Stepwise Earth oxygenation is an inherent property of global biogeochemical cycling

Oxygenation of Earth’s atmosphere and oceans occurred across three major steps during the Paleoproterozoic, Neoproterozoic, and Paleozoic eras, with each increase having profound consequences for the biosphere. Biological or tectonic revolutions have been proposed to explain each of these stepwise increases in oxygen, but the principal driver of each event remains unclear. Here we show, using a theoretical model, that the observed oxygenation steps are a simple consequence of internal feedbacks in the long-term biogeochemical cycles of carbon, oxygen, and phosphorus, and that there is no requirement for a specific stepwise external forcing to explain the course of Earth surface oxygenation. We conclude that Earth’s oxygenation events are entirely consistent with gradual oxygenation of the planetary surface after the evolution of oxygenic photosynthesis

Development of Iron Speciation Reference Materials for Palaeoredox Analysis

The development and application of geochemical techniques to identify redox conditions in modern and ancient aquatic environments has intensified over recent years. Iron (Fe) speciation has emerged as one of the most widely used procedures to distinguish different redox regimes in both the water column and sediments, and is the main technique used to identify oxic, ferruginous (anoxic, Fe(II) containing) and euxinic (anoxic, sulfidic) water column conditions. However, an international sediment reference material has never been developed. This has led to concern over the consistency of results published by the many laboratories that now utilise the technique. Here, we report an interlaboratory comparison of four Fe speciation reference materials for palaeoredox analysis, which span a range of compositions and reflect deposition under different redox conditions. We provide an update of extraction techniques used in Fe speciation, and assess the effects of both test portion mass, and the use of different analytical procedures, on the quantification of different Fe fractions in sedimentary rocks. While atomic adsorption spectroscopy and inductively coupled plasma‐optical emission spectrometry produced comparable Fe measurements for all extraction stages, the use of ferrozine consistently underestimated Fe in the extraction step targeting mixed ferrous‐ferric minerals such as magnetite. We therefore suggest that the use of ferrozine is discontinued for this Fe pool. Finally, we report the combined data of four independent Fe speciation laboratories to characterise the Fe speciation composition of the reference materials. These reference materials are available to the community to provide an essential validation of in‐house Fe speciation measurements

Development of Iron Speciation Reference Materials for Palaeoredox Analysis

The development and application of geochemical techniques to identify redox conditions in modern and ancient aquatic environments has intensified over recent years. Iron (Fe) speciation has emerged as one of the most widely used procedures to distinguish different redox regimes in both the water column and sediments, and is the main technique used to identify oxic, ferruginous (anoxic, Fe(II) containing) and euxinic (anoxic, sulfidic) water column conditions. However, an international sediment reference material has never been developed. This has led to concern over the consistency of results published by the many laboratories that now utilise the technique. Here, we report an interlaboratory comparison of four Fe speciation reference materials for palaeoredox analysis, which span a range of compositions and reflect deposition under different redox conditions. We provide an update of extraction techniques used in Fe speciation and assess the effects of both test portion mass, and the use of different analytical procedures, on the quantification of different Fe fractions in sedimentary rocks. While atomic absorption spectroscopy and inductively coupled plasma‐optical emission spectrometry produced comparable Fe measurements for all extraction stages, the use of ferrozine consistently underestimated Fe in the extraction step targeting mixed ferrous–ferric minerals such as magnetite. We therefore suggest that the use of ferrozine is discontinued for this Fe pool. Finally, we report the combined data of four independent Fe speciation laboratories to characterise the Fe speciation composition of the reference materials. These reference materials are available to the community to provide an essential validation of in‐house Fe speciation measurements

Crustal carbonate build-up as a driver for Earth’s oxygenation

Acknowledgements: L.J.A.’s contribution was funded by a Hutchinson Environmental Postdoctoral Fellowship. C.W. acknowledges funding from the NOMIS Foundation and the Leverhulme Centre for Life in the Universe. N.J.P. acknowledges support from the Alternative Earths NASA ICAR award. B.J.W.M. acknowledges support from UKRI project NE/X011208/1.AbstractOxygenation of Earth’s atmosphere and oceans played a pivotal role in the evolution of the surface environment and life. It is thought that the rise in oxygen over Earth’s history was driven by an increasing availability of the photosynthetic limiting nutrient phosphate combined with declining oxygen-consuming inputs from the mantle and crust. However, it has been difficult to assess whether these processes alone can explain Earth’s oxygenation history. Here we develop a theoretical framework for the long-term global oxygen, phosphorus and carbon cycles, incorporating potential trajectories for the emergence of continents, the degassing of mantle volatiles and the resulting increase in the size of the crustal carbonate reservoir. We find that we can adequately simulate the Earth’s oxygenation trajectory in both the atmosphere and oceans, alongside reasonable reconstructions of planetary temperature, atmospheric carbon dioxide concentration, phosphorus burial records and carbon isotope ratios. Importantly, this is only possible when we include the accumulation of carbonates in the crust, which permits ever-increasing carbon recycling rates through weathering and degassing. This carbonate build-up is a missing factor in models of Earth’s coupled climate, nutrient and oxygen evolution and is important for reconstructing Earth’s history and potential exoplanet biogeochemistry.</jats:p

Redox evolution and the development of oxygen minimum zones in the Eastern Mediterranean Levantine basin during the early Holocene

Oxygen Minimum Zones (OMZs) are expanding in modern oceans due to anthropogenically-driven climate and environmental change. In the Eastern Mediterranean Sea (EMS), OMZs developed in the early Holocene as a result of decreased intermediate water ventilation, increasing temperature, and increased Nile discharge and primary productivity. Here, we report benthic foraminiferal numbers (BFN) and species abundances, together with redox-sensitive trace metals (RSTM), and iron and phosphorus speciation from two sediment cores sampled at intermediate depths (1200 and 1430 m) from the SE Levantine shelf. The main aim of our study is to better understand the sequence of redox changes during sapropel S1 deposition caused by biogeochemical processes affecting the sapropel intermediate water mass. The use of benthic foraminifera indices (diversity and oxygen) together with iron speciation and RSTM (V, Mo and U) enables detailed description of the changing oxygen/redox status of the overlying water. Prior to sapropel S1 deposition at ∼10.2 ka BP, RSTM suggest that the overlying water was well oxygenated, but benthic foraminifera numbers (BFN) suggest that oxygen levels had already begun to decrease. There was then a pulse of increased export carbon from the enlarged Nile flood plume, as shown by increased BFN at the beginning of sapropel S1. Shortly after, RSTM and Fe-S systematics suggest that the water column transitioned from dysoxic to anoxic, non-sulfidic. Anoxic conditions then persisted at 1200 m depth, but RSTM and benthic foraminifera indices suggest that deeper waters at 1430 m were more likely dysoxic, until the 8.2 ka BP global cooling event. The benthic foraminifera and inorganic redox proxies then suggest a second period of anoxic, non-sulfidic conditions, with a gradual return to well ventilated waters at the end of sapropel deposition at ∼6 ka BP. There was enhanced burial of authigenic P throughout sapropel deposition, derived from the deposition and subsequent release of organic-P and iron bound-P during diagenesis. Phosphorus recycling from the sediment and in the overlying water column added reactive P to these mid-depth waters, a process which has the potential to result in a positive feedback in systems where such waters are upwelled into the photic zone. The past EMS thus represents a template which can be used to predict biogeochemical changes in settings that evolve towards anoxic, non sulfidic conditions, which may occur in some areas as modern climate and environment change causes the continued expansion of modern OMZs and hypoxic areas adjacent to modern major rivers