マンガン　　

WordNet

a hard brittle grey polyvalent metallic element that resembles iron but is not magnetic; used in making steel; occurs in many minerals (同)Mn, atomic number 25
a steel with a relatively large component (10-14%) of manganese; highly resistant to wear and shock (同)austenitic manganese steel
an oxide of manganese found naturally as hausmannite

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マンガン(金属元素;化学記号は『Mn』)
manganeseの化学記号

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/01/10 11:01:10」(JST)

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この項目では、元素について説明しています。麻雀の点の満貫については「麻雀の得点計算」をご覧ください。

マンガン（英: manganese、羅: manganum）は原子番号25の元素。元素記号は Mn。日本語カタカナ表記での名称のマンガンはドイツ語: Mangan をカタカナに変換したもので、日本における漢字表記の当て字は満俺である。

性質

銀白色の金属で、比重は7.2（体心立方類似構造）、融点は1244 °C。マンガン族元素に属する遷移元素。温度によりいくつかの同素体が存在し、常温常圧で安定な構造は立方晶系である。これは硬く非常に脆い。空気中では酸化被膜を生じて内部が保護され、赤みがかった灰白色となる。酸（希酸）には易溶であり、淡桃色の2価のマンガンイオン Mn²⁺(aq) を生成する。

比較的反応性の高い金属で粉末状にすると空気中の酸素、水などとも反応する。化合物は2〜7価までの原子価を取り得る（+2, +3, +4, +6, +7 が安定）。地球上には比較的豊富に存在するが、単体では産出しない。二酸化マンガンを触媒とする過酸化水素の水と酸素への分解反応は、日本の義務教育課程で触媒の実験の題材とされるため非常に有名である。

単体マンガン自体は常磁性であるが、合金にはホイスラー合金など強磁性を示すものがあり、さらに化合物には様々な磁気的性質を示すものがある。ビスマスとの合金は強磁性体として知られるほか、フェライトに添加することで様々な特性を付加する。

歴史

スウェーデンのカール・ヴィルヘルム・シェーレ (C. W. Scheele) が1774年に発見、同年ヨハン・ゴットリーブ・ガーン (J. G. Gahn) が単体を単離した^[1]。

用途

一番有名な用途は、二酸化マンガンがマンガン乾電池やアルカリ乾電池の正極に使われる。また、リチウム電池の正極にも用いられ、リチウムイオン二次電池の正極材料として研究されている。また、磁性材料として、マンガン、亜鉛、鉄を含む金属酸化物である MnZn フェライトがインダクタやトランスのコア材料として用いられている。

マンガン単体が金属材料として用いられることはほとんど無く、合金として、マンガン鋼の原料や、フェロマンガンとして鋼材の脱酸素剤・脱硫黄剤などに使用される。鉄鋼用途で耐磨耗性、耐食性、靭性を付加する為に、マンガン合金（フェロマンガン）や金属マンガンとしてマンガン分が添加される。

また、生物の必須元素としても知られており、硫酸マンガンなどの化合物は肥料としても用いられる。

産出

マンガンは単体としては産出せず、軟マンガン鉱 (MnO₂)、菱マンガン鉱 (MnCO₃) などとして産出する。深海底には、マンガン、鉄などの金属水酸化物の塊であるマンガン団塊（マンガンノジュール）として存在している。

戦前では日本国内でも製鉄用に採掘され、第二次世界大戦中には主に乾電池用としてマンガンを採掘する鉱山が多数開発された。とくに後者は日本各地で見られ、京都府中部（丹波地方）を中心に近畿地方に零細鉱山が集中して存在していた。しかし、1950年代以降の鉱物資源の輸入自由化によって激しい競争に晒され、全ての鉱山が1970年代までに閉山に追い込まれた。前者は東日本に多く（北海道上国鉱山、同大江鉱山など）、規模が比較的大きい事から1980年代まで存続したが、現在では岩手県の野田玉川鉱山において宝飾品材料としてバラ輝石が限定的・間欠的に採掘されている他は皆無である。

この金属は、日本国内において産業上重要性が高いものの、産出地に偏りがあり供給構造が脆弱である。日本では国内で消費する鉱物資源の多くを他国からの輸入で支えている実情から、万一の国際情勢の急変に対する安全保障策として国内消費量の最低60日分を国家備蓄すると定められている。

主要産出国は以下の通り（2011年実績）^[2]。

南アフリカ共和国
中華人民共和国
オーストラリア
ガボン
インド
ブラジル

結晶構造

マンガンは温度により4つの相を持つ。

αマンガン: 742 °C以下で安定。単位胞あたり58個の原子を含む複雑な立方晶（体心立方格子類似構造）。原子の位置により4種類の異なるスピンを持ち、全体としては磁気モーメントを持たない、広義の反強磁性体であると考えられている（詳細はいまだ明らかになっていない）。
βマンガン: 742-1,095 °Cで安定。単位胞あたり20個の原子を含む複雑な立方晶。常磁性体である。
γマンガン: 1,095-1,134 °Cで安定。面心立方構造。反強磁性体である。
δマンガン: 1,134-1,245 °C（融点）で安定。体心立方構造。常磁性体である。

主な化合物

過マンガン酸カリウム (KMnO₄) - 酸化剤
二酸化マンガン (MnO₂) - 触媒

同位体

詳細は「マンガンの同位体」を参照

人体への影響

生理作用

人体にとっての必須元素。骨の形成や代謝に関係し、消化などを助ける働きもある。一部では活性酸素対策としての必須ミネラルに挙げるものもいる。

不足すると成長異常、平衡感覚異常、疲れやすくなる、糖尿病（インスリンの合成能力が低下するため）、骨の異常（脆くなる等）、傷が治りにくくなる、生殖能力の低下や生殖腺機能障害などが起こる。しかしマンガンは川など天然の水などに含まれ、上水道水としては多すぎてむしろ除去する場合があるなど、普通に生活していてマンガンが不足することはまずない。

中毒

マンガン鉱石精錬所作業員・れんが職人・鋼管製造業者など、過剰に曝露されるとマンガン中毒を起こす。

頭痛・関節痛・易刺激性・眠気などを起こし、やがて情動不安定・錯乱に至る。大脳基底核や錐体路も障害し、パーキンソニズム・ジストニア・平衡覚障害を引き起こすほか、無関心・抑うつなどの精神症状も報告されている。マンガン曝露から離れれば、3〜4か月で症状は消える。

酸素欠乏

マンガンは脱酸素剤として使用されるように強い酸素吸着作用があるため、十分に酸化されていない天然マンガンが多い地層の洞窟や井戸などでは、貧酸素化した地下水を経由して内部の空気の酸素が欠乏し、そこへ十分な換気を行わず奥へ入った場合は酸素欠乏症になり最悪の場合死亡する恐れがある。また肥料の撒きすぎによる土壌の酸化などで土中のマンガンが還元されたり、湖などの水底に溜まったマンガンが貧酸素水などで還元され、結果としてマンガンが酸欠状態を保持したり流れに乗って移動させてしまう現象などもある。

出典

^ 桜井弘『元素111の新知識』講談社、1998年、139～140頁。ISBN 4-06-257192-7。
^ 「Mineral Commodity Summaries 2012」p. 101、USGS

参考文献

太田恵造　『磁気工学の基礎 I』　共立出版、1973年、ISBN 4-320-00200-8。（結晶構造に関して）

1 Characteristics
- 1.1 Physical properties
- 1.2 Isotopes
- 1.3 Chemical properties
2 History
3 Occurrence and production
4 Applications
- 4.1 Steel
- 4.2 Aluminium alloys
- 4.3 Other uses
5 Biological role
6 Precautions
7 Environmental health concerns
- 7.1 Manganese in drinking water
- 7.2 Manganese in gasoline
8 Role in neurological disorders
- 8.1 Manganism
- 8.2 Childhood developmental disorders
- 8.3 Neurodegenerative diseases
9 See also
10 References
11 External links

Characteristics

Physical properties

Electrolytically refined manganese chips and 1 cm³ cube

Manganese is a silvery-gray metal that resembles iron. It is hard and very brittle, difficult to fuse, but easy to oxidize.^[2] Manganese metal and its common ions are paramagnetic.^[3] Manganese tarnishes slowly in air and "rusts" like iron, in water containing dissolved oxygen.

Isotopes

Naturally occurring manganese is composed of one stable isotope, ⁵⁵Mn. Eighteen radioisotopes have been characterized, with the most stable being ⁵³Mn with a half-life of 3.7 million years, ⁵⁴Mn with a half-life of 312.3 days, and ⁵²Mn with a half-life of 5.591 days. All of the remaining radioactive isotopes have half-lives that are less than three hours and the majority of these have half-lives that are less than one minute. This element also has three meta states.^[4] Manganese is part of the iron group of elements, which are thought to be synthesized in large stars shortly before the supernova explosion. ⁵³Mn decays to ⁵³Cr with a half-life of 3.7 million years. Because of its relatively short half-life, ⁵³Mn occurs only in tiny amounts due to the action of cosmic rays on iron in rocks.^[5] Manganese isotopic contents are typically combined with chromium isotopic contents and have found application in isotope geology and radiometric dating. 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 indicate an initial ⁵³Mn/⁵⁵Mn ratio that suggests Mn–Cr isotopic composition must result from in situ decay of ⁵³Mn in differentiated planetary bodies. Hence ⁵³Mn provides additional evidence for nucleosynthetic processes immediately before coalescence of the solar system.^[4] The isotopes of manganese range in atomic weight from 46 u (⁴⁶Mn) to 65 u (⁶⁵Mn). The primary decay mode before the most abundant stable isotope, ⁵⁵Mn, is electron capture and the primary mode after is beta decay.^[4]

Chemical properties

Manganese(II) chloride crystals – the pale pink color of Mn(II) salts is due to a spin-forbidden 3d transition.^[6]

The most common oxidation states of manganese are +2, +3, +4, +6 and +7, though oxidation states from −3 to +7 are observed. Mn²⁺ often competes with Mg²⁺ in biological systems. Manganese compounds where manganese is in oxidation state +7, which are restricted to the unstable oxide Mn₂O₇ and compounds of the intensely purple permanganate anion MnO₄⁻, are powerful oxidizing agents.^[2] Compounds with oxidation states +5 (blue) and +6 (green) are strong oxidizing agents and are vulnerable to disproportionation.

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

The most stable oxidation state for manganese is +2, which has a pale pink color, and many manganese(II) compounds are known, such as manganese(II) sulfate (MnSO₄) and manganese(II) chloride (MnCl₂). This oxidation state is also seen in the mineral rhodochrosite (manganese(II) carbonate). The +2 oxidation of Mn results from removal of the two 4s electrons, leaving a "high spin" ion in which all five of the 3d orbitals contain a single electron. Absorption of visible light by this ion is accomplished only by a spin-forbidden transition in which one of the d electrons must pair with another, to give the atom a change in spin of two units. The unlikeliness of such a transition is seen in the uniformly pale and almost colorless nature of Mn(II) compounds relative to other oxidation states of manganese.^[7]

Oxidation states of manganese^[8]
0	Mn 2(CO) 10
+1	MnC 5H 4CH 3(CO) 3
+2	MnCl 2, MnCO 3, MnO
+3	MnF 3, Mn(OAc) 3, Mn 2O 3
+4	MnO 2
+5	K 3MnO 4
+6	K 2MnO 4
+7	KMnO 4, Mn 2O 7
Common oxidation states are in bold.

The +3 oxidation state is known in compounds like manganese(III) acetate, but these are quite powerful oxidizing agents and also prone to disproportionation in solution to manganese(II) and manganese(IV). Solid compounds of manganese(III) are characterized by their preference for distorted octahedral coordination due to the Jahn-Teller effect and its strong purple-red color. The oxidation state 5+ can be obtained if manganese dioxide is dissolved in molten sodium nitrite.^[9] Manganate (VI) salts can also be produced by dissolving Mn compounds, such as manganese dioxide, in molten alkali while exposed to air. Permanganate (+7 oxidation state) compounds are purple, and can give glass a violet color. Potassium permanganate, sodium permanganate and barium permanganate are all potent oxidizers. Potassium permanganate, also called Condy's crystals, is a commonly used laboratory reagent because of its oxidizing properties and finds use 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.^[10]

History

The origin of the name manganese is complex. In ancient times, two black minerals from Magnesia in what is now modern Greece, were both called magnes from their place of origin, but were thought to differ in gender. The male magnes attracted iron, and was the iron ore we now know 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 feminine magnes was later called magnesia, known now in modern times as pyrolusite or manganese dioxide. Neither this mineral nor manganese itself is magnetic. In the 16th century, manganese dioxide was called manganesum (note the two n's instead of one) by glassmakers, possibly as a corruption and concatenation of two words, since alchemists and glassmakers eventually had to differentiate a magnesia negra (the black ore) from magnesia alba (a white ore, also from Magnesia, also useful in glassmaking). Michele Mercati called magnesia negra manganesa, and finally the metal isolated from it became known as manganese (German: Mangan). The name magnesia eventually was then used to refer only to the white magnesia alba (magnesium oxide), which provided the name magnesium for that free element, when it was eventually isolated, much later.^[11]

Some of the cave paintings in Lascaux, France, use manganese-based pigments.^[12]

Several oxides of manganese, for example manganese dioxide, are abundant in nature, and owing to their color, these oxides have been used as pigments since the Stone Age. The cave paintings in Gargas contain manganese as pigments and these cave paintings are 30,000 to 24,000 years old.^[13]

Manganese compounds were used by Egyptian and Roman glassmakers, to either remove color from glass or add color to it.^[14] The use as "glassmakers soap" continued through the Middle Ages until modern times and is evident in 14th-century glass from Venice.^[15]

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

Because of the use in glassmaking, manganese dioxide was available to alchemists, the first chemists, and was used for experiments. Ignatius Gottfried Kaim (1770) and Johann Glauber (17th century) discovered that manganese dioxide could be converted to permanganate, a useful laboratory reagent.^[16] 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, later hydrochloric acid from the Leblanc process was used and the manganese dioxide was recycled by the Weldon process. The production of chlorine and hypochlorite containing bleaching agents was a large consumer of manganese ores.

Scheele and other chemists were aware that manganese dioxide contained a new element, but they were not able to isolate it. Johan Gottlieb Gahn was the first to isolate an impure sample of manganese metal in 1774, by reducing the dioxide with carbon.

The manganese content of some iron ores used in Greece led to the speculations that the steel produced from that ore contains inadvertent amounts of manganese, making the Spartan steel exceptionally hard.^[17] Around the beginning of the 19th century, manganese was used in steelmaking and several patents were granted. In 1816, it was noted that adding manganese to iron made it harder, without making it any more brittle. In 1837, British academic James Couper noted an association between heavy exposures to manganese in mines with a form of Parkinson's disease.^[18] In 1912, manganese phosphating electrochemical conversion coatings for protecting firearms against rust and corrosion were patented in the United States, and have seen widespread use ever since.^[19]

The invention of the Leclanché cell in 1866 and the subsequent improvement of the batteries containing manganese dioxide as cathodic depolarizer increased the demand of manganese dioxide. Until the introduction of the nickel-cadmium battery and lithium-containing batteries, most batteries contained manganese. The zinc-carbon battery and the alkaline battery normally use industrially produced manganese dioxide, because natural occurring manganese dioxide contains impurities. In the 20th century, manganese dioxide has seen wide commercial use as the chief cathodic material for commercial disposable dry cells and dry batteries of both the standard (zinc-carbon) and alkaline types.^[20]

Occurrence and production

Manganese makes up about 1000 ppm (0.1%) of the Earth's crust, making it the 12th most abundant element there.^[21] Soil contains 7–9000 ppm of manganese with an average of 440 ppm.^[21] Seawater has only 10 ppm manganese and the atmosphere contains 0.01 µg/m³.^[21] Manganese occurs principally as pyrolusite (MnO₂), braunite, (Mn²⁺Mn³⁺₆)(SiO₁₂),^[22] 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^[23]

The most important manganese ore is pyrolusite (MnO₂). Other economically important manganese ores usually show a close spatial relation to the iron ores.^[2] Land-based resources are large but irregularly distributed. About 80% of the known world manganese resources are found in South Africa; other important manganese deposits are in Ukraine, Australia, India, China, Gabon and Brazil.^[23] In 1978, 500 billion tons of manganese nodules were estimated to exist on the ocean floor.^[24] Attempts to find economically viable methods of harvesting manganese nodules were abandoned in the 1970s.^[25]

In South Africa most identified deposits are located near Hotazel in the Northern Cape Province with an estimated 15 billion tons in 2011. In 2011 South Africa was the world's largest producer of manganese producing 3.4 million tons.^[26]

Manganese is mined in South Africa, Australia, China, Brazil, Gabon, Ukraine, India and Ghana and Kazakhstan. US Import Sources (1998–2001): Manganese ore: Gabon, 70%; South Africa, 10%; Australia, 9%; Mexico, 5%; and other, 6%. Ferromanganese: South Africa, 47%; France, 22%; Mexico, 8%; Australia, 8%; and other, 15%. Manganese contained in all manganese imports: South Africa, 31%; Gabon, 21%; Australia, 13%; Mexico, 8%; and other, 27%.^[23]^[27]

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.^[28] The resulting ferromanganese has a manganese content of 30 to 80%.^[2] Pure manganese used for the production of iron-free alloys is produced by leaching manganese ore with sulfuric acid and a subsequent electrowinning process.^[29]

Process flow diagram for a manganese refining circuit.

A more progressive extraction process involves directly reducing manganese ore in a heap leach. 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 150–250 μm, this increases the surface area to aid in the leaching process. The ore is then added to a leach tank, which contains sulfuric acid and ferrous iron (Fe²⁺) in a 1.6:1 ratio. The iron reacts with the manganese dioxide to form iron hydroxide and elemental manganese. This process yields approximately 92% recovery of the manganese. For further purification, the manganese can then be sent to an electrowinning facility.^[30]

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. That triggered a rush of activity to attempt to collect manganese nodules, which was not actually practical. 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.^[31]

Applications

Manganese has no satisfactory substitute in its major applications, which are related to metallurgical alloy use.^[23] In minor applications, (e.g., manganese phosphating), zinc and sometimes vanadium are viable substitutes.

Steel

US Marine Corps steel helmet

Manganese is essential to iron and steel production by virtue of its sulfur-fixing, deoxidizing, and alloying properties. Steelmaking,^[32] including its ironmaking component, has accounted for most manganese demand, presently in the range of 85% to 90% of the total demand.^[29] Among a variety of other uses, manganese is a key component of low-cost stainless steel formulations.^[27]^[33]

Small amounts of manganese improve the workability of steel at high temperatures, because it forms a high-melting sulfide and therefore prevents 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 can have a high tensile strength of up to 863 MPa.^[34]^[35] Steel with 12% manganese was used for British steel helmets. This steel composition was discovered in 1882 by Robert Hadfield and is still known as Hadfield steel.^[36]

Aluminium alloys

The second large application for manganese is as an alloying agent for aluminium. Aluminium with a manganese content of roughly 1.5% has an increased resistance against corrosion due to the formation of grains absorbing impurities which would lead to galvanic corrosion.^[37] The corrosion-resistant aluminium alloys 3004 and 3104 with a manganese content of 0.8 to 1.5% are the alloys used for most of the beverage cans.^[38] Before year 2000, more than 1.6 million tonnes have been used of those alloys; with a content of 1% manganese, this amount would need 16,000 tonnes of manganese.^[38]

Other uses

Methylcyclopentadienyl manganese tricarbonyl is used as an additive in unleaded gasoline to boost octane rating and reduce engine knocking. The manganese in this unusual organometallic compound is in the +1 oxidation state.^[39]

Manganese(IV) oxide (manganese dioxide, MnO₂) is used as a reagent in organic chemistry for the oxidation of benzylic alcohols (i.e. adjacent to an aromatic ring). Manganese dioxide has been used since antiquity to oxidatively neutralize the greenish tinge in glass caused by trace amounts of iron contamination.^[15] MnO₂ is also used in the manufacture of oxygen and chlorine, and in drying black paints. In some preparations, it is a brown pigment that can be used to make paint and is a constituent of natural umber.

Manganese(IV) oxide was used in the original type of dry cell battery as an electron acceptor from zinc, and is the blackish material found when opening 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.^[40]

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.^[20]^[40]

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 very occasionally used in coins; until 2000, the only United States coin to use manganese was the "wartime" nickel from 1942 to 1945.^[41] 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.^[42] In both cases of nickel and dollar, the use of manganese in the coin was to duplicate the electromagnetic properties of a previous identically sized and valued coin, for vending purposes. In the case of the later U.S. dollar coins, the manganese alloy was an attempt to duplicate properties of the copper/nickel alloy used in the previous Susan B. Anthony dollar.

Manganese compounds have been used as pigments and for the coloring of ceramics and glass. The brown color of ceramic is sometimes based on manganese compounds.^[43] In the glass industry, manganese compounds are used for two effects. Manganese(III) reacts with iron(II) to induce a 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).^[15] Larger amounts of manganese are used to produce pink colored glass.

Biological role

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

Manganese is an important metal for human health, being absolutely necessary for development, metabolism, and the antioxidant system. Nevertheless, excessive exposure or intake may lead to a condition known as manganism, a neurodegenerative disorder that causes dopaminergic neuronal death and parkinsonian- like symptoms.^[21]^[44] The classes of enzymes that have manganese cofactors are very broad, and include oxidoreductases, transferases, hydrolases, lyases, isomerases, ligases, lectins, and integrins. The reverse transcriptases of many retroviruses (though not lentiviruses such as HIV) contain manganese. The best-known manganese-containing polypeptides may be arginase, the diphtheria toxin, and Mn-containing superoxide dismutase (Mn-SOD).^[45]

Mn-SOD is the type of SOD present in eukaryotic mitochondria, and also in most bacteria (this fact is in keeping with the bacterial-origin theory of mitochondria). The Mn-SOD enzyme is probably one of the most ancient, for nearly all organisms living in the presence of oxygen use it to deal with the toxic effects of superoxide (O−
2), formed from the 1-electron reduction of dioxygen. Exceptions include a few kinds of bacteria, such as Lactobacillus plantarum and related lactobacilli, which use a different nonenzymatic mechanism, involving manganese (Mn²⁺) ions complexed with polyphosphate directly for this task, indicating how this function possibly evolved in aerobic life.

The manganese dietary reference intake for a 44 y.o. human male is 2.3 mg per day from food, with 11 mg estimated as the tolerable upper limit for daily intake to avoid toxicity. Estimates for females and children are generally less.^[46] The essential minimum intake is unknown since manganese deficiency is so rare. The human body contains about 12 mg of manganese, which is stored mainly in the bones. The remaining manganese in soft tissue is mostly concentrated in the liver and kidneys.^[21] In the human brain, the manganese is bound to manganese metalloproteins, most notably glutamine synthetase in astrocytes.^[47]

Manganese is also important in photosynthetic oxygen evolution in chloroplasts in plants. The oxygen-evolving complex (OEC) is a part of photosystem II contained in the thylakoid membranes of chloroplasts; it is responsible for the terminal photooxidation of water during the light reactions of photosynthesis, and has a metalloenzyme core containing four atoms of manganese.^[48] For this reason, most broad-spectrum plant fertilizers contain manganese.

Precautions

Manganese compounds are less toxic than those of other widespread metals, such as nickel and copper.^[49] 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.^[50] Manganese poisoning has been linked to impaired motor skills and cognitive disorders.^[51]

The permanganate exhibits a higher toxicity than the manganese(II) compounds. The fatal dose is about 10 g, and several fatal intoxications have occurred. The strong oxidative effect leads to necrosis of the mucous membrane. For example, the esophagus is affected if the permanganate is swallowed. Only a limited amount is absorbed by the intestines, but this small amount shows severe effects on the kidneys and on the liver.^[52]^[53]

In 2005, a study suggested a possible link between manganese inhalation and central nervous system toxicity in rats.^[54]

Manganese exposure in United States is regulated by Occupational Safety and Health Administration.^[55]

Generally, exposure to ambient Mn air concentrations in excess of 5 μg Mn/m3 can lead to Mn-induced symptoms. Increased ferroportin protein expression in human embryonic kidney (HEK293) cells is associated with decreased intracellular Mn concentration and attenuated cytotoxicity, characterized by the reversal of Mn-reduced glutamate uptake and diminished lactate dehydrogenase leakage.^[56]

Environmental health concerns

Manganese in drinking water

Waterborne manganese has a greater bioavailability than dietary manganese. According to results from a 2010 study,^[57] 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 to the naturally occurring manganese in shower water puts up to 8.7 million Americans at risk.^[54]^[58]^[59]

Manganese in gasoline

Methylcyclopentadienyl manganese tricarbonyl (MMT) is a gasoline additive used to replace lead compounds for unleaded gasolines, to improve the octane number in low octane number petrol distillates. It functions as an antiknock agent by the action of the carbonyl groups. Fuels containing manganese tend to form manganese carbides, which damage exhaust valves. The need to use lead or manganese compounds is merely historic, as the availability of reformation processes which create high-octane rating fuels increased. The use of such fuels directly or in mixture with non-reformed distillates is universal in developed countries (EU, Japan, etc.). In USA the imperative to provide the lowest possible price per volume on motor fuels (low fuel taxation rate) and lax legislation of fuel content (before 2000) caused refineries to use MMT. Compared to 1953, levels of manganese in air have dropped.^[60] Many racing competitions specifically ban manganese compounds in racing fuel (cart, minibike). MMT contains 24.4–25.2% manganese. There is strong correlation between elevated atmospheric manganese concentrations and automobile traffic density.

Role in neurological disorders

Manganism

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^[61]^[62] have been at risk for developing manganism; however, current health and safety regulations protect workers in developed nations.^[55] The disorder was first described in 1837 by British academic John Couper, who studied two patients who were manganese grinders.^[18]

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.^[18]^[63] Unlike Parkinson's disease, manganism is not associated with loss of smell and patients are typically unresponsive to treatment with L-DOPA.^[64] 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.^[63]

Childhood developmental disorders

Several recent studies attempt to examine the effects of chronic low-dose manganese overexposure on development in children. The earliest study of this kind was conducted in the Chinese province of Shanxi. Drinking water there had been contaminated through improper sewage irrigation and contained 240–350 µg Mn/L. Although WMn concentrations at or below 300 µg Mn/L are considered safe by the US EPA and 400 µg Mn/L are considered safe by the World Health Organization, the 92 children sampled (between 11 and 13 years of age) from this province displayed lower performance on tests of manual dexterity and rapidity, short-term memory, and visual identification when compared to children from an uncontaminated area. More recently, a study of 10-year-old children in Bangladesh showed a relationship between WMn concentration in well water and diminished IQ scores. A third study conducted in Quebec examined school children between the ages of 6 and 15 living in homes that received water from a well containing 610 µg Mn/L; controls lived in homes that received water from a 160 µg Mn/L well. Children in the experimental group showed increased hyperactive and oppositional behaviors.^[57]

Neurodegenerative diseases

A protein called DMT1 is the major transporter involved 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 putative mechanism of action is that manganese overexposure and/or dysregulation lead to oxidative stress, mitochondrial dysfunction, glutamate-mediated excitoxicity, and aggregation of proteins.

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External links

Find more about Manganese at Wikipedia's sister projects
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National Pollutant Inventory – Manganese and compounds Fact Sheet
International Manganese Institute
NIOSH Manganese Topic Page
Manganese at The Periodic Table of Videos (University of Nottingham)
Development of a Standardised Method for Measuring Manganese Exposure by A Sánchez Jiménez and others. Institute of Occupational Medicine Research Report TM/10/04. (This study compares the concentrations of inhalable and respirable Manganese collected with three airborne samples: the CIS (Conical Inhalable Sampler), IOM ( the Institute of Occupational Medicine) and the Higgins Dewell cyclone.)

UpToDate Contents

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1. 食物中の微量ミネラルの概要 overview of dietary trace minerals
2. 肝性脳症の臨床症状および診断 clinical manifestations and diagnosis of hepatic encephalopathy
3. パーキンソン病の診断 diagnosis of parkinson disease
4. 労働衛生および環境衛生の概要 overview of occupational and environmental health
5. 小児における急性肝不全：マネージメント acute liver failure in children management

English Journal

Growth of gold-manganese oxide nanostructures on a 3D origami device for glucose-oxidase label based electrochemical immunosensor.

Li L1, Xu J1, Zheng X1, Ma C1, Song X2, Ge S1, Yu J1, Yan M3.
Biosensors & bioelectronics.Biosens Bioelectron.2014 Nov 15;61:76-82. doi: 10.1016/j.bios.2014.05.012. Epub 2014 May 14.
Flexible biosensors are of considerable current interest for the development of portable point-of-care medical products, minimally invasive implantable devices, and compact diagnostic platforms. Here, we reported an electrochemical paper based analytical device fabricated (EPADs) by sequentially gro
PMID 24858676

Simplified sample treatment for the determination of total concentrations and chemical fractionation forms of Ca, Fe, Mg and Mn in soluble coffees.

Pohl P1, Stelmach E2, Szymczycha-Madeja A2.
Food chemistry.Food Chem.2014 Nov 15;163:31-6. doi: 10.1016/j.foodchem.2014.04.073. Epub 2014 Apr 29.
A simpler, and faster than wet digestion, sample treatment was proposed prior to determination of total concentrations for selected macro- (Ca, Mg) and microelements (Fe, Mn) in soluble coffees by flame atomic absorption spectrometry. Samples were dissolved in water and acidified with HNO3. Precisio
PMID 24912692

Sonochemically synthesized MnO2 nanoparticles as electrode material for supercapacitors.

Gnana Sundara Raj B1, Asiri AM2, Qusti AH2, Wu JJ3, Anandan S4.
Ultrasonics sonochemistry.Ultrason Sonochem.2014 Nov;21(6):1933-8. doi: 10.1016/j.ultsonch.2013.11.018. Epub 2013 Dec 8.
In this study, manganese oxide (MnO2) nanoparticles were synthesized by sonochemical reduction of KMnO4 using polyethylene glycol (PEG) as a reducing agent as well as structure directing agent under room temperature in short duration of time and characterized by powder X-ray diffraction (XRD), Fouri
PMID 24360990

Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds; Synthesis, characterization and biological evolution.

Kumar Naik KH1, Selvaraj S2, Naik N3.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.Spectrochim Acta A Mol Biomol Spectrosc.2014 Oct 15;131:599-605. doi: 10.1016/j.saa.2014.03.038. Epub 2014 Apr 13.
Present work reviews that, the synthesis of (E)-N'-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M(2+)L]X2, where M(2+)=Mn, Co, Ni, Cu, Sr and Cd, L=(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)meth
PMID 24858195

Japanese Journal

Extracting the Redox Orbitals in Li Battery Materials with High-Resolution X-Ray Compton Scattering Spectroscopy

Suzuki K.,Barbiellini B.,Orikasa Y.,Go N.,Sakurai H.,Kaprzyk S.,Itou M.,Yamamoto K.,Uchimoto Y.,Wang Yung Jui,Hafiz H.,Bansil A.,Sakurai Y.
Physical Review Letters 114(8), 2015-02-25
… Moreover, the manganese 3d states are shown to experience spatial delocalization involving 0.16±0.05 electrons per Mn site during the battery operation. …
NAID 120005549955

小型回転加熱炉を用いたマンガン鉱石の加熱特性調査

渡辺吉夫,本間敏彦,梶谷正和 [他]
フェロアロイ 58(1), 34-42, 2015
NAID 40020411713

Synthesis of Spinel LiNi0.5Mn1.5O4 by a Wet Chemical Method and Characterization for Lithium-Ion Secondary Batteries

, , , , , , ,
Journal of the Ceramic Society of Japan 123(1433), 38-42, 2015
5 V cathode material LiNi0.5Mn1.5O4 was synthetized by a simple wet chemical reaction using acetates as precursor's materials. Cathode active materials were characterized by X-ray diffraction (XRD), s …
NAID 130004951088

A Theoretical Study on Superexchange Interaction in KCoF3 and Cs1-xNaxMnII(CN)3 by Chemical Bonding Rule

Journal of Computer Chemistry, Japan 13(6), 319-320, 2015
… In this study, we investigated the superexchange interaction between manganese atoms via cyano-ligand, by the use of chemical bonding rule. …
NAID 130004933675

Related Pictures

★リンクテーブル★

リンク元	「マンガン」「Mn」
拡張検索	「manganese superoxide dismutase」「manganese chloride tetrahydrate」

「マンガン」

Manganese, ₂₅Mn
General properties
Name, symbol	manganese, Mn
Pronunciation	/ˈmæŋɡəniːz/; MANG-gə-neez
Appearance	silvery metallic
Manganese in the periodic table
	chromium ← manganese → iron
Atomic number	25
Standard atomic weight	54.938044(3)
Element category	transition metal
Group, block	group 7, d-block
Period	period 4
Electron configuration	[Ar] 3d5 4s2
per shell	2, 8, 13, 2
Physical properties
Phase	solid
Melting point	1519 K (1246 °C, 2275 °F)
Boiling point	2334 K (2061 °C, 3742 °F)
Density near r.t.	7.21 g·cm−3
liquid, at m.p.	5.95 g·cm−3
Heat of fusion	12.91 kJ·mol−1
Heat of vaporization	221 kJ·mol−1
Molar heat capacity	26.32 J·mol−1·K−1
Atomic properties
Oxidation states	7, 6, 5, 4, 3, 2, 1, −1, −2, −3 acidic, basic or amphoteric; depending on the oxidation state
Electronegativity	Pauling scale: 1.55
Ionization energies	1st: 717.3 kJ·mol−1; 2nd: 1509.0 kJ·mol−1; 3rd: 3248 kJ·mol−1; (more)
Atomic radius	empirical: 127 pm
Covalent radius	Low spin: 139±5 pm; High spin: 161±8 pm
Miscellanea
Crystal structure	body-centered cubic (bcc)
Speed of sound thin rod, at 20 °C	5150 m·s−1
Thermal expansion	21.7 µm·m−1·K−1 (at 25 °C)
Thermal conductivity	7.81 W·m−1·K−1
Electrical resistivity	at 20 °C: 1.44 µΩ·m
Magnetic ordering	paramagnetic
Young's modulus	198 GPa
Bulk modulus	120 GPa
Mohs hardness	6.0
Brinell hardness	196 MPa
CAS number	7439-96-5
History
Discovery	Torbern Olof Bergman (1770)
First isolation	Johann Gottlieb Gahn (1774)
Most stable isotopes
	Main article: Isotopes of manganese
	view; talk; edit; · references

外見
	銀白色;
一般特性
名称, 記号, 番号	マンガン, Mn, 25
分類	遷移金属
族, 周期, ブロック	7, 4, d
原子量	54.938045(5)
電子配置	[Ar] 4s2 3d5
電子殻	2, 8, 13, 2（画像）
物理特性
相	固体
密度（室温付近）	7.21 g·cm-3
融点での液体密度	5.95 g·cm-3
融点	1519 K, 1246 °C, 2275 °F
沸点	2334 K, 2061 °C, 3742 °F
融解熱	12.91 kJ·mol-1
蒸発熱	221 kJ·mol-1
熱容量	(25 °C) 26.32 J·mol-1·K-1
蒸気圧
原子特性
酸化数	7, 6, 5, 4, 3, 2, 1, -1, -2, -3; (酸性酸化物、塩基性酸化物、両性酸化物)
電気陰性度	1.55（ポーリングの値）
イオン化エネルギー; （詳細）	第1： 717.3 kJ·mol-1
	第2： 1509.0 kJ·mol-1
	第3： 3248 kJ·mol-1
原子半径	127 pm
共有結合半径	139±5（低スピン）, 161±8（高スピン） pm
その他
結晶構造	体心立方
磁性	常磁性
電気抵抗率	(20 °C) 1.44 µΩ·m
熱伝導率	(300 K) 7.81 W·m-1·K-1
熱膨張率	(25 °C) 21.7 µm·m-1·K-1
音の伝わる速さ; （微細ロッド）	(20 °C) 5150 m/s
ヤング率	198 GPa
体積弾性率	120 GPa
モース硬度	6.0
ブリネル硬度	196 MPa
CAS登録番号	7439-96-5
最安定同位体
	詳細はマンガンの同位体を参照
	表示

　　[★]

英: manganese, Mn

臨床関連

マンガン中毒

「Mn」

　　[★] マンガン manganese 　

「manganese superoxide dismutase」

　　[★]

マンガンスーパーオキシドジスムターゼ、マンガンスーパーオキサイドジスムターゼ

関: Cu-Zn superoxide dismutase、Mn-SOD、MnSOD、superoxide dismutase

「manganese chloride tetrahydrate」

　　[★]

塩化マンガン四水和物

関: manganese chloride

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manganese