Explore the vast range of titles available.

Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O ₂ budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic–Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O ₂. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen.

Calcium sulfate minerals such as gypsum play important roles in natural and industrial processes, but their precipitation mechanisms remain largely unexplored. We used time-resolved sample quenching and high-resolution microscopy to demonstrate that gypsum forms via a three-stage process: (i) homogeneous precipitation of nanocrystalline hemihydrate bassanite below its predicted solubility, (ii) self-assembly of bassanite into elongated aggregates co-oriented along their c axis, and (iii) transformation into dihydrate gypsum. These findings indicate that a stable nanocrystalline precursor phase can form below its bulk solubility and that in the CaSO₄ system, the self-assembly of nanoparticles plays a crucial role. Understanding why bassanite forms prior to gypsum can lead to more efficient anti-scaling strategies for water desalination and may help to explain the persistence of CaS0 4 phases in regions of low water activity on Mars.

Calcium carbonate forms scales, geological deposits, biominerals, and ocean sediments. Huge amounts of carbon dioxide are retained as carbonate ions, and calcium ions represent a major contribution to water hardness. Despite its relevance, little is known about the precipitation mechanism of calcium carbonate, and specified complex crystal structures challenge the classical view on nucleation considering the formation of metastable ion clusters. We demonstrate that dissolved calcium carbonate in fact contains stable prenucleation ion clusters forming even in undersaturated solution. The cluster formation can be characterized by means of equilibrium thermodynamics, applying a multiple-binding model, which allows for structural preformation. Stable clusters are the relevant species in calcium carbonate nucleation. Such mechanisms may also be important for the crystallization of other minerals.

A primary consequence of plate tectonics is that basaltic oceanic crust subducts with lithospheric slabs into the mantle. Seismological studies extend this process to the lower mantle, and geochemical observations indicate return of oceanic crust to the upper mantle in plumes. There has been no direct petrologic evidence, however, of the return of subducted oceanic crustal components from the lower mantle. We analyzed superdeep diamonds from Juina-5 kimberlite, Brazil, which host inclusions with compositions comprising the entire phase assemblage expected to crystallize from basalt under lower-mantle conditions. The inclusion mineralogies require exhumation from the lower to upper mantle. Because the diamond hosts have carbon isotope signatures consistent with surface-derived carbon, we conclude that the deep carbon cycle extends into the lower mantle.

Iron oxides occur ubiquitously in environmental, geological, planetary, and technological settings. They exist in a rich variety of structures and hydration states. They are commonly fine-grained (nanophase) and poorly crystalline. This review summarizes recently measured thermodynamic data on their formation and surface energies. These data are essential for calculating the thermodynamic stability fields of the various iron oxide and oxyhydroxide phases and understanding their occurrence in natural and anthropogenic environments. The competition between surface enthalpy and the energetics of phase transformation leads to the general conclusion that polymorphs metastable as micrometer-sized or larger crystals can often be thermodynamically stabilized at the nanoscale. Such size-driven crossovers in stability help to explain patterns of occurrence of different iron oxides in nature.

Diamond distribution Diamond formation occurs in high-pressure conditions more than 150 kilometres deep in the Earth's mantle. The diamonds make it to the surface in vertical pipe-like structures made up of volcanic rocks called kimberlites. Several thousand such kimberlite pipes have been mapped so far, but research has focused on very old cratons, the areas of oldest continental crust, as this is where most economically viable diamonds are found. Trond Torsvik and colleagues use a plate-tectonic reconstruction for the past 540 million years to locate the positions of these cratons relative to the deep mantle at times when kimberlites were erupted. The kimberlites are shown to have been associated with the edges of large-scale heterogeneities in the deepest mantle, which the authors infer were zones at the core–mantle boundary where magma upwelling generated the mantle plumes that led to the formation of the kimberlites. These plumes may have controlled the distribution of almost all kimberlites that have erupted in the past 540 million years. Diamonds are formed under high pressure more than 150 kilometres deep in the Earth's mantle, and are brought to the surface mainly by volcanic rocks called kimberlites. Here, plate reconstructions and tomographic images have been used to show that the edges of the largest heterogeneities in the deepest mantle, stable for at least 200 million years and possibly for 540 million years, seem to have controlled the eruption of most Phanerozoic kimberlites. This has implications for future exploration for kimberlites. Diamonds are formed under high pressure more than 150 kilometres deep in the Earth’s mantle and are brought to the surface mainly by volcanic rocks called kimberlites. Several thousand kimberlites have been mapped on various scales 1 , 2 , 3 , 4 , but it is the distribution of kimberlites in the very old cratons (stable areas of the continental lithosphere that are more than 2.5 billion years old and 300 kilometres thick or more 5 ) that have generated the most interest, because kimberlites from those areas are the major carriers of economically viable diamond resources. Kimberlites, which are themselves derived from depths of more than 150 kilometres, provide invaluable information on the composition of the deep subcontinental mantle lithosphere, and on melting and metasomatic processes at or near the interface with the underlying flowing mantle. Here we use plate reconstructions and tomographic images to show that the edges of the largest heterogeneities in the deepest mantle, stable for at least 200 million years and possibly for 540 million years, seem to have controlled the eruption of most Phanerozoic kimberlites. We infer that future exploration for kimberlites and their included diamonds should therefore be concentrated in continents with old cratons that once overlay these plume-generation zones at the core–mantle boundary.

Metal-respiring bacteria as atmospheric oxidation agents Free oxygen appeared in Earth's atmosphere for the first time around 2.5 billion years ago, in what is known as the Great Oxidation Event, which resulted in profound changes to biogeochemical cycling. Konhauser et al . examine rocks from this time and find that chromium was largely immobile on land until around the Great Oxidation Event, but that within the following 160 million years, it was solubilized on a large scale. The authors suggest that this mobilization was possible only through the action of aerobic, bacterial respiration on abundant supplies of pyrite. This early exploitation of atmospheric oxygen also represents the first record of acid rock drainage. The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth’s land surface 1 , 2 . Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations 3 . However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed—and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4–6 )—marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr( iii ), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr( iii ) from ultramafic source rocks and residual soils 7 . This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate 8 and sulphide-hosted trace elements to the oceans around that time 1 , 9 . Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

Dolomite and magnesite are simple anhydrous calcium and/or magnesium carbonate minerals occurring mostly at Earth surfaces. However, laboratory synthesis of neither species at ambient temperature and pressure conditions has been proven practically possible, and the lack of success was assumed to be related to the strong solvation shells of magnesium ions in aqueous media. Here, we report the synthesis of MgCO ₃ and Mg ₓCa ₍₁₋ₓ₎CO ₃ (0 < x < 1) solid phases at ambient conditions in the absence of water. Experiments were carried out in dry organic solvent, and the results showed that, although anhydrous phases were readily precipitated in the water-free environment, the precipitates’ crystallinity was highly dependent on the Mg molar percentage content in the solution. In specific, magnesian calcite dominated in low [Mg ²⁺]/[Ca ²⁺] solutions but gave way to exclusive formation of amorphous Mg ₓCa ₍₁₋ₓ₎CO ₃ and MgCO ₃ in high-[Mg ²⁺]/[Ca ²⁺] and pure-Mg solutions. At conditions of [Mg ²⁺]/[Ca ²⁺] = 1, both nanocrystals of Ca-rich protodolomite and amorphous phase of Mg-rich Mg ₓCa ₍₁₋ₓ₎CO ₃ were formed. These findings exposed a previously unrecognized intrinsic barrier for Mg ²⁺ and CO ₃²⁻ to develop long-range orders at ambient conditions and suggested that the long-held belief of cation-hydration inhibition on dolomite and magnesite mineralization needed to be reevaluated. Our study provides significant insight into the long-standing “dolomite problem” in geochemistry and mineralogy and may promote a better understanding of the fundamental chemistry in biomineralization and mineral-carbonation processes.

Earth-like lunar apatite It is thought that the lunar interior is deficient relative to the Earth in hydrogen, chlorine and other volatiles, due to near-complete degassing from the Moon-forming impact. New analyses of lunar basalt 14053, a much-studied sample collected by the Apollo 14 astronauts, suggest that portions of the lunar mantle or crust may be more volatile-rich than previously thought. Concentrations of hydrogen, chlorine and sulphur in the mineral apatite from 14053 are indistinguishable from apatites in common terrestrial igneous rocks. Measurements of apatites from other available lunar rock types will help to clarify the generality and significance of the terrestrial-like properties of this basalt. These authors report the concentrations of hydrogen, chlorine and sulphur in the mineral apatite from a lunar basalt, and show that the concentrations are indistinguishable from apatites in common terrestrial igneous rocks. They conclude that both metamorphic and igneous models of apatite formation suggest a volatile inventory for at least some lunar materials that is similar to comparable materials within the Earth. The Moon is thought to be depleted relative to the Earth in volatile elements such as H, Cl and the alkalis 1 , 2 , 3 . Nevertheless, evidence for lunar explosive volcanism 4 , 5 has been used to infer that some lunar magmas exsolved a CO-rich and CO 2 -rich vapour phase before or during eruption 6 , 7 , 8 . Although there is also evidence for other volatile species on glass spherules 9 , until recently 10 there had been no unambiguous reports of indigenous H in lunar rocks. Here we report quantitative ion microprobe measurements of late-stage apatite from lunar basalt 14053 that document concentrations of H, Cl and S that are indistinguishable from apatites in common terrestrial igneous rocks. These volatile contents could reflect post-magmatic metamorphic volatile addition or growth from a late-stage, interstitial, sulphide-saturated melt that contained ∼1,600 parts per million H 2 O and ∼3,500 parts per million Cl. Both metamorphic and igneous models of apatite formation suggest a volatile inventory for at least some lunar materials that is similar to comparable terrestrial materials. One possible implication is that portions of the lunar mantle or crust are more volatile-rich than previously thought.

Quasicrystals are solids whose atomic arrangements have symmetries that are forbidden for periodic crystals, including configurations with fivefold symmetry. All examples identified to date have been synthesized in the laboratory under controlled conditions. Here we present evidence of a naturally occurring icosahedral quasicrystal that includes six distinct fivefold symmetry axes. The mineral, an alloy of aluminum, copper, and iron, occurs as micrometer-sized grains associated with crystalline khatyrkite and cupalite in samples reported to have come from the Koryak Mountains in Russia. The results suggest that quasicrystals can form and remain stable under geologic conditions, although there remain open questions as to how this mineral formed naturally.