The iron cycle (Fe) is the biogeochemical cycle of iron through the atmosphere, hydrosphere, biosphere and lithosphere. While Fe is highly abundant in the Earth's crust, [10] it is less common in oxygenated surface waters. Iron is a key micronutrient in primary productivity, [11] and a limiting nutrient in the Southern ocean, eastern equatorial Pacific, and the subarctic Pacific referred to as High-Nutrient, Low-Chlorophyll (HNLC) regions of the ocean. [12]
Iron exists in a range of oxidation states from -2 to +7; however, on Earth it is predominantly in its +2 or +3 redox state and is a primary redox-active metal on Earth. [13] The cycling of iron between its +2 and +3 oxidation states is referred to as the iron cycle. This process can be entirely abiotic or facilitated by microorganisms, especially iron-oxidizing bacteria. The abiotic processes include the rusting of iron-bearing metals, where Fe2+ is abiotically oxidized to Fe3+ in the presence of oxygen, and the reduction of Fe3+ to Fe2+ by iron-sulfide minerals. The biological cycling of Fe2+ is done by iron oxidizing and reducing microbes. [14] [15]
Iron is an essential micronutrient for almost every life form. It is a key component of hemoglobin, important to nitrogen fixation as part of the Nitrogenase enzyme family, and as part of the iron-sulfur core of ferredoxin it facilitates electron transport in chloroplasts, eukaryotic mitochondria, and bacteria. Due to the high reactivity of Fe2+ with oxygen and low solubility of Fe3+, iron is a limiting nutrient in most regions of the world.
Part of a series on |
Biogeochemical cycles |
---|
On the early Earth, when atmospheric oxygen levels were 0.001% of those present today, dissolved Fe2+ was thought to have been a lot more abundant in the oceans, and thus more bioavailable to microbial life. [16] Iron sulfide may have provided the energy and surfaces for the first organisms. [17] At this time, before the onset of oxygenic photosynthesis, primary production may have been dominated by photo-ferrotrophs, which would obtain energy from sunlight, and use the electrons from Fe2+ to fix carbon. [18]
During the Great Oxidation Event, 2.3-2.5 billion years ago, dissolved iron was oxidized by oxygen produced by cyanobacteria to form iron oxides. The iron oxides were denser than water and fell to the ocean floor forming banded iron formations (BIF). [19] Over time, rising oxygen levels removed increasing amounts of iron from the ocean. BIFs have been a key source of iron ore in modern times. [20] [21]
The iron cycle is an important component of the terrestrial ecosystems. The ferrous form of iron, Fe2+, is dominant in the Earth's mantle, core, or deep crust. The ferric form, Fe3+, is more stable in the presence of oxygen gas. [22] Dust is a key component in the Earth's iron cycle. Chemical and biological weathering break down iron-bearing minerals, releasing the nutrient into the atmosphere. Changes in hydrological cycle and vegetative cover impact these patterns and have a large impact on global dust production, with dust deposition estimates ranging between 1000 and 2000 Tg/year. [2] Aeolian dust is a critical part of the iron cycle by transporting iron particulates from the Earth's land via the atmosphere to the ocean. [23]
Volcanic eruptions are also a key contributor to the terrestrial iron cycle, releasing iron-rich dust into the atmosphere in either a large burst or in smaller spurts over time. [24] The atmospheric transport of iron-rich dust can impact the ocean concentrations. [2]
The ocean is a critical component of the Earth's climate system, and the iron cycle plays a key role in ocean primary productivity and marine ecosystem function. Iron limitation has been known to limit the efficiency of the biological carbon pump. The largest supply of iron to the oceans is from rivers, where it is suspended as sediment particles. [25] Coastal waters receive inputs of iron from rivers and anoxic sediments. [21] Other major sources of iron to the ocean include glacial particulates, atmospheric dust transport, and hydrothermal vents. [26] Iron supply is an important factor affecting growth of phytoplankton, the base of marine food web. [27] Offshore regions rely on atmospheric dust deposition and upwelling. [21] Other major sources of iron to the ocean include glacial particulates, hydrothermal vents, and volcanic ash. [28] In offshore regions, bacteria also compete with phytoplankton for uptake of iron. [21] In HNLC regions, iron limits the productivity of phytoplankton. [29]
Most commonly, iron was available as an inorganic source to phytoplankton; however, organic forms of iron can also be used by specific diatoms which use a process of surface reductase mechanism. Uptake of iron by phytoplankton leads to lowest iron concentrations in surface seawater. Remineralization occurs when the sinking phytoplankton are degraded by zooplankton and bacteria. Upwelling recycles iron and causes higher deep water iron concentrations. On average there is 0.07±0.04 nmol Fe kg−1 at the surface (<200 m) and 0.76±0.25 nmol Fe kg−1 at depth (>500 m). [21] Therefore, upwelling zones contain more iron than other areas of the surface oceans. Soluble iron in ferrous form is bioavailable for utilization which commonly comes from aeolian resources.
Iron primarily is present in particulate phases as ferric iron, and the dissolved iron fraction is removed out of the water column by coagulation. For this reason, the dissolved iron pool turns over rapidly, in around 100 years. [21]
The iron cycle interacts significantly with the sulfur, nitrogen, and phosphorus cycles. Soluble Fe(II) can act as the electron donor, reducing oxidized organic and inorganic electron receptors, including O2 and NO3, and become oxidized to Fe(III). The oxidized form of iron can then be the electron acceptor for reduced sulfur, H2, and organic carbon compounds. This returns the iron to the reduced Fe(II) state, completing the cycle. [32]
The transition of iron between Fe(II) and Fe(III) in aquatic systems interacts with the freshwater phosphorus cycle. With oxygen in the water, Fe(II) gets oxidized to Fe(III), either abiotically or by microbes via lithotrophic oxidation. Fe(III) can form iron hydroxides, which bind tightly to phosphorus, removing it from the bioavailable phosphorus pool, limiting primary productivity. In anoxic conditions, Fe(III) can be reduced, used by microbes to be the final electron acceptor from either organic carbon or H2. This releases the phosphorus back into the water for biological use. [33]
The iron and sulfur cycle can interact at several points. Purple sulfur bacteria and green sulfur bacteria can use Fe(II) as an electron donor during anoxic photosynthesis. [34] Sulfate reducing bacteria in anoxic environments can reduce sulfate to sulfide, which then binds to Fe(II) to create iron sulfide, a solid mineral that precipitates out of water and removes the iron and sulfur. The iron, phosphate, and sulfur cycles can all interact with each other. Sulfide can reduce Fe(III) from iron that is already bound to phosphate when there are no more metal ions available, which releases the phosphate and creates iron sulfide. [35]
Iron plays an important role in the nitrogen cycle, aside from its role as part of the enzymes involved in nitrogen fixation. In anoxic conditions, Fe(II) can donate an electron that is accepted by NO3− which is oxidized to several different forms of nitrogen compounds, NO2−, N2O, N2, and NH4+, while Fe(II) is reduced to Fe(III). [33]
Human impact on the iron cycle in the ocean is due to dust concentrations increasing at the beginning of the industrial era. Today, there is approximately double the amount of soluble iron in oceans than pre-industrial times from anthropogenic pollutants and soluble iron combustion sources. [29] Changes in human land-use activities and climate have augmented dust fluxes which increases the amount of aeolian dust to open regions of the ocean. [28] Other anthropogenic sources of iron are due to combustion. Highest combustion rates of iron occurs in East Asia, which contributes to 20-100% of ocean depositions around the globe. [29]
Humans have altered the cycle for Nitrogen from fossil fuel combustion and large-scale agriculture. [36] Due to increased Iron and Nitrogen raises marine nitrogen fixation in the subtropical North and South Pacific Ocean. In the subtropics, tropics and HNLC regions, increased inputs of iron may lead to increased CO2 uptake, impacting the global carbon cycle. [36]
The green sulfur bacteria are a phylum, Chlorobiota, of obligately anaerobic photoautotrophic bacteria that metabolize sulfur.
Anaerobic respiration is respiration using electron acceptors other than molecular oxygen (O2). Although oxygen is not the final electron acceptor, the process still uses a respiratory electron transport chain.
The pedosphere is the outermost layer of the Earth that is composed of soil and subject to soil formation processes. It exists at the interface of the lithosphere, atmosphere, hydrosphere and biosphere. The pedosphere is the skin of the Earth and only develops when there is a dynamic interaction between the atmosphere, biosphere, lithosphere and the hydrosphere. The pedosphere is the foundation of terrestrial life on Earth.
The sulfur cycle is a biogeochemical cycle in which the sulfur moves between rocks, waterways and living systems. It is important in geology as it affects many minerals and in life because sulfur is an essential element (CHNOPS), being a constituent of many proteins and cofactors, and sulfur compounds can be used as oxidants or reductants in microbial respiration. The global sulfur cycle involves the transformations of sulfur species through different oxidation states, which play an important role in both geological and biological processes. Steps of the sulfur cycle are:
Iron-oxidizing bacteria are chemotrophic bacteria that derive energy by oxidizing dissolved iron. They are known to grow and proliferate in waters containing iron concentrations as low as 0.1 mg/L. However, at least 0.3 ppm of dissolved oxygen is needed to carry out the oxidation.
Lithotrophs are a diverse group of organisms using an inorganic substrate to obtain reducing equivalents for use in biosynthesis or energy conservation via aerobic or anaerobic respiration. While lithotrophs in the broader sense include photolithotrophs like plants, chemolithotrophs are exclusively microorganisms; no known macrofauna possesses the ability to use inorganic compounds as electron sources. Macrofauna and lithotrophs can form symbiotic relationships, in which case the lithotrophs are called "prokaryotic symbionts". An example of this is chemolithotrophic bacteria in giant tube worms or plastids, which are organelles within plant cells that may have evolved from photolithotrophic cyanobacteria-like organisms. Chemolithotrophs belong to the domains Bacteria and Archaea. The term "lithotroph" was created from the Greek terms 'lithos' (rock) and 'troph' (consumer), meaning "eaters of rock". Many but not all lithoautotrophs are extremophiles.
Beggiatoa is a genus of Gammaproteobacteria belonging to the order Thiotrichales, in the Pseudomonadota phylum. This genus was one of the first bacteria discovered by Ukrainian botanist Sergei Winogradsky. During his research in Anton de Bary's laboratory of botany in 1887, he found that Beggiatoa oxidized hydrogen sulfide (H2S) as an energy source, forming intracellular sulfur droplets, with oxygen as the terminal electron acceptor and CO2 used as a carbon source. Winogradsky named it in honor of the Italian doctor and botanist Francesco Secondo Beggiato (1806 - 1883), from Venice. Winogradsky referred to this form of metabolism as "inorgoxidation" (oxidation of inorganic compounds), today called chemolithotrophy. These organisms live in sulfur-rich environments such as soil, both marine and freshwater, in the deep sea hydrothermal vents and in polluted marine environments. The finding represented the first discovery of lithotrophy. Two species of Beggiatoa have been formally described: the type species Beggiatoa alba and Beggiatoa leptomitoformis, the latter of which was only published in 2017. This colorless and filamentous bacterium, sometimes in association with other sulfur bacteria (for example the genus Thiothrix), can be arranged in biofilm visible to the naked eye formed by a very long white filamentous mat, the white color is due to the stored sulfur. Species of Beggiatoa have cells up to 200 µm in diameter and they are one of the largest prokaryotes on Earth.
Anoxic waters are areas of sea water, fresh water, or groundwater that are depleted of dissolved oxygen. The US Geological Survey defines anoxic groundwater as those with dissolved oxygen concentration of less than 0.5 milligrams per litre. Anoxic waters can be contrasted with hypoxic waters, which are low in dissolved oxygen. This condition is generally found in areas that have restricted water exchange.
Microbial metabolism is the means by which a microbe obtains the energy and nutrients it needs to live and reproduce. Microbes use many different types of metabolic strategies and species can often be differentiated from each other based on metabolic characteristics. The specific metabolic properties of a microbe are the major factors in determining that microbe's ecological niche, and often allow for that microbe to be useful in industrial processes or responsible for biogeochemical cycles.
Biomining is the technique of extracting metals from ores and other solid materials typically using prokaryotes, fungi or plants. These organisms secrete different organic compounds that chelate metals from the environment and bring it back to the cell where they are typically used to coordinate electrons. It was discovered in the mid 1900s that microorganisms use metals in the cell. Some microbes can use stable metals such as iron, copper, zinc, and gold as well as unstable atoms such as uranium and thorium. Large chemostats of microbes can be grown to leach metals from their media. These vats of culture can then be transformed into many marketable metal compounds. Biomining is an environmentally friendly technique compared to typical mining. Mining releases many pollutants while the only chemicals released from biomining is any metabolites or gasses that the bacteria secrete. The same concept can be used for bioremediation models. Bacteria can be inoculated into environments contaminated with metals, oils, or other toxic compounds. The bacteria can clean the environment by absorbing these toxic compounds to create energy in the cell. Bacteria can mine for metals, clean oil spills, purify gold, and use radioactive elements for energy.
A redox gradient is a series of reduction-oxidation (redox) reactions sorted according to redox potential. The redox ladder displays the order in which redox reactions occur based on the free energy gained from redox pairs. These redox gradients form both spatially and temporally as a result of differences in microbial processes, chemical composition of the environment, and oxidative potential. Common environments where redox gradients exist are coastal marshes, lakes, contaminant plumes, and soils.
The class Zetaproteobacteria is the sixth and most recently described class of the Pseudomonadota. Zetaproteobacteria can also refer to the group of organisms assigned to this class. The Zetaproteobacteria were originally represented by a single described species, Mariprofundus ferrooxydans, which is an iron-oxidizing neutrophilic chemolithoautotroph originally isolated from Kamaʻehuakanaloa Seamount in 1996 (post-eruption). Molecular cloning techniques focusing on the small subunit ribosomal RNA gene have also been used to identify a more diverse majority of the Zetaproteobacteria that have as yet been unculturable.
Sulfurimonas is a bacterial genus within the class of Campylobacterota, known for reducing nitrate, oxidizing both sulfur and hydrogen, and containing Group IV hydrogenases. This genus consists of four species: Sulfurimonas autorophica, Sulfurimonas denitrificans, Sulfurimonas gotlandica, and Sulfurimonas paralvinellae. The genus' name is derived from "sulfur" in Latin and "monas" from Greek, together meaning a “sulfur-oxidizing rod”. The size of the bacteria varies between about 1.5-2.5 μm in length and 0.5-1.0 μm in width. Members of the genus Sulfurimonas are found in a variety of different environments which include deep sea-vents, marine sediments, and terrestrial habitats. Their ability to survive in extreme conditions is attributed to multiple copies of one enzyme. Phylogenetic analysis suggests that members of the genus Sulfurimonas have limited dispersal ability and its speciation was affected by geographical isolation rather than hydrothermal composition. Deep ocean currents affect the dispersal of Sulfurimonas spp., influencing its speciation. As shown in the MLSA report of deep-sea hydrothermal vents Campylobacterota, Sulfurimonas has a higher dispersal capability compared with deep sea hydrothermal vent thermophiles, indicating allopatric speciation.
Marine biogeochemical cycles are biogeochemical cycles that occur within marine environments, that is, in the saltwater of seas or oceans or the brackish water of coastal estuaries. These biogeochemical cycles are the pathways chemical substances and elements move through within the marine environment. In addition, substances and elements can be imported into or exported from the marine environment. These imports and exports can occur as exchanges with the atmosphere above, the ocean floor below, or as runoff from the land.
Euxinia or euxinic conditions occur when water is both anoxic and sulfidic. This means that there is no oxygen (O2) and a raised level of free hydrogen sulfide (H2S). Euxinic bodies of water are frequently strongly stratified, have an oxic, highly productive, thin surface layer, and have anoxic, sulfidic bottom water. The word euxinia is derived from the Greek name for the Black Sea (Εὔξεινος Πόντος (Euxeinos Pontos)) which translates to "hospitable sea". Euxinic deep water is a key component of the Canfield ocean, a model of oceans during the Proterozoic period (known as the Boring Billion) proposed by Donald Canfield, an American geologist, in 1998. There is still debate within the scientific community on both the duration and frequency of euxinic conditions in the ancient oceans. Euxinia is relatively rare in modern bodies of water, but does still happen in places like the Black Sea and certain fjords.
Microbial oxidation of sulfur is the oxidation of sulfur by microorganisms to build their structural components. The oxidation of inorganic compounds is the strategy primarily used by chemolithotrophic microorganisms to obtain energy to survive, grow and reproduce. Some inorganic forms of reduced sulfur, mainly sulfide (H2S/HS−) and elemental sulfur (S0), can be oxidized by chemolithotrophic sulfur-oxidizing prokaryotes, usually coupled to the reduction of oxygen (O2) or nitrate (NO3−). Anaerobic sulfur oxidizers include photolithoautotrophs that obtain their energy from sunlight, hydrogen from sulfide, and carbon from carbon dioxide (CO2).
An oxygen minimum zone (OMZ) is characterized as an oxygen-deficient layer in the world's oceans. Typically found between 200m to 1500m deep below regions of high productivity, such as the western coasts of continents. OMZs can be seasonal following the spring-summer upwelling season. Upwelling of nutrient-rich water leads to high productivity and labile organic matter, that is respired by heterotrophs as it sinks down the water column. High respiration rates deplete the oxygen in the water column to concentrations of 2 mg/L or less forming the OMZ. OMZs are expanding, with increasing ocean deoxygenation. Under these oxygen-starved conditions, energy is diverted from higher trophic levels to microbial communities that have evolved to use other biogeochemical species instead of oxygen, these species include Nitrate, Nitrite, Sulphate etc. Several Bacteria and Archea have adapted to live in these environments by using these alternate chemical species and thrive. The most abundant phyla in OMZs are Pseudomonadota, Bacteroidota, Actinomycetota, and Planctomycetota.
The hydrothermal vent microbial community includes all unicellular organisms that live and reproduce in a chemically distinct area around hydrothermal vents. These include organisms in the microbial mat, free floating cells, or bacteria in an endosymbiotic relationship with animals. Chemolithoautotrophic bacteria derive nutrients and energy from the geological activity at Hydrothermal vents to fix carbon into organic forms. Viruses are also a part of the hydrothermal vent microbial community and their influence on the microbial ecology in these ecosystems is a burgeoning field of research.
Trace metal stable isotope biogeochemistry is the study of the distribution and relative abundances of trace metal isotopes in order to better understand the biological, geological, and chemical processes occurring in an environment. Trace metals are elements such as iron, magnesium, copper, and zinc that occur at low levels in the environment. Trace metals are critically important in biology and are involved in many processes that allow organisms to grow and generate energy. In addition, trace metals are constituents of numerous rocks and minerals, thus serving as an important component of the geosphere. Both stable and radioactive isotopes of trace metals exist, but this article focuses on those that are stable. Isotopic variations of trace metals in samples are used as isotopic fingerprints to elucidate the processes occurring in an environment and answer questions relating to biology, geochemistry, and medicine.
The gold cycle is the biogeochemical cycling of gold through the lithosphere, hydrosphere, atmosphere, and biosphere. Gold is a noble transition metal that is highly mobile in the environment and subject to biogeochemical cycling, driven largely by microorganisms. Gold undergoes processes of solubilization, stabilization, bioreduction, biomineralization, aggregation, and ligand utilization throughout its cycle. These processes are influenced by various microbial populations and cycling of other elements such as carbon, nitrogen, and sulfur. Gold exists in several forms in the Earth's surface environment including Au(I/III)-complexes, nanoparticles, and placer gold particles. The gold biogeochemical cycle is highly complex and strongly intertwined with cycling of other metals including silver, copper, iron, manganese, arsenic, and mercury. Gold is important in the biotech field for applications such as mineral exploration, processing and remediation, development of biosensors and drug delivery systems, industrial catalysts, and for recovery of gold from electronic waste.