Petrographic carbon in ancient sediments constrains Proterozoic Era atmospheric oxygen levels.

Oxygen concentration defines the chemical structure of Earth's ecosystems while it also fuels the metabolism of aerobic organisms. As different aerobes have different oxygen requirements, the evolution of oxygen levels through time has likely impacted both environmental chemistry and the history of life. Understanding the relationship between atmospheric oxygen levels, the chemical environment, and life, however, is hampered by uncertainties in the history of oxygen levels. We report over 5,700 Raman analyses of organic matter from nine geological formations spanning in time from 742 to 1,729 Ma. We find that organic matter was effectively oxidized during weathering and little was recycled into marine sediments. Indeed, during this time interval, organic matter was as efficiently oxidized during weathering as it is now. From these observations, we constrain minimum atmospheric oxygen levels to between 2 to 24% of present levels from the late Paleoproterozoic Era into the Neoproterozoic Era. Indeed, our results reveal that eukaryote evolution, including early animal evolution, was not likely hindered by oxygen through this time interval. Our results also show that due to efficient organic recycling during weathering, carbon cycle dynamics can be assessed directly from the sediment carbon record.

A Mesoproterozoic iron formation.

We describe a 1,400 million-year old (Ma) iron formation (IF) from the Xiamaling Formation of the North China Craton. We estimate this IF to have contained at least 520 gigatons of authigenic Fe, comparable in size to many IFs of the Paleoproterozoic Era (2,500-1,600 Ma). Therefore, substantial IFs formed in the time window between 1,800 and 800 Ma, where they are generally believed to have been absent. The Xiamaling IF is of exceptionally low thermal maturity, allowing the preservation of organic biomarkers and an unprecedented view of iron-cycle dynamics during IF emplacement. We identify tetramethyl aryl isoprenoid (TMAI) biomarkers linked to anoxygenic photosynthetic bacteria and thus phototrophic Fe oxidation. Although we cannot rule out other pathways of Fe oxidation, iron and organic matter likely deposited to the sediment in a ratio similar to that expected for anoxygenic photosynthesis. Fe reduction was likely a dominant and efficient pathway of organic matter mineralization, as indicated by organic matter maturation by Rock Eval pyrolysis combined with carbon isotope analyses: Indeed, Fe reduction was seemingly as efficient as oxic respiration. Overall, this Mesoproterozoic-aged IF shows many similarities to Archean-aged (>2,500 Ma) banded IFs (BIFs), but with an exceptional state of preservation, allowing an unprecedented exploration of Fe-cycle dynamics in IF deposition.

Sufficient oxygen for animal respiration 1,400 million years ago.

The Mesoproterozoic Eon [1,600-1,000 million years ago (Ma)] is emerging as a key interval in Earth history, with a unique geochemical history that might have influenced the course of biological evolution on Earth. Indeed, although this time interval is rather poorly understood, recent chromium isotope results suggest that atmospheric oxygen levels were <0.1% of present levels, sufficiently low to have inhibited the evolution of animal life. In contrast, using a different approach, we explore the distribution and enrichments of redox-sensitive trace metals in the 1,400 Ma sediments of Unit 3 of the Xiamaling Formation, North China Block. Patterns of trace metal enrichments reveal oxygenated bottom waters during deposition of the sediments, and biomarker results demonstrate the presence of green sulfur bacteria in the water column. Thus, we document an ancient oxygen minimum zone. We develop a simple, yet comprehensive, model of marine carbon-oxygen cycle dynamics to show that our geochemical results are consistent with atmospheric oxygen levels >4% of present-day levels. Therefore, in contrast to previous suggestions, we show that there was sufficient oxygen to fuel animal respiration long before the evolution of animals themselves.

Orbital forcing of climate 1.4 billion years ago.

Fluctuating climate is a hallmark of Earth. As one transcends deep into Earth time, however, both the evidence for and the causes of climate change become difficult to establish. We report geochemical and sedimentological evidence for repeated, short-term climate fluctuations from the exceptionally well-preserved ∼1.4-billion-year-old Xiamaling Formation of the North China Craton. We observe two patterns of climate fluctuations: On long time scales, over what amounts to tens of millions of years, sediments of the Xiamaling Formation record changes in geochemistry consistent with long-term changes in the location of the Xiamaling relative to the position of the Intertropical Convergence Zone. On shorter time scales, and within a precisely calibrated stratigraphic framework, cyclicity in sediment geochemical dynamics is consistent with orbital control. In particular, sediment geochemical fluctuations reflect what appear to be orbitally forced changes in wind patterns and ocean circulation as they influenced rates of organic carbon flux, trace metal accumulation, and the source of detrital particles to the sediment.

No climate paradox under the faint early Sun.

Environmental niches in which life first emerged and later evolved on the Earth have undergone dramatic changes in response to evolving tectonic/geochemical cycles and to biologic interventions, as well as increases in the Sun's luminosity of about 25 to 30 per cent over the Earth's history. It has been inferred that the greenhouse effect of atmospheric CO(2) and/or CH(4) compensated for the lower solar luminosity and dictated an Archaean climate in which liquid water was stable in the hydrosphere. Here we demonstrate, however, that the mineralogy of Archaean sediments, particularly the ubiquitous presence of mixed-valence Fe(II-III) oxides (magnetite) in banded iron formations is inconsistent with such high concentrations of greenhouse gases and the metabolic constraints of extant methanogens. Prompted by this, and the absence of geologic evidence for very high greenhouse-gas concentrations, we hypothesize that a lower albedo on the Earth, owing to considerably less continental area and to the lack of biologically induced cloud condensation nuclei, made an important contribution to moderating surface temperature in the Archaean eon. Our model calculations suggest that the lower albedo of the early Earth provided environmental conditions above the freezing point of water, thus alleviating the need for extreme greenhouse-gas concentrations to satisfy the faint early Sun paradox.

Towards a quantitative understanding of the late Neoproterozoic carbon cycle.

The cycles of carbon and oxygen at the Earth surface are intimately linked, where the burial of organic carbon into sediments represents a source of oxygen to the surface environment. This coupling is typically quantified through the isotope records of organic and inorganic carbon. Yet, the late Neoproterozoic Eon, the time when animals first evolved, experienced wild isotope fluctuations which do not conform to our normal understanding of the carbon cycle and carbon-oxygen coupling. We interpret these fluctuations with a new carbon cycle model and demonstrate that all of the main features of the carbonate and organic carbon isotope record can be explained by the release of methane hydrates from an anoxic dissolved organic carbon-rich ocean into an atmosphere containing oxygen levels considerably less than today.

Constructing a model including the cryptic sulfur cycle in Chesapeake Bay requires judicious choices for key processes and parameters.

A new biogeochemical model for Chesapeake Bay has been developed by merging two published models - the ECB model of Da et al. (2018) that has been calibrated for the Bay but only simulates nitrogen, carbon and oxygen and the BioRedoxCNPS model of al Azhar et al. (2014) and Hantsoo et al. (2018) that includes cryptic sulfur cycling. Comparison between these models shows that judicious choices are required for key processes and parameters. This manuscript documents the sources of differences between the two published models in order to select the most realistic configuration for our new model.•This study focuses on three sets of differences-processes only included in ECB (burial and dissolved organic matter), processes only included in BioRedoxCNPS (explicit dynamics for hydrogen sulfide, sulfate and nitrite, light attenuation that does not include CDOM or sediments), and differences in parameters common to the two codes.•Sensitivity studies that highlight particular choices (absorption by dissolved organic matter, nitrification rates, stoichiometric ratios) are also shown.•The new model includes sulfur cycling and has comparable skill in predicting oxygen as ECB, but also has improved simulation of nitrogen species compared with both original codes.

Widespread seafloor anoxia during generation of the Ediacaran Shuram carbon isotope excursion.

Reconstructing the oxygenation history of Earth's oceans during the Ediacaran period (635 to 539 million years ago) has been challenging, and this has led to a polarizing debate about the environmental conditions that played host to the rise of animals. One focal point of this debate is the largest negative inorganic C-isotope excursion recognized in the geologic record, the Shuram excursion, and whether this relic tracks the global-scale oxygenation of Earth's deep oceans. To help inform this debate, we conducted a detailed geochemical investigation of two siliciclastic-dominated successions from Oman deposited through the Shuram Formation. Iron speciation data from both successions indicate formation beneath an intermittently anoxic local water column. Authigenic thallium (Tl) isotopic compositions leached from both successions are indistinguishable from bulk upper continental crust (ε205 TlA ≈ -2) and, by analogy with modern equivalents, likely representative of the ancient seawater ε205 Tl value. A crustal seawater ε205 Tl value requires limited manganese (Mn) oxide burial on the ancient seafloor, and by extension widely distributed anoxic sediment porewaters. This inference is supported by muted redox-sensitive element enrichments (V, Mo, and U) and consistent with some combination of widespread (a) bottom water anoxia and (b) high sedimentary organic matter loading. Contrary to a classical hypothesis, our interpretations place the Shuram excursion, and any coeval animal evolutionary events, in a predominantly anoxic global ocean.

Minimum levels of atmospheric oxygen from fossil tree roots imply new plant-oxygen feedback.

The appearance and subsequent evolution of land plants is among the most important events in the earth system. Plant resulted in a change of earth surface albedo and the hydrological cycle, as well as increased rock weatherability thereby causing a persistent change in atmospheric CO2 and O2 . Land plants are, however, themselves dependent on O2 for respiration and long-term survival, something not considered in current geochemical models. In this perspective, we highlight two aspects of land plants' dependency on O2 relevant for the geobiological community: (a) fossil root systems can be used as a proxy for minimum levels of past atmospheric O2 consistent with a given fossil root depth; and (b) by identifying a positive feedback mechanism involving atmospheric O2 , root intensity, terrestrial primary production and organic carbon burial. As an example, we consider archaeopterid fossil root systems, resembling those of modern mature conifers. Our soil-plant model suggest that atmospheric O2 with 1 SD probably reached pressures of 18.2 ± 1.9 kPa and 16.8 ± 2.1 kPa by the Middle and Late Devonian, respectively, that is 86 ± 9% and 79 ± 10% of the present-day 21.2 kPa.

Cold spells in the Nordic Seas during the early Eocene Greenhouse.

The early Eocene (c. 56 - 48 million years ago) experienced some of the highest global temperatures in Earth's history since the Mesozoic, with no polar ice. Reports of contradictory ice-rafted erratics and cold water glendonites in the higher latitudes have been largely dismissed due to ambiguity of the significance of these purported cold-climate indicators. Here we apply clumped isotope paleothermometry to a traditionally qualitative abiotic proxy, glendonite calcite, to generate quantitative temperature estimates for northern mid-latitude bottom waters. Our data show that the glendonites of the Danish Basin formed in waters below 5 °C, at water depths of <300 m. Such near-freezing temperatures have not previously been reconstructed from proxy data for anywhere on the early Eocene Earth, and these data therefore suggest that regionalised cool episodes punctuated the background warmth of the early Eocene, likely linked to eruptive phases of the North Atlantic Igneous Province.

Paleoenvironmental proxies and what the Xiamaling Formation tells us about the mid-Proterozoic ocean.

The Mesoproterozoic Era (1,600-1,000 million years ago, Ma) geochemical record is sparse, but, nevertheless, critical in untangling relationships between the evolution of eukaryotic ecosystems and the evolution of Earth-surface chemistry. The ca. 1,400 Ma Xiamaling Formation has experienced only very low-grade thermal maturity and has emerged as a promising geochemical archive informing on the interplay between climate, ecosystem organization, and the chemistry of the atmosphere and oceans. Indeed, the geochemical record of portions of the Xiamaling Formation has been used to place minimum constraints on concentrations of atmospheric oxygen as well as possible influences of climate and climate change on water chemistry and sedimentation dynamics. A recent study has argued, however, that some portions of the Xiamaling Formation deposited in a highly restricted environment with only limited value as a geochemical archive. In this contribution, we fully explore these arguments as well as the underlying assumptions surrounding the use of many proxies used for paleo-environmental reconstructions. In doing so, we pay particular attention to deep-water oxygen-minimum zone environments and show that these generate unique geochemical signals that have been underappreciated. These signals, however, are compatible with the geochemical record of those parts of the Xiamaling Formation interpreted as most restricted. Overall, we conclude that the Xiamaling Formation was most likely open to the global ocean throughout its depositional history. More broadly, we show that proper paleo-environmental reconstructions require an understanding of the biogeochemical signals generated in all relevant modern analogue depositional environments. We also evaluate new data on the δ98 Mo of Xiamaling Formation shales, revealing possible unknown pathways of molybdenum sequestration into sediments and concluding, finally, that seawater at that time likely had a δ98 Mo value of about 1.1‰.

A model-based insight into the coupling of nitrogen and sulfur cycles in a coastal upwelling system.

The biogeochemical cycling in oxygen-minimum zones (OMZs) is dominated by the interactions of microbial nitrogen transformations and, as recently observed in the Chilean upwelling system, also through the energetically less favorable remineralization of sulfate reduction. The latter process is masked, however, by rapid sulfide oxidation, most likely through nitrate reduction. Thus, the cryptic sulfur cycle links with the nitrogen cycle in OMZ settings. Here, we model the physical-chemical water column structure and the observed process rates as driven by formation and sinking of organic detritus, to quantify the nitrogen and sulfur cycles in the Chilean OMZ. A new biogeochemical submodule was developed and coupled to the Regional Ocean Model System (ROMS). The model results generally agree with the observed distribution of reactive species and the measured process rates. Modeled heterotrophic nitrate reduction and sulfate reduction are responsible for 47% and 36%, respectively, of organic remineralization in a 150 m deep zone below mixed layer. Anammox contributes to 61% of the fixed nitrogen lost to N2 gas, while the rest of the loss is through canonical denitrification as a combination of organic matter oxidation by nitrite reduction and sulfide-driven denitrification. Mineralization coupled to heterotrophic nitrate reduction supplies ∼48% of the ammonium required by anammox. Due to active sulfate reduction, model results suggest that sulfide-driven denitrification contributes to 36% of the nitrogen loss as N2 gas. Our model results highlight the importance of considering the coupled nitrogen and sulfur cycle in examining open-ocean anoxic processes under present, past, and future conditions.

Ocean productivity before about 1.9 Gyr ago limited by phosphorus adsorption onto iron oxides.

After the evolution of oxygen-producing cyanobacteria at some time before 2.7 billion years ago, oxygen production on Earth is thought to have depended on the availability of nutrients in the oceans, such as phosphorus (in the form of orthophosphate). In the modern oceans, a significant removal pathway for phosphorus occurs by way of its adsorption onto iron oxide deposits. Such deposits were thought to be more abundant in the past when, under low sulphate conditions, the formation of large amounts of iron oxides resulted in the deposition of banded iron formations. Under these circumstances, phosphorus removal by iron oxide adsorption could have been enhanced. Here we analyse the phosphorus and iron content of banded iron formations to show that ocean orthophosphate concentrations from 3.2 to 1.9 billion years ago (during the Archaean and early Proterozoic eras) were probably only approximately 10-25% of present-day concentrations. We suggest therefore that low phosphorus availability should have significantly reduced rates of photosynthesis and carbon burial, thereby reducing the long-term oxygen production on the early Earth--as previously speculated--and contributing to the low concentrations of atmospheric oxygen during the late Archaean and early Proterozoic.