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The balance between photosynthetic organic carbon production and respiration controls atmospheric composition and climate 1 , 2 . The majority of organic carbon is respired back to carbon dioxide in the biosphere, but a small fraction escapes remineralization and is preserved over geological timescales 3 . By removing reduced carbon from Earth’s surface, this sequestration process promotes atmospheric oxygen accumulation 2 and carbon dioxide removal 1 . Two major mechanisms have been proposed to explain organic carbon preservation: selective preservation of biochemically unreactive compounds 4 , 5 and protection resulting from interactions with a mineral matrix 6 , 7 . Although both mechanisms can operate across a range of environments and timescales, their global relative importance on 1,000-year to 100,000-year timescales remains uncertain 4 . Here we present a global dataset of the distributions of organic carbon activation energy and corresponding radiocarbon ages in soils, sediments and dissolved organic carbon. We find that activation energy distributions broaden over time in all mineral-containing samples. This result requires increasing bond-strength diversity, consistent with the formation of organo-mineral bonds 8 but inconsistent with selective preservation. Radiocarbon ages further reveal that high-energy, mineral-bound organic carbon persists for millennia relative to low-energy, unbound organic carbon. Our results provide globally coherent evidence for the proposed 7 importance of mineral protection in promoting organic carbon preservation. We suggest that similar studies of bond-strength diversity in ancient sediments may reveal how and why organic carbon preservation—and thus atmospheric composition and climate—has varied over geological time. Broadening activation energy distributions and increasing radiocarbon ages reveal the global importance of mineral protection in promoting organic carbon preservation.

The rise of atmospheric oxygen fundamentally changed the chemistry of surficial environments and the nature of Earth’s habitability 1 . Early atmospheric oxygenation occurred over a protracted period of extreme climatic instability marked by multiple global glaciations 2 , 3 , with the initial rise of oxygen concentration to above 10 −5 of the present atmospheric level constrained to about 2.43 billion years ago 4 , 5 . Subsequent fluctuations in atmospheric oxygen levels have, however, been reported to have occurred until about 2.32 billion years ago 4 , which represents the estimated timing of irreversible oxygenation of the atmosphere 6 , 7 . Here we report a high-resolution reconstruction of atmospheric and local oceanic redox conditions across the final two glaciations of the early Palaeoproterozoic era, as documented by marine sediments from the Transvaal Supergroup, South Africa. Using multiple sulfur isotope and iron–sulfur–carbon systematics, we demonstrate continued oscillations in atmospheric oxygen levels after about 2.32 billion years ago that are linked to major perturbations in ocean redox chemistry and climate. Oxygen levels thus fluctuated across the threshold of 10 −5 of the present atmospheric level for about 200 million years, with permanent atmospheric oxygenation finally arriving with the Lomagundi carbon isotope excursion at about 2.22 billion years ago, some 100 million years later than currently estimated. Sulfur isotope and iron–sulfur–carbon systematics on marine sediments indicate that permanent atmospheric oxygenation occurred around 2.22 billion years ago, about 100 million years later than currently estimated.

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere in a changing climate is critical to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe and synthesize datasets and methodologies to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (EFOS) are based on energy statistics and cement production data, while emissions from land-use change (ELUC) are based on land-use and land-use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly, and its growth rate (GATM) is computed from the annual changes in concentration. The global net uptake of CO2 by the ocean (SOCEAN, called the ocean sink) is estimated with global ocean biogeochemistry models and observation-based fCO2 products (fCO2 is the fugacity of CO2). The global net uptake of CO2 by the land (SLAND, called the land sink) is estimated with dynamic global vegetation models. Additional lines of evidence on land and ocean sinks are provided by atmospheric inversions, atmospheric oxygen measurements, and Earth system models. The sum of all sources and sinks results in the carbon budget imbalance (BIM), a measure of imperfect data and incomplete understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the year 2023, EFOS increased by 1.3 % relative to 2022, with fossil emissions at 10.1 ± 0.5 GtC yr−1 (10.3 ± 0.5 GtC yr−1 when the cement carbonation sink is not included), and ELUC was 1.0 ± 0.7 GtC yr−1, for a total anthropogenic CO2 emission (including the cement carbonation sink) of 11.1 ± 0.9 GtC yr−1 (40.6 ± 3.2 GtCO2 yr−1). Also, for 2023, GATM was 5.9 ± 0.2 GtC yr−1 (2.79 ± 0.1 ppm yr−1; ppm denotes parts per million), SOCEAN was 2.9 ± 0.4 GtC yr−1, and SLAND was 2.3 ± 1.0 GtC yr−1, with a near-zero BIM (−0.02 GtC yr−1). The global atmospheric CO2 concentration averaged over 2023 reached 419.31 ± 0.1 ppm. Preliminary data for 2024 suggest an increase in EFOS relative to 2023 of +0.8 % (−0.2 % to 1.7 %) globally and an atmospheric CO2 concentration increase by 2.87 ppm, reaching 422.45 ppm, 52 % above the pre-industrial level (around 278 ppm in 1750). Overall, the mean of and trend in the components of the global carbon budget are consistently estimated over the period 1959–2023, with a near-zero overall budget imbalance, although discrepancies of up to around 1 GtC yr−1 persist for the representation of annual to semi-decadal variability in CO2 fluxes. Comparison of estimates from multiple approaches and observations shows the following: (1) a persistent large uncertainty in the estimate of land-use change emissions, (2) low agreement between the different methods on the magnitude of the land CO2 flux in the northern extra-tropics, and (3) a discrepancy between the different methods on the mean ocean sink. This living-data update documents changes in methods and datasets applied to this most recent global carbon budget as well as evolving community understanding of the global carbon cycle. The data presented in this work are available at https://doi.org/10.18160/GCP-2024 (Friedlingstein et al., 2024).

Reconciling the geology of Mars with models of atmospheric evolution remains a major challenge. Martian geology is characterized by past evidence for episodic surface liquid water, and geochemistry indicating a slow and intermittent transition from wetter to drier and more oxidizing surface conditions. Here we present a model that incorporates randomized injection of reducing greenhouse gases and oxidation due to hydrogen escape to investigate the conditions responsible for these diverse observations. We find that Mars could have transitioned repeatedly from reducing (hydrogen-rich) to oxidizing (oxygen-rich) atmospheric conditions in its early history. Our model predicts a generally cold early Mars, with mean annual temperatures below 240 K. If peak reducing-gas release rates and background carbon dioxide levels are high enough, it nonetheless exhibits episodic warm intervals sufficient to degrade crater walls, form valley networks and create other fluvial/lacustrine features. Our model also predicts transient build-up of atmospheric oxygen, which can help explain the occurrence of oxidized mineral species such as manganese oxides at Gale Crater. We suggest that the apparent Noachian–Hesperian transition from phyllosilicate deposition to sulfate deposition around 3.5 billion years ago can be explained as a combined outcome of increasing planetary oxidation, decreasing groundwater availability and a waning bolide impactor flux, which dramatically slowed the remobilization and thermochemical destruction of surface sulfates. Ultimately, rapid and repeated variations in Mars’s early climate and surface chemistry would have presented both challenges and opportunities for any emergent microbial life. Mars’s early climate and surface chemistry varied between a generally cold, oxidizing environment and warmer, more reducing conditions, according to a model of atmospheric evolution driven by stochastic, random injection of greenhouse gases.

Oceanic sulfate concentrations are widely thought to have reached millimolar levels during the Proterozoic Eon, 2.5 to 0.54 billion years ago. Yet the magnitude of the increase in seawater sulfate concentrations over the course of the Eon remains largely unquantified. A rise in seawater sulfate concentrations has been inferred from the increased range of marine sulfide δ34S values following the Great Oxidation Event and was induced by two processes: enhanced oxidative weathering of sulfides on land, and the onset of marine sulfur redox cycling. Here we use mass balance and diagenetic reaction-transport models to reconstruct the sulfate concentrations in Proterozoic seawater. We find that sulfate concentrations remained below 400 µM, and were possibly as low as 100 µM, throughout much of the Proterozoic. At these low sulfate concentrations, relatively large sulfate–pyrite sulfur isotope differences cannot be explained by sulfate reduction alone and are only possible through oxidative sediment sulfur cycling. This requires oxygen concentrations of at least 10 µM in shallow Proterozoic seawater, which translates to 1–10% of present atmospheric oxygen concentrations. At these oxygen and sulfate concentrations, the oceans would have been a substantial source of methane to the atmosphere (60–140 Tmol yr−1). This methane would have accumulated to high concentrations (more than 25 ppmv) and supported greenhouse warming during much of the Proterozoic Eon, with notable exceptions during the Palaeoproterozoic and Neoproterozoic eras.In the Proterozoic, sulfate concentrations in the oceans were low and atmospheric methane levels high, according to mass balance and diagenetic models that investigate the oxidation state of the Proterozoic oceans.

Phosphorus is a limiting nutrient that is thought to control oceanic oxygen levels to a large extent 1 – 3 . A possible increase in marine phosphorus concentrations during the Ediacaran Period (about 635–539 million years ago) has been proposed as a driver for increasing oxygen levels 4 – 6 . However, little is known about the nature and evolution of phosphorus cycling during this time 4 . Here we use carbonate-associated phosphate (CAP) from six globally distributed sections to reconstruct oceanic phosphorus concentrations during a large negative carbon-isotope excursion—the Shuram excursion (SE)—which co-occurred with global oceanic oxygenation 7 – 9 . Our data suggest pulsed increases in oceanic phosphorus concentrations during the falling and rising limbs of the SE. Using a quantitative biogeochemical model, we propose that this observation could be explained by carbon dioxide and phosphorus release from marine organic-matter oxidation primarily by sulfate, with further phosphorus release from carbon-dioxide-driven weathering on land. Collectively, this may have resulted in elevated organic-pyrite burial and ocean oxygenation. Our CAP data also seem to suggest equivalent oceanic phosphorus concentrations under maximum and minimum extents of ocean anoxia across the SE. This observation may reflect decoupled phosphorus and ocean anoxia cycles, as opposed to their coupled nature in the modern ocean. Our findings point to external stimuli such as sulfate weathering rather than internal oceanic phosphorus–oxygen cycling alone as a possible control on oceanic oxygenation in the Ediacaran. In turn, this may help explain the prolonged rise of atmospheric oxygen levels. Reconstruction of oceanic phosphorus concentrations during a large negative carbon-isotope excursion co-occurring with global oceanic oxygenation and evolution of some of Earth’s earliest animals suggests that decoupled phosphorus and ocean anoxia cycles during the Ediacaran may have prolonged the rise of atmospheric oxygen.

Frequent violent collisions of impactors from space punctuated the geological and atmospheric evolution of early Earth. It is generally accepted that the most massive collisions altered the chemistry of Earth’s earliest atmosphere, but the consequences of Archaean collisions for atmospheric oxidation are little understood. Early Archaean (4.0–3.5 billion years ago (Ga)) impact flux models are tightly constrained by lunar cratering and radiometric data. Further, a record of the late Archaean (3.5–2.5 Ga) impact flux is provided by terrestrial impact spherule layers—formed by collisions with bodies ≥10–20 km in diameter—although this record is probably incomplete and significant uncertainties remain. Here we show, on the basis of an assessment of impactor-related spherule records and modelling of the atmospheric effects of these impacts, that current bombardment models underestimate the number of late Archaean spherule layers. These findings suggest that the late Archaean impactor flux was up to a factor of ten higher than previously thought. We find that the delivered impactor mass was an important sink of oxygen, suggesting that early bombardment could have delayed Earth’s atmosphere oxidation. In addition, late Archaean large impacts (≥10 km) probably caused drastic oscillations of atmospheric oxygen, with an average time between consecutive collisions of about 15 Myr. This pattern is consistent with a known episode of atmospheric oxygen oscillation at ~2.5 Ga that is bracketed by large impacts recorded by Bee Gorge (~2.54 Ga) and Dales Gorge (~2.49 Ga) spherule layers. The oxygenation of Earth may have been delayed due to high late Archaean extraterrestrial impact rates, which acted as a fluctuating sink of atmospheric oxygen, according to a reassessment of past impactor fluxes and atmospheric chemistry modelling.

Phosphorus (P) is an essential macronutrient for plant growth, development and production. However, little is known about the effects of P deficiency on nutrient absorption, photosynthetic apparatus performance and antioxidant metabolism in citrus. Seedlings of ‘sour pummelo’ ( Citrus grandis ) were irrigated with a nutrient solution containing 0.2 mM (Control) or 0 mM (P deficiency) KH 2 PO 4 until saturated every other day for 16 weeks. P deficiency significantly decreased the dry weight (DW) of leaves and stems, and increased the root/shoot ratio in C . grandis but did not affect the DW of roots. The decreased DW of leaves and stems might be induced by the decreased chlorophyll (Chl) contents and CO 2 assimilation in P deficient seedlings. P deficiency heterogeneously affected the nutrient contents of leaves, stems and roots. The analysis of Chl a fluorescence transients showed that P deficiency impaired electron transport from the donor side of photosystem II (PSII) to the end acceptor side of PSI, which showed a greater impact on the performance of the donor side of PSII than that of the acceptor side of PSII and photosystem I (PSI). P deficiency increased the contents of ascorbate (ASC), H 2 O 2 and malondialdehyde (MDA) as well as the activities of superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), dehydroascorbate reductase (DHAR) and glutathione reductase (GR) in leaves. In contrast, P deficiency increased the ASC content, reduced the glutathione (GSH) content and the activities of SOD, CAT, APX and monodehydroascorbate reductase (MDHAR), but did not increase H 2 O 2 production, anthocyanins and MDA content in roots. Taking these results together, we conclude that P deficiency affects nutrient absorption and lowers photosynthetic performance, leading to ROS production, which might be a crucial cause of the inhibited growth of C . grandis .

Deep-ocean O2 concentrations over the past 3.5 billion years are estimated using the oxidation state of iron in submarine basalts and indicate that deep-ocean oxygenation occurred in the Phanerozoic. Oxygen in the deep Oxygenation of the deep ocean associated with a rise in atmospheric oxygen levels in the geological past is thought to signal the emergence of modern marine biogeochemical cycles. Estimates of the timing of deep-ocean oxygenation and the related increase in atmospheric oxygen levels range from about 800 to 400 million years ago and are generally based on geochemical signatures that indirectly reflect the geochemical state of the deep ocean. This paper presents a more direct, quantitative constraint on the deep-ocean oxygen content from the Archaean to the Cenozoic based on the oxidation state of iron in submarine basalts. The authors suggest that deep-ocean oxygenation occurred in the Phanerozoic and probably not until the late Palaeozoic, less than 420 million years ago. The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles 1 , 2 , 3 , 4 , 5 . It has also been linked to the origination and diversification of early animals 3 , 5 , 6 , 7 . It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago 3 , 5 , 7 , 11 , 13 . Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

The early evolutionary and much of the extinction history of marine animals is thought to be driven by changes in dissolved oxygen concentrations ([O 2 ]) in the ocean 1 – 3 . In turn, [O 2 ] is widely assumed to be dominated by the geological history of atmospheric oxygen ( p O 2 ) 4 , 5 . Here, by contrast, we show by means of a series of Earth system model experiments how continental rearrangement during the Phanerozoic Eon drives profound variations in ocean oxygenation and induces a fundamental decoupling in time between upper-ocean and benthic [O 2 ]. We further identify the presence of state transitions in the global ocean circulation, which lead to extensive deep-ocean anoxia developing in the early Phanerozoic even under modern p O 2 . Our finding that ocean oxygenation oscillates over stable thousand-year (kyr) periods also provides a causal mechanism that might explain elevated rates of metazoan radiation and extinction during the early Palaeozoic Era 6 . The absence, in our modelling, of any simple correlation between global climate and ocean ventilation, and the occurrence of profound variations in ocean oxygenation independent of atmospheric p O 2 , presents a challenge to the interpretation of marine redox proxies, but also points to a hitherto unrecognized role for continental configuration in the evolution of the biosphere. Analysis of a series of Earth system model experiments shows that continental rearrangement during the Phanerozoic had a marked influence on variations in ocean oxygenation, independent of atmospheric p O 2 .