Project description:Sulfur is an essential element of life that is assimilated by Earth's biosphere through the chemical breakdown of pyrite. On the early Earth, pyrite weathering by atmospheric oxygen was severely limited, and low marine sulfate concentrations persisted for much of the Archean eon. Here, we show an anoxic photochemical mechanism of pyrite weathering that could have provided substantial amounts of sulfate to the oceans as continents formed in the late Archean. Pyrite grains suspended in anoxic ferrous iron solutions produced millimolar sulfate concentrations when irradiated with ultraviolet light. The Fe2+(aq) was photooxidized, which, in turn, led to the chemical oxidation of pyritic sulfur. Additional experiments conducted with 2.68 Ga shale demonstrated that photochemically derived ferric iron oxidizes and dissolves sedimentary pyrite during chemical weathering. The results suggest that before the rise of atmospheric oxygen, oxidative pyrite weathering on Archean continents was controlled by the exposure of land to sunlight.
Project description:The Toarcian Oceanic Anoxic Event (T-OAE) was characterized by a major disturbance to the global carbon(C)-cycle, and depleted oxygen in Earth's oceans resulting in marine mass extinction. Numerical models predict that increased organic carbon burial should drive a rise in atmospheric oxygen (pO2) leading to termination of an OAE after ?1?Myr. Wildfire is highly responsive to changes in pO2 implying that fire-activity should vary across OAEs. Here we test this hypothesis by tracing variations in the abundance of fossil charcoal across the T-OAE. We report a sustained ?800?kyr enhancement of fire-activity beginning ?1?Myr after the onset of the T-OAE and peaking during its termination. This major enhancement of fire occurred across the timescale of predicted pO2 variations, and we argue this was primarily driven by increased pO2. Our study provides the first fossil-based evidence suggesting that fire-feedbacks to rising pO2 may have aided in terminating the T-OAE.
Project description:It is unclear why atmospheric oxygen remained trapped at low levels for more than 1.5 billion years following the Paleoproterozoic Great Oxidation Event. Here, we use models for erosion, weathering and biogeochemical cycling to show that this can be explained by the tectonic recycling of previously accumulated sedimentary organic carbon, combined with the oxygen sensitivity of oxidative weathering. Our results indicate a strong negative feedback regime when atmospheric oxygen concentration is of order pO2∼0.1 PAL (present atmospheric level), but that stability is lost at pO2<0.01 PAL. Within these limits, the carbonate carbon isotope (δ13C) record becomes insensitive to changes in organic carbon burial rate, due to counterbalancing changes in the weathering of isotopically light organic carbon. This can explain the lack of secular trend in the Precambrian δ13C record, and reopens the possibility that increased biological productivity and resultant organic carbon burial drove the Great Oxidation Event.
Project description:Recognizing whether a planet can support life is a primary goal of future exoplanet spectral characterization missions, but past research on habitability assessment has largely ignored the vastly different conditions that have existed in our planet's long habitable history. This study presents simulations of a habitable yet dramatically different phase of Earth's history, when the atmosphere contained a Titan-like, organic-rich haze. Prior work has claimed a haze-rich Archean Earth (3.8-2.5 billion years ago) would be frozen due to the haze's cooling effects. However, no previous studies have self-consistently taken into account climate, photochemistry, and fractal hazes. Here, we demonstrate using coupled climate-photochemical-microphysical simulations that hazes can cool the planet's surface by about 20 K, but habitable conditions with liquid surface water could be maintained with a relatively thick haze layer (????5 at 200?nm) even with the fainter young Sun. We find that optically thicker hazes are self-limiting due to their self-shielding properties, preventing catastrophic cooling of the planet. Hazes may even enhance planetary habitability through UV shielding, reducing surface UV flux by about 97% compared to a haze-free planet and potentially allowing survival of land-based organisms 2.7-2.6 billion years ago. The broad UV absorption signature produced by this haze may be visible across interstellar distances, allowing characterization of similar hazy exoplanets. The haze in Archean Earth's atmosphere was strongly dependent on biologically produced methane, and we propose that hydrocarbon haze may be a novel type of spectral biosignature on planets with substantial levels of CO2. Hazy Archean Earth is the most alien world for which we have geochemical constraints on environmental conditions, providing a useful analogue for similar habitable, anoxic exoplanets. Key Words: Haze-Archean Earth-Exoplanets-Spectra-Biosignatures-Planetary habitability. Astrobiology 16, 873-899.
Project description:Highly siderophile elements (HSE), including platinum, provide powerful geochemical tools for studying planet formation. Late accretion of chondritic components to Earth after core formation has been invoked as the main source of mantle HSE. However, core formation could also have contributed to the mantle's HSE content. Here we present measurements of platinum metal-silicate partitioning coefficients, obtained from laser-heated diamond anvil cell experiments, which demonstrate that platinum partitioning into metal is lower at high pressures and temperatures. Consequently, the mantle was likely enriched in platinum immediately following core-mantle differentiation. Core formation models that incorporate these results and simultaneously account for collateral geochemical constraints, lead to excess platinum in the mantle. A subsequent process such as iron exsolution or sulfide segregation is therefore required to remove excess platinum and to explain the mantle's modern HSE signature. A vestige of this platinum-enriched mantle can potentially account for 186Os-enriched ocean island basalt lavas.
Project description:We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO2-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175-221) Tg-CO2-eq ? y(-1) in 2007 to 275 (246-304) Tg-CO2-eq ? y(-1) in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63-95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.
Project description:During terrestrial differentiation, the relatively small amount of phosphorus that migrated to the lithosphere was incorporated into igneous rock, predominantly in the form of basic calcium orthophosphate (Ca10(PO4)6(OH,F,Cl)2, apatite). Yet, the highly insoluble nature of calcium apatite presents a significant problem to those contemplating the origin of life given the foundational role of phosphate (PO4 3-) in extant biology and the apparent requirement for PO4 3- as a catalyst, buffer and reagent in prebiotic chemistry. Reduced meteorites such as enstatite chondrites are highly enriched in phosphide minerals, and upon reaction with water these minerals can release phosphorus species of various oxidation states. Here, we demonstrate how reduced phosphorus species can be fully oxidized to PO4 3- simply by the action of ultraviolet light on H2S/HS-. We used low pressure Hg lamps to simulate UV output from the young Sun and 31P NMR spectroscopy to monitor the progress of reactions. Our experimental findings provide a cosmochemically and geochemically plausible means for supply of PO4 3- that was widely available to prebiotic chemistry and nascent life on early Earth, and potentially on other planets.
Project description:Delayed Earth system recovery following the end-Permian mass extinction is often attributed to severe ocean anoxia. However, the extent and duration of Early Triassic anoxia remains poorly constrained. Here we use paired records of uranium concentrations ([U]) and (238)U/(235)U isotopic compositions (?(238)U) of Upper Permian-Upper Triassic marine limestones from China and Turkey to quantify variations in global seafloor redox conditions. We observe abrupt decreases in [U] and ?(238)U across the end-Permian extinction horizon, from ?3 ppm and -0.15‰ to ?0.3 ppm and -0.77‰, followed by a gradual return to preextinction values over the subsequent 5 million years. These trends imply a factor of 100 increase in the extent of seafloor anoxia and suggest the presence of a shallow oxygen minimum zone (OMZ) that inhibited the recovery of benthic animal diversity and marine ecosystem function. We hypothesize that in the Early Triassic oceans-characterized by prolonged shallow anoxia that may have impinged onto continental shelves-global biogeochemical cycles and marine ecosystem structure became more sensitive to variation in the position of the OMZ. Under this hypothesis, the Middle Triassic decline in bottom water anoxia, stabilization of biogeochemical cycles, and diversification of marine animals together reflect the development of a deeper and less extensive OMZ, which regulated Earth system recovery following the end-Permian catastrophe.
Project description:The chemical composition of the Gaoping River in Taiwan reflects the weathering of both silicate and carbonate rocks found in its metasedimentary catchment. Major dissolved ion chemistry and radiocarbon signatures of dissolved inorganic carbon (DIC) reveal the importance of pyrite-derived sulphuric acid weathering on silicates and carbonates. Two-thirds of the dissolved load of the Gaoping River derives from sulphuric acid-mediated weathering of rocks within its catchment. This is reflected in the lowest reported signatures DI14C for a small mountainous river (43 to 71 percent modern carbon), with rock-derived carbonate constituting a 14C-free DIC source. Using an inverse modelling approach integrating riverine major dissolved ion chemistry and DI14C, we provide quantitative constraints of mineral weathering pathways and calculate atmospheric CO2 fluxes resulting from the erosion of the Taiwan orogeny over geological timescales. The results reveal that weathering on Taiwan releases 0.31?±?0.12 MtC/yr, which is offset by burial of terrestrial biospheric organic carbon in offshore sediments. The latter tips the balance with respect to the total CO2 budget of Taiwan such that the overall system acts as a net sink, with 0.24?±?0.13 MtC/yr of atmospheric CO2 consumed over geological timescales.
Project description:The origin of life is still an unsolved mystery in science. Hypothetically, prebiotic chemistry and the formation of protocells may have evolved in the hydrothermal environment of tectonic fault zones in the upper continental crust, an environment where sensitive molecules are protected against degradation induced e.g. by UV radiation. The composition of fluid inclusions in minerals such as quartz crystals which have grown in this environment during the Archean period might provide important information about the first organic molecules formed by hydrothermal synthesis. Here we present evidence for organic compounds which were preserved in fluid inclusions of Archean quartz minerals from Western Australia. We found a variety of organic compounds such as alkanes, halocarbons, alcohols and aldehydes which unambiguously show that simple and even more complex prebiotic organic molecules have been formed by hydrothermal processes. Stable-isotope analysis confirms that the methane found in the inclusions has most likely been formed from abiotic sources by hydrothermal chemistry. Obviously, the liquid phase in the continental Archean crust provided an interesting choice of functional organic molecules. We conclude that organic substances such as these could have made an important contribution to prebiotic chemistry which might eventually have led to the formation of living cells.