Earliest land plants created modern levels of atmospheric oxygen

The progressive oxygenation of the Earth’s atmosphere was pivotal to the evolution of life, but the puzzle of when and how atmospheric oxygen (O2) first approached modern levels (~21%) remains unresolved. Redox proxy data indicate the deep oceans were oxygenated during 435-392 Ma, and the appearance of fossil charcoal indicates O2>15-17% by 420-400 Ma. However, existing models have failed to predict oxygenation at this time. Here we show that the earliest plants, which colonized the land surface from ~470 Ma onwards, were responsible for this mid- Paleozoic oxygenation event, through greatly increasing global organic carbon burial – the net long-term source of O2. We use a trait-based ecophysiological model to predict that cryptogamic vegetation cover could have achieved ~30% of today’s global terrestrial net primary productivity by~445 Ma. Data from modern bryophytes suggests this plentiful early plant material had a much higher molar C:P ratio (~2000) than marine biomass (~100), such that a given weathering flux of phosphorus could support more organic carbon burial. Furthermore, recent experiments suggest that early plants selectively increased the flux of phosphorus (relative to alkalinity) weathered from rocks. Combining these effects in a model of long-term biogeochemical cycling, we reproduce a sustained +2‰ increase in the carbonate carbon isotope (δ13C) record by ~445 Ma, and predict a corresponding rise in O2 to present levels by 420-400 Ma, consistent with geochemical data. This oxygen rise represents a permanent shift in regulatory regime to one where fire-mediated negative feedbacks on organic carbon burial stabilise high O2 levels

Influence of palaeoweathering on trace metal concentrations and environmental proxies in black shales

The mineralogical and chemical compositions of Lower Carboniferous (Tournaisian) marine black shale from the Kowala quarry, the Holy Cross Mountains, Poland, were investigated. This study focuses on disturbances in palaeoenvironmental proxies caused by palaeoweathering, which progressively changed the major and trace element abundances. Palaeomagnetic investigations reveal that the Devonian – Carboniferous succession was weathered during the Permian-Triassic by the infiltration of oxidizing fluids related to karstification following post-Variscan exhumation. The weathering process led to vermiculitization of chlorite, partial dissolution of calcite and replacement of pyrite by hematite and goethite. Moreover, the concentrations of some trace metals, including Co, Cu, Pb, Mo, Ni, As and U, significantly decreased. Consequently, some elemental abundance ratios that are used as environmental proxies, including U/Th, Ni/Co and V/Cr, were altered. Elements that are bound to iron sulphides (e.g., Mo) appear to be especially prone to mobilization by even a lightly weathered black shale. The documented weathering, including changes in elemental concentrations, can potentially create misinterpretations of the original palaeoenvironmental conditions. In addition, the palaeoweathering of the studied samples appears to have substantially changed the carbon, oxygen, nitrogen and molybdenum stable isotope values. The nitrogen and molybdenum stable isotope ratios, in particular, appear to be most sensitive to the effects of weathering and therefore are good indicators of (palaeo)weathering processes. The major cause of these changes is the decay of organic matter and pyrite. For the organic carbon stable isotopes ratios, the main factor that controlls this process appears to be the preferential degradation of labile organic matter. A combination of the total organic carbon (TOC), total sulphur (TS) content, Mo concentration and stable isotope compositions seems to be the most useful for identify (palaeo)weathering. Our results suggest that reductions in TS and Mo in tandem with diminished Mo stable isotope values in the absence of obvious changes to the TOC content provide the most compelling evidence of (palaeo)weathering

Biogeochemistry: Early phosphorus redigested

Atmospheric oxygen was maintained at low levels throughout huge swathes of Earth's early history. Estimates of phosphorus availability through time suggest that scavenging from anoxic, iron-rich oceans stabilized this low-oxygen world

The climatic significance of Late Ordovician-early Silurian black

The Ordovician-Silurian transition (455-430 Ma) is characterized by repeated climatic perturbations, concomitant with major changes in the global oceanic redox state best exemplified by the periodic deposition of black shales. The relationship between the climatic evolution and the oceanic redox cycles, however, remains largely debated. Here, using an ocean-atmosphere general circulation model accounting for ocean biogeochemistry (MITgcm), we investigate the mechanisms responsible for the burial of organic carbon immediately before, during and right after the latest Ordovician Hirnantian (445-444 Ma) glacial peak. Our results are compared with recent sedimentological and geochemical data. We show that the late Katian time slice (445 Ma), typified by the deposition of black shales at tropical latitudes, represents an unperturbed oceanic state, with regional organic carbon burial driven by the surface primary productivity. During the Hirnantian, our experiments predict a global oxygenation event, in agreement with the disappearance of the black shales in the sedimentary record. This suggests that deep-water burial of organic matter may not be a tenable triggering factor for the positive carbon excursion reported at that time. Our simulations indicate that the perturbation of the ocean circulation induced by the release of freshwater, in the context of the post-Hirnantian deglaciation, does not sustain over sufficiently long geological periods to cause the Rhuddanian (444 Ma) oceanic anoxic event. Input of nutrients to the ocean, through increased continental weathering and the leaching of newly-exposed glaciogenic sediments, may instead constitute the dominant control on the spread of anoxia in the early Silurian

Terminal Proterozoic cyanobacterial blooms and phosphogenesis documented by the Doushantuo granular phosphorites II: Microbial diversity and C isotopes

An unprecedented period of phosphogenesis, along with massive deposition of black shales, major perturbations in the global carbon cycle and the rise of atmospheric oxygen, occurred in the terminal Proterozoic in the aftermath of the Marinoan glaciation. Although causal links between these processes have been postulated, evidence remains challenging. Correlated in situ micro-analyses of granular phosphorites from the Ediacaran Doushantuo Formation in Yichang, South China, suggested that cyanobacteria and associated extracellular polymeric substances (EPS) might have promoted aggregated granule growth and subsequent phosphatization (She et al., 2013). Here, we present new paleontological data for the Doushantuo phosphorites from Yichang, which, combined with Raman microspectroscopy and carbon isotope data, further document links between the biology of cyanobacteria and phosphogenesis. Mapping of microfossils in thin section shows that most phosphatic granules contain microfossils that are dominated by colonies of Myxococcoides, along with several filamentous genera generally considered to represent cyanobacterial sheaths. In addition, the phosphorites and associated rocks have δ13Corg values in the range of −26.0 to −29.7‰ VPDB, consistent with photoautotrophic carbon fixation with the Rubisco enzyme. Close association of phosphorites with the Marinoan tillites in stratigraphic level supports a genetic link between deglaciation and phosphogenesis, at least for the Doushantuo occurrence. Our new data suggest that major cyanobacterial blooms probably took place in the terminal Proterozoic, which might have resulted in rapid scavenging of bioavailable phosphorus and massive accumulations of organic matter (OM). Within a redox-stratified intra-shelf basin, the OM-bound phosphorus could have liberated by microbial sulfate reduction and other anaerobic metabolisms and subsequently concentrated by Fe-redox pumping below the chemocline. Upwelling of the bottom waters or upward fluctuation of the chemocline might have brought P-enriched waters to the photic zone, where it was again scavenged by cyanobacteria through their EPS to be subsequently precipitated as francolite. The feedbacks between enhanced continental weathering, cyanobacterial blooms, carbon burial, and accelerated phosphorus cycle thus controlled the marine biogeochemical changes, which led to further oxygenation of the atmosphere and oceans, ultimately paving the way for the rise of metazoans

A normalised seawater strontium isotope curve: possible implications for Neoproterozoic-Cambrian weathering rates and the further oxygenation of the Earth

The strontium isotope composition of seawater is strongly influenced on geological time scales by changes in the rates of continental weathering relative to ocean crust alteration. However, the potential of the seawater 87Sr/86Sr curve to trace globally integrated chemical weathering rates has not been fully realised because ocean 87Sr/86Sr is also influenced by the isotopic evolution of Sr sources to the ocean. A preliminary attempt is made here to normalise the seawater 87Sr/86Sr curve to plausible trends in the 87Sr/86Sr ratios of the three major Sr sources: carbonate dissolution, silicate weathering and submarine hydrothermal exchange. The normalised curve highlights the Neoproterozoic-Phanerozoic transition as a period of exceptionally high continental influence, indicating that this interval was characterised by a transient increase in global weathering rates and/or by the weathering of unusually radiogenic crustal rocks. Close correlation between the normalised 87Sr/86Sr curve, a published seawater δ34S curve and atmospheric pCO2 models is used here to argue that elevated chemical weathering rates were a major contributing factor to the steep rise in seawater 87Sr/86Sr from 650 Ma to 500 Ma. Elevated weathering rates during the Neoproterozoic-Cambrian interval led to increased nutrient availability, organic burial and to the further oxygenation of Earth's surface environment. Use of normalised seawater 87Sr/86Sr curves will, it is hoped, help to improve future geochemical models of Earth System dynamics

Distribution of naturally occurring radionuclides (U, Th) in Timahdit black shale (Morocco)

Attention has been focused recently on the use of Moroccan black oil shale as the raw material for production of a new type of adsorbent and its application to U and Th removal from contaminated wastewaters. The purpose of the present work is to provide a better understanding of the composition and structure of this shale and to determine its natural content in uranium and thorium. A black shale collected from Timahdit (Morocco) was analyzed by powder X-ray diffraction and SEM techniques. It was found that calcite, dolomite, quartz and clays constitute the main composition of the inorganic matrix. Pyrite crystals are also present. A selective leaching procedure, followed by radiochemical purification and α-counting, was performed to assess the distribution of naturally occurring radionuclides. Leaching results indicate that 238U, 235U, 234U, 232Th, 230Th and 228Th have multiple modes of occurrence in the shale. U is interpreted to have been concentrated under anaerobic conditions. An integrated isotopic approach showed the preferential mobilization of uranium carried by humic acids to carbonate and apatite phases. Th is partitioned between silicate minerals and pyrite

Reclaiming Illinois strip coal lands by forest planting

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