Todorokite
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Todorokite is a rare complex hydrous
manganese oxide Manganese oxide is any of a variety of manganese oxides and hydroxides.Wells A.F. (1984) ''Structural inorganic chemistry'' 5th edition Oxford Science Publications, . These include * Manganese(II) oxide, MnO * Manganese(II,III) oxide, Mn3O4 * Mang ...
mineral with the chemical formula . It was named in 1934 for the type locality, the Todoroki mine,
Hokkaido is Japan's second largest island and comprises the largest and northernmost prefecture, making up its own region. The Tsugaru Strait separates Hokkaidō from Honshu; the two islands are connected by the undersea railway Seikan Tunnel. The la ...
, Japan. It belongs to the
prismatic An optical prism is a transparent optical element with flat, polished surfaces that are designed to refract light. At least one surface must be angled — elements with two parallel surfaces are ''not'' prisms. The most familiar type of optical ...
class 2/m of the
monoclinic crystal system In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in the orthorhombic sy ...
, but the angle β between the a and c axes is close to 90°, making it seem
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic lattices result from stretching a cubic lattice along two of its orthogonal pairs by two different factors, resulting in a rectangular prism with a r ...
. It is a brown to black mineral which occurs in massive or tuberose forms. It is quite soft with a
Mohs hardness The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material. The scale was introduced in 1812 by th ...
of 1.5, and a
specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water (molecule), wa ...
of 3.49 - 3.82. It is a component of deep
ocean basin In hydrology, an oceanic basin (or ocean basin) is anywhere on Earth that is covered by seawater. Geologically, ocean basins are large  geologic basins that are below sea level. Most commonly the ocean is divided into basins foll ...
manganese nodules Polymetallic nodules, also called manganese nodules, are mineral concretions on the sea bottom formed of concentric layers of iron and manganese hydroxides around a core. As nodules can be found in vast quantities, and contain valuable metals, dep ...
.


Structure

Manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
occurs in different states, including , and . Todorokite is made up of
octahedra In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at ea ...
that share edges to form triple chains. These chains share corners to form roughly square tunnels parallel to the b crystal axis.Burns, Burns and Stockman (1983) American Mineralogist 68:972-980Post and Bish (1988) American Mineralogist 73: 861–869 The tunnels accommodate
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
molecules and large
cations An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
such as
potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
,
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
,
silver Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
,
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
,
calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
and
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
. The octahedra at the edges of the triple chains are larger than those in the middle and therefore are likely to accommodate the larger cations (
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
Mg,
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
,
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
,
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
Co,
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
Ni etc.), whilst the middle octahedra are occupied by the smaller cations. This structure is similar to that of
hollandite Hollandite (chemical formula: Ba(Mn4+6Mn3+2)O16) is an oxide mineral. It is the barium-manganese (III) endmember of the coronadite group. A mineral, with the chemical composition BaMn4+6Fe3+2O16, that was first found in the Kajlidongri mine in ...
() and romanèchite (), but with larger tunnels. Although tunnels formed from triple chains of octahedra are most common in todorokite, occasional tunnels have been observed in crystals from both terrestrial and
manganese nodule Polymetallic nodules, also called manganese nodules, are mineral concretions on the sea bottom formed of concentric layers of iron and manganese hydroxides around a core. As nodules can be found in vast quantities, and contain valuable metals, de ...
deposits that have one pair of sides formed by triple chains, but with the other pair of sides formed from chains 4, 5, 8 or more octahedra wide.


Unit cell

The
unit cell In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
has six
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
sites and twelve
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
sites constituting the octahedral framework. Mg and Al may substitute for Mn, and the tunnels contain large cations and water molecules. There is one formula unit per unit cell (Z = 1). The side lengths are a = 9.8 Å, b = 2.8 Å and c = 9.6 Å, with angle β = 94.1°. More detailed values given in the references are: *a = 9.764 Å, b = 2.842 Å, c = 9.551 Å, β = 94.14° *a = 9.7570(15) Å, b = 2.8419(5) Å, c = 9.5684(14) Å, β = 94.074(14)° *a = 9.75 Å, b = 2.849 Å, c = 9.59 Å β = 90°Straczek, Horen, Ross, and Warshaw (1960) American Mineralogist 45: 1174–1184 Varieties also occur with a = 14.6 Å and a = 24.38 Å, having the same b and c values as above.
Intergrowths of elongated
crystallite A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains. Bacillite is a type of crystallite. It is rodlike with parallel longulites. Stru ...
s resembling the twinned variety of acicular
rutile Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer Polymorphism (materials science), polymorphs of TiO2 are known, including anatase, akaogiite, and brookite. Rutile has one of the highest ...
have been observed by
electron microscopy An electron microscope is a microscope that uses a beam of accelerated electrons as a source of illumination. As the wavelength of an electron can be up to 100,000 times shorter than that of visible light photons, electron microscopes have a hi ...
in todorokites from an
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
-
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
concretion A concretion is a hard, compact mass of matter formed by the precipitation of mineral cement within the spaces between particles, and is found in sedimentary rock or soil. Concretions are often ovoid or spherical in shape, although irregular ...
from the
Pacific Ocean The Pacific Ocean is the largest and deepest of Earth's five oceanic divisions. It extends from the Arctic Ocean in the north to the Southern Ocean (or, depending on definition, to Antarctica) in the south, and is bounded by the continen ...
(a = 14.6 Å) and from the Bakal deposit (a = 14.6 Å and 24.4 Å). Todorokites with around 25 Å have been found in samples from Sterling Hill and the Takhte-Karacha deposit.American Mineralogist (1979) 64:1333 Extracted from Chukhrov, Gorschkov, Sivtsov and Berezovskaya (1978) Izvest. Akad. Nauk SSSR, Ser. geol., no 12:86-95 (In Russian)


Appearance

Todorokite occurs as spongy banded and
reniform Reniform is an adjective meaning "kidney-shaped" and may specifically refer to: * Reniform leaf The following is a list of terms which are used to describe leaf morphology in the description and taxonomy of plants. Leaves may be simple (a single ...
(kidney-shaped) aggregates composed of minute lathlike crystals. The crystals are flattened parallel to the plane containing the a and c crystal axes, and elongated parallel to the c axis. Minerals of the
hollandite Hollandite (chemical formula: Ba(Mn4+6Mn3+2)O16) is an oxide mineral. It is the barium-manganese (III) endmember of the coronadite group. A mineral, with the chemical composition BaMn4+6Fe3+2O16, that was first found in the Kajlidongri mine in ...
-
cryptomelane Cryptomelane is a potassium manganese oxide mineral with formula K(Mn4+,Mn2+)8O16. In 1942 the name ''cryptomelane'' was proposed as part of an effort to sort out the manganese oxide minerals referred to as ''psilomelane''. Cryptomelane was identi ...
and romanèchite groups also have
fibrous Fiber or fibre (from la, fibra, links=no) is a natural or artificial substance that is significantly longer than it is wide. Fibers are often used in the manufacture of other materials. The strongest engineering materials often incorporate ...
or acicular habits and two perfect cleavages parallel to the fiber axis. Todorokite is dark brown to brownish black in color and brown in transmitted light. It has a black to dark brown streak and the luster is metallic to dull, but silky in aggregates. It is
opaque Opacity or opaque may refer to: * Impediments to (especially, visible) light: ** Opacities, absorption coefficients ** Opacity (optics), property or degree of blocking the transmission of light * Metaphors derived from literal optics: ** In lingu ...
in all but the thinnest slivers, which are transparent.


Optical properties

Todorokite is
biaxial In crystal optics, the index ellipsoid (also known as the ''optical indicatrix'' or sometimes as the ''dielectric ellipsoid'') is a geometric construction which concisely represents the refractive index, refractive indices and as ...
, as are all
monoclinic In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in the orthorhombic s ...
(and
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic lattices result from stretching a cubic lattice along two of its orthogonal pairs by two different factors, resulting in a rectangular prism with a r ...
) minerals. In the polariscope,Polariscope, Gemstone Buzz
/ref> and in the
polarizing microscope A petrographic microscope is a type of optical microscope used in petrology and optical mineralogy to identify rocks and minerals in thin sections. The microscope is used in optical mineralogy and petrography, a branch of petrology which ...
, specimens may be illuminated from below by light that is polarized by the polarizer, and viewed from above through an analyzer that transmits light of only one direction of polarization. When the directions of polarization of the polarizer and analyzer are at right angles, the specimen is said to be viewed between crossed polars. When todorokite is rotated between crossed polars it appears dark and light in turn, being dark when the crystal face or cleavage face is parallel to one direction of polarization. This is called parallel extinction. All uniaxial minerals display parallel extinction, but so do orthorhombic biaxial minerals such as
olivine The mineral olivine () is a magnesium iron silicate with the chemical formula . It is a type of nesosilicate or orthosilicate. The primary component of the Earth's upper mantle, it is a common mineral in Earth's subsurface, but weathers quickl ...
and orthopyroxenes. The
refractive index In optics, the refractive index (or refraction index) of an optical medium is a dimensionless number that gives the indication of the light bending ability of that medium. The refractive index determines how much the path of light is bent, or ...
of todorokite has not been determined, except insofar as it is very high; the original report gave it as greater than 1.74, and a later investigation put it even higher, greater than 2.00. For comparison,
diamond Diamond is a Allotropes of carbon, solid form of the element carbon with its atoms arranged in a crystal structure called diamond cubic. Another solid form of carbon known as graphite is the Chemical stability, chemically stable form of car ...
has a refractive index of 2.42 and
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical form ...
1.54. A biaxial crystal has three mutually perpendicular optical directions, X, Y and Z, with different refractive indices α, β and γ for light vibrating in planes perpendicular to these directions. The
birefringence Birefringence is the optical property of a material having a refractive index that depends on the polarization and propagation direction of light. These optically anisotropic materials are said to be birefringent (or birefractive). The birefring ...
is the numerical difference between the greatest and the least of these indices; for todorokite it is nearly 0.02. Todorokite is distinctly
pleochroic Pleochroism (from Greek πλέων, ''pléōn'', "more" and χρῶμα, ''khrôma'', "color") is an optical phenomenon in which a substance has different colors when observed at different angles, especially with polarized light. Backgroun ...
, appearing dark brown when viewed along the X direction, and yellowish brown when viewed along the Z direction but the strength of the effect varies from faint to strong in material from different localities. The orientation of optical directions with respect to the
lattice parameters Lattice may refer to: Arts and design * Latticework, an ornamental criss-crossed framework, an arrangement of crossing laths or other thin strips of material * Lattice (music), an organized grid model of pitch ratios * Lattice (pastry), an orna ...
is Y parallel to b and Z near or parallel to c.


Physical properties

Todorokite has perfect cleavage parallel to the plane containing the b and c axes, and parallel to the plane containing the a and c axes. Contact twins occur frequently. The mineral is very soft, with
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
only . It is generally fibrous, making it difficult to measure the
specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water (molecule), wa ...
accurately. The Berman balance measures the relative weights of the specimen in air and in water; when todorokite was tested in this way it gave a value of 3.49. The
pycnometer Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water at its densest ...
measures the mass and the volume of the specimen directly; this method gave a value of 3.66 to 3.82 for todorokite. The pycnometer is more likely to give an accurate reading for a fibrous material.


Solubility

Todorokite is soluble in
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
(HCl) with the evolution of
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
(), and in concentrated
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
() forming a purple-red solution. It is also soluble in
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
() forming a residue of
manganese dioxide Manganese dioxide is the inorganic compound with the formula . This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for is for dry-cell ...
().


Other characteristics

When todorokite was first discovered, in 1934, modern methods of mineral analysis were not available, and one of the standard techniques was to use a blowpipe to heat a small sample of the mineral, and observe its behavior. Todorokite was tested in this way, and it was noted that under the blowpipe it turned brown and lost its metallic luster, but did not
fuse Fuse or FUSE may refer to: Devices * Fuse (electrical), a device used in electrical systems to protect against excessive current ** Fuse (automotive), a class of fuses for vehicles * Fuse (hydraulic), a device used in hydraulic systems to protect ...
.
X-ray diffraction X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
lines at 9.5 to 9.8 Å and 4.8 to 4.9 Å are characteristic. This is also true of
buserite Buserite is a hydrated layered Mn-oxide mineral with nominal chemical formula MnO2.''n''H2O. It was named after Swiss chemist professor W. Buser, who first identified it in 1952 in deep-sea manganese nodules. Buser named it 10 Å manganate becau ...
.


Type locality

The type locality is the Todoroki mine, Akaigawa Village (25 km SW of Ginzan),
Shiribeshi Province was a short-lived province in Hokkaidō. Satow, Ernest. (1882). "The Geography of Japan" in It corresponded to Shiribeshi Subprefecture minus Abuta District plus the northern part of Hiyama Subprefecture. History After 1869, the northern Ja ...
,
Hokkaido is Japan's second largest island and comprises the largest and northernmost prefecture, making up its own region. The Tsugaru Strait separates Hokkaidō from Honshu; the two islands are connected by the undersea railway Seikan Tunnel. The la ...
,
Japan Japan ( ja, 日本, or , and formally , ''Nihonkoku'') is an island country in East Asia. It is situated in the northwest Pacific Ocean, and is bordered on the west by the Sea of Japan, while extending from the Sea of Okhotsk in the north ...
.Catalogue of Type Mineral Specimens
/ref>
Type material In biology, a type is a particular specimen (or in some cases a group of specimens) of an organism to which the scientific name of that organism is formally attached. In other words, a type is an example that serves to anchor or centralizes the ...
is conserved at the
Harvard Mineralogical Museum The Mineralogical and Geological Museum at Harvard (MGMH), or the Harvard Mineralogical Museum, is located on the campus of Harvard University in Cambridge, Massachusetts. It is one of the three research museums which collectively comprise the col ...
,
Cambridge, Massachusetts Cambridge ( ) is a city in Middlesex County, Massachusetts, United States. As part of the Boston metropolitan area, the cities population of the 2020 U.S. census was 118,403, making it the fourth most populous city in the state, behind Boston, ...
, US, reference 106214.


Occurrence and associations

Although todorokite is a common product of
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
and leaching of
primary Primary or primaries may refer to: Arts, entertainment, and media Music Groups and labels * Primary (band), from Australia * Primary (musician), hip hop musician and record producer from South Korea * Primary Music, Israeli record label Works * ...
manganese carbonate and
silicate mineral Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust. In mineralogy, silica (silicon dioxide, ) is usually consid ...
s, its major occurrence is in deep-sea
ferromanganese nodules Ferromanganese nodules form in the oxidizing environment of the abyssal pelagic zone. They are the result of ion exchange reactions that precipitate ore components from the water (sedimentary) or out of the interstitial water of the sediments laye ...
. Todorokite has been synthesised from
birnessite Birnessite (nominally MnO2.''n''H2O) is a hydrous manganese dioxide mineral with a chemical formula of Na0.7Ca0.3Mn7O14·2.8H2O. It is the main manganese mineral species at the Earth's surface, and commonly occurs as fine-grained, poorly crystall ...
in the laboratory, and it is possible that most natural todorokite is derived from birnessite. At the type locality in
Akaigawa, Hokkaido is a village located in Shiribeshi, Hokkaido, Japan. As of September 2016, the village has an estimated population of 1,157. The total area is 280.11 km2. History The name derives from Ainu word "hure-pet", meaning "red river". *1899: A ...
, Japan, todorokite occurs as an alteration product of inesite () and
rhodochrosite Rhodochrosite is a manganese carbonate mineral with chemical composition MnCO3. In its (rare) pure form, it is typically a rose-red color, but impure specimens can be shades of pink to pale brown. It streaks white, and its Mohs hardness varies bet ...
). It is found as very fine fibrous flakes about 0.05 mm in length, loosely aggregated in sponge-like masses in druses in gold-bearing
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical form ...
veins Veins are blood vessels in humans and most other animals that carry blood towards the heart. Most veins carry deoxygenated blood from the tissues back to the heart; exceptions are the pulmonary and umbilical veins, both of which carry oxygenated b ...
. The original sample was rather impure since it contained a total of 2.43% insoluble
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
salts () and
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is one ...
().


Other localities


Austria

At Huttenberg,
Carinthia Carinthia (german: Kärnten ; sl, Koroška ) is the southernmost States of Austria, Austrian state, in the Eastern Alps, and is noted for its mountains and lakes. The main language is German language, German. Its regional dialects belong to t ...
,
Austria Austria, , bar, Östareich officially the Republic of Austria, is a country in the southern part of Central Europe, lying in the Eastern Alps. It is a federation of nine states, one of which is the capital, Vienna, the most populous ...
, todorokite occurs as nodular masses about 5 cm in diameter, with a fibrous structure and coarse concentric layering. It is fragile, soft and porous, and so light that it can float on water. It is brown, but lighter in color than samples from Charco Redondo in Cuba. The luster of fracture surfaces is dull, but the smooth outer surface of the nodules has a faintly bronze-like appearance. It has a relatively high
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
content, and also , perhaps due to a small admixture of
pyrolusite Pyrolusite is a mineral consisting essentially of manganese dioxide ( Mn O2) and is important as an ore of manganese.. It is a black, amorphous appearing mineral, often with a granular, fibrous, or columnar structure, sometimes forming reniform ...
().


Brazil

Todorokite is a rare constituent of the
manganese oxide Manganese oxide is any of a variety of manganese oxides and hydroxides.Wells A.F. (1984) ''Structural inorganic chemistry'' 5th edition Oxford Science Publications, . These include * Manganese(II) oxide, MnO * Manganese(II,III) oxide, Mn3O4 * Mang ...
deposits at Saude and Urandi, in
Bahia Bahia ( , , ; meaning "bay") is one of the 26 Federative units of Brazil, states of Brazil, located in the Northeast Region, Brazil, Northeast Region of the country. It is the fourth-largest Brazilian state by population (after São Paulo (sta ...
,
Brazil Brazil ( pt, Brasil; ), officially the Federative Republic of Brazil (Portuguese: ), is the largest country in both South America and Latin America. At and with over 217 million people, Brazil is the world's fifth-largest country by area ...
, as a result of
supergene A supergene is a chromosomal region encompassing multiple neighboring genes that are inherited together because of close genetic linkage, i.e. much less recombination than would normally be expected. This mode of inheritance can be due to genomic ...
enrichment of the
metamorphic Metamorphic rocks arise from the transformation of existing rock to new types of rock in a process called metamorphism. The original rock (protolith) is subjected to temperatures greater than and, often, elevated pressure of or more, causin ...
country rock Country rock is a genre of music which fuses rock and country. It was developed by rock musicians who began to record country-flavored records in the late 1960s and early 1970s. These musicians recorded rock records using country themes, vocal s ...
that contains
spessartine Spessartine is a nesosilicate, manganese aluminium garnet species, Mn2+3Al2(SiO4)3.Gemological Institute of America, ''GIA Gem Reference Guide'' 1995, This mineral is sometimes mistakenly referred to as ''spessartite''. Spessartine's name is a ...
() and other manganese minerals.


Cuba

At Charco Redondo in
Oriente Province Oriente (, "East") was the easternmost province of Cuba until 1976. The term "Oriente" is still used to refer to the eastern part of the country, which currently is divided into five different provinces. Fidel and Raúl Castro were born in a sm ...
,
Cuba Cuba ( , ), officially the Republic of Cuba ( es, República de Cuba, links=no ), is an island country comprising the island of Cuba, as well as Isla de la Juventud and several minor archipelagos. Cuba is located where the northern Caribbea ...
, fibrous todorokite has been found with fibers to 10 cm in length. It is dark brownish black with a weak silky sheen on fracture surfaces, otherwise the luster is dull. It is difficult to measure the
specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water (molecule), wa ...
because of the fibrous structure; measured values between 3.1 and 3.4 are probably too low.
Hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
is low but cannot be measured accurately. Commonly associated minerals are
pyrolusite Pyrolusite is a mineral consisting essentially of manganese dioxide ( Mn O2) and is important as an ore of manganese.. It is a black, amorphous appearing mineral, often with a granular, fibrous, or columnar structure, sometimes forming reniform ...
,
cryptomelane Cryptomelane is a potassium manganese oxide mineral with formula K(Mn4+,Mn2+)8O16. In 1942 the name ''cryptomelane'' was proposed as part of an effort to sort out the manganese oxide minerals referred to as ''psilomelane''. Cryptomelane was identi ...
,
manganite Manganite is a mineral composed of manganese oxide-hydroxide, MnO(OH), crystallizing in the monoclinic system (pseudo-orthorhombic). Crystals of manganite are prismatic and deeply striated parallel to their length; they are often grouped togethe ...
,
psilomelane Psilomelane is a group name for hard black manganese oxides including hollandite and romanechite. Psilomelane consists of hydrous manganese oxide with variable amounts of barium and potassium. Psilomelane is erroneously, and uncommonly, known as ...
,
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical form ...
,
feldspar Feldspars are a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagioclase'' (sodium-calcium) feldsp ...
and
calcite Calcite is a Carbonate minerals, carbonate mineral and the most stable Polymorphism (materials science), polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on ...
. The
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
ores are interbedded with volcanic
tuff Tuff is a type of rock made of volcanic ash ejected from a vent during a volcanic eruption. Following ejection and deposition, the ash is lithified into a solid rock. Rock that contains greater than 75% ash is considered tuff, while rock cont ...
,
jasper Jasper, an aggregate of microgranular quartz and/or cryptocrystalline chalcedony and other mineral phases,Kostov, R. I. 2010. Review on the mineralogical systematics of jasper and related rocks. – Archaeometry Workshop, 7, 3, 209-213PDF/ref> ...
and
limestone Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms whe ...
. The todorokite has been altered near the surface and along faults or
fissure A fissure is a long, narrow crack opening along the surface of Earth. The term is derived from the Latin word , which means 'cleft' or 'crack'. Fissures emerge in Earth's crust, on ice sheets and glaciers, and on volcanoes. Ground fissure A ...
s to
pyrolusite Pyrolusite is a mineral consisting essentially of manganese dioxide ( Mn O2) and is important as an ore of manganese.. It is a black, amorphous appearing mineral, often with a granular, fibrous, or columnar structure, sometimes forming reniform ...
, and perhaps to
manganite Manganite is a mineral composed of manganese oxide-hydroxide, MnO(OH), crystallizing in the monoclinic system (pseudo-orthorhombic). Crystals of manganite are prismatic and deeply striated parallel to their length; they are often grouped togethe ...
. The source of the
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
was probably
hot springs A hot spring, hydrothermal spring, or geothermal spring is a spring produced by the emergence of geothermally heated groundwater onto the surface of the Earth. The groundwater is heated either by shallow bodies of magma (molten rock) or by circ ...
.


Portugal

At Farragudo in the
Algarve The Algarve (, , ; from ) is the southernmost NUTS II region of continental Portugal. It has an area of with 467,495 permanent inhabitants and incorporates 16 municipalities ( ''concelhos'' or ''municípios'' in Portuguese). The region has it ...
,
Portugal Portugal, officially the Portuguese Republic ( pt, República Portuguesa, links=yes ), is a country whose mainland is located on the Iberian Peninsula of Southwestern Europe, and whose territory also includes the Atlantic archipelagos of ...
, a stalactitic mass of todorokite was found in a small collection of
secondary Secondary may refer to: Science and nature * Secondary emission, of particles ** Secondary electrons, electrons generated as ionization products * The secondary winding, or the electrical or electronic circuit connected to the secondary winding i ...
manganese minerals, chiefly
cryptomelane Cryptomelane is a potassium manganese oxide mineral with formula K(Mn4+,Mn2+)8O16. In 1942 the name ''cryptomelane'' was proposed as part of an effort to sort out the manganese oxide minerals referred to as ''psilomelane''. Cryptomelane was identi ...
). It is soft and porous, with a fibrous mode of aggregation and dark brown to brownish black color.


South Africa

Large crystals have been found in the Smartt Mine,
Hotazel Hotazel is a town in John Taolo Gaetsewe District Municipality in the Northern Cape province of South Africa. The town serves the manganese mines, 147 km (91 mi) north of Postmasburg and 46 km (28.6 mi) north-west of Kuruman ...
, and elsewhere in the
Kuruman Kuruman is a small town with just over 53,000 inhabitants in the Northern Cape province of South Africa. It is known for its scenic beauty and the Eye of Kuruman, a geological feature that brings water from deep underground. The abundance of water ...
district,
Cape Province The Province of the Cape of Good Hope ( af, Provinsie Kaap die Goeie Hoop), commonly referred to as the Cape Province ( af, Kaapprovinsie) and colloquially as The Cape ( af, Die Kaap), was a province in the Union of South Africa and subsequen ...
,
South Africa South Africa, officially the Republic of South Africa (RSA), is the southernmost country in Africa. It is bounded to the south by of coastline that stretch along the South Atlantic and Indian Oceans; to the north by the neighbouring countri ...
.


United States

At Sterling Hill,
New Jersey New Jersey is a state in the Mid-Atlantic and Northeastern regions of the United States. It is bordered on the north and east by the state of New York; on the east, southeast, and south by the Atlantic Ocean; on the west by the Delaware ...
, todorokite has been identified in a small collection of secondary manganese oxides from the old surface workings. It forms soft, dark brownish-black masses with a confused fibrous structure. Associated with chalcophanite ) and secondary calcite () crystals in
franklinite Franklinite is an oxide mineral belonging to the normal spinel subgroup's iron (Fe) series, with the formula ZnFe3+2O4. As with another spinel member magnetite, both ferrous (2+) and ferric (3+) iron may be present in Franklinite samples. Di ...
() -
willemite Willemite is a zinc silicate mineral () and a minor ore of zinc. It is highly fluorescent (green) under shortwave ultraviolet light. It occurs in a variety of colors in daylight, in fibrous masses and apple-green gemmy masses. Troostite is a vari ...
() ore. At
Saipan Saipan ( ch, Sa’ipan, cal, Seipél, formerly in es, Saipán, and in ja, 彩帆島, Saipan-tō) is the largest island of the Northern Mariana Islands, a Commonwealth (U.S. insular area), commonwealth of the United States in the western Pa ...
in the
Mariana Islands The Mariana Islands (; also the Marianas; in Chamorro: ''Manislan Mariånas'') are a crescent-shaped archipelago comprising the summits of fifteen longitudinally oriented, mostly dormant volcanic mountains in the northwestern Pacific Ocean, betw ...
, in the
Pacific Ocean The Pacific Ocean is the largest and deepest of Earth's five oceanic divisions. It extends from the Arctic Ocean in the north to the Southern Ocean (or, depending on definition, to Antarctica) in the south, and is bounded by the continen ...
, todorokite has been found with the same mode of aggregation and color as that from Charco Redondo in Cuba. It is relatively brittle and hard because it is intimately admixed with finely divided silica, amounting in some cases to as much as 50% of the sample. The content of
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
is greater than that of
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
or
calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
.


See also

*
Manganese oxide Manganese oxide is any of a variety of manganese oxides and hydroxides.Wells A.F. (1984) ''Structural inorganic chemistry'' 5th edition Oxford Science Publications, . These include * Manganese(II) oxide, MnO * Manganese(II,III) oxide, Mn3O4 * Mang ...


References

{{Manganese minerals Magnesium minerals Calcium minerals Barium minerals Potassium minerals Sodium minerals Manganese minerals Oxide minerals Monoclinic minerals Minerals in space group 11