Jarosite Crystal Structure
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Jarosite is a basic
hydrous In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
of
potassium Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
and ferric
iron Iron is a chemical element; it has symbol Fe () 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, forming much of Earth's o ...
(Fe-III) with a chemical formula of KFe3(SO4)2(OH)6. This
sulfate mineral The sulfate minerals are a class of minerals that include the sulfate ion () within their structure. The sulfate minerals occur commonly in primary evaporite depositional environments, as gangue minerals in hydrothermal Vein (geology), veins and as ...
is formed in
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically including metals, concentrated above background levels, and that is economically viable to mine and process. The grade of ore refers to the concentration ...
deposits by the
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
of iron
sulfide Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families o ...
s. Jarosite is often produced as a byproduct during the purification and refining of
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
and is also commonly associated with
acid mine drainage Acid mine drainage, acid and metalliferous drainage (AMD), or acid rock drainage (ARD) is the outflow of acidic water from metal mines and coal mines. Acid rock drainage occurs naturally within some environments as part of the rock weatherin ...
and
acid sulfate soil Acid sulfate soils are naturally occurring soils, sediments or organic substrates (e.g. peat) that are formed under waterlogged conditions. These soils contain iron sulfide minerals (predominantly as the mineral pyrite) and/or their oxidation produ ...
environments.


Physical properties

Jarosite has a
trigonal In crystallography, the hexagonal crystal family is one of the six crystal family, crystal families, which includes two crystal systems (hexagonal and trigonal) and two lattice systems (hexagonal and rhombohedral). While commonly confused, the tr ...
crystal structure and is brittle, with basal cleavage, a
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to plastic deformation, such as an indentation (over an area) or a scratch (linear), induced mechanically either by Pressing (metalworking), pressing or abrasion ...
of 2.5–3.5, and a
specific gravity Relative density, also called specific gravity, is a dimensionless quantity defined as the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for solids and liquids is nea ...
of 3.15–3.26. It is translucent to opaque with a vitreous to dull luster, and is colored dark yellow to yellowish-brown. It can sometimes be confused with
limonite Limonite () is an iron ore consisting of a mixture of hydrated iron(III) oxide-hydroxides in varying composition. The generic formula is frequently written as , although this is not entirely accurate as the ratio of oxide to hydroxide can vary qu ...
or
goethite Goethite (, ) is a mineral of the diaspore group, consisting of iron(III) oxide-hydroxide, specifically the α- polymorph. It is found in soil and other low-temperature environments such as sediment. Goethite has been well known since ancient t ...
with which it commonly occurs in the
gossan Gossan (eiserner hut or eisenhut) is intensely oxidized, weathered or decomposed rock, usually the upper and exposed part of an ore deposit or mineral vein. In the ''classic'' gossan or iron cap all that remains is iron oxides and quartz, often ...
(oxidized cap over an ore body). Jarosite is an iron analogue of the potassium aluminium sulfate,
alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula potassium, Kaluminium, Al3(sulfur, Soxygen, O4)2(Ohydrogen, H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum ...
.


Solid solution series

The alunite supergroup includes the
alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula potassium, Kaluminium, Al3(sulfur, Soxygen, O4)2(Ohydrogen, H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum ...
, jarosite,
beudantite Beudandite is a secondary mineral occurring in the Oxidation, oxidized zones of Polymetal, polymetallic deposits. It is a lead, iron, Arsenate mineral, arsenate, sulfate mineral, sulfate with Chemical formula, endmember formula: PbFe3(OH)6SO4AsO4 ...
, crandallite and florencite subgroups. The alunite supergroup minerals are isostructural with each other and substitution between them occurs, resulting in several
solid solution A solid solution, a term popularly used for metals, is a homogeneous mixture of two compounds in solid state and having a single crystal structure. Many examples can be found in metallurgy, geology, and solid-state chemistry. The word "solutio ...
series. The alunite supergroup has the general formula AB3(TO4)2(OH)6. In the alunite subgroup B is Al, and in the jarosite subgroup B is Fe3+. The beudantite subgroup has the general formula AB3(XO4)(SO4)(OH)6, the crandallite subgroup AB3(TO4)2(OH)5•H2O and the florencite subgroup AB3(TO4)2(OH)5 or 6. In the jarosite-alunite series Al may substitute for Fe and a complete solid solution series between jarosite and alunite, KAl3(SO4)2(OH)6, probably exists, but intermediate members are rare. The material from Kopec,
Czech Republic The Czech Republic, also known as Czechia, and historically known as Bohemia, is a landlocked country in Central Europe. The country is bordered by Austria to the south, Germany to the west, Poland to the northeast, and Slovakia to the south ...
, has about equal Fe and Al, but the amount of Al in jarosite is usually small. When jarosite forms from
pyrite The mineral pyrite ( ), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Fe S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic luster and pale brass-yellow hue ...
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
in sedimentary clays, the main sources of K+ are
illite Illite, also called hydromica or hydromuscovite, is a group of closely related non-expanding clay minerals. Illite is a secondary mineral precipitate, and an example of a phyllosilicate, or layered alumino-silicate. Its structure is a 2:1 sandw ...
, a non-swelling clay, or
K-feldspar Orthoclase, or orthoclase feldspar (endmember formula K Al Si3 O8), is an important tectosilicate mineral which forms igneous rock. The name is from the Ancient Greek for "straight fracture", because its two cleavage planes are at right angles t ...
. In other geological settings
mica Micas ( ) are a group of silicate minerals whose outstanding physical characteristic is that individual mica crystals can easily be split into fragile elastic plates. This characteristic is described as ''perfect basal cleavage''. Mica is co ...
's alteration can also be a source of potassium. In the jarosite-natrojarosite series Na substitutes for K to at least Na/K = 1:2.4 but the pure sodium end member NaFe3(SO4)2(OH)6 is not known in nature. Minerals with Na > K are known as natrojarosite. End member formation (jarosite and natrojarosite) is favoured by a low temperature environment, less than 100 °C, and is illustrated by the oscillatory zoning of jarosite and natrojarosite found in samples from the Apex Mine, Arizona, and
Gold Hill, Utah Gold Hill is an unincorporated community in far western Tooele County, Utah, located near the Nevada state line. History The town, located near the Deep Creek Mountains, was the center of a mining district that was active in the late nineteen ...
. This indicates that there is a wide
miscibility gap A miscibility gap is a region in a phase diagram for a mixture In chemistry, a mixture is a material made up of two or more different chemical substances which can be separated by physical method. It is an impure substance made up of 2 or more ...
between the two end members,American Mineralogist (2007) 92:444–447 and it is doubtful whether a complete series exists between jarosite and natrojarosite. In hydroniumjarositeAmerican Mineralogist (2007) 92:1464–1473 the
hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the cation , also written as , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved ...
ion H3O+ can also substitute for K+, with increased hydronium ion content causing a marked decrease in the lattice parameter ''c'', although there is little change in ''a''.American Mineralogist (1965) 50:1595–1607 Hydroniumjarosite will only form from alkali-deficient solutions, as alkali-rich jarosite forms preferentially. Divalent cations may also substitute for the monovalent cation K+ in the A site.American Mineralogist (1987) 72:178–187 Charge balance may be achieved in three ways. :Firstly by replacing two monovalent cations by one divalent cation, and leaving an A site vacancy, as in plumbogummite, Pb2+Al3(PO4)2(OH)5.H2O, which is a member of the crandallite subgroup. :Secondly by incorporating divalent ions in the B sites, as in osarizawaite, Pb2+Cu2+Al2(SO4)2(OH)6, alunite subgroup, and beaverite, Pb2+Cu2+(Fe3+,Al)2(SO4)2(OH)6, jarosite subgroup. :Thirdly by replacing divalent anions with trivalent anions, as in
beudantite Beudandite is a secondary mineral occurring in the Oxidation, oxidized zones of Polymetal, polymetallic deposits. It is a lead, iron, Arsenate mineral, arsenate, sulfate mineral, sulfate with Chemical formula, endmember formula: PbFe3(OH)6SO4AsO4 ...
, PbFe3+3(AsO4)3−(SO4)(OH)6, beudantite subgroup.


History

Jarosite was first described in 1852 by
August Breithaupt Johann Friedrich August Breithaupt (May 16, 1791 – September 22, 1873) was a German mineralogist and professor at Freiberg Mining Academy in Freiberg, Saxony. Biography He was born in Probstzella, Holy Roman Empire. He received his doctorate ...
in the Barranco del Jaroso in the Sierra Almagrera (near Los Lobos, Cuevas del Almanzora,
Almería Almería (, , ) is a city and municipalities in Spain, municipality of Spain, located in Andalusia. It is the capital of the province of Almería, province of the same name. It lies in southeastern Iberian Peninsula, Iberia on the Mediterranean S ...
,
Spain Spain, or the Kingdom of Spain, is a country in Southern Europe, Southern and Western Europe with territories in North Africa. Featuring the Punta de Tarifa, southernmost point of continental Europe, it is the largest country in Southern Eur ...
). The name jarosite is directly derived from "jara", the Spanish name of a yellow flower that belongs to the genus ''
Cistus ''Cistus'' (from the Greek ''kistos'') is a genus of flowering plants in the rockrose family Cistaceae, containing about 20 species (Ellul ''et al.'' 2002). They are perennial shrubs found on dry or rocky soils throughout the Mediterranean reg ...
'' and grows in the sierra. The mineral and the flower have the same color. Mysterious spheres of clay, in diameter and covered with jarosite, have been found beneath the Temple of the Feathered Serpent, an ancient six-level stepped pyramid from Mexico City.


Mars exploration

Ferric sulfate and jarosite have been detected by three martian rovers: '' Spirit'', ''
Opportunity Opportunity may refer to: Places * Opportunity, Montana, an unincorporated community, United States * Opportunity, Nebraska, an unincorporated community, United States * Opportunity, Washington, a former census-designated place, United States * ...
'' and ''
Curiosity Curiosity (from Latin , from "careful, diligent, curious", akin to "care") is a quality related to inquisitive thinking, such as exploration, investigation, and learning, evident in humans and other animals. Curiosity helps Developmental psyc ...
''. These substances are indicative of strongly oxidizing conditions prevailing at the surface of
Mars Mars is the fourth planet from the Sun. It is also known as the "Red Planet", because of its orange-red appearance. Mars is a desert-like rocky planet with a tenuous carbon dioxide () atmosphere. At the average surface level the atmosph ...
. In May 2009, the ''Spirit'' rover became stuck when it drove over a patch of soft ferric sulfate that had been hidden under a veneer of normal-looking soil. Because iron sulfate has very little cohesion, the rover's wheels could not gain sufficient traction to pull the body of the rover out of the iron sulfate patch. Multiple techniques were attempted to extricate the rover, but the wheels eventually sank so deeply into the iron sulfate that the body of the rover came to rest on the Martian surface, preventing the wheels from exerting any force on the material below them. As the
JPL The Jet Propulsion Laboratory (JPL) is a federally funded research and development center (FFRDC) in La Cañada Flintridge, California, Crescenta Valley, United States. Founded in 1936 by California Institute of Technology (Caltech) researche ...
team failed to recover the mobility of ''Spirit'', it signified the end of the journey for the rover.


Antarctica deep borehole

On Earth, jarosite is mainly associated with the ultimate stage of pyrite oxidation in clay environment, and can also be found in
mine tailings In mining, tailings or tails are the materials left over after the process of separating the valuable fraction from the uneconomic fraction (gangue) of an ore. Tailings are different from overburden, which is the waste rock or other material th ...
waste where acidic conditions prevail. Against all expectations, jarosite has also been fortuitously discovered in minute quantities in the form of small dust particles in ice cores recovered from a deep borehole in
Antarctica Antarctica () is Earth's southernmost and least-populated continent. Situated almost entirely south of the Antarctic Circle and surrounded by the Southern Ocean (also known as the Antarctic Ocean), it contains the geographic South Pole. ...
. That surprising discovery was made by geologists who were searching for specific minerals capable of indicating ice age cycles within the layers of a 1620-meter-long ice core. Geologists speculate that jarosite dust could also have accumulated within ice in glaciers on Mars. However, that hypothesis is a matter of controversy because, on Mars, jarosite deposits can be very thick (up to 10 meters). However, Mars is also a very dusty planet and, in the absence of
plate tectonics Plate tectonics (, ) is the scientific theory that the Earth's lithosphere comprises a number of large tectonic plates, which have been slowly moving since 3–4 billion years ago. The model builds on the concept of , an idea developed durin ...
on Mars, glacial dust deposits might have accumulated over long periods of time.


Use in materials science

Jarosite is also a more generic term denoting an extensive family of compounds of the form AM3(OH)6(SO4)2, where A+ = Na, K, Rb, NH4, H3O, Ag, Tl and M3+ = Fe, Cr, V. In
condensed matter physics Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid State of matter, phases, that arise from electromagnetic forces between atoms and elec ...
and
materials science Materials science is an interdisciplinary field of researching and discovering materials. Materials engineering is an engineering field of finding uses for materials in other fields and industries. The intellectual origins of materials sci ...
they are renowned for containing layers with
kagome lattice In geometry, the trihexagonal tiling is one of 11 uniform tilings of the Euclidean plane by regular polygons. See in particular Theorem 2.1.3, p. 59 (classification of uniform tilings); Figure 2.1.5, p.63 (illustration of this tiling), Theorem 2. ...
structure, relating to
geometrically frustrated magnet Geometry (; ) is a branch of mathematics concerned with properties of space such as the distance, shape, size, and relative position of figures. Geometry is, along with arithmetic, one of the oldest branches of mathematics. A mathematician w ...
s.


See also

*
Alunite Alunite is a hydroxylated aluminium potassium sulfate mineral, formula potassium, Kaluminium, Al3(sulfur, Soxygen, O4)2(Ohydrogen, H)6. It was first observed in the 15th century at Tolfa, near Rome, where it was mined for the manufacture of alum ...
*
Iron(III) sulfate Iron(III) sulfate or ferric sulfate (British English: sulphate instead of sulfate) is a family of inorganic compounds with the formula Fe2(SO4)3(H2O)n. A variety of hydrates are known, including the most commonly encountered form of "ferric sulf ...
* Spirit Mars rover final embedding event


References

* Palache C., Berman H., and Frondel C. (1951) Dana's system of mineralogy, (7th edition), v. II, 560–562.
Webmineral data


* ttp://news.discovery.com/history/archaeology/mysterious-spheres-emerge-from-ancient-temple-1304291.htm Discovery News (2013) "Robot Finds Mysterious Spheres in Ancient Temple"{{Webarchive, url=https://web.archive.org/web/20150319032519/http://news.discovery.com/history/archaeology/mysterious-spheres-emerge-from-ancient-temple-1304291.htm , date=2015-03-19


External links


Further information about the Jaros Hydrothermal system
Iron(III) minerals Potassium minerals Alunite group Trigonal minerals Minerals in space group 166