Iron minerals occur in many forms and can be imlicated as being related to life and living processes in a variety of environments.
Magnetite (Fe3O4) is a mangetic mineral with mixed oxidation states of iron that is used in biology for magnetotaxis. The presence and purity of magnetite in certain samples may implicate potential biogenicity.
Pro arguments address how likely it is that biologially precipitated pure magnetite is common in environments containing life, while Con arguments address when chemically pure magnetite is uncommon.
Biological Signal Strength - Background
Pro evidence supports hypotheses that biologically precipitated pure magnetite could be detectable in an environment vs. CON evidence that argues against the detectability of biologically precipitated chemically pure magnetite.
Abiotic Prevalence - Background
Pro arguments address how likely it is that chemically pure magnetite could have formed from abiotic processes. Con arguments discuss evidence against abiotic formation of chemically pure magnetite.
Abiotic Signal Strength - Background
Pro evidence supports hypotheses that pure magnetite associated with abiotic activity could be detectable in an environment vs. Con evidence that argues against the detectability of abiotically-derived pure magnetite.
eThe magnetite observed in martian meteorite ALH84001 resembles chemically pure terrestrial magnetite produced by magnetotactic bacteria rather than the chemically impure magnetite produced through inorganic processes.
The magnetite observed in martian meteorite ALH84001 resembles chemically pure terrestrial magnetite produced by magnetotactic bacteria rather than the chemically impure magnetite produced through inorganic processes.
Magnetotactic bacteria are bacteria that align themselves with Earth’s magnetic field by precipitating intracellular magnetite into magnetosomes that can be preserved as magnetofossils. This magnetite is chemically pure Fe3O4 with few trace elements included. This is in contrast to magnetite crystals observed in igneous and metamorphic rocks and hydrothermally produced magnetite that typically contain impurities and minor elements including Ti, V, Al, and Cr. For example, samples of Andean iron ores containing magnetite were measured to have impurities ranging from 100-1000 ppm Ti and 1000-2000 ppm V. The high levels of chemical purity of magnetite observed in ALH84001 resemble the pure magnetite precipitated by magnetotactic bacteria across a broad range of environments including in lake sediments, deep sea sediments, carbonate sediments, and soils rather than impure, inorganic magnetite, thus not eliminating a biological origin for the magnetite in the meteorite.
Using transmission electron microscopy (TEM), we have analyzed magnetite (Fe3O4) crystals acid-extracted from carbonate globules in Martian meteorite ALH84001. We studied 594 magnetites from ALH84001 and grouped them into three populations on the basis of morphology: 389 were irregularly shaped, 164 were elongated prisms, and 41 were whisker-like. As a possible terrestrial analog for the ALH84001 elongated prisms, we compared these magnetites with those produced by the terrestrial magnetotactic bacteria strain MV-1. By TEM again, we examined 206 magnetites recovered from strain MV-1 cells. Natural (Darwinian) selection in terrestrial magnetotactic bacteria appears to have resulted in the formation of intracellular magnetite crystals having the physical and chemical properties that optimize their magnetic moment. In this study, we describe six properties of magnetite produced by biologically controlled mechanisms (e.g., magnetotactic bacteria), properties that, collectively, are not observed in any known population of inorganic magnetites. These criteria can be used to distinguish one of the modes of origin for magnetites from samples with complex or unknown histories. Of the ALH84001 magnetites that we have examined, the elongated prismatic magnetite particles (similar to 27% of the total) are indistinguishable from the MV-1 magnetites in five of these six characteristics observed for biogenically controlled mineralization of magnetite crystals.
eMagnetotactic bacteria produce chemically pure magnetite in the form of magnetosomes, intracellular accumulations of magnetite that can be preserved as fossils.
Magnetotactic bacteria produce chemically pure magnetite in the form of magnetosomes, intracellular accumulations of magnetite that can be preserved as fossils.
Chemically pure magnetite, or stoichiometric Fe3O4, has been observed to be used in biological systems, as pure iron is used as a metal cofactor, a “helper molecule” in several common proteins. Additionally, minimizing the inclusion of trace elements increases the magnetic strength of magnetite crystals, allowing magnetotactic bacteria to more effectively align themselves with Earth’s magnetic field.
Evidence is Sourced from:
Title
The identification and biogeochemical interpretation of fossil magnetotactic bacteria
Authors
Kopp RE and Kirschvink JL
Abstract
Magnetotactic bacteria, which most commonly live within the oxic-anoxic transition zone (OATZ) of aquatic environments, produce intracellular crystals of magnetic minerals, specifically magnetite or greigite. The crystals cause the bacteria to orient themselves passively with respect to the geomagnetic field and thereby facilitate the bacteria's search for optimal conditions within the sharp chemical gradients of the OATZ. The bacteria may also gain energy from the redox cycling of their crystals.
Because magnetotactic bacteria benefit from their magnetic moments, natural selection has promoted the development of traits that increase the efficiency with which the intracellular crystals impart magnetic moments to cells. These traits also allow crystals produced by magnetotactic bacteria (called magnetofossils when preserved in sediments) to be distinguished from abiogenic particles and particles produced as extracellular byproducts of bacterial metabolism. Magnetofossils are recognizable based on their narrow size and shape distributions, distinctive morphologies with blunt crystal edges, chain arrangement, chemical purity, and crystallographic perfection. This article presents a scheme for rating magnetofossil robustness based on these traits.
The magnetofossil record extends robustly to the Cretaceous and with lesser certainty to the late Archean. Because magnetotactic bacteria predominantly live in the OATZ, the abundance and character of their fossils can reflect environmental changes that alter the chemical stratification of sediments and the water column. The magnetofossil record therefore provides an underutilized archive of paleoenvironmental information. Several studies have demonstrated a relationship between magnetofossil abundance and glacial/interglacial cycles, likely mediated by changes in pore water oxygen levels. More speculatively, a better-developed magnetofossil record might provide constraints on the long-term evolution of marine redox stratification.
More work in modern and ancient settings is necessary to explicate the mechanisms linking the abundance and character of magnetofossils to ancient biogeochemistry.
Chemically pure magnetite is indicative of biological processes because even when cultured in a medium with impurities, magnetotactic bacteria will still precipitate chemically pure magnetite.
Chemically pure magnetite is indicative of biological processes because even when cultured in a medium with impurities, magnetotactic bacteria will still precipitate chemically pure magnetite.
Wolfe’s Mineral Solution, a growth medium containing ions commonly found in inorganic magnetite including Cu, Co, Zn, Mo, Ni, Mg, Al and Mn, has frequently been used when culturing magnetotactic bacteria. Despite the availability of contaminating ions, magnetotactic bacteria have consistently been observed to precipitate chemically pure magnetite not containing these impurities.
Evidence is Sourced from:
Title
Truncated hexa-octahedral magnetite crystals in ALH84001: presumptive biosignatures
Authors
Thomas-Keprta, Kathie L and Clemett, Simon J and Bazylinski, Dennis A and Kirschvink, Joseph L and McKay, David S and Wentworth, Susan J and Vali, Hojatollah and Gibson, Everett K and McKay, Mary Fae and Romanek, Christopher S
Abstract
McKay et al. [(1996) Science 273, 924–930] suggested that carbonate globules in the meteorite ALH84001 contained the fossil remains of Martian microbes. We have characterized a subpopulation of magnetite (Fe3O4) crystals present in abundance within the Fe-rich rims of these carbonate globules. We find these Martian magnetites to be both chemically and physically identical to terrestrial, biogenically precipitated, intracellular magnetites produced by magnetotactic bacteria strain MV-1. Specifically, both magnetite populations are single-domain and chemically pure, and exhibit a unique crystal habit we describe as truncated hexa-octahedral. There are no known reports of inorganic processes to explain the observation of truncated hexa-octahedral magnetites in a terrestrial sample. In bacteria strain MV-1 their presence is therefore likely a product of Natural Selection. Unless there is an unknown and unexplained inorganic process on Mars that is conspicuously absent on the Earth and forms truncated hexa-octahedral magnetites, we suggest that these magnetite crystals in the Martian meteorite ALH84001 were likely produced by a biogenic process. As such, these crystals are interpreted as Martian magnetofossils and constitute evidence of the oldest life yet found.
eChemically pure magnetite has been synthesized in laboratory settings, indicating that biotic processes are not the only means to generate high purity levels.
Chemically pure magnetite has been synthesized in laboratory settings, indicating that biotic processes are not the only means to generate high purity levels.
A simple series of synthetic precipitation and heating steps applied to Fe-bearing chloride salts experimentally produced chemically pure magnetite crystals. These laboratory procedures experimentally replicate hydrothermal precipitation of Fe-rich carbonates that were subsequently heated by a meteor impact to produce chemically pure magnetite. This series of abiotic processes that could be expected to occur on Mars provide a mechanism for producing chemically pure magnetite without evoking the role of biological processes as initially proposed for magnetite observed in ALH84001.
Evidence is Sourced from:
Title
A simple inorganic process for formation of carbonates, magnetite, and sulfides in Martian meteorite ALH84001
Authors
Golden, DC and Ming, Douglas W and Schwandt, Craig S and Lauer Jr, Howard V and Socki, Richard A and Morris, Richard V and Lofgren, Gary E and McKay, Gordon A
Abstract
We show experimental evidence that the zoned Mg-Fe-Ca carbonates, magnetite, and Fe sulfides in Martian meteorite ALH84001 may have formed by simple, inorganic processes. Chemically zoned carbonate globules and Fe sulfides were rapidly precipitated under low-temperature (150 °C), hydrothermal, and non-equilibrium conditions from multiple fluxes of Ca-Mg-Fe-CO2-S-H2O solutions that have different compositions. Chemically pure, single-domain, defect-free magnetite crystals were formed by subsequent decomposition of previously precipitated Fe-rich carbonates by brief heating to 470 °C. The sequence of hydrothermal precipitation of carbonates from flowing CO2-rich waters followed by a transient thermal event provides an inorganic explanation for the formation of the carbonate globules, magnetite, and Fe sulfides in ALH84001. In separate experiments, kinetically controlled 13C enrichment was observed in synthetic carbonates that is similar in magnitude to the 13C enrichment in ALH84001 carbonates.
Chemically pure magnetite such as that observed in ALH84001 can be produced abiotically through a meteoric impact that sufficiently raises temperature and pressure conditions.
Chemically pure magnetite such as that observed in ALH84001 can be produced abiotically through a meteoric impact that sufficiently raises temperature and pressure conditions.
A meteor impact that instantaneously raises temperature and pressure conditions on a planetary surface will eventually slowly dissipate heat. This dissipation process allows for shock-induced minerals including magnetite to reach equilibrium conditions that promote the persistence of chemically pure, stoichiometric Fe3O4.
Evidence is Sourced from:
Title
Submicron magnetite grains and carbon compounds in Martian meteorite ALH84001: inorganic, abiotic formation by shock and thermal metamorphism
Authors
Treiman, Allan H
Abstract
Purported biogenic features of the ALH84001 Martian meteorite (the carbonate globules, their submicron magnetite grains, and organic matter) have reasonable inorganic origins, and a comprehensive hypothesis is offered here. The carbonate globules were deposited from hydrothermal water, without biological mediation. Thereafter, ALH84001 was affected by an impact shock event, which raised its temperature nearly instantaneously to 500-700K, and induced iron-rich carbonate in the globules to decompose to magnetite and other minerals. The rapidity of the temperature increase caused magnetite grains to nucleate in abundance; hence individual crystals were very small. Nucleation and growth of magnetite crystals were fastest along edges and faces of the precursor carbonate grains, forcing the magnetite grains to be platy or elongated, including the "truncated hexa-octahedra" shape. ALH84001 had formed at some depth within Mars where the lithostatic pressure was significantly above that of Mars' surface. Also, because the rock was at depth, the impact heat dissipated slowly. During this interval, magnetite crystals approached chemical equilibria with surrounding minerals and gas. Their composition, nearly pure Fe(3)O(4), reflects those of equilibria; elements that substitute into magnetite are either absent from iron-rich carbonate (e.g., Ti, Al, Cr), or partitioned into other minerals during magnetite formation (Mg, Mn). Many microstructural imperfections in the magnetite grains would have annealed out as the rock cooled. In this post-shock thermal regime, carbon-bearing gas from the decomposition of iron carbonates reacted with water in the rock (or from its surroundings) to produce organic matter via Fischer-Tropschlike reactions. Formation of such organic compounds like polycyclic aromatic hydrocarbons would have been catalyzed by the magnetite (formation of graphite, the thermochemically stable phase, would be kinetically hindered).
Magnetotactic bacteria cultured in a medium with high impurity concentrations can precipitate impure magnetite.
Though magnetite produced by magnetotactic bacteria was long thought to be chemically pure, further research established that bacteria grown in a laboratory in a solution with high manganese concentration can precipitate magnetite with impurities up to 2.8 atom% manganese as a percentage of total metal including iron, rather than remaining chemically pure. Natural, non-laboratory environments with similarly high manganese concentrations may allow bacteria to incorporate manganese into their precipitated magnetosomes and resemble inorganic magnetite.
Evidence is Sourced from:
Title
Manganese in biogenic magnetite crystals from magnetotactic bacteria
Authors
Keim, Carolina N and Lins, Ulysses and Farina, Marcos
Abstract
Magnetotactic bacteria produce either magnetite (Fe3O4) or greigite (Fe3S4) crystals in cytoplasmic organelles called magnetosomes. Whereas greigite magnetosomes can contain up to 10 atom% copper, magnetite produced by magnetotactic bacteria was considered chemically pure for a long time and this characteristic was used to distinguish between biogenic and abiogenic crystals. Recently, it was shown that magnetosomes containing cobalt could be produced by three strains of Magnetospirillum. Here we show that magnetite crystals produced by uncultured magnetotactic bacteria can incorporate manganese up to 2.8 atom% of the total metal content (Fe+Mn) when manganese chloride is added to microcosms. Thus, chemical purity can no longer be taken as a strict prerequisite to consider magnetite crystals to be of biogenic origin.
Chemically pure magnetite crystals are usually not produced abiotically because natural impurities are usually incorporated in the crystal lattice during their formation.
[Congruence]
eThe formation of abiotic magnetite will almost always be in the presence of other elements, and the elemental partition coefficients will be higher in abiotically formed magnetite.
The formation of abiotic magnetite will almost always be in the presence of other elements, and the elemental partition coefficients will be higher in abiotically formed magnetite.
When comparing the abiotic and biotic origins of magnetite, this study looked at the ratio of strontium/calcium. Specifically, the abiotic and biotic strontium/calcium ratios differed by about 5 orders of magnitude, with abiotically formed magnetite displaying high levels of these trace elements. For most trace elements involved in the formation of magnetite, the partition coefficient is approximately 100 times higher in abiotic magnetite than in biogenic magnetite. These values were measured by energy dispersive x-ray spectroscopy (EDXS), along with transmission electron microscopy (TEM).
Evidence is Sourced from:
Title
Chemical signature of magnetotactic bacteria
Authors
Amor, Matthieu and Busigny, Vincent and Durand-Dubief, Mickaël andTharaud, Mickaël and Ona-Nguema, Georges and Gélabert, Alexandre andAlphandéry, Edouard and Menguy, Nicolas and Benedetti, Marc F andChebbi, Imène and others
Abstract
There are longstanding and ongoing controversies about the abiotic or biological origin of nanocrystals of magnetite. On Earth, magnetotactic bacteria perform biomineralization of intracellular magnetite nanoparticles under a controlled pathway. These bacteria are ubiquitous in modern natural environments. However, their identification in ancient geological material remains challenging. Together with physical and mineralogical properties, the chemical composition of magnetite was proposed as a promising tracer for bacterial magnetofossil identification, but this had never been explored quantitatively and systematically for many trace elements. Here, we determine the incorporation of 34 trace elements in magnetite in both cases of abiotic aqueous precipitation and of production by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1. We show that, in biomagnetite, most elements are at least 100 times less concentrated than in abiotic magnetite and we provide a quantitative pattern of this depletion. Furthermore, we propose a previously unidentified method based on strontium and calcium incorporation to identify magnetite produced by magnetotactic bacteria in the geological record.
Magnetotactic bacteria precipitate chemically pure magnetite (stoichiometric Fe3O4) as magnetosomes, intracellular structures that can be preserved as magnetofossils. These magnetosomes allow the bacteria to align themselves with Earth’s magnetic field, a tool thought to help the bacteria identify areas with optimal oxygen concentrations. Whereas inorganic magnetite found in igneous and metamorphic terrestrial rocks typically contains various impurities in the form of trace elements, biologically precipitated magnetite was initially not observed to contain these same impurities. This chemical purity is thought to be the result of the role of pure iron as a cofactor in common bacterial enzymes. When chemically pure magnetite crystals were observed alongside other potential biosignatures in martian meteorite ALH84001, they were interpreted to be consistent with biologically precipitated terrestrial magnetite. However, further work has indicated that chemically [read more]Magnetotactic bacteria precipitate chemically pure magnetite (stoichiometric Fe3O4) as magnetosomes, intracellular structures that can be preserved as magnetofossils. These magnetosomes allow the bacteria to align themselves with Earth’s magnetic field, a tool thought to help the bacteria identify areas with optimal oxygen concentrations. Whereas inorganic magnetite found in igneous and metamorphic terrestrial rocks typically contains various impurities in the form of trace elements, biologically precipitated magnetite was initially not observed to contain these same impurities. This chemical purity is thought to be the result of the role of pure iron as a cofactor in common bacterial enzymes. When chemically pure magnetite crystals were observed alongside other potential biosignatures in martian meteorite ALH84001, they were interpreted to be consistent with biologically precipitated terrestrial magnetite. However, further work has indicated that chemically pure magnetite can be formed through abiotic means, with synthetic magnetite and thermally shocked magnetite displaying similar levels of chemical purity. Additionally, magnetotactic bacteria have also been observed to precipitate magnetite with impurities such as manganese and cobalt. All magnetite formation mechanisms must be carefully considered when evaluating chemically pure magnetite as a potential biosignature. [Tatiana Gibson]