In
ore
Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 Apr ...
deposit
geology
Geology () is a branch of natural science concerned with Earth and other astronomical objects, the features or rocks of which it is composed, and the processes by which they change over time. Modern geology significantly overlaps all other Ear ...
, supergene processes or enrichment are those that occur relatively near the surface as opposed to deep
hypogene In ore deposit geology, hypogene processes occur deep below the earth's surface, and tend to form deposits of primary minerals, as opposed to supergene processes that occur at or near the surface, and tend to form secondary minerals.
At great dept ...
processes. Supergene processes include the predominance of
meteoric water
Meteoric water is the water derived from precipitation (snow and rain). This includes water from lakes, rivers, and icemelts, which all originate from precipitation indirectly. While the bulk of rainwater or meltwater from snow and ice reaches the ...
circulation (i.e. water derived from
precipitation
In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls under gravitational pull from clouds. The main forms of precipitation include drizzle, rain, sleet, snow, ice pellets, graupel and hail. ...
) with concomitant
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 chemical
weathering
Weathering is the deterioration of rocks, soils and minerals as well as wood and artificial materials through contact with water, atmospheric gases, and biological organisms. Weathering occurs ''in situ'' (on site, with little or no movement), ...
. The descending meteoric waters
oxidize
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 ...
the primary (hypogene)
sulfide ore minerals and redistribute the metallic ore elements. Supergene ''enrichment'' occurs at the base of the oxidized portion of an ore deposit. Metals that have been leached from the oxidized ore are carried downward by percolating groundwater, and react with hypogene sulfides at the supergene-hypogene boundary. The reaction produces secondary sulfides with metal contents higher than those of the primary ore. This is particularly noted in
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 ...
ore deposits where the copper sulfide minerals
chalcocite
Chalcocite (), copper(I) sulfide (Cu2S), is an important copper ore mineral. It is opaque and dark gray to black, with a metallic luster. It has a hardness of 2.5–3 on the Mohs scale. It is a sulfide with a monoclinic crystal system.
The ...
(Cu
2S),
covellite
Covellite (also known as covelline) is a rare copper sulfide mineral with the formula CuS. This indigo blue mineral is commonly a secondary mineral in limited abundance and although it is not an important ore of copper itself, it is well known t ...
(CuS),
digenite
Digenite is a copper sulfide mineral with formula: Cu9S5. Digenite is a black to dark blue opaque mineral that crystallizes with a trigonal - hexagonal scalenohedral structure. In habit it is usually massive, but does often show pseudo-cubic f ...
(Cu
18S
10), and
djurleite
Djurleite is a copper sulfide mineral of secondary origin with formula Cu31S16 that crystallizes with monoclinic-prismatic symmetry. It is typically massive in form, but does at times develop thin tabular to prismatic crystals. It occurs with oth ...
(Cu
31S
16) are deposited by the descending surface waters.
[Guilbert, John M. and Charles F. Park Jr (1986) ''The Geology of Ore Deposits'', W. H. Freeman, ]
All such processes take place at essentially atmospheric conditions, around room temperature (25 °C) and standard
atmospheric pressure
Atmospheric pressure, also known as barometric pressure (after the barometer), is the pressure within the atmosphere of Earth. The standard atmosphere (symbol: atm) is a unit of pressure defined as , which is equivalent to 1013.25 millibars, 7 ...
(1
atm).
[Manual of Mineralogy (1993) Klein and Hurlbut. Wiley]
Zones
Distinct zones of supergene processes can be identified at various depths. From the surface down they are the gossan cap, leached zone, oxidized zone, water table, enriched zone (supergene enriched zone) and primary zone (hypogene zone).
[Understanding Mineral Deposits (2000). Kula C Misra. Kluwer Academic Publishers]
Gossan cap
Pyrite
The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral.
Pyrite's metallic Luster (mineralogy), lust ...
(FeS
2) has oxidised to form
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 ...
(FeO(OH)) and
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 FeO(OH)·H2O, although this is not entirely accurate as the ratio of oxide to hydroxid ...
(FeO(OH)·''n''H
2O),
[ which form a porous covering over the oxidized zone known as a ]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 i ...
cap or iron hat.[The Encyclopedia of Gemstones and Minerals (1991). Martin Holden. Publisher: Facts on File] Prospectors use gossan as an indication ore reserves.
Leached zone
Groundwater
Groundwater is the water present beneath Earth's surface in rock and soil pore spaces and in the fractures of rock formations. About 30 percent of all readily available freshwater in the world is groundwater. A unit of rock or an unconsolidate ...
contains dissolved 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 ...
and carbon dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
. As it travels downwards it oxidizes primary sulfide minerals
The sulfide minerals are a class of minerals containing sulfide (S2−) or disulfide (S22−) as the major anion. Some sulfide minerals are economically important as metal ores. The sulfide class also includes the selenides, the tellurides, the ...
, concomitant with forming 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 ...
and solutions
Solution may refer to:
* Solution (chemistry), a mixture where one substance is dissolved in another
* Solution (equation), in mathematics
** Numerical solution, in numerical analysis, approximate solutions within specified error bounds
* Soluti ...
of oxidized metals.[Field Guide to North American Rocks and Minerals (1992) The Audubon Society. Alfred A Knopf] For example, groundwater commonly interacts with pyrite (FeS2) to form an oxidized iron (FeO(OH)) and sulfuric acid (H2SO4), portrayed in the idealized chemical reaction below (intermediate steps omitted):
:
An intermediate in this process is ferric sulfate
Iron(III) sulfate (or ferric 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 sulfate". Solutions are used in dyeing as a morda ...
(FeSO4), which oxidizes pyrite and other sulfide minerals.
Oxidized zone
Above the water table the environment is oxidizing
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 below it is reducing.[John Rakovan (2003) Rocks & Minerals 78:419]
Solutions traveling downward from the leached zone react with other primary minerals A primary mineral is any mineral formed during the original crystallization of the host igneous primary rock and includes the essential mineral(s) used to classify the rock along with any accessory minerals. In ore deposit geology, hypogene processe ...
in the oxidised zone to form secondary minerals[ such as ]sulfates
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 a ...
and carbonates
A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate g ...
, and 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 FeO(OH)·H2O, although this is not entirely accurate as the ratio of oxide to hydroxid ...
, which is a characteristic product in all oxidised zones.[
In the formation of secondary carbonates, primary ]sulfide mineral
The sulfide minerals are a class of minerals containing sulfide (S2−) or disulfide (S22−) as the major anion. Some sulfide minerals are economically important as metal ores. The sulfide class also includes the selenides, the tellurides, the ...
s generally are first converted to sulfates, which in turn react with primary carbonates such as 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 ...
(CaCO3), dolomite Dolomite may refer to:
*Dolomite (mineral), a carbonate mineral
*Dolomite (rock), also known as dolostone, a sedimentary carbonate rock
*Dolomite, Alabama, United States, an unincorporated community
*Dolomite, California, United States, an unincor ...
(CaMg(CO3)2) or aragonite
Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including prec ...
(also CaCO3, polymorphic with calcite) to produce secondary carbonates.[ Soluble salts continue on down, but insoluble salts are left behind in the oxidised zone where they form. Examples of insoluble salts that are commonly found in the oxidized zone include ]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 ...
precipitates
In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading ...
like anglesite
Anglesite is a lead sulfate mineral with the chemical formula PbSO4. It occurs as an oxidation product of primary lead sulfide ore, galena. Anglesite occurs as prismatic orthorhombic crystals and earthy masses, and is isomorphous with barite and ...
(PbSO4) and pyromorphite
Pyromorphite is a mineral species composed of lead chlorophosphate: Pb5( P O4)3 Cl, sometimes occurring in sufficient abundance to be mined as an ore of lead. Crystals are common, and have the form of a hexagonal prism terminated by the basal pla ...
(Pb5(PO4)3Cl); 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 ...
precipitates like malachite
Malachite is a copper carbonate hydroxide mineral, with the formula Cu2CO3(OH)2. This opaque, green-banded mineral crystallizes in the monoclinic crystal system, and most often forms botryoidal, fibrous, or stalagmitic masses, in fractures ...
(Cu2(CO3(OH)2), azurite
Azurite is a soft, deep-blue copper mineral produced by weathering of copper ore deposits. During the early 19th century, it was also known as chessylite, after the Type locality (geology), type locality at Chessy, Rhône, Chessy-les-Mines near ...
(Cu3(CO3)2(OH)2), and cuprite
Cuprite is an oxide mineral composed of copper(I) oxide Cu2O, and is a minor ore of copper.
Its dark crystals with red internal reflections are in the isometric system hexoctahedral class, appearing as cubic, octahedral, or dodecahedral forms, o ...
(Cu2O); and smithsonite
Smithsonite, also known as zinc spar, is the mineral form of zinc carbonate ( Zn CO3). Historically, smithsonite was identified with hemimorphite before it was realized that they were two different minerals. The two minerals are very similar in app ...
(ZnCO3).[
]
Water table
At the water table
The water table is the upper surface of the zone of saturation. The zone of saturation is where the pores and fractures of the ground are saturated with water. It can also be simply explained as the depth below which the ground is saturated.
T ...
the environment changes from an oxidizing
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 ...
environment to a reducing one.[
]
Enriched zone
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 ...
ions
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 conven ...
that move down into this reducing environment form a zone of supergene sulfide
Sulfide (British English also sulphide) 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 chemical compounds lar ...
enrichment.[ ]Covellite
Covellite (also known as covelline) is a rare copper sulfide mineral with the formula CuS. This indigo blue mineral is commonly a secondary mineral in limited abundance and although it is not an important ore of copper itself, it is well known t ...
(CuS), chalcocite
Chalcocite (), copper(I) sulfide (Cu2S), is an important copper ore mineral. It is opaque and dark gray to black, with a metallic luster. It has a hardness of 2.5–3 on the Mohs scale. It is a sulfide with a monoclinic crystal system.
The ...
(Cu2S) and native copper
Native copper is an uncombined form of copper that occurs as a natural mineral. Copper is one of the few metallic elements to occur in native form, although it most commonly occurs in oxidized states and mixed with other elements. Native coppe ...
(Cu) are stable in these conditions[ and they are characteristic of the enriched zone.][
The net effect of these supergene processes is to move metal ions from the leached zone to the enriched zone, increasing the concentration there to levels higher than in the unmodified primary zone below, possibly producing a deposit worth mining.
]
Primary zone
The primary zone contains unaltered primary minerals A primary mineral is any mineral formed during the original crystallization of the host igneous primary rock and includes the essential mineral(s) used to classify the rock along with any accessory minerals. In ore deposit geology, hypogene processe ...
.[
]
Mineral alterations
Chalcopyrite
Chalcopyrite ( ) is a copper iron sulfide mineral and the most abundant copper ore mineral. It has the chemical formula CuFeS2 and crystallizes in the tetragonal system. It has a brassy to golden yellow color and a hardness of 3.5 to 4 on the Mo ...
CuFeS2 (primary) readily alters to the secondary minerals bornite
Bornite, also known as peacock ore, is a sulfide mineral with chemical composition Cu5 Fe S4 that crystallizes in the orthorhombic system (pseudo-cubic).
Appearance
Bornite has a brown to copper-red color on fresh surfaces that tarnishes to v ...
Cu5FeS4, covellite
Covellite (also known as covelline) is a rare copper sulfide mineral with the formula CuS. This indigo blue mineral is commonly a secondary mineral in limited abundance and although it is not an important ore of copper itself, it is well known t ...
CuS and brochantite
Brochantite is a sulfate mineral, one of a number of cupric sulfates. Its chemical formula is Cu4SO4(OH)6. Formed in arid climates or in rapidly oxidizing copper sulfide deposits, it was named by Armand Lévy for his fellow Frenchman, geologist ...
Cu4SO4(OH)6.[
]Galena
Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver.
Galena is one of the most abundant and widely distributed sulfide minerals. It cryst ...
PbS (primary) alters to secondary anglesite
Anglesite is a lead sulfate mineral with the chemical formula PbSO4. It occurs as an oxidation product of primary lead sulfide ore, galena. Anglesite occurs as prismatic orthorhombic crystals and earthy masses, and is isomorphous with barite and ...
PbSO4 and cerussite
Cerussite (also known as lead carbonate or white lead ore) is a mineral consisting of lead carbonate (PbCO3), and is an important ore of lead. The name is from the Latin ''cerussa'', white lead. ''Cerussa nativa'' was mentioned by Conrad Gessner ...
PbCO3.[
]Sphalerite
Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
ZnS (primary) alters to secondary hemimorphite
Hemimorphite is the chemical compound Zn4( Si2O7)( OH)2 ·H2O, a component of mineral calamine. It is a silicate mineral which, together with smithsonite (ZnCO3), has been historically mined from the upper parts of zinc and lead ores. Both comp ...
Zn4Si2O7(OH)2.H2O, smithsonite
Smithsonite, also known as zinc spar, is the mineral form of zinc carbonate ( Zn CO3). Historically, smithsonite was identified with hemimorphite before it was realized that they were two different minerals. The two minerals are very similar in app ...
ZnCO3 and 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 ...
-bearing 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 ...
Zn2SiO4.[
]Pyrite
The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral.
Pyrite's metallic Luster (mineralogy), lust ...
FeS2 (primary) alters to secondary melanterite
Melanterite is a mineral form of hydrous iron(II) sulfate: FeSO4·7H2O. It is the iron analogue of the copper sulfate chalcanthite. It alters to siderotil by loss of water. It is a secondary sulfate mineral which forms from the oxidation of pri ...
FeSO4.7H2O.[
If the original deposits contain ]arsenic
Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
and 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 ...
bearing minerals, secondary arsenates
The arsenate ion is .
An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid.
The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V).
Arsenate resem ...
and phosphates
In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid .
The phosphate or orthophosphate ion is derived from phosph ...
will be formed.[
]
Etymology
The word ''supergene'' is derived from the Latin root meaning 'above' and the Greek root ''-gene'' () meaning 'born' or 'produced'. The terms ''supergene'' and ''hypogene'' refer to the depth at which they occur.
See also
*Hypogene In ore deposit geology, hypogene processes occur deep below the earth's surface, and tend to form deposits of primary minerals, as opposed to supergene processes that occur at or near the surface, and tend to form secondary minerals.
At great dept ...
References
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Economic geology