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Oxygen and carbon are 2 elements critical for life on Earth. Earth's most dramatic oxygenation events and carbon isotope excursions (CIE) occurred during the Proterozoic, including the Paleoproterozoic Great Oxidation Event and the associated Lomagundi CIE, the Neoproterozoic Oxygenation event, and the Shuram negative CIE during the late Neoproterozoic. A specific pattern of a long-lived positive CIE followed by a negative CIE is observed in association with oxygenation events during the Paleo- and Neo-proterozoic. We present results from a carbon cycle model designed to couple the surface and interior cycling of carbon that reproduce this pattern. The model assumes organic carbon resides in the mantle longer than carbonate, leading to systematic temporal variations in the δ13C of volcanic CO2 emissions. When the model is perturbed by periods of enhanced continental weathering, increased amounts of carbonate and organic carbon are buried. Increased deposition of organic carbon allows O2 accumulation, while positive CIEs are driven by rapid release of subducted carbonate-derived CO2 at arcs. The subsequent negative CIEs are driven by the delayed release of organic C-derived CO2 at ocean islands. Our model reproduces the sequences observed in the Paleo- and Neo-proterozoic, that is oxygenation accompanied by a positive CIE followed by a negative CIE. Periods of enhanced weathering correspond temporally to supercontinent break-up, suggesting an important connection between global tectonics and the evolution of oxygen and carbon on Earth.

The authors acknowledge funding support from the NSF FESD and Earth-Life Transitions programs (T.L.), the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate (T.L.), the key project of the Natural Science Foundation of China (C.-F.C.) (No. 41730424), and the program of China Scholarships Council (Y.C.) (No. 201504910582). Nitrogen and carbon isotope analyses were funded by startup funds from Virginia Tech to B.C.G. The Ediacaran-Cambrian transition is characterized by the evolution of complex eukaryotes and rapid diversification of metazoans. However, linkages between environmental triggers and evolutionary patterns remain unclear. Here, we present high-resolution records of carbon and nitrogen isotopic data (δ13C, δ15N) for a drill core extending from the early Ediacaran Doushantuo Formation to the early Cambrian Jiumenchong Formation, located on the slope of the Yangtze Block. Our data show that sedimentary bulk nitrogen isotope values (δ15Nbulk) decrease progressively from the early Ediacaran to the early Cambrian, broadly concurrent with nitrogen isotope data from other sections throughout the Yangtze Block. During the early Ediacaran, however, δ15Nbulk values from our study are higher (maximum 11.2‰) compared to those from more restricted coeval sections, suggesting a higher degree of denitrification in our slope section. The early Ediacaran δ15Nbulk data from the Yangtze Block may thus provide indirect evidence for an upwelling system that led to a shallower redoxcline in slope environments of the Upper Yangtze region. Widespread light δ15Nbulk values from the early Cambrian (minimum −7.5‰) paired with excess silicate-bound nitrogen throughout much of the Yangtze Block are most parsimoniously interpreted as non-quantitative assimilation of ammonium (NH4+) with relatively high concentrations of NH4+ accumulating in the deep basin. Overall, the spatial and temporal trends in nitrogen cycling across the Yangtze Block suggest that fixed nitrogen was more bioavailable in the Ediacaran-Cambrian Yangtze Basin compared to previously studied Mesoproterozoic sections, although nitrogen speciation in the photic zone may have varied with time. Environmental factors such as oxygen levels and nitrogen bioavailability may have shaped the evolutionary trajectory of life on the Yangtze Block and potentially elsewhere across the Ediacaran-Cambrian transition. Postprint

The long history of life on Earth has unfolded as a cause-and-effect relationship with the evolving amount of oxygen (O2) in the oceans and atmosphere. Oxygen deficiency characterized our planet's first 2 billion years, yet evidence for biological O2 production and local enrichments in the surface ocean appear long before the first accumulations of O2 in the atmosphere roughly 2.4 to 2.3 billion years ago. Much has been written about this fundamental transition and the related balance between biological O2 production and sinks coupled to deep Earth processes that could buffer against the accumulation of biogenic O2. However, the relationship between complex life (eukaryotes, including animals) and later oxygenation is less clear. Some data suggest O2 was higher but still mostly low for another billion and a half years before increasing again around 800 million years ago, potentially setting a challenging course for complex life during its initial development and ecological expansion. The apparent rise in O2 around 800 million years ago is coincident with major developments in complex life. Multiple geochemical and paleontological records point to a major biogeochemical transition at that time, but whether rising and still dynamic biospheric oxygen triggered or merely followed from innovations in eukaryotic ecology, including the emergence of animals, is still debated. This paper focuses on the geochemical records of Earth's middle history, roughly 1.8 to 0.5 billion years ago, as a backdrop for exploring possible cause-and-effect relationships with biological evolution and the primary controls that may have set its pace, including solid Earth/tectonic processes, nutrient limitation, and their possible linkages. A richer mechanistic understanding of the interplay between coevolving life and Earth surface environments can provide a template for understanding and remotely searching for sustained habitability and even life on distant exoplanets.

Agreement is often in short supply within the community of researchers asking questions about Earth’s earliest history. One exception, however, is the near-consensus view that oxygen (O2) was mostly absent from the atmosphere and oceans before about 2.4 to 2.3 Ga—the so-called Great Oxidation Event (GOE). It is also widely accepted that the cycles for iron (Fe) and manganese (Mn) in the early oceans are essential themes in our still nascent understanding of the earliest chapters of life’s coevolution with its host environments at Earth’s surface. Yet, despite this community accord over the importance of Fe and Mn, we still know very little about the principal pathways of oxidation for these metals and the implications for early O2. There are three fundamental possibilities: 1) biologically mediated reactions in the presence of even small amounts of O2, 2) anoxygenic photosynthesis with Fe(II) or Mn(II) as electron donors yielding oxidized forms of those metals as by-products, and 3) sunlight-catalyzed photochemical oxidation by ultraviolet (UV) radiation without contributions from life or O2. The latter is perhaps the least appreciated among these three, even though abiotic reactions likely had elevated importance in early oceans as life was finding its first footholds. Liu et al. (1) refocus attention on the photochemical possibility by exploring the details of photooxidation of Mn(II) in the mineral rhodochrosite (MnCO3; Fig. 1) in a series of elegant experiments and by examining the implications of their results in terms of oceanic and atmospheric chemistry during the Archean Eon (4.0 to 2.5 Ga). Fig. 1. Gem-quality crystalline rhodochrosite (MnCO3)—an eye-catching version of the far more mundane small mineral grains that may have settled through the early oceans and accumulated on the seafloor. As the grains settled and accumulated, UV radiation may have oxidized the … [↵][1]1To whom correspondence may be addressed. Email: timothy.lyons{at}ucr.edu. [1]: #xref-corresp-1-1

Animal life on Earth is generally accepted to have risen during a period of increasingly well-oxygenated conditions, but direct evidence for that relationship has previously eluded scientists. This gap reflects both the enigmatic nature of the early animal fossil record and the coarse temporal resolution of Precambrian environmental change. Here, we combine paleontological data from the Ediacara Biota, the earliest fossil animals, with geochemical evidence for fluctuating redox conditions. Using morphological and ecological novelties that broadly reflect oxygen demand, we show that the appearance of abundant oxygen-demanding organisms within the Ediacara Biota corresponds with a period of elevated global oxygen concentrations. This correlation suggests that a putative rise in oxygen levels may have provided the necessary environments for the diversification of complex body plans and energetically demanding ecologies. The potential loss of organisms with relatively high oxygen requirements in the latest Ediacaran coupled with an apparent return to low oxygen concentrations further supports the availability of oxygen as a control on early animal evolution. While the advent of animal life was probably the product of a variety of factors, the recognition of a possible connection between changing environmental conditions and the diversification of animal morphologies suggests that the availability of oxygen played a significant role in the evolution of animals on Earth.

The Early Paleozoic (Cambrian-Devonian) witnessed a series of significant environmental changes including ocean-atmosphere oxygenation and progressive cooling due to a decline in CO2 levels. These changes were temporally associated with major radiations and extinctions of marine fauna and the establishment of complex ecosystem structure. Specifically, it is thought that an increase in shallow-water O2 concentrations accompanied rapid diversification and colonization of marine invertebrates in the Cambrian and Ordovician, and expanded oceanic anoxia was linked with several extinction events. Temporal coincidence does not, however, imply causation, and many questions related to these relationships remain unanswered. Overall, a better understanding of the coevolution of animals and marine environments is expected through detailed exploration of their wide-ranging interactions during the Early Paleozoic. In this contribution, we review these topics in detail and thereby provide context for the contributions to this special issue.

The trace element content of pyrite is a recently developed proxy for metal abundance in paleo-oceans. Previous studies have shown that the results broadly match those of whole rock studies through geologic time. However, no detailed study has evaluated the more traditional proxies for ocean chemistry for comparison to pyrite trace element data from the same samples. In this study we compare pyrite trace element data from 14 samples from the Wuhe section of the Ediacaran-age Doushantuo Formation, south China, measured by laser ablation inductively coupled plasma mass spectrometry with new and existing whole rock trace element concentrations; total organic carbon; Fe mineral speciation; S isotope ratios; and pyrite textural relationships. This approach allows for comparison of data for individual trace elements within the broader environmental context defined by the other chemical parameters. The results for discrete pyrite analyses show that several chalcophile and siderophile elements (Ag, Sb, Se, Pb, Cd, Te, Bi, Mo, Ni, and Au) vary among the samples with patterns that mirror those of the independent whole rock data. A comparison with existing databases for sedimentary and hydrothermal pyrite allows us to discriminate between signatures of changing ocean conditions and those of known hydrothermal sources. In the case of the Wuhe samples, the observed patterns for trace element variation point to primary marine controls rather than higher temperature processes. Specifically, our new data are consistent with previous arguments for pulses of redox sensitive trace elements interpreted to be due to marine oxygenation against a backdrop of mostly O2-poor conditions in the Ediacaran ocean—with important implications for the availability of bioessential elements. The agreement between the pyrite and whole rock data supports the use of trace element content of pyrite as a tracer of ocean chemistry in ways that complement existing approaches, while also opening additional windows of opportunity. For example, unlike the potential vulnerability of whole rock data to secondary alteration, the pyrite record may survive greenschist facies metamorphism. Furthermore, early-formed pyrite can be identified through textural relationships as a proxy of primary marine chemistry even in the presence of hydrothermal overprints on whole rock chemistry via secondary fluids. Finally, pyrite analyses may allow for the possibility of more quantitative interpretations of the ancient ocean once the elemental partitioning between the mineral and host fluids are better constrained. Collectively, these advances can greatly increase the number of basins that may be investigated for early ocean chemistry, especially those of Precambrian age.

The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene–Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene–Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic–anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.

It is often assumed that rising environmental oxygen concentrations played a significant role in the timing of the first appearance of animals and the trajectory of their early proliferation and diversification. The inherent large size and complexity of animals come with large energy requirements — levels of energy that can best, if not only, be acquired through aerobic respiration. There is also abundant geochemical evidence for an increase in ocean–atmosphere O2 concentrations in temporal proximity with the emergence of the group. To adequately test this hypothesis, however, a thorough understanding of the history of environmental oxygenation in the time between the first appearance of eukaryotes and the eventual appearance of animals is necessary. In this review, we summarize the evidence for the prevailing long-term conditions of the Proterozoic Eon prior to the emergence of Metazoa and go on to highlight multiple independent geochemical proxy records that suggest at least two transient oxygenation events — at ca. 1.4 and ca. 1.1 billion years ago (Ga) — during this time. These emerging datasets open the door to an important possibility: while prevailing conditions during much of this time would likely have presented challenges for early animals, there were intervals when oxygenated conditions were more widespread and could have favored yet undetermined advances in eukaryotic innovation, including critical early steps toward animal evolution.

Despite a surge of recent work, the evolution of mid-Proterozoic oceanic-atmospheric redox remains heavily debated. Constraining the dynamics of Proterozoic redox evolution is essential to determine the role, if any, that anoxia played in protracting the development of eukaryotic diversity. We present a multiproxy suite of high-resolution geochemical measurements from a drill core capturing the ~1.4 Ga Xiamaling Formation, North China Craton. Specifically, we analyzed major and trace element concentrations, sulfur and molybdenum isotopes, and iron speciation not only to better understand the local redox conditions but also to establish how relevant our data are to understanding the contemporaneous global ocean. Our results suggest that throughout deposition of the Xiamaling Formation, the basin experienced varying degrees of isolation from the global ocean. During deposition of the lower organic-rich shales (130-85 m depth), the basin was extremely restricted, and the reservoirs of sulfate and trace metals were drawn down almost completely. Above a depth of 85 m, shales were deposited in dominantly euxinic waters that more closely resembled a marine system and thus potentially bear signatures of coeval seawater. In the most highly enriched sample from this upper interval, the concentration of molybdenum is 51 ppm with a δ98 Mo value of +1.7‰. Concentrations of Mo and other redox-sensitive elements in our samples are consistent with a deep ocean that was largely anoxic on a global scale. Our maximum δ98 Mo value, in contrast, is high compared to published mid-Proterozoic data. This high value raises the possibility that the Earth's surface environments were transiently more oxygenated at ~1.4 Ga compared to preceding or postdating times. More broadly, this study demonstrates the importance of integrating all available data when attempting to reconstruct surface O2 dynamics based on rocks of any age.

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 were0.1% 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 levels4% 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.