Nanoparticulate apatite and greenalite in oldest, well-preserved hydrothermal vent precipitates.

Paleoarchean jaspilites are used to track ancient ocean chemistry and photoautotrophy because they contain hematite interpreted to have formed following biological oxidation of vent-derived Fe(II) and seawater P-scavenging. However, recent studies have triggered debate about ancient seawater Fe and P deposition. Here, we report greenalite and fluorapatite (FAP) nanoparticles in the oldest, well-preserved jaspilites from the ~3.5-billion-year Dresser Formation, Pilbara Craton, Australia. We argue that both phases are vent plume particles, whereas coexisting hematite is linked to secondary oxidation. Geochemical modeling predicts that hydrothermal alteration of seafloor basalts by anoxic, sulfate-free seawater releases Fe(II) and P that simultaneously precipitate as greenalite and FAP upon venting. The formation, transport, and preservation of FAP nanoparticles indicate that seawater P concentrations were ≥1 to 2 orders of magnitude higher than in modern deepwater. We speculate that Archean seafloor vents were nanoparticle "factories" that, on prebiotic Earth, produced countless Fe(II)- and P-rich templates available for catalysis and biosynthesis.

Organic carbon generation in 3.5-billion-year-old basalt-hosted seafloor hydrothermal vent systems.

Carbon is the key element of life, and its origin in ancient sedimentary rocks is central to questions about the emergence and early evolution of life. The oldest well-preserved carbon occurs with fossil-like structures in 3.5-billion-year-old black chert. The carbonaceous matter, which is associated with hydrothermal chert-barite vent systems originating in underlying basaltic-komatiitic lavas, is thought to be derived from microbial life. Here, we show that 3.5-billion-year-old black chert vein systems from the Pilbara Craton, Australia contain abundant residues of migrated organic carbon. Using younger analogs, we argue that the black cherts formed during precipitation from silica-rich, carbon-bearing hydrothermal fluids in vein systems and vent-proximal seafloor sediments. Given the volcanic setting and lack of organic-rich sediments, we speculate that the vent-mound systems contain carbon derived from rock-powered organic synthesis in the underlying mafic-ultramafic lavas, providing a glimpse of a prebiotic world awash in terrestrial organic compounds.

Products of the iron cycle on the early Earth.

Traditional models for pre-GOE oceans commonly view iron as a critical link to multiple biogeochemical cycles, and an important source of electrons to primary producers. However, an accurate and detailed understanding of the ancient iron cycle has been limited by: (1) our ability to constrain primary depositional processes through observations of the ancient sedimentary rock record, and (2) a quantitative understanding of the aqueous geochemistry of ferrous iron. Recent advances in high resolution petrography and experimental geochemistry, however, have contributed to a new understanding of certain aspects of the early Fe cycle. Most importantly, high resolution petrographic studies of late Archean/early Paleoproterozoic iron formation have documented the prolific deposition of Fe(II)-silicate-rich chemical muds from a dominantly anoxic ocean. At the same time, recent experimental work has shed new light on processes likely to have controlled steady state Fe concentrations in Archean oceans. These studies suggest that spontaneous precipitation of Fe(II)-carbonate was probably rare in Archean oceans, and that Fe(II)-carbonate would have more commonly precipitated on the surfaces of suitable mineral substrates within clastic and chemical sediments, consistent with petrographic observations. In addition, although experimental investigations suggest that maximum Fe concentrations in Archean oceans would have been limited by authigenic Fe(II)-silicate production (rather than Fe(II)-carbonate), the rock record indicates that this process was rarely operative. Instead, sedimentology, stratigraphy, and geochemical modelling suggest that much of the precursor sediment to late Archean iron formation was produced as hydrothermal effluent interacted with seawater in close proximity to seafloor vents. Together, these observations help define a new topology for the ancient Fe cycle. In this view, hydrothermal effluent-seawater mixing would have strongly attenuated the flux of dissolved Fe2+ to Archean oceans, and early diagenetic siderite formation may have balanced globally averaged riverine and hydrothermal Fe2+ input fluxes. In contrast to previous models, this emerging picture of the early Fe cycle suggests that Fe played only a negligible role in supporting anoxygenic phototrophs, reinforcing the concept that electron donors were in comparatively limited supply before the advent of oxygenic photosynthesis.

Fungus-like mycelial fossils in 2.4-billion-year-old vesicular basalt.

Fungi have recently been found to comprise a significant part of the deep biosphere in oceanic sediments and crustal rocks. Fossils occupying fractures and pores in Phanerozoic volcanics indicate that this habitat is at least 400 million years old, but its origin may be considerably older. A 2.4-billion-year-old basalt from the Palaeoproterozoic Ongeluk Formation in South Africa contains filamentous fossils in vesicles and fractures. The filaments form mycelium-like structures growing from a basal film attached to the internal rock surfaces. Filaments branch and anastomose, touch and entangle each other. They are indistinguishable from mycelial fossils found in similar deep-biosphere habitats in the Phanerozoic, where they are attributed to fungi on the basis of chemical and morphological similarities to living fungi. The Ongeluk fossils, however, are two to three times older than current age estimates of the fungal clade. Unless they represent an unknown branch of fungus-like organisms, the fossils imply that the fungal clade is considerably older than previously thought, and that fungal origin and early evolution may lie in the oceanic deep biosphere rather than on land. The Ongeluk discovery suggests that life has inhabited submarine volcanics for more than 2.4 billion years.

Deposition of 1.88-billion-year-old iron formations as a consequence of rapid crustal growth.

Iron formations are chemical sedimentary rocks comprising layers of iron-rich and silica-rich minerals whose deposition requires anoxic and iron-rich (ferruginous) sea water. Their demise after the rise in atmospheric oxygen by 2.32 billion years (Gyr) ago has been attributed to the removal of dissolved iron through progressive oxidation or sulphidation of the deep ocean. Therefore, a sudden return of voluminous iron formations nearly 500 million years later poses an apparent conundrum. Most late Palaeoproterozoic iron formations are about 1.88 Gyr old and occur in the Superior region of North America. Major iron formations are also preserved in Australia, but these were apparently deposited after the transition to a sulphidic ocean at 1.84 Gyr ago that should have terminated iron formation deposition, implying that they reflect local marine conditions. Here we date zircons in tuff layers to show that iron formations in the Frere Formation of Western Australia are about 1.88 Gyr old, indicating that the deposition of iron formations from two disparate cratons was coeval and probably reflects global ocean chemistry. The sudden reappearance of major iron formations at 1.88 Gyr ago--contemporaneous with peaks in global mafic-ultramafic magmatism, juvenile continental and oceanic crust formation, mantle depletion and volcanogenic massive sulphide formation--suggests deposition of iron formations as a consequence of major mantle activity and rapid crustal growth. Our findings support the idea that enhanced submarine volcanism and hydrothermal activity linked to a peak in mantle melting released large volumes of ferrous iron and other reductants that overwhelmed the sulphate and oxygen reservoirs of the ocean, decoupling atmospheric and seawater redox states, and causing the return of widespread ferruginous conditions. Iron formations formed on clastic-starved coastal shelves where dissolved iron upwelled and mixed with oxygenated surface water. The disappearance of iron formations after this event may reflect waning mafic-ultramafic magmatism and a diminished flux of hydrothermal iron relative to seawater oxidants.