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We present a framework for interpreting the carbon isotopic composition of sedimentary rocks, which in turn requires a fundamental reinterpretation of the carbon cycle and redox budgets over Earth's history. We propose that authigenic carbonate, produced in sediment pore fluids during early diagenesis, has played a major role in the carbon cycle in the past. This sink constitutes a minor component of the carbon isotope mass balance under the modern, high levels of atmospheric oxygen but was much larger in times of low atmospheric O 2 or widespread marine anoxia. Waxing and waning of a global authigenic carbonate sink helps to explain extreme carbon isotope variations in the Proterozoic, Paleozoic, and Triassic.

Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models. Groundwater discharge is a mechanism that transports chemicals from inland systems to the ocean, but it has been considered of secondary influence compared to rivers. Here the authors assess the global significance of groundwater discharge, finding that it has a unique and important contribution to ocean chemistry and Earth-system models.

Authigenic clay minerals formed on or in the seafloor occur in every type of marine sediment. They are recognized to be a major sink of many elements in the ocean but are difficult to study directly due to dilution by detrital clay minerals. The extremely low dust fluxes and marine sedimentation rates in the South Pacific Gyre (SPG) provide a unique opportunity to examine relatively undiluted authigenic clay. Here, using Mg isotopes and element concentrations combined with multivariate statistical modeling, we fingerprint and quantify the abundance of authigenic clay within SPG sediment. Key reactants include volcanic ash (source of reactive aluminium) and reactive biogenic silica on or shallowly buried within the seafloor. Our results, together with previous studies, suggest that global reorganizations of biogenic silica burial over the Cenozoic reduced marine authigenic clay formation, contributing to the rise in seawater Mg/Ca and decline in atmospheric CO 2 over the past 50 million years. Reverse weathering reactions on or in the seafloor are a major sink of many elements and alkalinity in seawater. Here, the authors show how reduced rates of reverse weathering may be responsible for global cooling and increased seawater Mg/Ca over the past 50 million years.

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the 15N/14N ratio (δ15N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ15N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ15N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. δ15N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed.

Here, we present direct measurements of atmospheric composition and Antarctic climate from the mid-Pleistocene (∼1 Ma) from ice cores drilled in the Allan Hills blue ice area, Antarctica. The 1-Ma ice is dated from the deficit in ⁴⁰Ar relative to the modern atmosphere and is present as a stratigraphically disturbed 12-m section at the base of a 126-m ice core. The 1-Ma ice appears to represent most of the amplitude of contemporaneous climate cycles and CO ₂ and CH ₄ concentrations in the ice range from 221 to 277 ppm and 411 to 569 parts per billion (ppb), respectively. These concentrations, together with measured δD of the ice, are at the warm end of the field for glacial–interglacial cycles of the last 800 ky and span only about one-half of the range. The highest CO ₂ values in the 1-Ma ice fall within the range of interglacial values of the last 400 ka but are up to 7 ppm higher than any interglacial values between 450 and 800 ka. The lowest CO ₂ values are 30 ppm higher than during any glacial period between 450 and 800 ka. This study shows that the coupling of Antarctic temperature and atmospheric CO ₂ extended into the mid-Pleistocene and demonstrates the feasibility of discontinuously extending the current ice core record beyond 800 ka by shallow coring in Antarctic blue ice areas. Significance Bubbles of ancient air trapped in ice cores permit the direct reconstruction of atmospheric composition and allow us to link greenhouse gases and global climate over the last 800 ky. Here, we present new ice core records of atmospheric composition roughly 1 Ma from a shallow ice core drilled in the Allan Hills blue ice area, Antarctica. These records confirm that interglacial CO ₂ concentrations decreased by 800 ka. They also show that the link between CO ₂ and Antarctic temperature extended into the warmer world of the mid-Pleistocene.

Pleistocene glacial–interglacial cycles are hypothesized to be modulated by Earth’s orbital parameters through their influence on the Northern Hemisphere summer insolation. Changes in obliquity—Earth’s axial tilt—can explain the 41,000-year glacial cycles in the Early Pleistocene. However, the absence of 19,000- and 23,000-year frequencies corresponding to Earth’s precession of the rotation axis from those cycles remains enigmatic. Here we investigate how these orbital forcings may have changed by developing an insolation proxy based on the oxygen-to-nitrogen ratio of gases trapped in ice core samples collected from the Allan Hills Blue Ice Area in East Antarctica. We find that East Antarctic temperature was positively correlated with local, Southern Hemisphere summer insolation in the Early Pleistocene, while this correlation became negative in the late Pleistocene, with only the latter being consistent with the previous findings that Northern Hemisphere insolation paced Antarctic climate. If Early Pleistocene ice volume and local Antarctic temperature co-varied, our result supports the hypothesis that attributes the absence of precession in the 41,000-year glacial cycles to cancellation of precession frequencies in hemispheric ice volume changes that are responding to local insolation, suggesting a more dynamic East Antarctic Ice Sheet in the Early Pleistocene than in the past 800,000 years.East Antarctic surface temperature co-varied with local insolation in the Early Pleistocene, leading to the cancellation of global orbital ice sheet forcing from precession, according to temperature proxies and insolation-related gas ratios in ice cores.

Over the past eight hundred thousand years, glacial–interglacial cycles oscillated with a period of one hundred thousand years (‘100k world’ 1 ). Ice core and ocean sediment data have shown that atmospheric carbon dioxide, Antarctic temperature, deep ocean temperature, and global ice volume correlated strongly with each other in the 100k world 2 – 6 . Between about 2.8 and 1.2 million years ago, glacial cycles were smaller in magnitude and shorter in duration (‘40k world’ 7 ). Proxy data from deep-sea sediments suggest that the variability of atmospheric carbon dioxide in the 40k world was also lower than in the 100k world 8 – 10 , but we do not have direct observations of atmospheric greenhouse gases from this period. Here we report the recovery of stratigraphically discontinuous ice more than two million years old from the Allan Hills Blue Ice Area, East Antarctica. Concentrations of carbon dioxide and methane in ice core samples older than two million years have been altered by respiration, but some younger samples are pristine. The recovered ice cores extend direct observations of atmospheric carbon dioxide, methane, and Antarctic temperature (based on the deuterium/hydrogen isotope ratio δD ice , a proxy for regional temperature) into the 40k world. All climate properties before eight hundred thousand years ago fall within the envelope of observations from continuous deep Antarctic ice cores that characterize the 100k world. However, the lowest measured carbon dioxide and methane concentrations and Antarctic temperature in the 40k world are well above glacial values from the past eight hundred thousand years. Our results confirm that the amplitudes of glacial–interglacial variations in atmospheric greenhouse gases and Antarctic climate were reduced in the 40k world, and that the transition from the 40k to the 100k world was accompanied by a decline in minimum carbon dioxide concentrations during glacial maxima. Analysis of two-million-year-old ice from Antarctica provides a direct comparison of atmospheric gas levels before and after the shift from glacial cycles of 100 thousand years to 40-thousand-year cycles around one million years ago.

Carbonate mud represents one of the most important geochemical archives for reconstructing ancient climatic, environmental, and evolutionary change from the rock record. Mud also represents a major sink in the global carbon cycle. Yet, there remains no consensus about how and where carbonate mud is formed. Here, we present stable isotope and trace-element data from carbonate constituents in the Bahamas, including ooids, corals, foraminifera, and algae. We use geochemical fingerprinting to demonstrate that carbonate mud cannot be sourced from the abrasion and mixture of any combination of these macroscopic grains. Instead, an inverse Bayesian mixing model requires the presence of an additional aragonite source.We posit that this source represents a direct seawater precipitate. We use geological and geochemical data to show that “whitings” are unlikely to be the dominant source of this precipitate and, instead, present a model for mud precipitation on the bank margins that can explain the geographical distribution, clumped-isotope thermometry, and stable isotope signature of carbonate mud. Next, we address the enigma of why mud and ooids are so abundant in the Bahamas, yet so rare in the rest of the world: Mediterranean outflow feeds the Bahamas with the most alkaline waters in themodern ocean (>99.7th-percentile). Such high alkalinity appears to be a prerequisite for the nonskeletal carbonate factory because, when Mediterranean outflow was reduced in the Miocene, Bahamian carbonate export ceased for 3-million-years. Finally, we show how shutting off and turning on the shallow carbonate factory can send ripples through the global climate system.

The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth’s climate 1 – 3 . Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth’s surface environments 4 – 12 . Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants 13 , 14 . Analysis of shallow-water marine carbonate samples from 101 stratigraphic units allows construction of a record of lithium isotopes from the past 3 billion years, tracking the evolution of the global carbon and silicon cycles.

The geochemistry of biogenic carbonates has long been used as proxies to record changing seawater parameters. However, the effect of ocean acidification (OA) on seawater chemistry and organism physiology could impact isotopic signatures and how elements are incorporated into the shell. In this study, we investigated the geochemistry of three reservoirs important for biomineralization – seawater, the extrapallial fluid (EPF), and the shell – in two bivalve species: Crassostrea virginica and Arctica islandica. Additionally, we examined the effects of three ocean acidification conditions (ambient: 500 ppm CO2, moderate: 900 ppm CO2, and high: 2800 ppm CO2) on the geochemistry of the same three reservoirs for C. virginica. We present data on calcification rates, EPF pH, measured elemental ratios (Mg/Ca, B/Ca), and isotopic signatures (δ26Mg, δ11B). In both species, comparisons of seawater and EPF Mg/Ca and B/Ca, Ca2+, and δ26Mg indicate that the EPF has a distinct composition that differs from seawater. Shell δ11B did not faithfully record seawater pH, and δ11B-calculated pH values were consistently higher than pH measurements of the EPF with microelectrodes, indicating that the shell δ11B may reflect a localized environment within the entire EPF reservoir. In C. virginica, EPF Mg/Ca and B/Ca, as well as absolute concentrations of Mg2+, B, and Ca2+, were all significantly affected by ocean acidification, indicating that OA affects the physiological pathways regulating or storing these ions, an observation that complicates their use as proxies. Reduction in EPF Ca2+ may represent an additional mechanism underlying reduction in calcification in C. virginica in response to seawater acidification. The complexity of dynamics of EPF chemistry suggests boron proxies in these two mollusk species are not straightforwardly related to seawater pH, but ocean acidification does lead to both a decrease in microelectrode pH and boron-isotope-based pH, potentially showing applicability of boron isotopes in recording physiological changes. Collectively, our findings show that bivalves have high physiological control over the internal calcifying fluid, which presents a challenge in using boron isotopes for reconstructing seawater pH.