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Manganese
Manganese
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Manganese, 25Mn
A rough fragment of lustrous silvery manganese metal
Pure manganese cube and oxidized manganese chips
Manganese
Pronunciation
Appearancesilvery metallic
Standard atomic weight Ar°(Mn)
Manganese 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


Mn

Tc
chromiummanganeseiron
Atomic number (Z)25
Groupgroup 7
Periodperiod 4
Block  d-block
Electron configuration[Ar] 3d5 4s2
Electrons per shell2, 8, 13, 2
Physical properties
Phase at STPsolid
Melting point1519 K ​(1246 °C, ​2275 °F)
Boiling point2334 K ​(2061 °C, ​3742 °F)
Density (at 20° C)7.476 g/cm3[3]
when liquid (at m.p.)5.95 g/cm3
Heat of fusion12.91 kJ/mol
Heat of vaporization221 kJ/mol
Molar heat capacity26.32 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1228 1347 1493 1691 1955 2333
Atomic properties
Oxidation statescommon: +2, +4, +7
−3,[4] −2,[5][4] −1,[4] 0,[4] +1,[4] +3,[4] +5,[4] +6[4]
ElectronegativityPauling scale: 1.55
Ionization energies
  • 1st: 717.3 kJ/mol
  • 2nd: 1509.0 kJ/mol
  • 3rd: 3248 kJ/mol
  • (more)
Atomic radiusempirical: 127 pm
Covalent radiusLow spin: 139±5 pm
High spin: 161±8 pm
Color lines in a spectral range
Spectral lines of manganese
Other properties
Natural occurrenceprimordial
Crystal structureα-Mn: ​body-centered cubic (bcc) (cI58)
Lattice constant
Body-centered cubic crystal structure for α-Mn: manganese
a = 891.16 pm (at 20 °C)[3]
Thermal expansion23.61×10−6/K (at 20 °C)[3]
Thermal conductivity7.81 W/(m⋅K)
Electrical resistivity1.44 µΩ⋅m (at 20 °C)
Magnetic orderingparamagnetic
Molar magnetic susceptibility(α) +529.0×10−6 cm3/mol (293 K)[6]
Young's modulus198 GPa
Bulk modulus120 GPa
Speed of sound thin rod5150 m/s (at 20 °C)
Mohs hardness6.0
Brinell hardness196 MPa
CAS Number7439-96-5
History
Namingafter Magnesia, Greece
DiscoveryCarl Wilhelm Scheele (1774)
First isolationJohann Gottlieb Gahn (1774)
Isotopes of manganese
Main isotopes[7] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
52Mn synth 5.591 d β+ 52Cr
53Mn trace 3.7×106 y ε 53Cr
54Mn synth 312.08 d ε 54Cr
β 54Fe
β+ 54Cr
55Mn 100% stable
 Category: Manganese
| references

Manganese is a chemical element; it has symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. First isolated in the 1770s, manganese is a transition metal with many industrial alloy uses, particularly in stainless steels. It improves strength, workability, and resistance to wear. Manganese oxide is used as an oxidising agent, as a rubber additive, and in glass making, fertilizers, and ceramics. Manganese sulfate can be used as a fungicide.

Manganese is also an essential human dietary element, important in macronutrient metabolism, bone formation, and free radical defense systems. It is a critical component in dozens of proteins and enzymes.[8] It is found mostly in the bones, but also the liver, kidneys, and brain.[9] In the human brain, the manganese is bound to manganese metalloproteins, most notably glutamine synthetase in astrocytes.

Manganese is commonly found in laboratories in the form of the deep violet salt potassium permanganate where it is used as an oxidizer. Potassium permanganate is also used as a biocide in water treatment.

It occurs at the active sites in some enzymes.[10] Of particular interest is the use of a Mn–O cluster, the oxygen-evolving complex, in the production of oxygen by plants.

Characteristics

[edit]

Physical properties

[edit]

Manganese is a silvery-gray metal that resembles iron. It is hard and very brittle, difficult to melt, but oxidizes easily.[11] Manganese and its common ions are paramagnetic.[12] Manganese tarnishes slowly in air and oxidizes ("rusts") like iron in water containing dissolved oxygen.[13]

Isotopes

[edit]

Naturally occurring manganese is composed of one stable isotope, 55Mn. Several radioisotopes have been isolated and described, ranging from 46Mn to 72Mn. The most stable are 53Mn with a half-life of 3.7 million years, 54Mn with a half-life of 312.08 days, and 52Mn with a half-life of 5.591 days. All of the remaining radioactive isotopes have half-lives of less than three hours, and the majority of less than one minute. The primary decay mode in isotopes lighter than the most abundant stable isotope, 55Mn, is electron capture, and the primary mode in heavier isotopes is beta decay. Manganese also has three meta states.[14]

Manganese is part of the iron group of elements, which are thought to be synthesized in massive stars shortly before the supernova explosion.[15] 53Mn decays to 53Cr with a half-life of 3.7 million years. Because of its short half-life, 53Mn is relatively rare; it is produced by the impact of cosmic rays on iron.[16]

Chromium and manganese are found together sufficiently for measurement of both to find application in isotope geology, and the Mn/Cr ratios here for dating the early Solar System. Mn–Cr isotopic ratios reinforce the evidence from 26Al and 107Pd for the early history of the Solar System. Variations in 53Cr/52Cr and Mn/Cr ratios from several meteorites suggest a non-zero initial 53Mn/55Mn ratio, which indicate that Cr isotopic composition variations must result from in situ decay of 53Mn in differentiated planetary bodies. Hence, 53Mn provides additional evidence for nucleosynthetic processes immediately before the coalescence of the Solar System.[17]

Allotropes

[edit]
Unit cell of an α-Mn crystal
Unit cell of a β-Mn crystal

Four allotropes (structural forms) of solid manganese are known, labeled α, β, γ and δ, and occur at successively higher temperatures. All are metallic, stable at standard pressure, and have a cubic crystal lattice, but they vary widely in their atomic structures.[18][19][20]

Alpha manganese (α-Mn) is the equilibrium phase at room temperature. It has a body-centered cubic lattice and is unusual among elemental metals in that it has a very complex unit cell, with 58 atoms per cell (29 atoms per primitive unit cell) with manganese atoms in four different types of surroundings (sites).[21][18] It is paramagnetic at room temperature and antiferromagnetic at temperatures below 95 K (−178 °C).[22]

Phase diagram of manganese[18]

Beta manganese (β-Mn) forms when heated above the transition temperature of 973 K (700 °C; 1,290 °F). It has a primitive cubic structure with 20 atoms per unit cell at two types of sites, which is as complex as that of any other elemental metal.[23] It is easily obtained as a metastable phase at room temperature by rapid quenching of manganese at 850 °C (1,120 K; 1,560 °F) in ice water. It does not show magnetic ordering, remaining paramagnetic down to the lowest temperature measured (1.1 K).[23][24][25]

Gamma manganese (γ-Mn) forms when heated above 1,370 K (1,100 °C; 2,010 °F). It has a simple face-centered cubic structure (four atoms per unit cell). When quenched to room temperature it converts to β-Mn, but it can be stabilized at room temperature by alloying it with at least 5 percent of other elements (such as C, Fe, Ni, Cu, Pd or Au). These solute-stabilized alloys distort into a face-centered tetragonal structure.[26][25]

Delta manganese (δ-Mn) forms when heated above 1,406 K (1,130 °C; 2,070 °F) and is stable up to the manganese melting point of 1,519 K (1,250 °C; 2,270 °F). It has a body-centered cubic structure (two atoms per cubic unit cell).[19][25]

Chemical compounds

[edit]
Manganese(II) chloride crystals – the pale pink color of Mn(II) salts is due to a spin-forbidden 3d transition.[27]

Common oxidation states of manganese are +2, +3, +4, +6, and +7, although all oxidation states from −3 to +7 have been observed. Manganese in oxidation state +7 is represented by salts of the intensely purple permanganate anion MnO4.[28] Potassium permanganate is a commonly used laboratory reagent because of its oxidizing properties; it is used as a topical medicine (for example, in the treatment of fish diseases). Solutions of potassium permanganate were among the first stains and fixatives to be used in the preparation of biological cells and tissues for electron microscopy.[29]

Aside from various permanganate salts, Mn(VII) is represented by the unstable, volatile derivative Mn2O7. Oxyhalides (MnO3F and MnO3Cl) are powerful oxidizing agents.[11] The most prominent example of Mn in the +6 oxidation state is the green anion manganate, [MnO4]2−. Manganate salts are intermediates in the extraction of manganese from its ores. Compounds with oxidation states +5 are somewhat elusive, and often found associated to an oxide (O2−) or nitride (N3−) ligand.[30] One example is the blue anion hypomanganate [MnO4]3−.[31]

Mn(IV) is somewhat enigmatic because it is common in nature but far rarer in synthetic chemistry. The most common Mn ore, pyrolusite, is MnO2. It is the dark brown pigment of many cave drawings[32] and is also a common ingredient in dry cell batteries.[33] Complexes of Mn(IV), such as in K2[MnF6], are known but are rarer than those of manganese in the lower oxidation states. Mn(IV)-OH complexes are an intermediate in some enzymes, including the oxygen-evolving center (OEC) in plants.[34][35]

Simple derivatives of Mn3+ are rarely encountered but can be stabilized by suitably alkaline ligands. Manganese(III) acetate is an oxidant useful in organic synthesis. Solid compounds of manganese(III) are characterized by a strong purple-red color and a preference for distorted octahedral coordination resulting from the Jahn-Teller effect.[36]

Aqueous solution of KMnO4 illustrating the deep purple of Mn(VII) as it occurs in permanganate

A particularly common oxidation state for manganese in aqueous solution is +2, which has a pale pink color. Many manganese(II) compounds are known, such as the aquo complexes derived from manganese(II) sulfate (MnSO4) and manganese(II) chloride (MnCl2). This oxidation state is also seen in the mineral rhodochrosite (manganese(II) carbonate). Manganese(II) commonly exists with a high-spin ground state, with 5 unpaired electrons, because of its high pairing energy. There are no spin-allowed d–d transitions in manganese(II), which explain its faint color.[37]

Oxidation states of manganese[38]
−3 Mn(CO)(NO)
3
−2 [Mn(1,5-COD)2]2−
−1 HMn(CO)
5
0 Mn
2
(CO)
10
+1 MnC
5
H
4
CH
3
(CO)
3
+2 MnCl
2
, MnCO
3
, MnO
+3 MnF
3
, Mn(OAc)
3
, Mn
2
O
3
+4 MnO
2
+5 K
3
MnO
4
+6 K
2
MnO
4
+7 KMnO
4
, Mn
2
O
7
Common oxidation states are in bold.

Organomanganese compounds

[edit]

Manganese forms a large variety of organometallic derivatives, i.e., compounds with Mn-C bonds. The organometallic derivatives include numerous examples of Mn in its lower oxidation states, i.e. Mn(−III) up through Mn(I). This area of organometallic chemistry is attractive because Mn is inexpensive and of relatively low toxicity.[39]

Of greatest commercial interest is methylcyclopentadienyl manganese tricarbonyl (MMT), which is used as an anti-knock compound added to gasoline in some countries, featuring Mn(I).[40] Consistent with other aspects of Mn(II) chemistry, manganocene (Mn(C5H5)2) is high-spin. In contrast, its neighboring metal, iron, forms an air-stable, low-spin derivative in the form of ferrocene (Fe(C5H5)2). When conducted under an atmosphere of carbon monoxide, reduction of Mn(II) salts gives dimanganese decacarbonyl Mn2(CO)10, an orange and volatile solid. The air-stability of this Mn(0) compound (and its many derivatives) reflects the powerful electron-acceptor properties of carbon monoxide. Many alkene complexes and alkyne complexes are derived from Mn2(CO)10.[41]

In Mn(CH3)2(dmpe)2, Mn(II) is low spin, which contrasts with the high spin character of its precursor, MnBr2(dmpe)2 (dmpe = (CH3)2PCH2CH2P(CH3)2).[42] Polyalkyl and polyaryl derivatives of manganese often exist in higher oxidation states, reflecting the electron-releasing properties of alkyl and aryl ligands. One example is [Mn(CH3)6]2−.[43]

History

[edit]

The origin of the name manganese is complex. In ancient times, two black minerals were identified from the regions of the Magnetes (either Magnesia, located within modern Greece, or Magnesia ad Sipylum, located within modern Turkey).[44] They were both called magnes from their place of origin, but were considered to differ in sex. The male magnes attracted iron, and was the iron ore now known as lodestone or magnetite, and which probably gave us the term magnet. The female magnes ore did not attract iron, but was used to decolorize glass. This female magnes was later called magnesia, known now in modern times as pyrolusite or manganese dioxide.[45] Neither this mineral nor elemental manganese is magnetic. In the 16th century, manganese dioxide was called manganesum (note the two Ns instead of one) by glassmakers, possibly as a corruption and concatenation of two words, since alchemists and glassmakers eventually had to differentiate a magnesia nigra (the black ore) from magnesia alba (a white ore, also from Magnesia, also useful in glassmaking). Italian physician Michele Mercati called magnesia nigra manganesa, and finally the metal isolated from it became known as manganese (German: Mangan). The name magnesia was eventually used to refer only to the white magnesia alba (magnesium oxide), which provided the name magnesium for the free element when it was isolated much later.[46]

A drawing of a left-facing bull, in black, on a cave wall
Some of the cave paintings in Lascaux, France, use manganese-based pigments.[47]

Manganese dioxide, which is abundant in nature, has long been used as a pigment. The cave paintings in Gargas that are 30,000 to 24,000 years old are made from the mineral form of MnO2 pigments.[48]

Manganese compounds were used by Egyptian and Roman glassmakers, either to add to, or remove, color from glass.[49] Use as "glassmakers soap" continued through the Middle Ages until modern times and is evident in 14th-century glass from Venice.[50]

Credit for first isolating manganese is usually given to Johan Gottlieb Gahn.

Because it was used in glassmaking, manganese dioxide was available for experiments by alchemists, the first chemists. Ignatius Gottfried Kaim (1770) and Johann Glauber (17th century) discovered that manganese dioxide could be converted to permanganate, a useful laboratory reagent.[51] By the mid-18th century, the Swedish chemist Carl Wilhelm Scheele used manganese dioxide to produce chlorine. First, hydrochloric acid, or a mixture of dilute sulfuric acid and sodium chloride was made to react with manganese dioxide, and later hydrochloric acid from the Leblanc process was used and the manganese dioxide was recycled by the Weldon process.[52][40]

Scheele and others were aware that pyrolusite (mineral form of manganese dioxide) contained a new element. Johan Gottlieb Gahn isolated an impure sample of manganese metal in 1774, which he did by reducing the dioxide with carbon.[53] Ignatius Gottfried Kaim also may have reduced manganese dioxide to isolate the metal, but that is uncertain.[54][55]

The manganese content of some iron ores used in Greece led to speculations that steel produced from that ore contains additional manganese, making the Spartan steel exceptionally hard.[56] Around the beginning of the 19th century, manganese was used in steelmaking and several patents were granted. In 1816, it was documented that iron alloyed with manganese was harder but not more brittle. In 1837, British academic James Couper noted an association between miners' heavy exposure to manganese and a form of Parkinson's disease.[57][58] In 1912, United States patents were granted for protecting firearms against rust and corrosion with manganese phosphate electrochemical conversion coatings, and the process has seen widespread use ever since.[59]

The invention of the Leclanché cell in 1866 and the subsequent improvement of batteries containing manganese dioxide as cathodic depolarizer increased the demand for manganese dioxide. Until the development of batteries with nickel–cadmium and lithium, most batteries contained manganese. The zinc–carbon battery and the alkaline battery normally use industrially produced manganese dioxide because naturally occurring manganese dioxide contains impurities. In the 20th century, manganese dioxide was widely used as the cathode for commercial disposable dry batteries of both the standard (zinc–carbon) and alkaline types.[60]

Manganese is essential to iron and steel production by virtue of its sulfur-fixing, deoxidizing, and alloying properties.[61] This application was first recognized by the British metallurgist Robert Forester Mushet (1811–1891), who introduced the element to the steel manufacture process in 1856 in the form of spiegeleisen.[62]

Occurrence

[edit]

Manganese comprises about 1000 ppm (0.1%) of the Earth's crust and is the 12th most abundant element.[9] Soil contains 7–9000 ppm of manganese with an average of 440 ppm.[9] The atmosphere contains 0.01 μg/m3.[9] Manganese occurs principally as pyrolusite (MnO2), braunite (Mn2+Mn3+6)SiO12),[63] psilomelane (Ba,H2O)2Mn5O10, and to a lesser extent as rhodochrosite (MnCO3).

Manganese ore Psilomelane (manganese ore) Spiegeleisen is an iron alloy with a manganese content of approximately 15%. Manganese oxide dendrites on limestone from Solnhofen, Germany – a kind of pseudofossil. Scale is in mm Mineral rhodochrosite (manganese(II) carbonate)
Percentage of manganese output in 2006 by countries[61]

The most important manganese ore is pyrolusite (MnO2). Other economically important manganese ores usually show a close spatial relation to the iron ores, such as sphalerite.[11][64] Land-based resources are large but irregularly distributed. About 80% of the known world manganese resources are in South Africa; other important manganese deposits are in Ukraine, Australia, India, China, Gabon and Brazil.[61]

Manganese is mainly mined in South Africa, Australia, China, Gabon, Brazil, India, Kazakhstan, Ghana, Ukraine and Malaysia.[65] In South Africa, most identified deposits are located near Hotazel in the Northern Cape Province, (Kalahari manganese fields), with a 2011 estimate of 15 billion tons. In 2011 South Africa produced 3.4 million tons, topping all other nations.[66]

Oceanic environment

[edit]

An abundant resource of manganese in the form of manganese nodules found on the ocean floor.[67] These nodules, which are composed of 29% manganese,[68] are located along the ocean floor. The environmental impacts of nodule collection are of interest.[69][70] According to 1978 estimate, the ocean floor has 500 billion tons of manganese nodules.[71] As of April 2025, attempts to find economically viable methods of harvesting manganese nodules are still ongoing, however, none has been commercialized.[72]

In 1972, the CIA's Project Azorian, through billionaire Howard Hughes, commissioned the ship Hughes Glomar Explorer with the cover story of harvesting manganese nodules from the sea floor.[73] This cover story triggered a rush of activity to collect manganese nodules. The real mission of Hughes Glomar Explorer was to raise a sunken Soviet submarine, the K-129, with the goal of retrieving Soviet code books.[74]

Manganese also occurs in the oceanic environment, as dissolved manganese (dMn), which is found throughout the world's oceans, 90% of which originates from hydrothermal vents.[75] Particulate Mn develops in buoyant plumes over an active vent source, while the dMn behaves conservatively.[76] Mn concentrations vary between the water columns of the ocean. At the surface, dMn is elevated due to input from external sources such as rivers, dust, and shelf sediments. Coastal sediments normally have lower Mn concentrations, but can increase due to anthropogenic discharges from industries such as mining and steel manufacturing, which enter the ocean from river inputs. Surface dMn concentrations can also be elevated biologically through photosynthesis and physically from coastal upwelling and wind-driven surface currents. Internal cycling such as photo-reduction from UV radiation can also elevate levels by speeding up the dissolution of Mn-oxides and oxidative scavenging, preventing Mn from sinking to deeper waters.[77] Elevated levels at mid-depths can occur near mid-ocean ridges and hydrothermal vents. The hydrothermal vents release dMn enriched fluid into the water. The dMn can then travel up to 4,000 km due to the microbial capsules present, preventing exchange with particles, lowing the sinking rates. Dissolved Mn concentrations are even higher when oxygen levels are low. Overall, dMn concentrations are normally higher in coastal regions and decrease when moving offshore.[77]

Soils

[edit]

Manganese occurs in soils in three oxidation states: the divalent cation, Mn2+ and as brownish-black oxides and hydroxides containing Mn (III,IV), such as MnOOH and MnO2. Soil pH and oxidation-reduction conditions affect which of these three forms of Mn is dominant in a given soil. At pH values less than 6 or under anaerobic conditions, Mn(II) dominates, while under more alkaline and aerobic conditions, Mn(III,IV) oxides and hydroxides predominate. These effects of soil acidity and aeration state on the form of Mn can be modified or controlled by microbial activity. Microbial respiration can cause both the oxidation of Mn2+ to the oxides, and it can cause reduction of the oxides to the divalent cation.[78]

The Mn(III,IV) oxides exist as brownish-black stains and small nodules on sand, silt, and clay particles. These surface coatings on other soil particles have high surface area and carry negative charge. The charged sites can adsorb and retain various cations, especially heavy metals (e.g., Cr3+, Cu2+, Zn2+, and Pb2+). In addition, the oxides can adsorb organic acids and other compounds. The adsorption of the metals and organic compounds can then cause them to be oxidized while the Mn(III,IV) oxides are reduced to Mn2+ (e.g., Cr3+ to Cr(VI) and colorless hydroquinone to tea-colored quinone polymers).[79]

Production

[edit]

A significant proportion of the manganese ore mined, around 85% in the United States, is used in iron and steel production, such as in the production of ferromanganese.[80] For the production of ferromanganese, the manganese ore is mixed with iron ore and carbon, and then reduced either in a blast furnace or in an electric arc furnace.[81] The resulting ferromanganese has a manganese content of 30–80%.[11] Pure manganese used for the production of iron-free alloys is produced by leaching manganese ore with sulfuric acid and a subsequent electrowinning process.[82]

Contains reactions and temperatures, as well as showing advanced processes such as the heat exchanger and milling process.
Process flow diagram for a manganese refining circuit

A more progressive extraction process involves directly reducing (a low grade) manganese ore by heap leaching. This is done by percolating natural gas through the bottom of the heap; the natural gas provides the heat (needs to be at least 850 °C) and the reducing agent (carbon monoxide). This reduces all of the manganese ore to manganese oxide (MnO), which is a leachable form. The ore then travels through a grinding circuit to reduce the particle size of the ore to between 150 and 250 μm, increasing the surface area to aid leaching. The ore is then added to a leach tank of sulfuric acid and ferrous iron (Fe2+) in a 1.6:1 ratio. The iron reacts with the manganese dioxide (MnO2) to form iron hydroxide (FeO(OH)) and elemental manganese (Mn).[83]

This process yields greater than 90% recovery of the manganese. For further purification, the manganese can then be sent to an electrowinning facility.[83]

Applications

[edit]

Steel

[edit]
U.S. M1917 combat helmet, a variant of Brodie helmet, made from Hadfield steel manganese alloy

Manganese is essential to iron and steel production by virtue of its sulfur-fixing, deoxidizing, and alloying properties. Manganese has no satisfactory substitute in these applications in metallurgy.[61] Steelmaking,[84] including its ironmaking component, has accounted for most manganese demand, presently in the range of 85% to 90% of the total demand.[82] Manganese is a key component of low-cost stainless steel.[85][86] Often ferromanganese (usually about 80% manganese) is the intermediate in modern processes.

Small amounts of manganese improve the workability of steel at high temperatures by forming a high-melting sulfide and preventing the formation of a liquid iron sulfide at the grain boundaries. If the manganese content reaches 4%, the embrittlement of the steel becomes a dominant feature. The embrittlement decreases at higher manganese concentrations and reaches an acceptable level at 8%. Steel containing 8 to 15% of manganese has a high tensile strength of up to 863 MPa.[87][88] Steel with 12% manganese was discovered in 1882 by Robert Hadfield and is still known as Hadfield steel (mangalloy). It was used for British military steel helmets and later by the U.S. military.[89]

Aluminium alloys

[edit]

Manganese is used in production of alloys with aluminium. Aluminium with roughly 1.5% manganese has increased resistance to corrosion through grains that absorb impurities which would lead to galvanic corrosion.[90] The corrosion-resistant aluminium alloys 3004 and 3104 (0.8 to 1.5% manganese) are used for most beverage cans.[91] Before 2000, more than 1.6 million tonnes of those alloys were used; at 1% manganese, this consumed 16,000 tonnes of manganese.[91]

Batteries

[edit]

Manganese(IV) oxide was used in the original type of dry cell battery as an electron acceptor from zinc, and is the blackish material in carbon–zinc type flashlight cells. The manganese dioxide is reduced to the manganese oxide-hydroxide MnO(OH) during discharging, preventing the formation of hydrogen at the anode of the battery.[92]

MnO2 + H2O + e → MnO(OH) + OH

The same material also functions in newer alkaline batteries (usually battery cells), which use the same basic reaction, but a different electrolyte mixture. In 2002, more than 230,000 tons of manganese dioxide was used for this purpose.[60][92]

Resistors

[edit]

Copper alloys of manganese, such as Manganin, are commonly found in metal element shunt resistors used for measuring relatively large amounts of current. These alloys have very low temperature coefficient of resistance and are resistant to sulfur. This makes the alloys particularly useful in harsh automotive and industrial environments.[93][94]

Fertilizers and feed additive

[edit]

Manganese oxide and sulfate are components of fertilizers. In the year 2000, an estimated 20,000 tons of these compounds were used in fertilizers in the US alone. A comparable amount of Mn compounds was also used in animal feeds.[40]

Niche

[edit]

Methylcyclopentadienyl manganese tricarbonyl is an additive in some unleaded gasoline to boost octane rating and reduce engine knocking.[95]

Manganese(IV) oxide (manganese dioxide, MnO2) is used as a reagent in organic chemistry for the oxidation of benzylic alcohols (where the hydroxyl group is adjacent to an aromatic ring).[96] Manganese dioxide has been used since antiquity to oxidize and neutralize the greenish tinge in glass from trace amounts of iron contamination.[50] MnO2 is also used in the manufacture of oxygen and chlorine and in drying black paints. In some preparations, it is a brown pigment for paint and is a constituent of natural umber.[97]

Tetravalent manganese is used as an activator in red-emitting phosphors. While many compounds are known which show luminescence,[98] the majority are not used in commercial application due to low efficiency or deep red emission.[99][100] However, several Mn4+ activated fluorides were reported as potential red-emitting phosphors for warm-white LEDs.[101][102] But to this day, only K2SiF6:Mn4+ is commercially available for use in warm-white LEDs.[103]

World-War-II-era 5-cent coin (1942-5 identified by mint mark P, D or S above dome) made from a 56% copper-35% silver-9% manganese alloy

The metal is occasionally used in coins; until 2000, the only United States coin to use manganese was the "wartime" nickel from 1942 to 1945.[104] An alloy of 75% copper and 25% nickel was traditionally used for the production of nickel coins. However, because of shortage of nickel metal during the war, it was substituted by more available silver and manganese, thus resulting in an alloy of 56% copper, 35% silver and 9% manganese. Since 2000, dollar coins, for example the Sacagawea dollar and the Presidential $1 coins, are made from a brass containing 7% of manganese with a pure copper core.[105]

Manganese compounds have been used as pigments and for the coloring of ceramics and glass. The brown color of ceramic is sometimes the result of manganese compounds.[106] In the glass industry, manganese compounds are used for two effects. Manganese(III) reacts with iron(II) to reduce strong green color in glass by forming less-colored iron(III) and slightly pink manganese(II), compensating for the residual color of the iron(III).[50] Larger quantities of manganese are used to produce pink colored glass. In 2009, Mas Subramanian and associates at Oregon State University discovered that manganese can be combined with yttrium and indium to form an intensely blue, non-toxic, inert, fade-resistant pigment, YInMn Blue,[107] the first new blue pigment discovered in 200 years.[108]

Biochemistry

[edit]
Reactive center of arginase with boronic acid inhibitor – the manganese atoms are shown in yellow.

Many classes of enzymes contain manganese cofactors including oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Other enzymes containing manganese are arginase and a Mn-containing superoxide dismutase (Mn-SOD). Some reverse transcriptases of many retroviruses (although not lentiviruses such as HIV) contain manganese. Manganese-containing polypeptides are the diphtheria toxin, lectins, and integrins.[109]

The oxygen-evolving complex (OEC), containing four atoms of manganese, is a part of photosystem II contained in the thylakoid membranes of chloroplasts. The OEC is responsible for the terminal photooxidation of water during the light reactions of photosynthesis, i.e., it is the catalyst that makes the O2 produced by plants.[110][111]

Human health and nutrition

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Manganese is an essential human dietary element and is present as a coenzyme in several biological processes, which include macronutrient metabolism, bone formation, and free radical defense systems. Manganese is a critical component in dozens of proteins and enzymes.[8] The human body contains about 12 mg of manganese, mostly in the bones. The soft tissue remainder is concentrated in the liver and kidneys.[9] In the human brain, the manganese is bound to manganese metalloproteins, most notably glutamine synthetase in astrocytes.[112]

Current AIs of Mn by age group and sex[113]
Males Females
Age AI (mg/day) Age AI (mg/day)
1–3 1.2 1–3 1.2
4–8 1.5 4–8 1.5
9–13 1.9 9–13 1.6
14–18 2.2 14–18 1.6
19+ 2.3 19+ 1.8
pregnant: 2
lactating: 2.6

Regulation

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The U.S. Institute of Medicine (IOM) updated Estimated Average Requirements (EARs) and Recommended Dietary Allowances (RDAs) for minerals in 2001. For manganese, there was not sufficient information to set EARs and RDAs, so needs are described as estimates for Adequate Intakes (AIs). As for safety, the IOM sets Tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of manganese, the adult UL is set at 11 mg/day. Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes (DRIs).[113] Manganese deficiency is rare.[114]

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 15 and older, the AI is set at 3.0 mg/day. AIs for pregnancy and lactation are 3.0 mg/day. For children ages 1–14 years, the AIs increase with age from 0.5 to 2.0 mg/day. The adult AIs are higher than the U.S. RDAs.[115] The EFSA reviewed the same safety question and decided that there was insufficient information to set a UL.[116]

For U.S. food and dietary supplement labeling purposes, the amount in a serving is expressed as a percent of Daily Value (%DV). For manganese labeling purposes, 100% of the Daily Value was 2.0 mg, but as of 27 May 2016 it was revised to 2.3 mg to bring it into agreement with the RDA.[117][118] A table of the old and new adult daily values is provided at Reference Daily Intake.

Excessive exposure or intake may lead to a condition known as manganism, a neurodegenerative disorder that causes dopaminergic neuronal death and symptoms similar to Parkinson's disease.[9][119]

Deficiency

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Manganese deficiency in humans, which is rare, results in a number of medical problems.[113] A deficiency of manganese causes skeletal deformation in animals and inhibits the production of collagen in wound healing.[120]

Exposure

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In water

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Waterborne manganese has a greater bioavailability than dietary manganese. According to results from a 2010 study,[121] higher levels of exposure to manganese in drinking water are associated with increased intellectual impairment and reduced intelligence quotients in school-age children. It is hypothesized that long-term exposure due to inhaling the naturally occurring manganese in shower water puts up to 8.7 million Americans at risk.[122] However, data indicates that the human body can recover from certain adverse effects of overexposure to manganese if the exposure is stopped and the body can clear the excess.[123]

Mn levels can increase in seawater when hypoxic periods occur.[124] Since 1990 there have been reports of Mn accumulation in marine organisms including fish, crustaceans, mollusks, and echinoderms. Specific tissues are targets in different species, including the gills, brain, blood, kidney, and liver/hepatopancreas. Physiological effects have been reported in these species. Mn can affect the renewal of immunocytes and their functionality, such as phagocytosis and activation of pro-phenoloxidase, suppressing the organisms' immune systems. This causes the organisms to be more susceptible to infections. As climate change occurs, pathogen distributions increase, and in order for organisms to survive and defend themselves against these pathogens, they need a healthy, strong immune system. If their systems are compromised from high Mn levels, they will not be able to fight off these pathogens and die.[75]

Gasoline

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Molecular model of methylcyclopentadienyl manganese tricarbonyl (MMT)

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an additive developed to replace lead compounds for gasolines to improve the octane rating. MMT is used only in a few countries. When exposed to the environment, fuels containing methylcyclopentadienyl manganese tricarbonyl degrade, releasing manganese into water and soils.[125]

Air

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Manganese levels in the air decreased between 1953 and 1982, with higher levels in 1953. In general, breathing air with more than 5 micrograms of manganese per cubic meter can cause symptoms of manganese exposure. In lab-grown human kidney cells, higher levels of a protein called ferroportin are linked to lower manganese levels inside the cells and reduced cell damage, shown by better glutamate uptake and less leakage of a damage marker known as lactate dehydrogenase.[126][127]

Regulation

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Manganese exposure in United States is regulated by the Occupational Safety and Health Administration (OSHA).[128] People can be exposed to manganese in the workplace by breathing it in or swallowing it. OSHA has set the legal limit (permissible exposure limit) for manganese exposure in the workplace as 5 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 1 mg/m3 over an 8-hour workday and a short term limit of 3 mg/m3. At levels of 500 mg/m3, manganese is immediately dangerous to life and health.[129] In other countries, such as Germany, a general ceiling value for airborne manganese has been set to 0.5 mg/m3 (Maximale Arbeitsplatz-Konzentration [de]) and the maximum level of manganese in the body has been set to 20 mg/L.[40]

Health and safety

[edit]
Manganese
Hazards
GHS labelling:
H401
P273, P501[130]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g. sodium chlorideFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
0
0

Manganese is essential for human health, albeit in milligram amounts.[113] The current maximum safe concentration under U.S. EPA rules is 50 μg Mn/L.[131]

Manganism

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Manganese overexposure is most frequently associated with manganism, a rare neurological disorder associated with excessive manganese ingestion or inhalation. Historically, persons employed in the production or processing of manganese alloys[132][133][134] have been at risk for developing manganism; however, health and safety regulations protect workers in developed nations.[128] The disorder was first described in 1837 by British academic John Couper, who studied two patients who were manganese grinders.[57]

Manganism is a biphasic disorder. In its early stages, an intoxicated person may experience depression, mood swings, compulsive behaviors, and psychosis. Early neurological symptoms give way to late-stage manganism, which resembles Parkinson's disease. Symptoms include weakness, monotone and slowed speech, an expressionless face, tremor, forward-leaning gait, inability to walk backwards without falling, rigidity, and general problems with dexterity, gait and balance.[57][135] Unlike Parkinson's disease, manganism is not associated with loss of the sense of smell and patients are typically unresponsive to treatment with L-DOPA.[136] Symptoms of late-stage manganism become more severe over time even if the source of exposure is removed and brain manganese levels return to normal.[135]

Chronic manganese exposure has been shown to produce a parkinsonism-like illness characterized by movement abnormalities.[137] This condition is not responsive to typical therapies used in the treatment of PD, suggesting an alternative pathway to the typical dopaminergic loss within the substantia nigra.[137] Manganese may accumulate in the basal ganglia, leading to the abnormal movements.[138] A mutation of the SLC30A10 gene, a manganese efflux transporter necessary for decreasing intracellular Mn, has been linked with the development of this Parkinsonism-like disease.[139] The Lewy bodies typical to PD are not seen in Mn-induced parkinsonism.[138]

Animal experiments have given the opportunity to examine the consequences of manganese overexposure under controlled conditions. In (non-aggressive) rats, manganese induces mouse-killing behavior.[140]

Toxicity

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Manganese compounds are less toxic than those of other widespread metals, such as nickel and copper.[141] However, exposure to manganese dusts and fumes should not exceed the ceiling value of 5 mg/m3 even for short periods because of its toxicity level.[142] Manganese poisoning has been linked to impaired motor skills and cognitive disorders.[143]

Neurodegenerative diseases

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A protein called DMT1 is the major transporter in manganese absorption from the intestine and may be the major transporter of manganese across the blood–brain barrier. DMT1 also transports inhaled manganese across the nasal epithelium. The proposed mechanism for manganese toxicity is that dysregulation leads to oxidative stress, mitochondrial dysfunction, glutamate-mediated excitotoxicity, and aggregation of proteins.[144]

See also

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References

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[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Manganese (French: manganèse; Arabic: المنغنيز, transliterated as مَنْغَنِيز or مَنْجَنِيز) is a with the symbol Mn and 25, classified as a in group 7 of the periodic table. It is a hard, brittle, silvery-gray metal that is reactive with and acids, with a of 1,246 °C and a density of 7.21 g/cm³ at 25 °C. First isolated in 1774 by Swedish chemist Johan Gottlieb Gahn through the reduction of , it does not occur naturally in its pure form but is found in various minerals such as pyrolusite (MnO₂). Manganese is the 12th most abundant element in the , comprising about 0.1% by weight, and is widely distributed in rocks, soils, and , particularly concentrated in deep-sea nodules. Industrially, it is primarily extracted from ores and used as an alloying agent in production, where it improves strength, hardness, and resistance to wear; over 90% of global manganese consumption goes into as a deoxidizer and desulfurizer. Other applications include batteries (e.g., alkaline and lithium-ion), fertilizers, pigments, and chemicals. Biologically, manganese is an essential required for human health, serving as a cofactor for numerous enzymes involved in , defense, bone formation, and blood clotting. It plays a critical role in as part of the in , enabling to produce oxygen; it is vital for microbial and animal physiology, though excessive exposure can lead to resembling . Dietary sources include nuts, whole grains, leafy greens, and teas, with adults needing about 1.8–2.3 mg daily to prevent deficiency, which is rare in balanced diets.

Physical and chemical properties

Physical properties

is a element with the 25 and the Mn. Its is 54.938044 u. The of the manganese atom is [Ar] 3d^5 4s^2. In its pure form, manganese is a silvery-gray, brittle metal. The of manganese varies depending on its allotrope, ranging from 7.21 to 7.44 g/cm³. It has a of 1,246 °C and a of 2,061 °C. Manganese exhibits a Mohs hardness of 6 in its alpha form and a Vickers hardness of 400 MPa, reflecting its relatively hard and brittle nature. At , manganese is paramagnetic. It transitions to an antiferromagnetic state below approximately 100 , though certain allotropes and conditions can influence this behavior. The electrical resistivity of manganese is 1.44 μΩ·m at 20 °C, indicating moderate electrical conductivity for a metal. Its thermal conductivity is 7.81 W/(m·), which is notably low among pure metals.
PropertyValue
Atomic number25
SymbolMn
Atomic mass54.938044 u
Electron configuration[Ar] 3d⁵ 4s²
AppearanceSilvery-gray, brittle metal
Density (varies by allotrope)7.21–7.44 g/cm³
Melting point1,246 °C
Boiling point2,061 °C
Mohs hardness (α-Mn)6
Vickers hardness400 MPa
Magnetic property (room temp)Paramagnetic
Electrical resistivity (20 °C)1.44 μΩ·m
Thermal conductivity7.81 W/(m·K)

Chemical properties

Manganese, as a first-row , displays a range of s from +2 to +7, reflecting its variable and ability to form diverse compounds. The +2 is the most stable, particularly in aqueous solutions where the pale pink Mn²⁺ ion predominates due to its high-spin d⁵ configuration. The +4 state is common in stable oxides like MnO₂, while the +7 state appears in the ion (MnO₄⁻), characterized by its deep purple color and potent oxidizing properties. These states enable manganese's role in processes, with higher states acting as oxidants and lower ones as reductants. Manganese metal exhibits moderate reactivity typical of transition metals. Manganese is unreactive with under normal conditions. In dilute acids, such as hydrochloric or , it dissolves readily, evolving gas and forming soluble Mn²⁺ salts. Upon heating in air, manganese oxidizes stepwise; at around 800 °C, it forms manganese(III) oxide (Mn₂O₃), a black solid. The redox behavior of manganese is quantified by its standard reduction potentials, which span a wide range indicative of its versatility. For instance, the reduction of permanganate to Mn²⁺ in acidic medium is highly favorable: MnO4+8H++5eMn2++4H2OE=+1.51V\text{MnO}_4^- + 8\text{H}^+ + 5\text{e}^- \rightarrow \text{Mn}^{2+} + 4\text{H}_2\text{O} \quad E^\circ = +1.51 \, \text{V} This makes permanganate a strong oxidant. Conversely, the reduction of Mn²⁺ to metallic manganese is unfavorable: Mn2++2eMnE=1.18V\text{Mn}^{2+} + 2\text{e}^- \rightarrow \text{Mn} \quad E^\circ = -1.18 \, \text{V} highlighting manganese's tendency to remain in higher oxidation states under oxidizing conditions. In coordination chemistry, manganese ions predominantly adopt octahedral geometries due to the d-orbital splitting favoring six-coordinate structures, as seen in numerous Mn(II) and Mn(III) complexes. For example, Mn(II) often forms high-spin octahedral complexes with water or ligands. In organomanganese compounds, such as alkylmanganese species, bonding is more covalent, involving sigma interactions between manganese and carbon atoms, which contrasts with the ionic character in simple salts.

Isotopes and allotropes

Isotopes

Manganese possesses a single stable isotope, 55^{55}Mn, which accounts for 100% of its natural abundance. This isotope has a nuclear spin of 5/25/2^-. Twenty-seven radioactive isotopes of manganese have been characterized, with mass numbers ranging from 44 to 73. Among these, 53^{53}Mn is the longest-lived with a half-life of approximately 3.7 million years and is used in cosmogenic nuclide dating. 52^{52}Mn has a half-life of 5.59 days and serves as a positron emitter in medical imaging applications such as positron emission tomography (PET). Similarly, 54^{54}Mn is an electron capture nuclide with a half-life of 312 days, often emitting gamma radiation during decay. Radioactive isotopes of manganese are commonly produced via neutron activation of the stable 55^{55}Mn in nuclear reactors, as exemplified by the reaction 55^{55}Mn(n,γ\gamma)56^{56}Mn. Key nuclear properties of 55^{55}Mn include a thermal neutron capture cross-section of 13.3 barns, which influences its behavior in neutron interactions. Manganese isotopes contribute to stellar nucleosynthesis through the s-process, where slow neutron captures in asymptotic giant branch stars help build heavier elements beyond iron, including contributions to 55^{55}Mn abundance.

Allotropes

Manganese exhibits four distinct allotropic forms in the solid state, known as α-Mn, β-Mn, γ-Mn, and δ-Mn, each characterized by unique crystal structures and temperature stability ranges. The α-Mn phase is the thermodynamically stable form at room temperature and remains so up to approximately 727 °C; it possesses a complex body-centered cubic structure in the space group I¯43m, featuring a large 58-atom unit cell that arises from the close packing of icosahedral clusters. Upon heating, α-Mn undergoes a phase transition to β-Mn at 727 °C, with the β phase stable from 727 °C to 1,100 °C and exhibiting a cubic structure in the space group P4₁3₂ with a 20-atom unit cell composed of tetrahedral and octahedral coordination environments. Further heating leads to the γ-Mn phase, which is face-centered cubic (space group Fm¯3m) and stable between 1,100 °C and 1,135 °C, followed by the δ-Mn phase above 1,135 °C up to the melting point at 1,246 °C, where δ-Mn adopts a simple body-centered cubic structure (space group Im¯3m). These phase transitions are , involving changes in atomic packing and coordination that influence the material's and mechanical . For instance, the of α-Mn is 7.44 g/cm³ at , slightly higher than that of β-Mn at 7.29 g/cm³ (measured under stabilized conditions), while the high-temperature γ-Mn has a lower of approximately 6.37 g/cm³ at 1,100 °C due to . The structural complexity of α-Mn and β-Mn contributes to variations in physical properties, such as hardness; α-Mn is the hardest and most brittle allotrope, rendering it challenging to machine, whereas γ-Mn's face-centered cubic lattice resembles that of austenitic steels, providing greater in its stability range. Pure samples of these allotropes are synthesized through methods that control the cooling rate from the molten state to stabilize lower-temperature phases or by electrodeposition from aqueous electrolytes under specific pH, current density, and additive conditions to selectively deposit α-Mn or β-Mn. For example, rapid quenching from above the β-Mn stability range can retain the β phase at room temperature, while slower cooling favors the equilibrium α phase. These structural differences underpin key physical properties like brittleness in α-Mn, though detailed mechanical metrics are phase-specific and temperature-dependent.

History

Discovery and isolation

Manganese compounds were utilized in antiquity for glassmaking, where pyrolusite served as a decolorizing agent to remove greenish tints caused by iron impurities, a practice documented by in the 1st century AD. The black mineral pyrolusite, known as "magnesia negra" since the , was distinguished from iron ores during early chemical analyses. In 1740, German chemist Johann Heinrich Pott conducted experiments on pyrolusite, demonstrating that it contained no iron and represented a distinct substance, marking an early step toward recognizing manganese as a unique element. By the mid-18th century, further investigations clarified pyrolusite's composition. In 1770, Swedish chemist Torbern Olof Bergman identified it as the calx (oxide) of a new metal but failed to reduce it to the elemental form. In 1774, , a Swedish apothecary and , performed detailed studies on pyrolusite, confirming its nature through reactions that also led to the discovery of ; he proposed the name "manganese" for the element derived from the mineral. That same year, Johan Gottlieb Gahn, collaborating with Scheele and Bergman in , successfully isolated metallic manganese by heating pyrolusite (MnO₂) with carbon in a furnace, yielding the pure metal for the first time. The name manganese originates from the Latin "magnes," meaning magnet, referring to the magnetic properties observed in some manganese oxides like pyrolusite. In , Swedish determined the atomic weight of manganese through precise analytical methods, contributing to its integration into early periodic systems.

Historical uses

Manganese dioxide (MnO₂), primarily in the form of the mineral pyrolusite, served as a black pigment in prehistoric cave art. Evidence shows deliberate collection and grinding of pyrolusite by Neanderthals dating back approximately 50,000 years ago at sites like Pech-de-l'Azé I in , likely for fire-making purposes. In ancient Egypt during the New Kingdom around 1500 BCE, manganese compounds were incorporated into early formulations, often as trace elements in colorants like to produce deep blues or to mitigate unwanted tints from iron impurities, marking one of the earliest known applications in vitreous materials. From the medieval period through the , pyrolusite found widespread application in ceramics and brick-making across and the Islamic world, where it was ground and added to glazes or clay bodies to impart , black, or reddish hues; for instance, in 14th- to 15th-century Valencian lusterware, it combined with hausmannite to achieve stable tones in . Its role as a coloring agent extended to the brick industry, where small additions enhanced fired colors for architectural elements, leveraging manganese's oxidizing properties during kiln firing to deepen shades without altering structural integrity. During the , the European glass industry, including in , employed as a decolorizing agent to neutralize tints from iron impurities in . In the , manganese's metallurgical uses emerged prominently. British metallurgist Josiah Marshall Heath patented in 1839 a process for adding manganese—often as a carburet compound—to molten , acting as a deoxidizer to remove oxygen and improve fluidity and quality, thereby enabling more reliable production of from . The 1856 invention of the for steelmaking further amplified demand, as the air-blown conversion of depleted carbon and other elements, necessitating the subsequent addition of 0.5–1% ferromanganese or spiegeleisen to recarburize, deoxidize, and enhance malleability, which spurred global mining and supply chains for manganese ores. The development of early manganese alloys advanced quality in the mid-19th century. Ferromanganese, first utilized systematically by around 1860 as a means to introduce controlled amounts of manganese during production, saw expanded application in the 1870s through the basic invented by Sidney Gilchrist Thomas and Percy Gilchrist; this method lined converters with basic materials like dolomite to capture as , while ferromanganese additions neutralized residual impurities and improved the 's strength for phosphoric iron ores prevalent in .

Occurrence

Abundance and sources

Manganese ranks as the 12th most abundant element in the , where it constitutes approximately 0.1% by , or about 1,000 ppm. In the broader cosmic context, manganese is less prevalent, with an estimated abundance of about 10 parts per million by in solar system materials, placing it among the moderately abundant heavy elements produced primarily through . The primary ores of manganese include pyrolusite (β-MnO₂), which typically contains 50–70% manganese and serves as the most important commercial source due to its high purity and widespread occurrence; psilomelane, a complex hydrated mineral often associated with cryptomelane; and (MnCO₃), a manganese ore. These minerals form through sedimentary, hydrothermal, and processes, with pyrolusite being particularly dominant in oxidized deposits. Global manganese reserves are estimated at 1.7 billion metric tons, according to data from the U.S. Geological Survey (USGS) for 2025, reflecting economically extractable resources under current conditions. Major deposits are concentrated in the Kalahari Manganese Field in , which accounts for about 70% of the world's identified resources and a significant portion of reserves (approximately 560 million metric tons); other key locations include (61 million metric tons of reserves), (500 million metric tons), and (270 million metric tons). An additional potential source lies in seafloor polymetallic nodules, potato-sized concretions on the deep ocean floor that contain 20–30% manganese along with valuable metals like , , and , representing a vast but largely untapped resource estimated in billions of tons across abyssal plains.

Distribution in environments

Manganese is distributed across various environmental compartments through geochemical cycling, primarily originating from geological ores and processes. In oceanic environments, dissolved manganese concentrations typically range from 0.1 to 10 nM in open , with higher levels near hydrothermal vents or coastal zones due to inputs from reduced sediments and . Polymetallic manganese nodules, enriched in manganese oxides, cover approximately 20% of the abyssal seafloor, particularly in the Pacific Ocean's Clarion-Clipperton Zone, with global estimates exceeding 10¹² tonnes of nodule material. in regions like the Peruvian shelf transports reduced manganese from deeper waters to the surface, enhancing its and contributing to cycling in oxygenated surface layers. In terrestrial ecosystems, manganese concentrations in soils average 200 to 3,000 ppm, varying with parent rock composition and pedogenic processes. is strongly influenced by , with higher and uptake in acidic conditions (pH < 6) where Mn²⁺ dominates, while alkaline calcareous soils (pH > 7) promote oxidation to less soluble forms, often leading to deficiencies for plant growth. Atmospheric manganese arises mainly from aeolian dust via and activities, with concentrations ranging from 0.01 to 1 μg/m³ in ambient air, elevated near industrial sources. Volcanic emissions also contribute, releasing manganese-bearing aerosols during eruptions, which deposit into other environmental reservoirs and influence global . Within the hydrologic cycle, rivers transport manganese at concentrations of 10 to 400 μg/L, sourced from watershed and runoff, facilitating its delivery to coastal and oceanic systems. In , levels can reach up to 1 mg/L, particularly in regions overlying manganese deposits, where reductive dissolution under low-oxygen conditions mobilizes the element.

Production

Mining and global supply

Manganese mining primarily targets oxide ores such as pyrolusite (MnO₂), which constitute the bulk of economically viable deposits. Global production of contained manganese reached an estimated 20 million tonnes in 2024, an increase of about 2% from 19.6 million tonnes in 2023, despite disruptions such as a in ; gross ore production totaled around 52 million tonnes. The leading producers in 2024 were with 7.4 million tonnes of manganese content, followed by at 4.6 million tonnes, at 2.8 million tonnes, at 0.77 million tonnes, and at 0.59 million tonnes (estimates), according to data from the U.S. Geological Survey. World reserves stand at 1.7 billion tonnes, though supply chains face risks from geopolitical tensions, including sanctions on following its 2022 invasion of , which have disrupted exports from that region. Approximately 90% of manganese is exported in the form of ore, with the relying entirely on imports, sourcing approximately 1.0 million tonnes of manganese products (gross weight) in 2024, predominantly from for ores. As of mid-2025, global production trends suggest stabilization or slight growth, with Australia's mine resuming operations.

Extraction and processing

Manganese ores, often containing less than 40% manganese, undergo beneficiation to the valuable mineral prior to extraction. This involves initial crushing and screening to reduce particle size and liberate manganese-bearing phases like pyrolusite (MnO₂) from materials such as silica and iron s. separation methods, including jigs and shaking tables, exploit differences to recover heavier manganese minerals, achieving concentrates with manganese content exceeding 40%. is applied to ores with ferromagnetic impurities, while flotation techniques, using collectors like fatty acids, are effective for and ores to further upgrade the and minimize silica content. High-carbon ferromanganese, an containing 75–80% manganese, is the primary product from pyrometallurgical and is obtained via carbothermic reduction of beneficiated manganese ores. The ore is mixed with coke as the reductant and fluxes like or dolomite to form a , then charged into a or submerged arc furnace. At temperatures of 1,200–1,400 °C, the reduction proceeds according to the reaction: MnO2+2CMn+2CO\mathrm{MnO_2 + 2C \rightarrow Mn + 2CO} This yields a molten tapped from the furnace, with manganese recovery rates typically reaching 80–90% under optimized conditions. Electrolytic manganese metal, valued for its high purity, is produced through a hydrometallurgical route suitable for applications requiring minimal impurities. Beneficiated is leached with to dissolve manganese as MnSO₄, followed by purification steps such as or solvent extraction to remove iron, silica, and other contaminants. The purified is then electrolyzed in cells with lead anodes and cathodes at approximately 35 °C and a of 200–400 A/m². At the , the reduction occurs via: Mn2++2eMn\mathrm{Mn^{2+} + 2e^- \rightarrow Mn} Depositing dendritic manganese metal with 99.9% purity, which is subsequently stripped, washed, and dried. Silicomanganese, an containing 60–68% manganese and 14–21% , is manufactured by carbothermic reduction in a submerged arc furnace to serve as a deoxidizer and alloying agent in . The charge consists of manganese , high-carbon ferromanganese , as the silica source, and coke, heated to 1,600–1,650 °C to facilitate simultaneous reduction of MnO and SiO₂. The process is highly energy-intensive, consuming 3–5 MWh per of alloy due to the high temperatures and required for the silicothermic reactions.

Chemical compounds

Inorganic compounds

Manganese forms a variety of inorganic compounds, primarily in oxidation states ranging from +2 to +7, with key examples including oxides, halides, permanganates, sulfates, and carbonates. These compounds exhibit diverse colors, structures, and reactivities due to the variable oxidation states of manganese.

Oxides

The oxides of manganese are among the most common inorganic compounds, with structures influenced by the oxidation state of the metal. Manganese(II) oxide (MnO) is a green solid that adopts a rock salt structure, where Mn²⁺ ions are octahedrally coordinated by oxide ions. It occurs naturally as the rare mineral manganosite and can be synthesized by the thermal decomposition of manganese(II) carbonate (MnCO₃) at temperatures around 500–600°C or by heating manganese(II) hydroxide (Mn(OH)₂). Manganese(III) oxide (Mn₂O₃) appears as a red-brown powder and features a corundum-type structure with Mn³⁺ ions in a distorted octahedral environment due to the Jahn-Teller effect. It is prepared via thermal decomposition of manganese(II) nitrate or by oxidation of MnO in air at 600–800°C. Manganese(IV) oxide (MnO₂), known as pyrolusite in its mineral form, is a black, amorphous or crystalline solid with a rutile-like structure where Mn⁴⁺ is octahedrally coordinated. It serves as the primary ore of manganese and is synthesized by thermal decomposition of manganese(II) nitrate at 200–400 °C or by calcination of manganese carbonate at 350–500 °C in air, though it also forms naturally through weathering processes.

Halides

Manganese halides are typically ionic in nature, with properties varying by halide and . Manganese(II) chloride (MnCl₂) forms pink hydrated crystals, such as the tetrahydrate, due to the pale pink color of the aqueous [Mn(H₂O)₆]²⁺ ; the form is a polymeric solid with a layered CdCl₂-like structure. It is prepared by the direct reaction of manganese metal with gas at elevated temperatures (around 300–500°C). Manganese(IV) fluoride (MnF₄) is a highly reactive, dark red solid that represents the highest fluoride of manganese, featuring Mn⁴⁺ in a tetrahedral coordination. It decomposes above 300°C and is notably unstable, oxidizing even ; it can be synthesized by the reaction of MnF₂ with fluorine gas or through fluorination of MnF₃.

Permanganates

Permanganates are strong oxidizing agents characterized by the tetrahedral [MnO₄]⁻ anion, where manganese is in the +7 oxidation state. Potassium permanganate (KMnO₄) is a deep purple crystalline solid, widely recognized for its disinfectant properties owing to its ability to release oxygen upon reduction. It is industrially prepared by fusing manganese(IV) oxide (MnO₂) with potassium hydroxide (KOH) in the presence of oxygen or air at 400–500°C to form the green potassium manganate (K₂MnO₄), followed by electrolytic oxidation in an alkaline solution to yield KMnO₄.

Sulfates and Carbonates

Manganese(II) sulfate monohydrate (MnSO₄·H₂O) is a pink, efflorescent solid that adopts a monoclinic structure, commonly used in fertilizers and pigments. It is produced by dissolving manganese(II) carbonate or oxide in dilute sulfuric acid, followed by crystallization. Manganese(II) carbonate (MnCO₃) occurs naturally as the rose-pink mineral rhodochrosite, which has a calcite-like structure with Mn²⁺ in octahedral coordination. Synthetic MnCO₃ is prepared by reacting manganese(II) sulfate with sodium carbonate in aqueous solution.

Organomanganese compounds

Organomanganese compounds encompass a diverse class of organometallic complexes featuring direct carbon-manganese bonds, primarily in the Mn(0) and Mn(I) oxidation states, which exhibit significant synthetic utility in catalysis and organic transformations. These compounds often incorporate carbonyl or cyclopentadienyl ligands to stabilize the metal center, enabling applications in carbonylation reactions and fuel additives. Unlike inorganic manganese species, organomanganese derivatives highlight covalent metal-carbon interactions, with reactivity influenced by the electronic and steric properties of the ligands. Prominent types include alkylmanganese carbonyls, such as methylmanganese pentacarbonyl (MeMn(CO)5MeMn(CO)_5), which serve as prototypical examples of σ\sigma-bonded organometallics. These are typically synthesized via ligand exchange reactions, for instance, by irradiating (Mn2(CO)10Mn_2(CO)_{10}) with alkyl halides to generate the alkyl radical that couples with the Mn(CO)5Mn(CO)_5 fragment, yielding RMn(CO)5RMn(CO)_5 species. Cyclopentadienyl complexes, like cymantrene ((η5C5H5)Mn(CO)3(\eta^5-C_5H_5)Mn(CO)_3), represent another key category, prepared through the reaction of with manganese halides followed by . These alkyl and cyclopentadienyl derivatives vary in stability; many are air-sensitive due to the low of manganese, requiring inert atmosphere handling, though some, like cymantrene, display relative thermal robustness. Notable examples include (MMT, (η5C5H4CH3)Mn(CO)3(\eta^5-C_5H_4CH_3)Mn(CO)_3), a commercially significant compound used as an antiknock additive in to boost ratings, synthesized analogously to cymantrene via cyclopentadienyl sodium and Mn2(CO)10Mn_2(CO)_{10}. analogs, such as decamethylmanganocene ((η5C5Me5)2Mn(\eta^5-C_5Me_5)_2Mn), feature two pentamethylcyclopentadienyl ligands and adopt a low-spin d5d^5 configuration, with its structure confirmed by showing a sandwich geometry similar to but with longer Mn-C distances due to the larger of Mn(II). These compounds exhibit distinctive reactivity, including migratory insertion of CO into the M-C bond—as seen in the conversion of MeMn(CO)5MeMn(CO)_5 to acetylmanganese pentacarbonyl (CH3COMn(CO)5CH_3COMn(CO)_5) under pressure, proceeding via alkyl migration to a coordinated carbonyl —and to substrates like alkyl halides. Organomanganese compounds also find application in catalysis, particularly in olefin polymerization systems where bis(cyclopentadienyl)manganese derivatives, such as Cp2MnCp_2Mn, act as precursors in conjunction with activators like methylaluminoxane to produce with moderate activity and control over molecular weight. Their role in such processes stems from the ability to form active alkyl species through β\beta-hydride elimination or insertion mechanisms, though manganese-based catalysts generally exhibit lower efficiency compared to group 4 metallocenes. Overall, these complexes underscore manganese's versatility in , bridging stoichiometric reagents and catalytic platforms.

Applications

Metallurgy

Manganese plays a pivotal role in , primarily as an alloying element in production, which accounts for approximately 85% to 90% of global manganese consumption. In , manganese enhances mechanical properties such as strength, , and while serving as a deoxidizer and desulfurizer during refinement. About 6 to 9 kilograms of manganese are typically added per metric ton of , with roughly 30% used in refinement and 70% incorporated into the final product. In steel deoxidation, manganese is added at levels of 0.1% to 1% to remove dissolved oxygen and impurities by forming stable compounds like (MnO) and (MnS), which prevents and improves castability. This process also boosts tensile strength and , with manganese countering the harmful effects of on . For specialized applications, higher concentrations are used; Hadfield , containing 12% to 14% manganese and 1% to 1.4% carbon, exhibits exceptional wear resistance and work-hardening under impact, making it suitable for mining equipment and railroad components. Ferromanganese alloys are the dominant form of manganese used in , comprising about 90% of metallurgical applications. High-carbon ferromanganese typically contains 74% to 82% manganese and 7% to 7.5% carbon, serving as a cost-effective source for alloying and deoxidation in basic oxygen and furnaces. Silicomanganese, with 65% to 68% manganese and 16% to 21% , is preferred for its dual role in deoxidation and silicon addition, reducing carbon input compared to separate and high-carbon ferromanganese additions. These alloys are produced via carbothermic reduction in submerged arc furnaces, enabling efficient integration into melts. Beyond alloys, manganese is incorporated into non- metals at 1% to 2% levels to improve strength and corrosion resistance. In aluminum alloys like 3004 (Al-Mn-Mg), manganese content ranges from 1.0% to 1.5%, enhancing formability and resistance to atmospheric corrosion, which supports its use in beverage cans and automotive panels. Copper-manganese alloys, such as manganese (copper-zinc-manganese-nickel), provide durability and antimicrobial properties, historically used in coinage like the U.S. dollar coin for their golden appearance and wear resistance. Recycling contributes 37% to manganese supply through steel scrap processing, as of 2009, where manganese is recovered indirectly as part of the iron content during electric arc furnace melting. In ladle metallurgy, recycled or added manganese aids desulfurization by promoting MnS formation in the slag-metal interface, achieving sulfur levels below 0.005% for high-quality steels. This secondary recovery enhances sustainability, though efficiency depends on scrap quality and alloy dilution.

Batteries and energy storage

Manganese plays a critical role in rechargeable lithium-ion batteries, particularly as a key component in materials that offer cost advantages and high voltage operation. The spinel-structured , \ceLiMn2O4\ce{LiMn2O4}, serves as a prominent material, delivering an operating voltage of approximately 4 V versus and a specific capacity ranging from 100 to 150 mAh/g. This provides three-dimensional pathways for , enabling reasonable rate performance, though its practical capacity is often limited by structural instability during cycling. Layered \ceLiMnO2\ce{LiMnO2} represents another manganese-based variant, featuring a akin to \ceLiCoO2\ce{LiCoO2} that theoretically supports higher capacities through layered intercalation, but it suffers from phase transitions that degrade performance over repeated charge-discharge cycles. A major challenge for these manganese-rich cathodes is the Jahn-Teller distortion, which arises from the instability of \ceMn3+\ce{Mn^{3+}} ions, leading to lattice strain, manganese dissolution, and capacity fade. This effect is mitigated through doping strategies, such as incorporating elements like magnesium, aluminum, or , which stabilize the framework by increasing the average manganese and suppressing phase transformations. For instance, synergistic doping and surface coatings have demonstrated improved cycle life by reducing manganese dissolution and maintaining structural integrity over hundreds of cycles. Emerging lithium manganese-rich (LMR) layered cathodes address these limitations while pushing densities higher, exemplified by compositions like \ceLi1.2Mn0.54Ni0.13Co0.13O2\ce{Li_{1.2}Mn_{0.54}Ni_{0.13}Co_{0.13}O2}, which integrate -rich and transition-metal-rich phases for enhanced capacity. These materials achieve densities of 250–300 Wh/kg at the cell level, surpassing traditional nickel-manganese-cobalt (NMC) cathodes, and are estimated to be 20–30% cheaper due to reduced reliance on costly and . High-purity manganese sulfate monohydrate (HPMSM) serves as a key precursor for synthesizing these manganese-containing cathodes, such as LMR, NMC, and lithium manganese oxide (LMO), typically via co-precipitation processes. and have targeted commercialization of LMR-based batteries by 2028, aiming to enable electric vehicles with over 500 miles of range through optimized and cost reductions. Beyond lithium systems, aqueous manganese-ion batteries utilize \ceMnO2\ce{MnO2} for both anodes and cathodes in neutral electrolytes, operating at voltages of 1.5–2 V and offering inherent safety advantages over organic electrolytes due to non-flammable aqueous media. These systems leverage reversible manganese couples for , with recent 2025 advancements in Co-doped \ceMn3O4/MnOOH\ce{Mn3O4/MnOOH} multiphase oxides demonstrating 80% capacity retention after 800 cycles at 0.6 A g⁻¹ by reducing Jahn-Teller and improving kinetics. Manganese also features in other battery chemistries, including primary alkaline zinc-manganese dioxide cells that provide a nominal voltage of 1.5 V and dominate low-cost, single-use applications like . In rechargeable sodium-ion batteries, manganese-based open frameworks, such as sodium manganese hexacyanomanganate, enable efficient sodium intercalation with high capacity and rate capability, positioning them as sustainable alternatives for large-scale storage. Driven by the expansion of electric vehicles and grid storage, global demand for battery-grade manganese is projected to reach approximately 500,000 tonnes by 2030, underscoring the need for scaled production of high-purity electrolytic manganese.

Other industrial uses

Manganese sulfate (MnSO₄), typically in its monohydrate form containing approximately 32% manganese, is widely used as a to amend manganese-deficient soils, with application rates of 10 to 20 kg/ha commonly applied in band form during planting to enhance crop yields. In , such amendments are targeted at soils with pH above 6.5 where manganese availability is reduced, promoting activation and in like soybeans and . In animal , manganese supplements, often as MnSO₄, are added to at levels of 60 to 120 mg Mn per kg of diet to prevent skeletal disorders such as perosis, which causes leg deformities and reduced mobility in broilers. These additions support bone mineralization and synthesis, with deficiencies more prevalent in high-calcium diets that impair manganese absorption. Potassium permanganate (KMnO₄) serves as a strong oxidant in , dosed at 0.5 to 2 mg/L to disinfect and remove iron, manganese, and organic contaminants, oxidizing them into insoluble forms for filtration. This application is particularly effective in municipal supplies for taste and odor control, where lower doses around 0.5 mg/L minimize residual color while achieving over 90% removal of soluble manganese. Historically, (MnO₂) was the primary material in batteries, comprising up to 80% of portable battery production before the rise of lithium-ion technologies in the . Electrolytic MnO₂ provided high capacity and stability in zinc-carbon and alkaline cells, enabling billions of units annually for until alternatives displaced it for higher needs. In ceramics, MnO₂ is incorporated into glazes at 3 to 7% to produce brown hues, as seen in traditional Rockingham ware, where it reacts with to form stable manganese silicates during firing at 1000–1200°C. This compound imparts durable, speckled finishes resistant to leaching, valued in decorative tiles and for its earthy tones without requiring high pigments. Manganese-based ferrites, particularly Mn-Zn compositions, are essential in high-frequency electronic components like resistors and inductors, exhibiting low losses up to 20 MHz for suppression in power supplies. These materials function as frequency-dependent resistors, converting electromagnetic noise into heat, with permeability exceeding 2000 at 1 MHz, enabling compact designs in switch-mode converters. Additional niche uses include manganese compounds in fluxes, where they act as deoxidizers to improve weld bead quality and reduce in fabrication. In display technology, Mn²⁺-doped phosphors, such as those in BaAl₁₁O₁₆N hosts, emit narrow-band green light for LCD backlights, achieving color purities over 90% and enhancing wide-gamut displays in modern televisions.

Biological role

Biochemical functions

Manganese serves as an essential cofactor for numerous enzymes involved in critical metabolic processes across prokaryotes, , and animals, facilitating reactions in , defense, energy production, and . In particular, the Mn²⁺ activates metalloenzymes by stabilizing transition states or participating in reactions, underscoring its role in maintaining cellular and preventing oxidative damage. These functions highlight manganese's indispensability for life, from microbial cycling to eukaryotic respiration and . One prominent role of manganese is in the , where it acts as a cofactor for arginase, binding Mn²⁺ at the enzyme's to catalyze the of L-arginine to L-ornithine and , thereby detoxifying . Similarly, manganese enables to assimilate by incorporating into glutamate, forming , a key step in essential for in , plants, and mammals. In antioxidant defense, manganese-containing (Mn-SOD), localized in the , dismutates radicals to and oxygen, protecting cells from generated during respiration. In photosynthetic organisms, manganese forms the Mn₄CaO₅ cluster within the (OEC) of (PSII), where it drives water oxidation to produce molecular oxygen. This cluster undergoes a series of transitions known as the S-state cycle (S₀ to S₄), culminating in the reaction: 2H2OO2+4H++4e2\mathrm{H_2O} \rightarrow \mathrm{O_2} + 4\mathrm{H^+} + 4e^- which replenishes electrons for the photosynthetic and sustains atmospheric oxygen levels. Manganese also supports as a cofactor for , which carboxylates pyruvate to oxaloacetate, a pivotal anaplerotic reaction in and the tricarboxylic acid cycle. Additionally, it activates glycosyltransferases that transfer sugar moieties during the synthesis of glycoproteins and mucopolysaccharides, contributing to bone matrix formation and integrity. Manganese is tightly regulated, with the containing 10–20 mg total, approximately 25% of which resides in . Cellular uptake occurs primarily via the divalent metal transporter 1 (DMT1/SLC11A2) and SLC39A8 (ZIP8) in the intestines and other tissues, ensuring adequate delivery to active sites while preventing excess accumulation.

Essential nutrient in nutrition

Manganese is an essential trace mineral that serves as a cofactor for numerous enzymes involved in , , and , as well as in defense systems. In , adequate intake is crucial to support these biochemical roles without exceeding safe limits. The Adequate Intake (AI) for manganese is 1.8 mg per day for adult women and 2.3 mg per day for adult men. The tolerable upper intake level (UL) is set at 11 mg per day for adults to prevent potential adverse effects from excessive supplementation. During , the AI increases slightly to 2.0 mg per day to meet heightened demands. Rich dietary sources of manganese include nuts such as hazelnuts and pecans, which contain 1–3 mg per 100 g, along with whole grains like wheat bran, , and leafy green vegetables such as . However, the bioavailability of manganese from these foods is limited to 1–5%, primarily due to inhibitory effects from phytates in grains and s and oxalates in certain vegetables and teas. The absorption rate of manganese from yeast (such as manganese-enriched yeast) is generally similar to that of other manganese sources, typically low at 1-5% in humans. No specific higher absorption rate is consistently reported for yeast forms in authoritative sources; bioavailability is considered comparable to inorganic forms like manganese sulfate. Manganese absorption occurs mainly in the , where 3–5% of ingested manganese is taken up by enterocytes via the divalent metal transporter 1 (DMT1). This process is regulated by iron mechanisms, including hepcidin-mediated control of export transporters like , which influence manganese efflux into the bloodstream. Homeostatic balance is maintained through biliary excretion into the feces, which accounts for the majority of manganese elimination in humans. In animal nutrition, particularly for ruminants such as and sheep, dietary manganese requirements range from 20 to 40 ppm in feed to support growth, reproduction, and skeletal development. Deficiency in ruminants can impair reproductive performance and viability, though it is uncommon in well-managed herds due to and variability.

Health effects

Deficiency

Manganese deficiency in humans is rare, primarily because the mineral is widely available in many foods, including whole grains, nuts, , and teas, meeting typical dietary needs without supplementation. The adequate for adults is established at 1.8 mg/day for women and 2.3 mg/day for men, reflecting the low risk of inadequacy in balanced diets. Symptoms of manganese deficiency in humans, when observed, are typically mild and include , poor , slowed growth of and nails, and altered glucose tolerance. In severe cases, such as prolonged deficiency, skeletal abnormalities like demineralization and impaired growth, particularly in children, have been reported. Additional manifestations may involve skin rashes, depigmentation, decreased serum cholesterol levels, and activity. Causes of manganese deficiency primarily stem from inadequate intake or absorption issues, with notable cases linked to total (TPN) lacking manganese supplementation, as seen in patients during the 1970s when TPN protocols initially omitted trace elements. Genetic disorders, such as mutations in the SLC39A8 gene encoding the ZIP8 manganese transporter, also impair manganese uptake, leading to severe deficiency and associated defects. The prevalence of manganese deficiency is estimated at less than 1% in general populations, with no documented widespread epidemics due to its dietary ubiquity. Higher risk occurs in individuals with celiac disease, where and consumption of high-phytate gluten-free products reduce manganese bioavailability. In animal models, manganese deficiency manifests distinctly by species. In rats, it leads to impaired growth, reproductive failure, and skeletal abnormalities, highlighting manganese's role in development and . Chickens exhibit perosis, or slipped , characterized by hock swelling, leg deformities, and shortened bones, often resulting from diets low in bioavailable manganese.

Toxicity and manganism

Manganese toxicity primarily arises from occupational or environmental overexposure, with being the most significant route for acute and chronic effects in industrial settings. The (OSHA) has established a (PEL) for manganese compounds and fumes (as Mn) of 5 mg/m³ as a ceiling value, meaning exposures should not exceed this level at any time during an 8-hour shift. Chronic of manganese dust or fumes leads to accumulation in the brain, particularly in the , resulting in , a resembling but distinguished by prominent and bradykinesia rather than resting . is often irreversible once advanced, manifesting as gait instability, muscle rigidity, and cognitive impairments. Oral toxicity of manganese is relatively low due to limited gastrointestinal absorption, typically less than 5% in adults under normal conditions. The (LD50) for oral manganese in rats exceeds 9 g/kg body weight, indicating low acute risk from ingestion. However, chronic exposure to elevated manganese levels in , above 0.3 mg/L, has been associated with hyperactivity and behavioral changes in children, potentially due to increased absorption during development. The mechanisms of manganese neurotoxicity involve generated by cycling between Mn³⁺ and Mn⁴⁺ ions, which promotes formation and cellular damage. Manganese also disrupts synthesis by inhibiting and altering mitochondrial function in neurons. Animal models, such as exposed to manganese , demonstrate damage to the , including neuronal loss and , mirroring human pathology. Treatment for manganism focuses on immediate removal from the source of exposure, which can reverse early psychiatric and mild motor symptoms. using calcium disodium EDTA (CaNa₂EDTA) enhances urinary manganese excretion and has shown efficacy in reducing brain accumulation when administered intravenously in acute cases.

Recent health research

Recent epidemiological research has linked elevated manganese levels to adverse sleep outcomes in adults. A 2025 of Iranian adults using the found that higher manganese exposure was associated with an increased risk of sleep disturbances (OR 1.27, 95% CI 1.08–1.52), potentially due to neurotoxic accumulation in the disrupting neurological activity and contributing to daytime . This aligns with subgroup analyses from NHANES data (2011–2016) indicating a positive trend between manganese levels and risk among individuals aged 60 and above, though not statistically significant in single-exposure models (OR 0.94, 95% CI 0.72–1.22). In the realm of gastrointestinal health, a 2024 study from the investigated manganese's role in (IBD) using mouse models. Researchers found that low manganese levels, associated with variants in the SLC39A8 transporter , exacerbated experimental by weakening the intestinal epithelial barrier and impairing immune responses, leading to increased intestinal injury and inflammation. Manganese deficiency in these models disrupted epithelial integrity, highlighting its essential function in maintaining gut and suggesting potential therapeutic implications for IBD patients with manganese imbalances. Emerging reviews on manganese in emphasize its dual role in immune responses against cancer. A 2025 review detailed how manganese enhances + T-cell proliferation and activation through the cGAS-STING pathway, promoting antitumor immunity, while excess manganese can foster tumor evasion by altering the and supporting immunosuppressive mechanisms. Furthermore, polymorphisms in the manganese (MnSOD) gene have been implicated in elevated cancer risks; for instance, the Ala/Ala is associated with a 70% increased risk of (OR 1.72, 95% CI 0.96–3.08), particularly high-grade tumors, and a modestly higher risk in premenopausal women (OR 1.8, 95% CI 0.9–3.7), exacerbated by low intake. Analyses of large-scale surveys have uncovered connections between manganese status and hematological health. A 2025 study utilizing NHANES data from 2011–2018 (n=11,300 U.S. adults) revealed a U-shaped relationship between blood manganese levels and prevalence (10.1% overall), where concentrations below 8.69 μg/L were linked to higher odds due to disrupted iron and , with each unit increase in this low range reducing risk (adjusted OR 0.838, 95% CI 0.735–0.954); conversely, levels at or above this threshold increased risk (OR 1.160, 95% CI 1.124–1.196). This suggests manganese's involvement in synthesis via shared absorption pathways with iron, such as divalent metal transporter 1 (DMT-1). Post-2020 cohort studies have advanced understanding of manganese's impact on child neurodevelopment. A 2025 prospective study in a Chinese birth cohort (n=1,088) showed that higher prenatal urinary manganese exposure was associated with reduced cognitive scores at age 2 (β -2.48 points per IQR increase in Mental Development Index, 95% CI -3.87 to -1.08), mediated by cord blood metabolomic changes like upregulated amino acids and downregulated glutamine. Optimal manganese levels, however, appear protective against behavioral issues; prenatal exposure has been linked to altered ADHD symptom risk, with elevated infant temperament factors mitigating adverse effects from high manganese and copper accumulation in the placenta. These findings underscore the need for balanced maternal manganese exposure to support neurocognitive outcomes while avoiding excesses that impair development.

Environmental impacts

Mining and pollution

Open-pit mining for manganese, a common extraction method, causes substantial habitat loss by removing vegetation and topsoil across large areas, as evidenced in the Kalahari region of where proposed operations disrupt native ecosystems and faunal migrations. This leads to biodiversity declines through fragmentation of habitats and alteration of local and . Soil erosion is intensified, with rates in affected mining catchments reaching up to 76 t/ha/year due to overburden removal and destabilization. Acid mine drainage further exacerbates impacts by lowering pH levels to 3–4, which mobilizes manganese and iron, increasing their solubility and transport into surrounding soils and waterways. Air emissions from manganese and processing include particulate matter, with PM10 dust levels near operational sites frequently surpassing 50 μg/m³, posing risks to air quality. Smelters contribute (SO₂) through the release of sulfurous gases during processing. Concerns over emissions were highlighted in the 2024 Hermosa project in , where potential annual outputs of oxides () and (CO) could exceed 100 tons, triggering major source classifications under environmental regulations. As of 2025, the Hermosa project has begun decline construction for its battery-grade manganese deposit and received a $166 million U.S. Department of Energy grant, amid ongoing concerns about groundwater depletion and emissions compliance under tightened Clean Air Act permits. Water pollution from manganese tailings involves leaching of dissolved manganese exceeding 1 mg/L into adjacent water bodies, surpassing ecological guidelines and causing chronic contamination. Such concentrations prove toxic to aquatic organisms, with 96-hour LC50 values for fish species like Heteropneustes fossilis ranging from 3 to 5 mg/L. In Gabon, a major manganese producer, mining has contaminated rivers such as the Moulili, introducing potentially toxic metals and altering sediment quality despite restoration efforts. Efforts to mitigate these environmental consequences include , employing hyperaccumulators like , which can sequester manganese up to 1% of its dry weight in leaves. The International Manganese Institute (IMnI) in 2024 emphasized health, safety, and environmental (HSE) initiatives, including life cycle assessments and emission quantification tools to support practices aimed at minimizing discharges.

Exposure and regulations

Humans are exposed to manganese through various environmental and occupational pathways, including of airborne particles, via and food, and dermal contact in certain settings. In , the U.S. Environmental Protection Agency (EPA) has established a secondary maximum contaminant level (SMCL) of 0.05 mg/L to prevent aesthetic issues such as black staining of plumbing fixtures and bitter metallic taste. For ambient air, the (WHO) sets an air quality guideline of 0.15 μg/m³ to protect from long-term exposure. Dietary intake represents the primary non-occupational route, with average daily consumption estimated at 4–5 mg for adults from sources like grains, nuts, and leafy vegetables. Occupational exposure to manganese is particularly significant in industries such as , , and , where workers may inhale fumes or dust containing the metal. The National Institute for Occupational Safety and Health (NIOSH) recommends an exposure limit of 1 mg/m³ as an 8-hour time-weighted average (TWA) for manganese in welding fumes to minimize respiratory and neurological risks. In the transportation sector, the gasoline additive (MMT) has historically contributed to airborne manganese, but the EPA restricts its use to a maximum of 1/32 gram of manganese per of , effectively phasing out higher concentrations since the early 2000s with ongoing enforcement. Regulatory frameworks worldwide aim to limit manganese exposure across consumer products, workplaces, and the environment. Under the European Union's REACH regulation and Directive, the migration of manganese from toys is limited to 60 mg/kg in categories toy materials (dry, brittle, powder-like or pliable; and liquid or sticky) and 250 mg/kg in category III materials (scraped-off), as specified in EN 71-3:2019+A2:2024, to safeguard children's health from potential migration and ingestion. Recent updates in mining regulations, such as those in in 2024, have tightened air quality permits for operations like the Hermosa project, mandating stricter emission controls for manganese particulates to comply with federal Clean Air Act standards following EPA objections. Biomonitoring programs track manganese exposure through measurements in and , with normal levels ranging from 4 to 15 μg/L in the general . levels typically fall between 1 and 8 μg/L under low-exposure conditions. Global trends indicate declining occupational manganese exposure since , attributed to enhanced ventilation technologies, stricter permissible exposure limits, and reduced use of manganese-containing materials in manufacturing.

References

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