Ferrihydrite
Encyclopedia
Ferrihydrite is a widespread hydrous ferric oxyhydroxide mineral
at the Earth's surface, and a likely constituent in extraterrestrial materials
. It forms in several types of environments, from freshwater
to marine systems, aquifer
s to hydrothermal hot spring
s and scales, soil
s, and areas affected by mining. It can be precipitated directly from oxygenated iron
-rich aqueous solutions, or by bacteria
either as a result of a metabolic activity or passive sorption
of dissolved iron followed by nucleation
reactions. Ferrihydrite also occurs in the core of the ferritin
protein
from many living organisms, for the purpose of intra-cellular iron storage.
in 1973 with the nominal chemical formula 5Fe2O3•9H2O. However, its formula is fundamentally indeterminate as its water content is variable. The two-line form is also called hydrous ferric oxides (HFO).
Due to the nanoparticluate nature of ferrihydrite, the structure has remained elusive for many years and is still a matter of controversy. Drits et al., using X-ray diffraction data, proposed a multiphase material with three components: defect-free crystallite
s (f-phase) with double-hexagonal stacking of oxygen and hydroxyl layers (ABAC sequence) and disordered octahedral Fe occupancies, defective crystallites (d-phase) with a short-range feroxyhite
-like (δ-FeOOH) structure, and subordinate ultradisperse hematite
(α-Fe2O3). Recently, a new single phase model for both ferrihydrite and hydromaghemite has been proposed by Michel et al., based on pair distribution function (PDF) analysis of x-ray total scattering data. The structural model, isostructural with the mineral akdalaite
(Al10O14(OH)2), contains 20% tetrahedrally and 80% octahedrally coordinated iron.
s, Fh is nanoporous
yielding large surface areas of several hundred square meters per gram. In addition to having a high surface area to volume ratio, Fh also has a high density of local or point defects, such as dangling bonds and vacancies. These properties confer a high ability to adsorb many environmentally important chemical species, including arsenic
, lead
, phosphate
, and organic molecules (e.g., humic
and fulvic acids). Its strong and extensive interaction with trace metals and metalloids is used in industry, at large-scale in water purification
plants, as in North Germany and to produce the city water at Hiroshima
, and at small scale to clean wastewater
s and groundwater
s, for example to remove arsenic from industrial effluents and drinking water
. Its nanoporosity and high affinity for gold
can be used to elaborate Fh-supported nanosized Au particles for the catalytic oxidation
of CO at temperatures below 0°C.
and goethite
by aggregation-based crystal growth
. However, its transformation in natural systems generally is blocked by chemical impurities adsorbed at its surface, for example silica as most of natural ferrihydrites are siliceous.
Under reducing conditions as those found in gley soil
s, or in deep environments depleted in oxygen, and often with the assistance of microbial activity, ferrihydrite can be transformed in green rust, a layered double hydroxide (LDH), also known as the mineral fougerite
. However, a short exposure of green rust to atmospheric oxygen is sufficient to oxidize it back to ferrihydrite, making it a very elusive compound.
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...
at the Earth's surface, and a likely constituent in extraterrestrial materials
Extraterrestrial materials
Most atoms on Earth came from the interstellar dust and gas from which the Sun and Solar System formed. However, in the space science community, "extraterrestrial materials" generally refers to objects now on Earth that were solidified prior to arriving on earth...
. It forms in several types of environments, from freshwater
Freshwater
Fresh water is naturally occurring water on the Earth's surface in ice sheets, ice caps, glaciers, bogs, ponds, lakes, rivers and streams, and underground as groundwater in aquifers and underground streams. Fresh water is generally characterized by having low concentrations of dissolved salts and...
to marine systems, aquifer
Aquifer
An aquifer is a wet underground layer of water-bearing permeable rock or unconsolidated materials from which groundwater can be usefully extracted using a water well. The study of water flow in aquifers and the characterization of aquifers is called hydrogeology...
s to hydrothermal hot spring
Hot spring
A hot spring is a spring that is produced by the emergence of geothermally heated groundwater from the Earth's crust. There are geothermal hot springs in many locations all over the crust of the earth.-Definitions:...
s and scales, soil
Soil
Soil is a natural body consisting of layers of mineral constituents of variable thicknesses, which differ from the parent materials in their morphological, physical, chemical, and mineralogical characteristics...
s, and areas affected by mining. It can be precipitated directly from oxygenated iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...
-rich aqueous solutions, or by bacteria
Bacteria
Bacteria are a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria have a wide range of shapes, ranging from spheres to rods and spirals...
either as a result of a metabolic activity or passive sorption
Sorption
Sorption refers to the action of absorption* Absorption is the incorporation of a substance in one state into another of a different state ....
of dissolved iron followed by nucleation
Nucleation
Nucleation is the extremely localized budding of a distinct thermodynamic phase. Some examples of phases that may form by way of nucleation in liquids are gaseous bubbles, crystals or glassy regions. Creation of liquid droplets in saturated vapor is also characterized by nucleation...
reactions. Ferrihydrite also occurs in the core of the ferritin
Ferritin
Ferritin is a ubiquitous intracellular protein that stores iron and releases it in a controlled fashion. The amount of ferritin stored reflects the amount of iron stored. The protein is produced by almost all living organisms, including bacteria, algae and higher plants, and animals...
protein
Protein
Proteins are biochemical compounds consisting of one or more polypeptides typically folded into a globular or fibrous form, facilitating a biological function. A polypeptide is a single linear polymer chain of amino acids bonded together by peptide bonds between the carboxyl and amino groups of...
from many living organisms, for the purpose of intra-cellular iron storage.
Structure
Ferrihydrite only exists as a fine grained and highly defective nanomaterial. The powder X-ray diffraction pattern of Fh contains two scattering bands in its most disordered state, and a maximum of six strong lines in its most crystalline state. The principal difference between these two diffraction end-members, commonly named two-line and six-line ferrihydrites, is the size of the constitutive crystallites. The six-line form has been classified as a mineral by the IMAInternational Mineralogical Association
The International Mineralogical Association is an international group of 38 national societies. The goal is to promote the science of mineralogy and to standardize the nomenclature of the 4000 plus known mineral species...
in 1973 with the nominal chemical formula 5Fe2O3•9H2O. However, its formula is fundamentally indeterminate as its water content is variable. The two-line form is also called hydrous ferric oxides (HFO).
Due to the nanoparticluate nature of ferrihydrite, the structure has remained elusive for many years and is still a matter of controversy. Drits et al., using X-ray diffraction data, proposed a multiphase material with three components: defect-free crystallite
Crystallite
Crystallites are small, often microscopic crystals that, held together through highly defective boundaries, constitute a polycrystalline solid. Metallurgists often refer to crystallites as grains.- Details :...
s (f-phase) with double-hexagonal stacking of oxygen and hydroxyl layers (ABAC sequence) and disordered octahedral Fe occupancies, defective crystallites (d-phase) with a short-range feroxyhite
Feroxyhyte
Feroxyhyte is an oxide/hydroxide of iron, δ-Fe3+O. Feroxyhyte crystallizes in the hexagonal system. It forms as brown rounded to concretionary masses. Feroxyhyte is opaque, magnetic, has a yellow streak, and has a relative density of 4.2....
-like (δ-FeOOH) structure, and subordinate ultradisperse hematite
Hematite
Hematite, also spelled as haematite, is the mineral form of iron oxide , one of several iron oxides. Hematite crystallizes in the rhombohedral system, and it has the same crystal structure as ilmenite and corundum...
(α-Fe2O3). Recently, a new single phase model for both ferrihydrite and hydromaghemite has been proposed by Michel et al., based on pair distribution function (PDF) analysis of x-ray total scattering data. The structural model, isostructural with the mineral akdalaite
Akdalaite
Akdalaite is a very rare mineral found in Kazakhstan and has the formula 5Al2O3·H2O. It was formerly believed to be 4Al2O3·H2O. It is therefore the same as tohdite an artificailly produced phase. Studies on the crystal structure and spectra indicate that this is an aluminium oxide hydroxide.-...
(Al10O14(OH)2), contains 20% tetrahedrally and 80% octahedrally coordinated iron.
Porosity and environmental absorbent potential
Because of the small size of individual nanocrystalNanocrystal
B. D. Fahlman has described a nanocrystal as any nanomaterial with at least one dimension ≤ 100nm and that is singlecrystalline.-Summary:More properly, any material with a dimension of less than 1 micrometre, i.e., 1000 nanometers, should be referred to as a nanoparticle, not a nanocrystal...
s, Fh is nanoporous
Nanoporous
Nanoporous materials consist of a regular organic or inorganic framework supporting a regular, porous structure. Pores are by definition roughly in the nanometre range, that is between 1x10−7 and 0.2x10−9 m.Subdivisions:...
yielding large surface areas of several hundred square meters per gram. In addition to having a high surface area to volume ratio, Fh also has a high density of local or point defects, such as dangling bonds and vacancies. These properties confer a high ability to adsorb many environmentally important chemical species, including arsenic
Arsenic
Arsenic is a chemical element with the symbol As, atomic number 33 and relative atomic mass 74.92. Arsenic occurs in many minerals, usually in conjunction with sulfur and metals, and also as a pure elemental crystal. It was first documented by Albertus Magnus in 1250.Arsenic is a metalloid...
, lead
Lead
Lead is a main-group element in the carbon group with the symbol Pb and atomic number 82. Lead is a soft, malleable poor metal. It is also counted as one of the heavy metals. Metallic lead has a bluish-white color after being freshly cut, but it soon tarnishes to a dull grayish color when exposed...
, phosphate
Phosphate
A phosphate, an inorganic chemical, is a salt of phosphoric acid. In organic chemistry, a phosphate, or organophosphate, is an ester of phosphoric acid. Organic phosphates are important in biochemistry and biogeochemistry or ecology. Inorganic phosphates are mined to obtain phosphorus for use in...
, and organic molecules (e.g., humic
Humic acid
Humic acid is a principal component of humic substances, which are the major organic constituents of soil , peat, coal, many upland streams, dystrophic lakes, and ocean water. It is produced by biodegradation of dead organic matter...
and fulvic acids). Its strong and extensive interaction with trace metals and metalloids is used in industry, at large-scale in water purification
Water purification
Water purification is the process of removing undesirable chemicals, materials, and biological contaminants from contaminated water. The goal is to produce water fit for a specific purpose...
plants, as in North Germany and to produce the city water at Hiroshima
Hiroshima
is the capital of Hiroshima Prefecture, and the largest city in the Chūgoku region of western Honshu, the largest island of Japan. It became best known as the first city in history to be destroyed by a nuclear weapon when the United States Army Air Forces dropped an atomic bomb on it at 8:15 A.M...
, and at small scale to clean wastewater
Wastewater
Wastewater is any water that has been adversely affected in quality by anthropogenic influence. It comprises liquid waste discharged by domestic residences, commercial properties, industry, and/or agriculture and can encompass a wide range of potential contaminants and concentrations...
s and groundwater
Groundwater
Groundwater is water located beneath the ground surface in soil pore spaces and in the fractures of rock formations. A unit of rock or an unconsolidated deposit is called an aquifer when it can yield a usable quantity of water. The depth at which soil pore spaces or fractures and voids in rock...
s, for example to remove arsenic from industrial effluents and drinking water
Drinking water
Drinking water or potable water is water pure enough to be consumed or used with low risk of immediate or long term harm. In most developed countries, the water supplied to households, commerce and industry is all of drinking water standard, even though only a very small proportion is actually...
. Its nanoporosity and high affinity for gold
Gold
Gold is a chemical element with the symbol Au and an atomic number of 79. Gold is a dense, soft, shiny, malleable and ductile metal. Pure gold has a bright yellow color and luster traditionally considered attractive, which it maintains without oxidizing in air or water. Chemically, gold is a...
can be used to elaborate Fh-supported nanosized Au particles for the catalytic oxidation
Catalytic oxidation
Catalytic oxidation combines the production of random and honeycomb block catalysts with fixed bed technology and integrated tube or plate heat exchangers. It is used for destroying contaminants in the exhaust gases from industrial processes....
of CO at temperatures below 0°C.
Metastability
Ferrihydrite is a metastable mineral. It is known to be a precursor of more crystalline minerals like hematiteHematite
Hematite, also spelled as haematite, is the mineral form of iron oxide , one of several iron oxides. Hematite crystallizes in the rhombohedral system, and it has the same crystal structure as ilmenite and corundum...
and goethite
Goethite
Goethite , named after the German polymath Johann Wolfgang von Goethe, is an iron bearing oxide mineral found in soil and other low-temperature environments. Goethite has been well known since prehistoric times for its use as a pigment. Evidence has been found of its use in paint pigment samples...
by aggregation-based crystal growth
Crystal growth
A crystal is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Crystal growth is a major stage of a crystallization process, and consists in the addition of new atoms, ions, or polymer strings into...
. However, its transformation in natural systems generally is blocked by chemical impurities adsorbed at its surface, for example silica as most of natural ferrihydrites are siliceous.
Under reducing conditions as those found in gley soil
Gley soil
Gley soil in soil science is a type of hydric soil which exhibits a greenish-blue-grey soil color due to wetland conditions. On exposure to the air, gley colors are transformed to a mottled pattern of reddish, yellow or orange patches. During gley soil formation , the oxygen supply in the soil...
s, or in deep environments depleted in oxygen, and often with the assistance of microbial activity, ferrihydrite can be transformed in green rust, a layered double hydroxide (LDH), also known as the mineral fougerite
Fougerite
Fougerite is a recently discovered representative of clay minerals, chemically and structurally related to so-called green rust, hydrotalcite-like minerals and other layered double hydroxides. The formula of the mineral is complex due to structural variabilities, as is for green rust, thus...
. However, a short exposure of green rust to atmospheric oxygen is sufficient to oxidize it back to ferrihydrite, making it a very elusive compound.
See also
Better crystallized and less hydrated iron oxy-hydroxides are amongst others:- AkaganéiteAkaganéiteAkaganéite is an iron oxide-hydroxide / chloride mineral with formula: Fe3+O e.g; β-FeO. It is formed by the weathering of pyrrhotite . Nickel also has been reported in the structure. It has a monoclinic crystal structure, a metallic luster and a brownish yellow streak. It is named after the...
- FeroxyhyteFeroxyhyteFeroxyhyte is an oxide/hydroxide of iron, δ-Fe3+O. Feroxyhyte crystallizes in the hexagonal system. It forms as brown rounded to concretionary masses. Feroxyhyte is opaque, magnetic, has a yellow streak, and has a relative density of 4.2....
- GoethiteGoethiteGoethite , named after the German polymath Johann Wolfgang von Goethe, is an iron bearing oxide mineral found in soil and other low-temperature environments. Goethite has been well known since prehistoric times for its use as a pigment. Evidence has been found of its use in paint pigment samples...
- HematiteHematiteHematite, also spelled as haematite, is the mineral form of iron oxide , one of several iron oxides. Hematite crystallizes in the rhombohedral system, and it has the same crystal structure as ilmenite and corundum...
- LepidocrociteLepidocrociteLepidocrocite , also called esmeraldite or hydrohematite, is an iron oxide-hydroxide mineral. Lepidocrocite has an orthorhombic crystal structure, a hardness of 5, specific gravity of 4, a submetallic luster and a yellow-brown streak. It is red to reddish brown and forms when iron-containing...
- LimoniteLimoniteLimonite is an ore consisting in a mixture of hydrated iron oxide-hydroxide of varying composition. The generic formula is frequently written as FeO·nH2O, although this is not entirely accurate as limonite often contains a varying amount of oxide compared to hydroxide.Together with hematite, it has...
- MaghemiteMaghemiteMaghemite is a member of the family of iron oxides. It has the same structure as magnetite, that is, it is spinel ferrite and is also ferrimagnetic.Maghemite can be considered as an Fe-deficient magnetite with formula...
- MagnetiteMagnetiteMagnetite is a ferrimagnetic mineral with chemical formula Fe3O4, one of several iron oxides and a member of the spinel group. The chemical IUPAC name is iron oxide and the common chemical name is ferrous-ferric oxide. The formula for magnetite may also be written as FeO·Fe2O3, which is one part...