Although it is not known when or where life on Earth began, some of the earliest habitable environments may have been submarine-hydrothermal vents. Here we describe putative fossilized microorganisms that are at least 3,770 million and possibly 4,280 million years old in ferruginous sedimentary rocks, interpreted as seafloor-hydrothermal vent-related precipitates, from the Nuvvuagittuq belt in Quebec, Canada. These structures occur as micrometre-scale haematite tubes and filaments with morphologies and mineral assemblages similar to those of filamentous microorganisms from modern hydrothermal vent precipitates and analogous microfossils in younger rocks. The Nuvvuagittuq rocks contain isotopically light carbon in carbonate and carbonaceous material, which occurs as graphitic inclusions in diagenetic carbonate rosettes, apatite blades intergrown among carbonate rosettes and magnetite-haematite granules, and is associated with carbonate in direct contact with the putative microfossils. Collectively, these observations are consistent with an oxidized biomass and provide evidence for biological activity in submarine-hydrothermal environments more than 3,770 million years ago.
Biological materials are often based on simple constituents and grown by the principle of self-assembly under ambient conditions. In particular, biomineralization approaches exploit efficient pathways of inorganic material synthesis. There is still a large gap between the complexity of natural systems and the practical utilization of bioinspired formation mechanisms. Here we describe a simple self-assembly route leading to a CaCO(3) microlens array, somewhat reminiscent of the brittlestars' microlenses, with uniform size and focal length, by using a minimum number of components and equipment at ambient conditions. The formation mechanism of the amorphous CaCO(3) microlens arrays was elucidated by confocal Raman spectroscopic imaging to be a two-step growth process mediated by the organic surfactant. CaCO(3) microlens arrays are easy to fabricate, biocompatible and functional in amorphous or more stable crystalline forms. This shows that advanced optical materials can be generated by a simple mineral precipitation.
Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans.
We attempted to control the incorporation of twin boundaries in self-catalyzed GaAs nanowires (NWs). Self-catalyzed GaAs NWs were grown on a Si substrate under various arsenic pressures using molecular beam epitaxy and the vapor-liquid-solid method. When the arsenic flux is low, wurtzite structures are dominant in the GaAs NWs. On the other hand, zinc blende structures become dominant as the arsenic flux rises. We discussed this phenomenon on the basis of thermodynamics and examined the probability of twin-boundary formation in detail.
Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates
- Proceedings of the National Academy of Sciences of the United States of America
- Published about 5 years ago
The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.
Biological activity is a major factor in Earth’s chemical cycles, including facilitating CO2 sequestration and providing climate feedbacks. Thus a key question in Earth’s evolution is when did life arise and impact hydrosphere-atmosphere-lithosphere chemical cycles? Until now, evidence for the oldest life on Earth focused on debated stable isotopic signatures of 3,800-3,700 million year (Myr)-old metamorphosed sedimentary rocks and minerals from the Isua supracrustal belt (ISB), southwest Greenland. Here we report evidence for ancient life from a newly exposed outcrop of 3,700-Myr-old metacarbonate rocks in the ISB that contain 1-4-cm-high stromatolites-macroscopically layered structures produced by microbial communities. The ISB stromatolites grew in a shallow marine environment, as indicated by seawater-like rare-earth element plus yttrium trace element signatures of the metacarbonates, and by interlayered detrital sedimentary rocks with cross-lamination and storm-wave generated breccias. The ISB stromatolites predate by 220 Myr the previous most convincing and generally accepted multidisciplinary evidence for oldest life remains in the 3,480-Myr-old Dresser Formation of the Pilbara Craton, Australia. The presence of the ISB stromatolites demonstrates the establishment of shallow marine carbonate production with biotic CO2 sequestration by 3,700 million years ago (Ma), near the start of Earth’s sedimentary record. A sophistication of life by 3,700 Ma is in accord with genetic molecular clock studies placing life’s origin in the Hadean eon (>4,000 Ma).
- Proceedings of the National Academy of Sciences of the United States of America
- Published over 2 years ago
Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.
Meteorites represent the only samples available for study on Earth of a number of planetary bodies. The minerals within meteorites therefore hold the key to addressing numerous questions about our solar system. Of particular interest is the Ca-phosphate mineral merrillite, the anhydrous end-member of the merrillite-whitlockite solid solution series. For example, the anhydrous nature of merrillite in Martian meteorites has been interpreted as evidence of water-limited late-stage Martian melts. However, recent research on apatite in the same meteorites suggests higher water content in melts. One complication of using meteorites rather than direct samples is the shock compression all meteorites have experienced, which can alter meteorite mineralogy. Here we show whitlockite transformation into merrillite by shock-compression levels relevant to meteorites, including Martian meteorites. The results open the possibility that at least part of meteoritic merrillite may have originally been H(+)-bearing whitlockite with implications for interpreting meteorites and the need for future sample return.
Large Hesperian-aged (~3.7 Ga) layered deposits of sulfate-rich sediments in the equatorial regions of Mars have been suggested to be evidence for ephemeral playa environments. But early Mars may not have been warm enough to support conditions similar to what occurs in arid environments on Earth. Instead cold, icy environments may have been widespread. Under cryogenic conditions sulfate formation might be blocked, since kinetics of silicate weathering are typically strongly retarded at temperatures well below 0 °C. But cryo-concentration of acidic solutions may counteract the slow kinetics. Here we show that cryo-concentrated acidic brines rapidly chemically weather olivine minerals and form sulfate minerals at temperatures as low as -60 °C. These experimental results demonstrate the viability of sulfate formation under current Martian conditions, even in the polar regions. An ice-hosted sedimentation and weathering model may provide a compelling description of the origin of large Hesperian-aged layered sulfate deposits on Mars.
Carbon capture and storage (CCS) provides a solution toward decarbonization of the global economy. The success of this solution depends on the ability to safely and permanently store CO2 This study demonstrates for the first time the permanent disposal of CO2 as environmentally benign carbonate minerals in basaltic rocks. We find that over 95% of the CO2 injected into the CarbFix site in Iceland was mineralized to carbonate minerals in less than 2 years. This result contrasts with the common view that the immobilization of CO2 as carbonate minerals within geologic reservoirs takes several hundreds to thousands of years. Our results, therefore, demonstrate that the safe long-term storage of anthropogenic CO2 emissions through mineralization can be far faster than previously postulated.