Lithium isotopic constraints on the evolution of continental clay mineral factory and marine oxygenation in the earliest Paleozoic Era.

The evolution of oxygen cycles on Earth's surface has been regulated by the balance between molecular oxygen production and consumption. The Neoproterozoic-Paleozoic transition likely marks the second rise in atmospheric and oceanic oxygen levels, widely attributed to enhanced burial of organic carbon. However, it remains disputed how marine organic carbon production and burial respond to global environmental changes and whether these feedbacks trigger global oxygenation during this interval. Here, we report a large lithium isotopic and elemental dataset from marine mudstones spanning the upper Neoproterozoic to middle Cambrian [~660 million years ago (Ma) to 500 Ma]. These data indicate a dramatic increase in continental clay formation after ~525 Ma, likely linked to secular changes in global climate and compositions of the continental crust. Using a global biogeochemical model, we suggest that intensified continental weathering and clay delivery to the oceans could have notably increased the burial efficiency of organic carbon and facilitated greater oxygen accumulation in the earliest Paleozoic oceans.

Enhanced weathering in the US Corn Belt delivers carbon removal with agronomic benefits.

Terrestrial enhanced weathering (EW) of silicate rocks, such as crushed basalt, on farmlands is a promising scalable atmospheric carbon dioxide removal (CDR) strategy that urgently requires performance assessment with commercial farming practices. We report findings from a large-scale replicated EW field trial across a typical maize-soybean rotation on an experimental farm in the heart of the United Sates Corn Belt over 4 y (2016 to 2020). We show an average combined loss of major cations (Ca2+ and Mg2+) from crushed basalt applied each fall over 4 y (50 t ha-1 y-1) gave a conservative time-integrated cumulative CDR potential of 10.5 ± 3.8 t CO2 ha-1. Maize and soybean yields increased significantly (P < 0.05) by 12 to 16% with EW following improved soil fertility, decreased soil acidification, and upregulation of root nutrient transport genes. Yield enhancements with EW were achieved with significantly (P < 0.05) increased key micro- and macronutrient concentrations (including potassium, magnesium, manganese, phosphorus, and zinc), thus improving or maintaining crop nutritional status. We observed no significant increase in the content of trace metals in grains of maize or soybean or soil exchangeable pools relative to controls. Our findings suggest that widespread adoption of EW across farming sectors has the potential to contribute significantly to net-zero greenhouse gas emissions goals while simultaneously improving food and soil security.

Initial Validation of a Soil-Based Mass-Balance Approach for Empirical Monitoring of Enhanced Rock Weathering Rates.

Enhanced rock weathering (ERW) is a promising scalable and cost-effective carbon dioxide removal (CDR) strategy with significant environmental and agronomic co-benefits. A major barrier to large-scale implementation of ERW is a robust monitoring, reporting, and verification (MRV) framework. To successfully quantify the amount of carbon dioxide removed by ERW, MRV must be accurate, precise, and cost-effective. Here, we outline a mass-balance-based method in which analysis of the chemical composition of soil samples is used to track in situ silicate rock weathering. We show that signal-to-noise issues of in situ soil analysis can be mitigated by using isotope-dilution mass spectrometry to reduce analytical error. We implement a proof-of-concept experiment demonstrating the method in controlled mesocosms. In our experiment, a basalt rock feedstock is added to soil columns containing the cereal crop Sorghum bicolor at a rate equivalent to 50 t ha-1. Using our approach, we calculate rock weathering corresponding to an average initial CDR value of 1.44 ± 0.27 tCO2eq ha-1 from our experiments after 235 days, within error of an independent estimate calculated using conventional elemental budgeting of reaction products. Our method provides a robust time-integrated estimate of initial CDR, to feed into models that track and validate large-scale carbon removal through ERW.

Techno-Economic and Life Cycle Assessment of Enhanced Rock Weathering: A Case Study from the Midwestern United States.

Enhanced rock weathering (ERW) is a carbon dioxide removal (CDR) strategy for combating climate change. The CDR potentials of ERW have been assessed at the process and national/global levels, but the environmental and economic implications of ERW have not been fully quantified for U.S. applications with real-world supply chain considerations. This study develops an optimization-based, integrated life cycle assessment and techno-economic analysis framework for ERW, which is demonstrated by a case study applying mining waste to croplands in the Midwestern U.S. The case study explores maximum transportation distances for intermodal transportation at varied mineral CDR yields and costs, informing supply chain design for economically viable ERW. ERW costs (US$45 to 472/tonne of net CO2e captured) and cradle-to-farm gate GHG emissions (41 to 359 kg CO2e/tonne of CO2e captured) are estimated based on a range of CDR yields and by transportation distances to and from two Midwest port destinations: Chicago and Duluth. Our sensitivity analysis identifies CDR yields, and transportation modes and distances as driving factors for result variations. Our study reveals the importance of ERW supply chain design and provides an example of U.S. CDR implementation. Our framework and findings can be applied to other regional ERW projects.

Technical comment on "Reexamination of 2.5-Ga 'whiff' of oxygen interval points to anoxic ocean before GOE".

Many lines of inorganic geochemical evidence suggest transient "whiffs" of environmental oxygenation before the Great Oxidation Event (GOE). Slotznick et al. assert that analyses of paleoredox proxies in the Mount McRae Shale, Western Australia, were misinterpreted and hence that environmental O2 levels were persistently negligible before the GOE. We find these arguments logically flawed and factually incomplete.

New estimates of the storage permanence and ocean co-benefits of enhanced rock weathering.

Avoiding many of the most severe consequences of anthropogenic climate change in the coming century will very likely require the development of "negative emissions technologies"-practices that lead to net carbon dioxide removal (CDR) from Earth's atmosphere. However, feedbacks within the carbon cycle place intrinsic limits on the long-term impact of CDR on atmospheric CO2 that are likely to vary across CDR technologies in ways that are poorly constrained. Here, we use an ensemble of Earth system models to provide new insights into the efficiency of CDR through enhanced rock weathering (ERW) by explicitly quantifying long-term storage of carbon in the ocean during ERW relative to an equivalent modulated emissions scenario. We find that although the backflux of CO2 to the atmosphere in the face of CDR is in all cases significant and time-varying, even for direct removal and underground storage, the leakage of initially captured carbon associated with ERW is well below that currently assumed. In addition, net alkalinity addition to the surface ocean from ERW leads to significant increases in seawater carbonate mineral saturation state relative to an equivalent emissions trajectory, a co-benefit for calcifying marine organisms. These results suggest that potential carbon leakage from the oceans during ERW is a small component of the overall ERW life cycle and that it can be rigorously quantified and incorporated into technoeconomic assessments of ERW at scale.

Revisiting marine redox conditions during the Ediacaran Shuram carbon isotope excursion.

The Neoproterozoic carbonate record contains multiple carbon isotope anomalies, which are the subject of intense debate. The largest of these anomalies, the Shuram excursion (SE), occurred in the mid-Ediacaran (~574-567 Ma). Accurately reconstructing marine redox landscape is a clear path toward making sense of the mechanism that drives this δ13 C anomaly. Here, we report new uranium isotopic data from the shallow-marine carbonates of the Wonoka Formation, Flinders Ranges, South Australia, where the SE is well preserved. Our data indicate that the δ238 U trend during the SE is highly reproducible across globally disparate sections from different depositional settings. Previously, it was proposed that the positive shift of δ238 U values during the SE suggests an extensive, near-modern level of marine oxygenation. However, recent publications suggest that the fractionation of uranium isotopes in ferruginous and anoxic conditions is comparable, opening up the possibility of non-unique interpretations of the carbonate uranium isotopic record. Here, we build on this idea by investigating the SE in conjunction with additional geochemical proxies. Using a revised uranium isotope mass balance model and an inverse stochastic carbon cycle model, we reevaluate models for δ13 C and δ238 U trends during the SE. We suggest that global seawater δ238 U values during the SE could be explained by an expansion of ferruginous conditions and do not require a near-modern level of oxygenation during the mid-Ediacaran.

The evolution of the marine carbonate factory.

Calcium carbonate formation is the primary pathway by which carbon is returned from the ocean-atmosphere system to the solid Earth1,2. The removal of dissolved inorganic carbon from seawater by precipitation of carbonate minerals-the marine carbonate factory-plays a critical role in shaping marine biogeochemical cycling1,2. A paucity of empirical constraints has led to widely divergent views on how the marine carbonate factory has changed over time3-5. Here we use geochemical insights from stable strontium isotopes to provide a new perspective on the evolution of the marine carbonate factory and carbonate mineral saturation states. Although the production of carbonates in the surface ocean and in shallow seafloor settings have been widely considered the predominant carbonate sinks for most of the history of the Earth6, we propose that alternative processes-such as porewater production of authigenic carbonates-may have represented a major carbonate sink throughout the Precambrian. Our results also suggest that the rise of the skeletal carbonate factory decreased seawater carbonate saturation states.

A sedimentary record of the evolution of the global marine phosphorus cycle.

Phosphorus (P) is typically considered to be the ultimate limiting nutrient for Earth's biosphere on geologic timescales. As P is monoisotopic, its sedimentary enrichment can provide some insights into how the marine P cycle has changed through time. A previous compilation of shale P enrichments argued for a significant change in P cycling during the Ediacaran Period (635-541 Ma). Here, using an updated P compilation-with more than twice the number of samples-we bolster the case that there was a significant transition in P cycling moving from the Precambrian into the Phanerozoic. However, our analysis suggests this state change may have occurred earlier than previously suggested. Specifically in the updated database, there is evidence for a transition ~35 million years before the onset of the Sturtian Snowball Earth glaciation in the Visingsö Group, potentially divorcing the climatic upheavals of the Neoproterozoic from changes in the Earth's P cycle. We attribute the transition in Earth's sedimentary P record to the onset of a more modern-like Earth system state characterized by less reducing marine conditions, higher marine P concentrations, and a greater predominance of eukaryotic organisms encompassing both primary producers and consumers. This view is consistent with organic biomarker evidence for a significant eukaryotic contribution to the preserved sedimentary organic matter in this succession and other contemporaneous Tonian marine sedimentary rocks. However, we stress that, even with an expanded dataset, we are likely far from pinpointing exactly when this transition occurred or whether Earth's history is characterized by a single or multiple transitions in the P cycle.

The deposition and significance of an Ediacaran non-glacial iron formation.

Most Neoproterozoic iron formations (NIF) are closely associated with global or near-global "Snowball Earth" glaciations. Increasingly, however, studies indicate that some NIFs show no robust evidence of glacial association. Many aspects of non-glacial NIF genesis, including the paleo-environmental setting, Fe(II) source, and oxidation mechanisms, are poorly understood. Here, we present a detailed case study of the Jiapigou NIF, a major non-glacial NIF within a Neoproterozoic volcano-sedimentary sequence in North Qilian, northwestern China. New U-Pb geochronological data place the depositional age of the Jiapigou NIF at ~600 Ma. Petrographic and geochemical evidence supports its identification as a primary chemical sediment with significant detrital input. Major and trace element concentrations, REE + Y systematics, and εNd (t) values indicate that iron was sourced from mixed seawater and hydrothermal fluids. Iron isotopic values (δ56 Fe = -0.04‰-1.43‰) are indicative of partial oxidation of an Fe(II) reservoir. We infer that the Jiapigou NIF was deposited in a redox stratified water column, where hydrothermally sourced Fe(II)-rich fluids underwent oxidation under suboxic conditions. Lastly, the Jiapigou NIF has strong phosphorous enrichments, which in other iron formations are typically interpreted as signals for high marine phosphate concentrations. This suggests that oceanic phosphorus concentrations could have been enriched throughout the Neoproterozoic, as opposed to simply during glacial intervals.

Marine siliceous ecosystem decline led to sustained anomalous Early Triassic warmth.

In the wake of rapid CO2 release tied to the emplacement of the Siberian Traps, elevated temperatures were maintained for over five million years during the end-Permian biotic crisis. This protracted recovery defies our current understanding of climate regulation via the silicate weathering feedback, and hints at a fundamentally altered carbon and silica cycle. Here, we propose that the development of widespread marine anoxia and Si-rich conditions, linked to the collapse of the biological silica factory, warming, and increased weathering, was capable of trapping Earth's system within a hyperthermal by enhancing ocean-atmosphere CO2 recycling via authigenic clay formation. While solid-Earth degassing may have acted as a trigger, subsequent biotic feedbacks likely exacerbated and prolonged the environmental crisis. This refined view of the carbon-silica cycle highlights that the ecological success of siliceous organisms exerts a potentially significant influence on Earth's climate regime.

Marine anoxia linked to abrupt global warming during Earth's penultimate icehouse.

Piecing together the history of carbon (C) perturbation events throughout Earth's history has provided key insights into how the Earth system responds to abrupt warming. Previous studies, however, focused on short-term warming events that were superimposed on longer-term greenhouse climate states. Here, we present an integrated proxy (C and uranium [U] isotopes and paleo CO2) and multicomponent modeling approach to investigate an abrupt C perturbation and global warming event (∼304 Ma) that occurred during a paleo-glacial state. We report pronounced negative C and U isotopic excursions coincident with a doubling of atmospheric CO2 partial pressure and a biodiversity nadir. The isotopic excursions can be linked to an injection of ∼9,000 Gt of organic matter­derived C over ∼300 kyr and to near 20% of areal extent of seafloor anoxia. Earth system modeling indicates that widespread anoxic conditions can be linked to enhanced thermocline stratification and increased nutrient fluxes during this global warming within an icehouse.

Biofilms as agents of Ediacara-style fossilization.

Earth's earliest fossils of complex macroscopic life are recorded in Ediacaran-aged siliciclastic deposits as exceptionally well-preserved three-dimensional casts and molds, known as "Ediacara-style" preservation. Ediacara-style fossil assemblages commonly include both macrofossils of the enigmatic Ediacara Biota and associated textural impressions attributed to microbial matgrounds that were integral to the ecology of Ediacara communities. Here, we use an experimental approach to interrogate to what extent the presence of mat-forming microorganisms was likewise critical to the Ediacara-style fossilization of these soft-bodied organisms. We find evidence that biofilms can play an instrumental role in fostering fossilization. Rapid silica precipitation associated with macroorganism tissues is enhanced in the presence of mat- and biofilm-forming microorganisms. These results indicate that the occurrence of microbial mats and biofilms may have strongly shaped the preservational window for Ediacara-style fossils associated with early diagenetic silica cements, and therefore influenced the distribution and palaeoecological interpretation of the Ediacara Biota fossil record.

Perturbation of the deep-Earth carbon cycle in response to the Cambrian Explosion.

Earth's carbon cycle is strongly influenced by subduction of sedimentary material into the mantle. The composition of the sedimentary subduction flux has changed considerably over Earth's history, but the impact of these changes on the mantle carbon cycle is unclear. Here, we show that the carbon isotopes of kimberlite magmas record a fundamental change in their deep-mantle source compositions during the Phanerozoic Eon. The 13C/12C of kimberlites before ~250 Ma preserves typical mantle values, whereas younger kimberlites exhibit lower and more variable ratios-a switch coincident with a recognized surge in kimberlite magmatism. We attribute these changes to increased deep subduction of organic carbon with low 13C/12C following the Cambrian Explosion when organic carbon deposition in marine sediments increased significantly. These observations demonstrate that biogeochemical processes at Earth's surface have a profound influence on the deep mantle, revealing an integral link between the deep and shallow carbon cycles.

Strong evidence for a weakly oxygenated ocean-atmosphere system during the Proterozoic.

Earth's surface has undergone a protracted oxygenation, which is commonly assumed to have profoundly affected the biosphere. However, basic aspects of this history are still debated-foremost oxygen (O2) levels in the oceans and atmosphere during the billion years leading up to the rise of algae and animals. Here we use isotope ratios of iron (Fe) in ironstones-Fe-rich sedimentary rocks deposited in nearshore marine settings-as a proxy for O2 levels in shallow seawater. We show that partial oxidation of dissolved Fe(II) was characteristic of Proterozoic shallow marine environments, whereas younger ironstones formed via complete oxidation of Fe(II). Regardless of the Fe(II) source, partial Fe(II) oxidation requires low O2 in the shallow oceans, settings crucial to eukaryotic evolution. Low O2 in surface waters can be linked to markedly low atmospheric O2-likely requiring less than 1% of modern levels. Based on our records, these conditions persisted (at least periodically) until a shift toward higher surface O2 levels between ca 900 and 750 Ma, coincident with an apparent rise in eukaryotic ecosystem complexity. This supports the case that a first-order shift in surface O2 levels during this interval may have selected for life modes adapted to more oxygenated habitats.

Intensified continental chemical weathering and carbon-cycle perturbations linked to volcanism during the Triassic-Jurassic transition.

Direct evidence of intense chemical weathering induced by volcanism is rare in sedimentary successions. Here, we undertake a multiproxy analysis (including organic carbon isotopes, mercury (Hg) concentrations and isotopes, chemical index of alteration (CIA), and clay minerals) of two well-dated Triassic-Jurassic (T-J) boundary sections representing high- and low/middle-paleolatitude sites. Both sections show increasing CIA in association with Hg peaks near the T-J boundary. We interpret these results as reflecting volcanism-induced intensification of continental chemical weathering, which is also supported by negative mass-independent fractionation (MIF) of odd Hg isotopes. The interval of enhanced chemical weathering persisted for ~2 million years, which is consistent with carbon-cycle model results of the time needed to drawdown excess atmospheric CO2 following a carbon release event. Lastly, these data also demonstrate that high-latitude continental settings are more sensitive than low/middle-latitude sites to shifts in weathering intensity during climatic warming events.

The History of Ocean Oxygenation.

The large-scale dynamics of ocean oxygenation have changed dramatically throughout Earth's history, in step with major changes in the abundance of O2 in the atmosphere and changes to marine nutrient availability. A comprehensive mechanistic understanding of this history requires insights from oceanography, marine geology, geochemistry, geomicrobiology, evolutionary ecology, and Earth system modeling. Here, we attempt to synthesize the major features of evolving ocean oxygenation on Earth through more than 3 billion years of planetary history. We review the fundamental first-order controls on ocean oxygen distribution and summarize the current understanding of the history of ocean oxygenation on Earth from empirical and theoretical perspectives-integrating geochemical reconstructions of oceanic and atmospheric chemistry, genomic constraints on evolving microbial metabolism, and mechanistic biogeochemical models. These changes are used to illustrate primary regimes of large-scale ocean oxygenation and to highlight feedbacks that can act to stabilize and destabilize the ocean-atmosphere system in anoxic, low-oxygen, and high-oxygen states.

Neoproterozoic syn-glacial carbonate precipitation and implications for a snowball Earth.

The Neoproterozoic 'snowball Earth' hypothesis suggests that a runaway ice-albedo feedback led to two intense glaciations around 717-635 million years ago, and this global ice cover would have drastically impacted biogeochemical cycles. Testing the predictions of this hypothesis against the rock record is key to understanding Earth's surface evolution in the Neoproterozoic. A central tenet of the snowball Earth hypothesis is that extremely high atmospheric CO2  levels-supplied by volcanic degassing over millions of years-would be required to overcome a strong ice-albedo feedback and trigger deglaciation. This requires severely diminished continental weathering (and associated CO2 drawdown) during glaciation, and implies that carbonate minerals would not precipitate from syn-glacial seawater due to a lack of alkalinity influxes into ice-covered oceans. In this scenario, syn-glacial seawater chemistry should instead be dominated by chemical exchange with the oceanic crust and volcanic systems, developing low pH and low Mg/Ca ratios. However, sedimentary rocks deposited during the Sturtian glaciation from the Adelaide Fold Belt-and contemporaneous successions globally-show evidence for syn-sedimentary dolomite precipitation in glaciomarine environments. The dolomitic composition of these syn-glacial sediments and post-glacial 'cap carbonates' implies that carbonate precipitation and Mg cycling must have remained active during the ~50 million-year Sturtian glaciation. These syn-glacial carbonates highlight a gap in our understanding of continental weathering-and therefore, the carbon cycle-during snowball Earth. In light of these observations, a Precambrian global biogeochemical model (PreCOSCIOUS) was modified to explore scenarios of syn-glacial chemical weathering, ocean chemistry and Sturtian carbonate mineralogy. Modelling results suggest that a small degree of chemical weathering during glaciation would have been capable of maintaining high seawater Mg/Ca ratios and carbonate precipitation throughout the Sturtian glaciation. This is consistent with a severe ice age during the Sturtian, but challenges predictions of biogeochemical cycling during the endmember 'hard snowball' models. A small degree of continental weathering might also help explain the extreme duration of the Sturtian glaciation, which appears to have been the longest ice age in Earth history.