionein in intestinal cells is capable of adjusting absorption of zinc by 15 40 208 However inadequate or excessive zinc intake can be harmful excess zinc particularly impairs copper absorption because metallothionein absorbs both metals 209 The human dopamine transporter contains a high affinity extracellular zinc binding site which upon zinc binding inhibits dopamine reuptake and amplifies amphetamine induced dopamine efflux in vitro 210 211 212 The human serotonin transporter and norepinephrine transporter do not contain zinc binding sites 212 Some EF hand calcium binding proteins such as S100 or NCS 1 are also able to bind zinc ions 213 Nutrition Edit Dietary recommendations Edit The U S Institute of Medicine IOM updated Estimated Average Requirements EARs and Recommended Dietary Allowances RDAs for zinc in 2001 The current EARs for zinc for women and men ages 14 and up is 6 8 and 9 4 mg day respectively The RDAs are 8 and 11 mg day RDAs are higher than EARs so as to identify amounts that will cover people with higher than average requirements RDA for pregnancy is 11 mg day RDA for lactation is 12 mg day For infants up to 12 months the RDA is 3 mg day For children ages 1 13 years the RDA increases with age from 3 to 8 mg day As for safety the IOM sets Tolerable upper intake levels ULs for vitamins and minerals when evidence is sufficient In the case of zinc the adult UL is 40 mg day lower for children Collectively the EARs RDAs AIs and ULs are referred to as Dietary Reference Intakes DRIs 196 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 are defined the same as in the United States For people ages 18 and older the PRI calculations are complex as the EFSA has set higher and higher values as the phytate content of the diet increases For women PRIs increase from 7 5 to 12 7 mg day as phytate intake increases from 300 to 1200 mg day for men the range is 9 4 to 16 3 mg day These PRIs are higher than the U S RDAs 214 The EFSA reviewed the same safety question and set its UL at 25 mg day which is much lower than the U S value 215 For U S food and dietary supplement labeling purposes the amount in a serving is expressed as a percent of Daily Value DV For zinc labeling purposes 100 of the Daily Value was 15 mg but on May 27 2016 it was revised to 11 mg 216 217 A table of the old and new adult daily values is provided at Reference Daily Intake Dietary intake Edit Foods and spices containing zinc Animal products such as meat fish shellfish fowl eggs and dairy contain zinc The concentration of zinc in plants varies with the level in the soil With adequate zinc in the soil the food plants that contain the most zinc are wheat germ and bran and various seeds including sesame poppy alfalfa celery and mustard 218 Zinc is also found in beans nuts almonds whole grains pumpkin seeds sunflower seeds and blackcurrant 219 Other sources include fortified food and dietary supplements in various forms A 1998 review concluded that zinc oxide one of the most common supplements in the United States and zinc carbonate are nearly insoluble and poorly absorbed in the body 220 This review cited studies that found lower plasma zinc concentrations in the subjects who consumed zinc oxide and zinc carbonate than in those who took zinc acetate and sulfate salts 220 For fortification however a 2003 review recommended cereals containing zinc oxide as a cheap stable source that is as easily absorbed as the more expensive forms 221 A 2005 study found that various compounds of zinc including oxide and sulfate did not show statistically significant differences in absorption when added as fortificants to maize tortillas 222 Deficiency Edit Main article Zinc deficiency Nearly two billion people in the developing world are deficient in zinc Groups at risk include children in developing countries and elderly with chronic illnesses 11 In children it causes an increase in infection and diarrhea and contributes to the death of about 800 000 children worldwide per year 9 The World Health Organization advocates zinc supplementation for severe malnutrition and diarrhea 223 Zinc supplements help prevent disease and reduce mortality especially among children with low birth weight or stunted growth 223 However zinc supplements should not be administered alone because many in the developing world have several deficiencies and zinc interacts with other micronutrients 224 While zinc deficiency is usually due to insufficient dietary intake it can be associated with malabsorption acrodermatitis enteropathica chronic liver disease chronic renal disease sickle cell disease diabetes malignancy and other chronic illnesses 11 In the United States a federal survey of food consumption determined that for women and men over the age of 19 average consumption was 9 7 and 14 2 mg day respectively For women 17 consumed less than the EAR for men 11 The percentages below EAR increased with age 225 The most recent published update of the survey NHANES 2013 2014 reported lower averages 9 3 and 13 2 mg day again with intake decreasing with age 226 Symptoms of mild zinc deficiency are diverse 196 Clinical outcomes include depressed growth diarrhea impotence and delayed sexual maturation alopecia eye and skin lesions impaired appetite altered cognition impaired immune functions defects in carbohydrate utilization and reproductive teratogenesis 196 Zinc deficiency depresses immunity 227 but excessive zinc does also 186 Despite some concerns 228 western vegetarians and vegans do not suffer any more from overt zinc deficiency than meat eaters 229 Major plant sources of zinc include cooked dried beans sea vegetables fortified cereals soy foods nuts peas and seeds 228 However phytates in many whole grains and fibers may interfere with zinc absorption and marginal zinc intake has poorly understood effects The zinc chelator phytate found in seeds and cereal bran can contribute to zinc malabsorption 11 Some evidence suggests that more than the US RDA 8 mg day for adult women 11 mg day for adult men may be needed in those whose diet is high in phytates such as some vegetarians 228 The European Food Safety Authority EFSA guidelines attempt to compensate for this by recommending higher zinc intake when dietary phytate intake is greater 214 These considerations must be balanced against the paucity of adequate zinc biomarkers and the most widely used indicator plasma zinc has poor sensitivity and specificity 230 Soil remediation Edit Species of Calluna Erica and Vaccinium can grow in zinc metalliferous soils because translocation of toxic ions is prevented by the action of ericoid mycorrhizal fungi 231 Agriculture Edit Zinc deficiency appears to be the most common micronutrient deficiency in crop plants it is particularly common in high pH soils 232 Zinc deficient soil is cultivated in the cropland of about half of Turkey and India a third of China and most of Western Australia Substantial responses to zinc fertilization have been reported in these areas 7 Plants that grow in soils that are zinc deficient are more susceptible to disease Zinc is added to the soil primarily through the weathering of rocks but humans have added zinc through fossil fuel combustion mine waste phosphate fertilizers pesticide zinc phosphide limestone manure sewage sludge and particles from galvanized surfaces Excess zinc is toxic to plants although zinc toxicity is far less widespread 7 Precautions EditMain article Zinc toxicity Toxicity Edit Although zinc is an essential requirement for good health excess zinc can be harmful Excessive absorption of zinc suppresses copper and iron absorption 209 The free zinc ion in solution is highly toxic to plants invertebrates and even vertebrate fish 233 The Free Ion Activity Model is well established in the literature and shows that just micromolar amounts of the free ion kills some organisms A recent example showed 6 micromolar killing 93 of all Daphnia in water 234 The free zinc ion is a powerful Lewis acid up to the point of being corrosive Stomach acid contains hydrochloric acid in which metallic zinc dissolves readily to give corrosive zinc chloride Swallowing a post 1982 American one cent piece 97 5 zinc can cause damage to the stomach lining through the high solubility of the zinc ion in the acidic stomach 235 Evidence shows that people taking 100 300 mg of zinc daily may suffer induced copper deficiency A 2007 trial observed that elderly men taking 80 mg daily were hospitalized for urinary complications more often than those taking a placebo 236 Levels of 100 300 mg may interfere with the utilization of copper and iron or adversely affect cholesterol 209 Zinc in excess of 500 ppm in soil interferes with the plant absorption of other essential metals such as iron and manganese 108 A condition called the zinc shakes or zinc chills can be induced by inhalation of zinc fumes while brazing or welding galvanized materials 140 Zinc is a common ingredient of denture cream which may contain between 17 and 38 mg of zinc per gram Disability and even deaths from excessive use of these products have been claimed 237 The U S Food and Drug Administration FDA states that zinc damages nerve receptors in the nose causing anosmia Reports of anosmia were also observed in the 1930s when zinc preparations were used in a failed attempt to prevent polio infections 238 On June 16 2009 the FDA ordered removal of zinc based intranasal cold products from store shelves The FDA said the loss of smell can be life threatening because people with impaired smell cannot detect leaking gas or smoke and cannot tell if food has spoiled before they eat it 239 Recent research suggests that the topical antimicrobial zinc pyrithione is a potent heat shock response inducer that may impair genomic integrity with induction of PARP dependent energy crisis in cultured human keratinocytes and melanocytes 240 Poisoning Edit In 1982 the US Mint began minting pennies coated in copper but containing primarily zinc Zinc pennies pose a risk of zinc toxicosis which can be fatal One reported case of chronic ingestion of 425 pennies over 1 kg of zinc resulted in death due to gastrointestinal bacterial and fungal sepsis Another patient who ingested 12 grams of zinc showed only lethargy and ataxia gross lack of coordination of muscle movements 241 Several other cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins 242 243 Pennies and other small coins are sometimes ingested by dogs requiring veterinary removal of the foreign objects The zinc content of some coins can cause zinc toxicity commonly fatal in dogs through severe hemolytic anemia and liver or kidney damage vomiting and diarrhea are possible symptoms 244 Zinc is highly toxic in parrots and poisoning can often be fatal 245 The consumption of fruit juices stored in galvanized cans has resulted in mass parrot poisonings with zinc 70 See also EditList of countries by zinc production Spelter Wet storage stain Zinc alloy electroplating Metal fume fever Piotr SteinkellerNotes Edit The elements are from different metal groups See periodic table An East India Company ship carrying a cargo of nearly pure zinc metal from the Orient sank off the coast Sweden in 1745 Emsley 2001 p 502 Electric current will naturally flow 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