Nickel

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Nickel   ₂₈Ni

General properties
Name, symbol	nickel, Ni
Pronunciation	/ˈnɪkəl/ NIK-əl
Appearance	lustrous, metallic, and silver with a gold tinge
Nickel in the periodic table
- ↑ Ni ↓ Pd cobalt ← nickel → copper
Atomic number	28
Standard atomic weight	58.6934(4)
Element category	transition metal
Group, period, block	group 10, period 4, d-block
Electron configuration	[Ar] 3d8 4s2 or [Ar] 3d9 4s1 (see text) per shell: 2, 8, 16, 2 or 2, 8, 17, 1
Physical properties
Phase	solid
Melting point	1728 K ​(1455 °C, ​2651 °F)
Boiling point	3003 K ​(2730 °C, ​4946 °F)
Density (near r.t.)	8.908 g·cm−3 (at 0 °C, 101.325 kPa)
Liquid density	at m.p.: 7.81 g·cm−3
Heat of fusion	17.48 kJ·mol−1
Heat of vaporization	379 kJ·mol−1
Molar heat capacity	26.07 J·mol−1·K−1
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 1783 1950 2154 2410 2741 3184
Atomic properties
Oxidation states	4,[1] 3, 2, 1,[2] −1 ​(a mildly basic oxide)
Electronegativity	1.91 (Pauling scale)
Ionization energies	1st: 737.1 kJ·mol−1 2nd: 1753.0 kJ·mol−1 3rd: 3395 kJ·mol−1 (more)
Atomic radius	empirical: 124 pm
Covalent radius	124±4 pm
Van der Waals radius	163 pm
Miscellanea
Crystal structure	​face-centered cubic (fcc)
Speed of sound	thin rod: 4900 m·s−1 (at r.t.)
Thermal expansion	13.4 µm·m−1·K−1 (at 25 °C)
Thermal conductivity	90.9 W·m−1·K−1
Electrical resistivity	at 20 °C: 69.3 nΩ·m
Magnetic ordering	ferromagnetic
Young's modulus	200 GPa
Shear modulus	76 GPa
Bulk modulus	180 GPa
Poisson ratio	0.31
Mohs hardness	4.0
Vickers hardness	638 MPa
Brinell hardness	700 MPa
CAS Number	7440-02-0
History
Discovery	Axel Fredrik Cronstedt (1751)
First isolation	Axel Fredrik Cronstedt (1751)
Most stable isotopes
Main article: Isotopes of nickel
iso NA half-life DM DE (MeV) DP 58Ni 68.077% >7×1020 y (β+β+) 1.9258 58Fe 59Ni trace 7.6×104 y ε - 59Co 60Ni 26.223% 60Ni is stable with 32 neutrons 61Ni 1.14% 61Ni is stable with 33 neutrons 62Ni 3.634% 62Ni is stable with 34 neutrons 63Ni syn 100.1 y β− 0.0669 63Cu 64Ni 0.926% 64Ni is stable with 36 neutrons
Decay modes in parentheses are predicted, but have not yet been observed

Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile. Pure nickel shows a significant chemical activity that can be observed when nickel is powdered to maximize the exposed surface area on which reactions can occur, but larger pieces of the metal are slow to react with air at ambient conditions due to the formation of a protective oxide surface. Even then, nickel is reactive enough with oxygen that native nickel is rarely found on Earth's surface, being mostly confined to the interiors of larger nickel–iron meteorites that were protected from oxidation during their time in space. On Earth, such native nickel is always found in combination with iron, a reflection of those elements' origin as major end products of supernova nucleosynthesis.^{[citation needed]} An iron–nickel mixture is thought to compose Earth's inner core.^[3]

The use of nickel (as a natural meteoric nickel–iron alloy) has been traced as far back as 3500 BC. Nickel was first isolated and classified as a chemical element in 1751 by Axel Fredrik Cronstedt, who initially mistook its ore for a copper mineral. The element's name comes from a mischievous sprite of German miner mythology, Nickel (similar to Old Nick), that personified the fact that copper-nickel ores resisted refinement into copper. An economically important source of nickel is the iron ore limonite, which often contains 1-2% nickel. Nickel's other important ore minerals include garnierite, and pentlandite. Major production sites include the Sudbury region in Canada (which is thought to be of meteoric origin), New Caledonia in the Pacific, and Norilsk in Russia.

Because of nickel's slow rate of oxidation at room temperature, it is considered corrosion-resistant. Historically, this has led to its use for plating metals such as iron and brass, coating chemistry equipment, and manufacturing certain alloys that retain a high silvery polish, such as German silver. About 6% of world nickel production is still used for corrosion-resistant pure-nickel plating. Nickel-plated items are noted for provoking nickel allergy. Nickel has been widely used in coins, though its rising price has led to some replacement with cheaper metals in recent years.

Nickel is one of four elements that are ferromagnetic around room temperature. Alnico permanent magnets based partly on nickel are of intermediate strength between iron-based permanent magnets and rare-earth magnets. The metal is chiefly valuable in the modern world for the alloys it forms; about 60% of world production is used in nickel-steels (particularly stainless steel). Other common alloys, as well as some new superalloys, make up most of the remainder of world nickel use, with chemical uses for nickel compounds consuming less than 3% of production.^[4] As a compound, nickel has a number of niche chemical manufacturing uses, such as a catalyst for hydrogenation. Enzymes of some microorganisms and plants contain nickel as an active site, which makes the metal an essential nutrient for them.

Characteristics

Atomic and physical properties

Nickel is a silvery-white metal with a slight golden tinge that takes a high polish. It is one of only four elements that are magnetic at or near room temperature, the others being iron, cobalt and gadolinium. Its Curie temperature is 355 °C (671 °F), meaning that bulk nickel is non-magnetic above this temperature.^[5] The unit cell of nickel is a face centered cube with the lattice parameter of 0.352 nm, giving an atomic radius of 0.124 nm. Nickel belongs to the transition metals and is hard and ductile.

Electron configuration dispute

The nickel atom has two electron configurations, [Ar] 3d⁸ 4s² and [Ar] 3d⁹ 4s¹, which are very close in energy – the symbol [Ar] refers to the argon-like core structure. There is some disagreement as to which should be considered the lowest energy configuration.^[6] Chemistry textbooks quote the electron configuration of nickel as [Ar] 4s² 3d⁸,^[7] or equivalently as [Ar] 3d⁸ 4s².^[8] This configuration agrees with the Madelung energy ordering rule, which predicts that 4s is filled before 3d. It is supported by the experimental fact that the lowest energy state of the nickel atom is a 3d⁸ 4s² energy level, specifically the 3d⁸(³F) 4s^{2 3}F, J = 4 level.^[9]

However, each of these configurations in fact gives rise to a set of states of different energies.^[9] The two sets of energies overlap, and the average energy of states having configuration [Ar] 3d⁹ 4s¹ is in fact lower than the average energy of states having configuration [Ar] 3d⁸ 4s². For this reason, the research literature on atomic calculations quotes the ground state configuration of nickel as [Ar] 3d⁹ 4s¹.^[6]

Isotopes

Naturally occurring nickel is composed of five stable isotopes; 58
Ni, 60Ni, 61Ni, 62Ni and 64Ni with 58Ni being the most abundant (68.077% natural abundance). 62Ni has the highest nuclear binding energy of any nuclide. Its binding energy is greater than both 56Fe, often incorrectly cited as the largest, and 58Fe.^[10] 18 radioisotopes have been characterised with the most stable being 59Ni with a half-life of 76,000 years, 63Ni with a half-life of 100.1 years, and 56Ni with a half-life of 6.077 days. All of the remaining radioactive isotopes have half-lives that are less than 60 hours and the majority of these have half-lives that are less than 30 seconds. This element also has one meta state.^[11]

Nickel-56 is produced by the silicon burning process and later set free in large quantities during type Ia supernovae. The shape of the light curve of these supernovae at intermediate to late-times corresponds to the decay via electron capture of nickel-56 to cobalt-56 and ultimately to iron-56.^[12] Nickel-59 is a long-lived cosmogenic radionuclide with a half-life of 76,000 years. 59Ni has found many applications in isotope geology. 59Ni has been used to date the terrestrial age of meteorites and to determine abundances of extraterrestrial dust in ice and sediment. Nickel-60 is the daughter product of the extinct radionuclide 60Fe, which decays with a half-life of 2.6 million years. Because 60Fe has such a long half-life, its persistence in materials in the solar system at high enough concentrations may have generated observable variations in the isotopic composition of 60Ni. Therefore, the abundance of 60Ni present in extraterrestrial material may provide insight into the origin of the solar system and its early history. Nickel-62 has the highest binding energy per nucleon of any isotope for any element (8.7946 MeV/nucleon).^[13] Isotopes heavier than 62Ni cannot be formed by nuclear fusion without losing energy. ⁴⁸Ni, discovered in 1999, is the most proton-rich heavy element isotope known. With 28 protons and 20 neutrons ⁴⁸Ni is "double magic" (like ²⁰⁸Pb) and therefore unusually stable.^[11][14]

The isotopes of nickel range in atomic weight from 48 u (48Ni) to 78 u (78Ni). Nickel-78's half-life was recently measured at 110 milliseconds, and is believed an important isotope in supernova nucleosynthesis of elements heavier than iron.^[15]

Occurrence

Widmanstätten pattern showing the two forms of nickel-iron, Kamacite and Taenite, in an octahedrite meteorite

On Earth, nickel occurs most often in combination with sulfur and iron in pentlandite, with sulfur in millerite, with arsenic in the mineral nickeline, and with arsenic and sulfur in nickel galena.^[16] Nickel is commonly found in iron meteorites as the alloys kamacite and taenite.

The bulk of the nickel mined comes from two types of ore deposits. The first are laterites, where the principal ore minerals are nickeliferous limonite: (Fe, Ni)O(OH) and garnierite (a hydrous nickel silicate): (Ni, Mg)
3Si
2O
5(OH)
4. The second are magmatic sulfide deposits, where the principal ore mineral is pentlandite: (Ni, Fe)
9S
8.

Australia and New Caledonia have the biggest estimate reserves (45% all together).^[17]

In terms of World Resources, identified land-based resources averaging 1% nickel or greater contain at least 130 million tons of nickel (about the double of known reserves). About 60% is in laterites and 40% is in sulfide deposits.^[17]

Based on geophysical evidence, most of the nickel on Earth is postulated to be concentrated in the Earth's outer and inner cores. Kamacite and taenite are naturally occurring alloys of iron and nickel. For kamacite, the alloy is usually in the proportion of 90:10 to 95:5, although impurities (such as cobalt or carbon) may be present, while for taenite the nickel content is between 20% and 65%. Kamacite and taenite occur in nickel iron meteorites.^[18]

Compounds

Tetracarbonyl nickel

The most common oxidation state of nickel is +2, but compounds of Ni⁰, Ni⁺, and Ni³⁺ are well known, as well as exotic oxidation states Ni^2-, Ni^1-, and Ni⁴⁺.^[19]

Nickel(0)

Tetracarbonylnickel (Ni(CO)
4), discovered by Ludwig Mond,^[20] is a volatile, highly toxic liquid at room temperature. On heating, the complex decomposes back to nickel and carbon monoxide:

Ni(CO)
4 Ni + 4 CO

This behavior is exploited in the Mond process for purifying nickel, as described above. The related nickel(0) complex bis(cyclooctadiene)nickel(0) is a useful catalyst in organonickel chemistry due to the easily displaced cod ligands.

Nickel(I)

Nickel(I) complexes are uncommon, one example being the tetrahedral complex NiBr(PPh₃)₃. Many feature Ni-Ni bonding, such as the dark red diamagnetic K
4[Ni
2(CN)
6] prepared by reduction of K
2[Ni
2(CN)
6] with sodium amalgam. This compound is oxidised in water, liberating H
2.^[21]

Structure of [Ni
2(CN)
6]2− ion^[21]

Nickel(II)

Color of various Ni(II) complexes in aqueous solution. From left to right, [Ni(NH
3)
6]2+, [Ni(C₂H₄(NH₂)₂)]²⁺, [NiCl
4]2−, [Ni(H
2O)
6]2+

Crystals of hydrated nickel sulfate.

Nickel(II) forms compounds with all common anions, i.e. the sulfide, sulfate, carbonate, hydroxide, carboxylates, and halides. Nickel(II) sulfate is produced in large quantities by dissolving nickel metal or oxides in sulfuric acid. It exists as both a hexa- and heptahydrates.^[22] This compound is useful for electroplating nickel. Common salts of nickel, such as the chloride, nitrate, and sulfate, dissolve in water to give green solutions containing the metal aquo complex [Ni(H
2O
6]2+.

The four halides form nickel compounds. The structures of these solids feature octahedral Ni centres. Nickel(II) chloride is most common, and its behavior is illustrative of the other halides. Nickel(II) chloride is produced by dissolving nickel or its oxide in hydrochloric acid. It is usually encountered as the green hexahydrate, the formula of which is usually written NiCl₂•6H₂O. When dissolved in water, this salt forms the metal aquo complex [Ni(H
2O)
6]2+. Dehydration of NiCl₂•6H₂O gives the yellow anhydrous NiCl
2.

Some tetracoordinate nickel(II) complexes, e.g. bis(triphenylphosphine)nickel chloride, exist both in tetrahedral and square planar geometries. The tetrahedral complexes are paramagnetic whereas the square planar complexes are diamagnetic. This equilibrium as well as the formation of octahedral complexes contrasts with the behavior of the divalent complexes of the heavier group 10 metals, palladium(II) and platinum(II), which tend to adopt only square-planar geometry.^[19]

Nickelocene is known; it has an electron count of 20, making it relatively unstable.

Nickel(III) antimonide

Nickel(III) and (IV)

For simple compounds, nickel(III) and nickel(IV) only occurs with fluoride and oxides, with the exception of KNiIO
6, which can be considered as a formal salt of the [IO
6]5− ion.^[21] Ni(IV) is present in the mixed oxide BaNiO
3, while Ni(III) is present in nickel(III) oxide, which is used as the cathode in many rechargeable batteries, including nickel-cadmium, nickel-iron, nickel hydrogen, and nickel-metal hydride, and used by certain manufacturers in Li-ion batteries.^[23] Nickel(III) can be stabilized by σ-donor ligands such as thiols and phosphines.^[21]

History

Because the ores of nickel are easily mistaken for ores of silver, understanding of this metal and its use dates to relatively recent times. However, the unintentional use of nickel is ancient, and can be traced back as far as 3500 BC. Bronzes from what is now Syria have been found to contain up to 2% nickel.^[24] Further, there are Chinese manuscripts suggesting that "white copper" (cupronickel, known as baitong) was used there between 1700 and 1400 BC. This Paktong white copper was exported to Britain as early as the 17th century, but the nickel content of this alloy was not discovered until 1822.^[25]

In medieval Germany, a red mineral was found in the Erzgebirge (Ore Mountains) that resembled copper ore. However, when miners were unable to extract any copper from it, they blamed a mischievous sprite of German mythology, Nickel (similar to Old Nick), for besetting the copper. They called this ore Kupfernickel from the German Kupfer for copper.^{[26][27][28][29]} This ore is now known to be nickeline or niccolite, a nickel arsenide. In 1751, Baron Axel Fredrik Cronstedt was trying to extract copper from kupfernickel—and instead produced a white metal that he named after the spirit that had given its name to the mineral, nickel.^[30] In modern German, Kupfernickel or Kupfer-Nickel designates the alloy cupronickel.

After its discovery, the only source for nickel was the rare Kupfernickel but, from 1824 on, nickel was obtained as a byproduct of cobalt blue production. The first large-scale producer of nickel was Norway, which exploited nickel-rich pyrrhotite from 1848 on. The introduction of nickel in steel production in 1889 increased the demand for nickel, and the nickel deposits of New Caledonia, which were discovered in 1865, provided most of the world's supply between 1875 and 1915. The discovery of the large deposits in the Sudbury Basin, Canada, in 1883, in Norilsk-Talnakh, Russia, in 1920, and in the Merensky Reef, South Africa, in 1924 made large-scale production of nickel possible.^[25]

Dutch coins made of pure nickel

Nickel has been a component of coins since the mid-19th century. In the United States, the term "nickel" or "nick" originally applied to the copper-nickel Flying Eagle cent, which replaced copper with 12% nickel 1857–58, then the Indian Head cent of the same alloy from 1859–1864. Still later, in 1865, the term designated the three-cent nickel, with nickel increased to 25%. In 1866, the five-cent shield nickel (25% nickel, 75% copper) appropriated the designation. Along with the alloy proportion, this term has been used to the present in the United States. Coins of nearly pure nickel were first used in 1881 in Switzerland, and more notably 99.9% nickel five-cent coins were struck in Canada (the world's largest nickel producer at the time) during non-war years from 1922–1981, and their metal content made these coins magnetic.^[31] During the wartime period 1942–45, most or all nickel was removed from Canadian and U.S. coins, due to nickel's war-critical use in armor.^[27][32] Canada used 99.9% nickel from 1968 in its higher-value coins until 2000. In the 21st century, the high price of nickel has led to some replacement of the metal in coins around the world. Coins still made with nickel alloys include one- and two- Euro coins, 5¢, 10¢, 25¢ and 50¢ U.S. coins and 20p, 50p, £1 and £2 UK coins. The replacement of nickel-alloy 5p and 10p UK coins with nickel-plated steel models, begun in 2012, has caused dermatological controversy.^[33]

World production

Time trend of nickel production ^[34]

The Philippines, Indonesia, Russia, Canada and Australia are the world's largest producers of nickel, as reported by the US Geological Survey.^[17] The largest deposits of nickel in non-Russian Europe are located in Finland and Greece. Identified land-based resources averaging 1% nickel or greater contain at least 130 million tons of nickel. About 60% is in laterites and 40% is in sulfide deposits. In addition, extensive deep-sea resources of nickel are in manganese crusts and nodules covering large areas of the ocean floor, particularly in the Pacific Ocean.^[35]

The one locality in the United States where nickel was commercially mined is Riddle, Oregon, where several square miles of nickel-bearing garnierite surface deposits are located. The mine closed in 1987.^[36][37] The Eagle mine project is a new nickel mine in Michigan's upper peninsula. Completed in 2013, it is expected to begin operations in the fourth quarter of 2014.^[38]

Mine production and reserves[35]	2012 (metric tons)	2011 (metric tons)	Reserves (metric tons)
Australia	230,000	215,000	20,000,000
Botswana	26,000	26,000	490,000
Brazil	140,000	209,000	7,500,000
Canada	220,000	220,000	3,300,000
China	91,000	89,800	3,000,000
Colombia	80,000	76,000	1,100,000
Cuba	72,000	71,000	5,500,000
Dominican Republic	24,000	21,700	970,000
Indonesia	320,000	290,000	3,900,000
Madagascar	22,000	5,900	1,600,000
New Caledonia	140,000	131,000	12,000,000
Philippines	330,000	270,000	1,100,000
Russia	270,000	267,000	6,100,000
South Africa	42,000	44,000	3,700,000
Other countries	120,000	103,000	4,600,000
World total (metric tons, rounded)	2,100,000	1,940,000	75,000,000

Extraction and purification

Nickel is recovered through extractive metallurgy: it is extracted from its ores by conventional roasting and reduction processes that yield a metal of greater than 75% purity. In many stainless steel applications, 75% pure nickel can be used without further purification, depending on the composition of the impurities.

Most sulfide ores have traditionally been processed using pyrometallurgical techniques to produce a matte for further refining. Recent advances in hydrometallurgical techniques have resulted in significant nickel purification using these processes. Most sulfide deposits have traditionally been processed by concentration through a froth flotation process followed by pyrometallurgical extraction. In hydrometallurgical processes, nickel sulfide ores undergo flotation (differential flotation if Ni/Fe ratio is too low) and then smelted. After producing the nickel matte, further processing is done via the Sherritt-Gordon process. First, copper is removed by adding hydrogen sulfide, leaving a concentrate of only cobalt and nickel. Then, solvent extraction is used to separate the cobalt and nickel, with the final nickel concentration greater than 99%.

Electrolytically refined nickel nodule, with green, crystallized nickel-electrolyte salts visible in the pores.

Electrorefining

A second common form of further refining involves the leaching of the metal matte into a nickel salt solution, followed by the electro-winning of the nickel from solution by plating it onto a cathode as electrolytic nickel.

Mond process

Highly purified nickel spheres made by the Mond process.

 Purification of nickel oxides to obtain the purest metal is performed via the Mond process, which increases the nickel concentrate to greater than 99.99% purity.^[39] This process was patented by Ludwig Mond and has been in industrial use since before the beginning of the 20th century. In the process, nickel is reacted with carbon monoxide at around 40–80 °C to form nickel carbonyl in the presence of a sulfur catalyst. Iron gives iron pentacarbonyl, too, but this reaction is slow. If necessary, the nickel may be separated by distillation. Dicobalt octacarbonyl is also formed in nickel distillation as a by-product, but it decomposes to tetracobalt dodecacarbonyl at the reaction temperature to give a non-volatile solid.^[4]

Nickel is re-obtained from the nickel carbonyl by one of two processes. It may be passed through a large chamber at high temperatures in which tens of thousands of nickel spheres, called pellets, are constantly stirred. It then decomposes, depositing pure nickel onto the nickel spheres. Alternatively, the nickel carbonyl may be decomposed in a smaller chamber at 230 °C to create a fine nickel powder. The resultant carbon monoxide is re-circulated and reused through the process. The highly pure nickel produced by this process is known as "carbonyl nickel".^[40]

Metal value

The market price of nickel surged throughout 2006 and the early months of 2007; as of April 5, 2007, the metal was trading at US$52,300/tonne or $1.47/oz.^[41] The price subsequently fell dramatically from these peaks, and as of September 19, 2013 the metal was trading at $13,778/tonne, or $0.39/oz.^[42][43]

The US nickel coin contains 0.04 ounces (1.1 g) of nickel, which at the April 2007 price was worth 6.5 cents, along with 3.75 grams of copper worth about 3 cents, making the metal value over 9 cents. Since the face value of a nickel is 5 cents, this made it an attractive target for melting by people wanting to sell the metals at a profit. However, the United States Mint, in anticipation of this practice, implemented new interim rules on December 14, 2006, subject to public comment for 30 days, which criminalized the melting and export of cents and nickels.^[44] Violators can be punished with a fine of up to $10,000 and/or imprisoned for a maximum of five years.

As of September 19, 2013, the melt value of a U.S. nickel (copper and nickel included) is $0.0450258, which is 90% of its face value.^[45]

Applications

Nickel superalloy jet engine (RB199) turbine blade

The fraction of global nickel production presently used for various applications is as follows: 46% for making nickel steels; 34% in nonferrous alloys and superalloys; 14% electroplating, and 6% into other uses.^[17][46]

Nickel is used in many specific and recognizable industrial and consumer products, including stainless steel, alnico magnets, coinage, rechargeable batteries, electric guitar strings, microphone capsules, and special alloys. It is also used for plating and as a green tint in glass. Nickel is preeminently an alloy metal, and its chief use is in the nickel steels and nickel cast irons, of which there are many varieties. It is also widely used in many other alloys, such as nickel brasses and bronzes, and alloys with copper, chromium, aluminium, lead, cobalt, silver, and gold (Inconel, Incoloy, Monel, Nimonic).^[47]

A "horseshoe magnet" made of alnico nickel alloy.

Because of its resistance to corrosion, nickel has been occasionally used historically as a substitute for decorative silver. Nickel was also occasionally used in some countries after 1859 as a cheap coinage metal (see above) but in the later years of the 20th century was largely replaced by cheaper stainless steel (i.e., iron) alloys, except notably in the United States.

Nickel is an excellent alloying agent for certain other precious metals, and so used in the so-called fire assay, as a collector of platinum group elements (PGE). As such, nickel is capable of full collection of all 6 PGE elements from ores, in addition to partial collection of gold. High-throughput nickel mines may also engage in PGE recovery (primarily platinum and palladium); examples are Norilsk in Russia and the Sudbury Basin in Canada.

Nickel foam or nickel mesh is used in gas diffusion electrodes for alkaline fuel cells.^[48][49]
Nickel and its alloys are frequently used as catalysts for hydrogenation reactions. Raney nickel, a finely divided nickel-aluminium alloy, is one common form, however related catalysts are also often used, including related 'Raney-type' catalysts.

Nickel is a naturally magnetostrictive material, meaning that, in the presence of a magnetic field, the material undergoes a small change in length.^[50][51] In the case of nickel, this change in length is negative (contraction of the material), which is known as negative magnetostriction and is on the order of 50 ppm.

Nickel is used as a binder in the cemented tungsten carbide or hardmetal industry and used in proportions of six to 12% by weight. Nickel can make the tungsten carbide magnetic and adds corrosion-resistant properties to the cemented tungsten carbide parts, although the hardness is lower than those of parts made with cobalt binder.^[52]

Biological role

Although not recognized until the 1970s, nickel plays important roles in the biology of microorganisms and plants.^[53][54] The plant enzyme urease (an enzyme that assists in the hydrolysis of urea) contains nickel. The NiFe-hydrogenases contain nickel in addition to iron-sulfur clusters. Such [NiFe]-hydrogenases characteristically oxidise H
2. A nickel-tetrapyrrole coenzyme, Cofactor F430, is present in the methyl coenzyme M reductase, which powers methanogenic archaea. One of the carbon monoxide dehydrogenase enzymes consists of an Fe-Ni-S cluster.^[55] Other nickel-containing enzymes include a rare bacterial class of superoxide dismutase^[56] and glyoxalase I enzymes in bacteria and several parasitic eukaryotic trypanosomal parasites ^[57] (this enzyme in higher organisms, including yeast and mammals, uses divalent zinc, Zn²⁺).^{[58][59][60][61][62]}

Nickel can have an impact on human health through nickel-dependent infectious diseases.^[63] Nickel released from Siberian Traps volcanic eruptions (site of the modern city of Norilsk) is suspected of having had a significant impact on the role played by Methanosarcina, a genus of euryarchaeote archaea that produced methane during the biggest extinction event on record.^[64]

Toxicity

In the US, the minimal risk level of nickel and its compounds is set to 0.2 µg/m³ for inhalation during 15–364 days.^[65] Nickel sulfide fume and dust are believed carcinogenic, and various other nickel compounds may be as well.^[66][67] Nickel carbonyl, [Ni(CO)
4], is an extremely toxic gas. The toxicity of metal carbonyls is a function of both the toxicity of the metal as well as the carbonyl's ability to give off highly toxic carbon monoxide gas, and this one is no exception; nickel carbonyl is also explosive in air.^[68][69]

In the US, the Tolerable Upper Limit of dietary nickel is 1000 µg/day,^[70] while estimated average ingestion is 69-162 µg/day.^[71] Large amounts of nickel (and chromium) – comparable to the estimated average ingestion above – leach into food cooked in stainless steel. For example, the amount of nickel leached after 10 cooking cycles into one serving of tomato sauce averages 88 µg.^[72][73]

Sensitized individuals may show an allergy to nickel, affecting their skin, known as dermatitis. Sensitivity to nickel may also be present in patients with pompholyx. Nickel is an important cause of contact allergy, partly due to its use in jewellery intended for pierced ears.^[74] Nickel allergies affecting pierced ears are often marked by itchy, red skin. Many earrings are now made nickel-free due to this problem. The amount of nickel allowed in products that come into contact with human skin is regulated by the European Union. In 2002, researchers found amounts of nickel being emitted by 1 and 2 Euro coins far in excess of those standards. This is believed to be due to a galvanic reaction.^[75] Nickel was voted Allergen of the Year in 2008 by the American Contact Dermatitis Society.^[76]

Reports also showed that both the nickel-induced activation of hypoxia-inducible factor (HIF-1) and the up-regulation of hypoxia-inducible genes are due to depleted intracellular ascorbate levels. The addition of ascorbate to the culture medium increased the intracellular ascorbate level and reversed both the metal-induced stabilization of HIF-1- and HIF-1α-dependent gene expression.^[77][78]

The most toxic compound containing nickel is Cyclopentadienyl nickel nitrosyl, (C
5 H
5)NiNO). It is a blood-red color liquid.

Whale

From Wikipedia, the free encyclopedia

Whale Temporal range: 50–0Ma PreЄ Є O S D C P T J K Pg N Eocene – Recent
North Atlantic right whales, mother and calf
Scientific classification
Kingdom:	Animalia
Phylum:	Chordata
Class:	Mammalia
Subclass:	Eutheria
Order:	Cetacea

Whale (origin Old English hwæl from Proto-Germanic *hwalaz) is the common name for various marine mammals of the order Cetacea.^[1] The term whale sometimes refers to all cetaceans, but more often it excludes dolphins and porpoises, which belong to the suborder Odontoceti (toothed whales). This suborder includes the sperm whale, killer whale, pilot whale, and beluga whale. The other Cetacean suborder, Mysticeti (baleen whales), comprises filter feeders that eat small organisms caught by straining seawater through a comblike structure found in the mouth called baleen. This suborder includes the blue whale, the humpback whale, the bowhead whale and the minke whale. All cetaceans have forelimbs modified as fins, a tail with horizontal flukes, and nasal openings (blowholes) on top of the head.

Whales range in size from the blue whale, the largest animal known to have ever existed^[2] at 30 m (98 ft) and 180 tonnes (180 long tons; 200 short tons), to pygmy species such as the pygmy sperm whale at 3.5 m (11 ft). Whales inhabit all the world's oceans and number in the millions, with annual population growth rate estimates for various species ranging from 3% to 13%.^[3] Whales are long-lived, humpback whales living for up to 77 years, while bowhead whales may live for over a century.

Human hunting of whales from the 17th century until 1986 radically reduced the populations of some whale species. Whales have appeared in literature since the time of the Old Testament, play a role in Inuit creation myths, and are revered by coastal people in Ghana and Vietnam.

Taxonomy

Cetaceans are divided into two suborders:

• The largest suborder, Mysticeti (baleen whales), is characterized by baleen, a sieve-like structure in the upper jaw made of keratin, which it uses to filter plankton from the water.
• Odontoceti (toothed whales) bear sharp teeth for hunting. Odontoceti includes dolphins and porpoises, which means that if they are considered not to be whales, the informal grouping 'whale' is not a clade.

Cetaceans and artiodactyls are now classified under the super-order Cetartiodactyla, which includes both whales and hippopotami. Whales are the hippopotamus's closest living relatives.^[4]

Evolution

Ambulocetus natans – a primitive cetacean

All cetaceans, including whales, dolphins and porpoises, are descendants of land-dwelling mammals of the Artiodactyl order (even-toed ungulates). Both are related to the Indohyus, an extinct semi-aquatic deer-like ungulate, from which they split around 54 million years ago.^[5][6] These primitive cetaceans first took to the sea about 50 million years ago and became fully aquatic about 5–10 million years later.^[7] Their features became adapted for living in the marine environment. Major anatomical changes include streamlining of the body, the migration of the nasal openings towards the top of the cranium, the shrinking and eventual disappearance of the hind limbs, the modification of the forelimbs into flippers, and the growth of flukes on the tail.

Anatomy

Like all mammals, whales breathe air, are warm-blooded, nurse their young with milk from mammary glands, and have body hair.^[8] Beneath the skin lies a layer of fat called blubber, which stores energy and insulates the body. Whales have a spinal column, a vestigial pelvic bone, and a four-chambered heart. The neck vertebrae are typically fused, trading flexibility for stability during swimming.^[9][10]

Blowhole(s)

Features of a blue whale

Whales breathe via blowholes; baleen whales have two and toothed whales have one. These are located on the top of the head, allowing the animal to remain almost completely submerged while breathing. Breathing involves expelling stale air (which is warm and moist), as well as some mucus and excess water from the blowhole, forming an upward, steamy spout, followed by inhaling fresh air into the lungs.^[11] Spout shapes differ among species and help with identification.

Appendages

The body shape is fusiform and the modified forelimbs, or fins, are paddle-shaped. The end of the tail is composed of two flukes, which propel the animal by vertical movement, as opposed to the horizontal movement of a fish tail. Although whales do not possess fully developed hind limbs, some (such as sperm whales and baleen whales) possess discrete rudimentary appendages, which may have feet and digits. Most species have a dorsal fin.^[12][13]

In March 2014 in Japan a bottle-nosed dolphin with hind fins about as big as a man's hands, was captured.^[14]

Dentition

Toothed whales, such as the sperm whale, possess teeth with cementum cells overlying dentine cells.
Unlike human teeth, which are composed mostly of enamel on the portion of the tooth outside of the gum, whale teeth have cementum outside the gum. Only in larger whales, where the cementum is worn away on the tip of the tooth, does enamel show.^[15]

Instead of teeth, baleen whales have a row of baleen plates on the upper side of their jaws that resemble the teeth of a comb.

Ears

The whale ear has specific adaptations to the marine environment. In humans, the middle ear works as an impedance matcher between the outside air's low impedance and the cochlear fluid's high impedance. However, in aquatic mammals, such as whales, there is no great difference between the outer and inner environments. Instead of sound passing through the outer ear to the middle ear, whales receive sound through the throat, from which it passes through a low-impedance fat-filled cavity to the inner ear.^[16] The whale ear is acoustically isolated from the skull by air-filled sinus pockets, which allow for greater directional hearing underwater.^[17]

Life history and behavior

Reproduction

Males are called 'bulls', females, 'cows' and newborns, 'calves'. Most species do not maintain fixed partnerships and females have several mates each season.^[18][19]
The female usually delivers a single calf, which is birthed tail-first to minimize the risk of drowning. Whale cows nurse by actively squirting milk into the mouths of their young. This milk is so rich in fat that it has the consistency of toothpaste.^[18] In many species, nursing continues for more than a year and is associated with a strong bond between mother and calf. Reproductive maturity typically occurs at seven to ten years. This mode of reproduction produces few offspring, but increases the survival probability of each one.

Socialization

Whales are known to teach, learn, cooperate, scheme, and even grieve.^[20] The neocortex of many species of whale is home to elongated spindle neurons that, prior to 2007, were known only in hominids.^[21] In humans these cells are involved in social conduct, emotions, judgment, and theory of mind.^[22] Whale spindle neurons are found in areas of the brain that are homologous to where they are found in humans, suggesting that they perform a similar function.^[23]

Sleep

A humpback whale breaching.

Unlike most animals, whales are conscious breathers. All mammals sleep, but whales cannot afford to become unconscious for long because they may drown. While knowledge of sleep in wild cetaceans is limited, toothed cetaceans in captivity have been recorded to sleep with one side of their brain at a time, ostensibly so that they may swim, breathe consciously, avoid predators and social contact during their period of rest. It is thought that only one hemisphere of the whale's brain sleeps at a time, so that they rest but are never completely asleep.^[24]

A 2008 study found that wild sperm whales (Physeter macrocephalus) sleep in vertical postures just under the surface in passive shallow 'drift-dives', generally during the day, during which whales do not respond to passing vessels unless they are in contact, leading to the suggestion that whales possibly sleep during such dives.^[25]

Surfacing behavior

Many whales exhibit behaviors that expose large parts of their bodies to the air, such as breaching and tail slapping.

Sounding

Sounding is a term used for whales diving. It is typically only used for longer dives. Whales typically stay close to the surface for a series of short, shallow dives while building their oxygen reserves. They then have a sounding dive.

Lifespan

Whale lifespans vary among species and are not well characterized. Whaling left few older individuals to observe directly. R.M. Nowak of Johns Hopkins University estimated that humpback whales may live as long as 77 years.^[26] In 2007, a 19th-century lance fragment was found in a bowhead whale off Alaska, suggesting the individual could be between 115 and 130 years old.^[27] Aspartic acid racemization in the whale eye, combined with a harpoon fragment, indicated an age of 211 years for another male, which, if true, would make bowheads the longest-lived extant mammal species.^[28][29] The accuracy of this technique has been questioned because racemization does not correlate well with other dating methods.^[30]

Vocalization

	Humpback Whale "Song" Menu 0:00 Recording of Humpback Whales singing and Clicking.
Problems playing this file? See media help.

Some species, such as the humpback whale, communicate using melodic sounds, known as whale song. These sounds can be extremely loud, depending on the species. Sperm whales have only been heard making clicks, while toothed whales (Odontoceti) use echolocation that can generate about 20,000 watts of sound (+73 dBm or +43 dBw^[31]) and be heard for many miles. Whale vocalization is likely to serve many purposes, including echolocation, mating, and identification.^[32]

Captive whales have occasionally been known to mimic human speech. Scientists have suggested this indicates a strong desire on behalf of the whales to communicate with humans, as whales have a very different vocal mechanism, so producing human speech likely takes considerable effort.^[33]

Ecology

"Whale pump" - the role played by whales in nutrient recycling in the oceans.

Whales are considered as "marine ecosystem engineers" for the following reasons:^[34]

• Whales are major consumers of fish and oceanic invertebrates.
• Whales act as reservoirs of nutrients, such as iron and nitrogen, and recycle them both horizontally and vertically in the water column.
• Whale detritus provides energy and habitat for deep sea organisms.

Feeding

Whales are generally classed as predators, but their food ranges from microscopic plankton to very large animals.

Toothed whales eat fish and squid, which they hunt by the use of echolocation. Killer whales sometimes eat other marine mammals, including whales.

Baleen whales, such as humpbacks and blues, mainly eat krill when feeding in the higher latitudes (such as the Southern Ocean). They imbibe enormous amounts of seawater, which they expel through their baleen plates; the krill is retained on the plates and then swallowed.^[18] Whales do not drink seawater but indirectly extract water from their food by metabolizing fat.^[18]

Whale pump

A 2010 study considered whales to be a positive influence to the productivity of ocean fisheries, in what has been termed a "whale pump." Whales carry nutrients such as nitrogen from the depths back to the surface. This functions as an upward biological pump, reversing an earlier assumption that whales accelerate the loss of nutrients to the bottom. This nitrogen input in the Gulf of Maine is "more than the input of all rivers combined", some 23,000 metric tons each year.^[35][36]

Whale fall

Whale carcasses fall to the deep ocean and being massive, with body weights of the range 30 to 160 tonnes (30,000 to 160,000 kg), provide a substantial habitat for marine creatures. Evidence of whale falls in present day and fossil records shows that deep sea whale falls support a rich assemblage of creatures, with a global diversity of 407 species as per Smith & Baco (2003), comparable to other neritic biodiversity hotspots, such as cold seeps and hydrothermal vents.^[37]
Deterioration of whale carcasses happens though a series of three stages. Initially, moving organisms such as sharks and hagfish, scavenge the soft tissues at a rapid rate over a period of months, and as long as two years. This is followed by the colonisation of bones and surrounding sediments (which contain organic matter) by enrichment opportunists, such as crustaceans and polychaetes over a period of years. Finally, sulfophilic bacteria reduce the bones releasing hydrogen sulfide enabling the growth of chemoautotrophic organisms, which in turn support other organisms such as mussels, clams, limpets and sea snails. This stage can last for decades and supports rich assemblage of species, averaging 185 species per site as per Smith & Baco (2003).^[37]

Interaction with humans

Whaling

Dutch whalers near Spitsbergen. Abraham Storck, 1690

World map of International Whaling Commission (IWC) members/non-members(member countries in blue)

World population graph of blue whales (Balaenoptera musculus)

Some species of large whales are listed as endangered by multinational organizations, such as CITES, as well as governments and advocacy groups; this is primarily due to the impact of whaling. Whales have been hunted commercially for whale oil, meat, baleen and ambergris (a perfume ingredient from the intestine of sperm whales) since the 17th century.^[38] More than 2 million were taken in the 20th century,^[39] and by the middle of the century, many populations were severely depleted.

The International Whaling Commission banned commercial whaling in 1986.^[40] The ban is not absolute, however, and some whaling continues under the auspices of scientific research^[40] (sometimes not proved^[41]) or aboriginal rights; current whaling nations are Norway, Iceland and Japan and the aboriginal communities of Siberia, Alaska and northern Canada.

Bycatch

Several species of small whales are caught as bycatch in fisheries for other species. In the Eastern Tropical Pacific tuna fishery, thousands of dolphins drowned in purse-seine nets, until preventive measures were introduced. Gear and deployment modifications, and eco-labelling (dolphin-safe or dolphin-friendly brands of tuna), have contributed to a reduction in dolphin mortality by tuna vessels.^[42]

Naval sonar

Environmentalists speculate that advanced naval sonar endangers some cetaceans, including whales. In 2003, British and Spanish scientists suggested in Nature that the effects of sonar trigger whale beachings and to signs that such whales have experienced decompression sickness.^[43] Responses in Nature the following year discounted the explanation.^[44]
Mass beachings occur in many species, mostly beaked whales that use echolocation for deep diving. The frequency and size of beachings around the world, recorded over the last 1,000 years in religious tracts and more recently in scientific surveys, have been used to estimate the population of various whale species by assuming that the proportion of the total whale population beaching in any one year is constant. Beached whales can give other clues about population conditions, especially health problems. For example, bleeding around ears, internal lesions, and nitrogen bubbles in organ tissue suggest decompression sickness.^[20]

Following public concern, the U.S. Defense department was ordered by the 9th Circuit Court to strictly limit use of its Low Frequency Active Sonar during peacetime. Attempts by the UK-based Whale and Dolphin Conservation Society to obtain a public inquiry into the possible dangers of the Royal Navy's equivalent (the "2087" sonar launched in December 2004) failed as of 2008. The European Parliament has requested that EU members refrain from using the powerful sonar system until an environmental impact study has been carried out.

Human mythology

Whale weather-vane atop the Nantucket Historical Association Whaling Museum displaying a sperm whale.

Whales were little understood for most of human history as they spend up to 90% of their lives underwater, only surfacing briefly to breathe.^[45] Many cultures, even those that have hunted them, hold whales in awe and feature them in their mythologies.

In China, Yu-kiang, a whale with the hands and feet of a man was said to rule the ocean.^[46]

In the Tyrol region of Austria, it was said that if a sunbeam were to fall on a maiden entering womanhood, she would be carried away in the belly of a whale.^[47]

Paikea, the youngest and favourite son of the chief Uenuku from the island of Mangaia, in the present day Cook Islands, was said by the Kati Kuri people of Kaikoura to have come from the Pacific Islands on the back of a whale many centuries before.^[48]

The whale features in Inuit creation myths. When 'Big Raven', a deity in human form, found a stranded whale, he was told by the Great Spirit where to find special mushrooms that would give him the strength to drag the whale back to the sea and thus return order to the world.^[46]

The Tlingit people of northern Canada said that the Orcas were created when the hunter Natsihlane carved eight fish from yellow cedar, sang his most powerful spirit song and commanded the fish to leap into the water.^[49]

In Icelandic legend a man threw a stone at a fin whale and hit the blowhole, causing the whale to burst. The man was told not to go to sea for twenty years, but in the nineteenth year he went fishing and a whale came and killed him.^[50]

In East African legend, King Sulemani asked God that he might permit him to feed all the beings on earth. A whale came and ate until there was no corn left and then told Sulemani that he was still hungry and that there were 70,000 more in his tribe. Sulemani then prayed to God for forgiveness and thanked the creature for teaching him a lesson in humility.^[46]

Some cultures associate divinity with whales, such as among Ghanaians and Vietnamese, who occasionally hold funerals for beached whales, a throwback to Vietnam's ancient sea-based Austro-Asiatic culture.^{[51][52][53][54]}

The Bible mentions whales in Genesis 1:21, Job 7:12, Ezekiel and 32:2. The "sea monsters" in Lamentations 4:3 have been taken by some commentators to refer to marine mammals, in particular whales, although most modern versions use the word "jackals" instead.^[55] The story of Jonah being swallowed by a "big Fish" is told both in the Qur'an^[56] and in the Bible. The Old Testament contains the Book of Jonah and in the New Testament, Jesus mentions this story in Matthew 12:40.^[57]

The engraving by William van der Gouwen shows a 20 m (65.6 ft) long whale, stranded on the Dutch coast between Scheveningen and Katwijk on 3 February 1598.

The 1851 American novel, Moby-Dick by Herman Melville concerns a vexed captain's hunt for a gigantic white whale. Rudyard Kipling's 1902 Just So Stories includes the tale of "How the Whale got his Throat".^[58] The film Whale Rider directed by Niki Caro has a Maori girl ride a whale in her quest to be a suitable heir to the chiefship.^[59] An enormous whale called Monstro is the final antagonist featured in Walt Disney's 1940 animated film Pinocchio.

And God Created Great Whales, written in 1970 by American composer Alan Hovhaness, is a work for orchestra and whale songs including the recorded sounds of humpback, bowhead, and killer whales.^[60] The song "Il n'y a plus rien", from French singer-songwriter Léo Ferré's eponymous album (1973), is an example of biomusic that begins and ends with recorded whale songs mixed with a symphonic orchestra and his voice talking over. Recorded whale song is used in the Missa_Gaia/Earth_Mass by Paul Winter (1982) which is performed at the Cathedral of Saint John the Divine each year to celebrate the Feast of St. Francis. The Sanctus and Benedictus portion uses a four note motif derived from humpback whale song to open and close that segment of the work.^[61]