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Funding: These field and related experimental studies were supported through US NSF grants: 0549547, 0751771, 0813861, 0961188 and 1736679 (WES). Mid-ocean ridge (MOR) hydrothermal vent fluids are enriched with dissolved barium, but due to barite (BaSO4) precipitation during mixing between Ba-bearing vent fluids and SO4-bearing seawater, the magnitude of hydrothermal Ba input to the ocean remains uncertain. Deep-ocean Ba isotopes show evidence for non-conservative behavior, which might be explained by input of isotopically heavy hydrothermal Ba. In this study we present the first Ba isotope data in mid-ocean ridge hydrothermal vent fluids and particles from systems on the Mid-Atlantic Ridge (Rainbow 36°N and TAG 26°N), the East Pacific Rise (EPR9–10°N and 13°N) and the Juan de Fuca Ridge (MEF and ASHES). The vent fluids display a wide range of dissolved Ba concentrations from 0.43 to 97.9 μmol/kg and δ138/134Ba values from −0.26 to +0.91‰, but are modified relative to initial composition due to precipitation of barite. Calculated endmember vent fluid δ138/134Ba values, prior to barite precipitation, are between −0.17 and +0.09‰, consistent with the values observed in oceanic basalts and pelagic sediments. Water-rock interaction at depth in the oceanic crust appears to occur without Ba isotope fractionation. During subsequent venting and mixing with seawater, barite precipitation preferentially removes isotopically light Ba from vent fluids with a fractionation factor of Δ138/134Bahyd-barite-fluid = −0.35 ± 0.10‰ (2SE, n = 2). Based on knowledge of barite saturation and isotope fractionation during precipitation, the effective hydrothermal Ba component that mixes with seawater after barite precipitation has completed can be calculated: δ138/134Bahyd = +1.7 ± 0.7‰ (2SD). This value is isotopically heavier than deep ocean waters and may explain the observed non-conservative of Ba isotopes in deep waters. These new constraints on hydrothermal Ba compositions enable the hydrothermal input of Ba to Atlantic deep waters to be assessed at ≈3–9% of the observed Ba. Barium isotopes might be used as a tracer to reconstruct the history of hydrothermal Ba inputs and seawater SO4 concentrations in the past. Postprint

Measurements of trace gases in planetary atmospheres help us explore chemical conditions different to those on Earth. Our nearest neighbour, Venus, has cloud decks that are temperate but hyperacidic. Here we report the apparent presence of phosphine (PH3) gas in Venus’s atmosphere, where any phosphorus should be in oxidized forms. Single-line millimetre-waveband spectral detections (quality up to ~15σ) from the JCMT and ALMA telescopes have no other plausible identification. Atmospheric PH3 at ~20 ppb abundance is inferred. The presence of PH3 is unexplained after exhaustive study of steady-state chemistry and photochemical pathways, with no currently known abiotic production routes in Venus’s atmosphere, clouds, surface and subsurface, or from lightning, volcanic or meteoritic delivery. PH3 could originate from unknown photochemistry or geochemistry, or, by analogy with biological production of PH3 on Earth, from the presence of life. Other PH3 spectral features should be sought, while in situ cloud and surface sampling could examine sources of this gas. The detection of ~20 ppb of phosphine in Venus clouds by observations in the millimetre-wavelength range from JCMT and ALMA is puzzling, because according to our knowledge of Venus, no phosphine should be there. As the most plausible formation paths do not work, the source could be unknown chemical processes—maybe even life?

The concentration and isotopic composition of sedimentary molybdenum (Mo) has been used to distinguish different redox environments in modern marine settings and in the geological record. We report Mo concentrations and δ98Mo from porewaters and sediments in three anoxic East Anglian salt marsh pond environments: (1) ‘iron-rich’ sediments containing high concentrations of dissolved ferrous iron (up to 2 mM), (2) ‘sulfide-rich’ sediments containing very high concentrations of aqueous sulfide (up to 10 mM) and, (3) sediments that we consider to be intermediate between ‘iron-rich’ and ‘sulfide-rich’ conditions. In iron-rich sediments, we suggest that iron speciation and mineralogy controls the concentration and isotopic composition of Mo. Despite similar aqueous sulfide profiles, the intermediate and sulfide-rich pond sediment have different porewater Mo concentrations and δ98Mo. In the sulfide-rich pond sediment, we suggest that the concentration and isotopic composition of Mo is controlled by solubility equilibrium with an Fe-Mo-S mineral species (e.g. FeMoS4) due to similarities in sediment and porewater δ98Mo throughout the sediment column. In the intermediate pond sediment, we conclude that active breakdown of iron oxides redistributes porewater Mo, observable as a peak of dissolved Mo (>100 ppb), which diffuses within the sedimentary porewaters. The sedimentary δ98Mo is higher in sulfide-rich and intermediate pond sediment (mean = 1.66‰, range = 0.98–1.92‰) than in iron-rich pond sediment (mean = 1.10‰, range = 0.28–1.65‰) with all ponds having sedimentary δ98Mo that is lower than seawater. The maximum sedimentary δ98Mo observed in these anoxic sediments, which is 0.5–0.7‰ lower than seawater, appears to be set by Fe-Mo-S equilibration with ambient thiomolybdate species. We suggest diagenetic overprinting can cause more efficient capture of pond water Mo and causes sediment δ98Mo of originally iron-rich pond sediment to evolve to higher values at progressively higher aqueous sulfide concentrations.

Pyrite formation in marine sedimentary environments plays a key role in the global biogeochemical cycles of carbon, sulfur and iron, regulating Earth's surface redox balance over geological time scales. The sulfur isotopic composition of pyrite is one of the major geochemical tools for investigating early diagenetic processes in modern marine sediments and substantive changes to the Earth's surface environment in ancient sedimentary rocks. We studied sulfur–iron diagenesis and the sulfur isotopic evolution in sediments of the Bornholm Basin, southwestern Baltic Sea, to track the formation of pyrite in the near-surface sediments. Pyrite accumulation is observed with depth over the uppermost 100 cm before the extent of pyritization of the highly reactive iron pool (Fepy/FeHR) stays constant at ca. 0.9, suggesting that the use of a single iron-speciation parameter as a proxy for anoxic and sulfidic conditions needs to be supported by other independent indicators in sedimentary records. Stable sulfur isotopic analysis demonstrates that the bulk pools of elemental sulfur and iron monosulfide do not exchange isotopes completely with aqueous sulfide. We suggest that the reactions with polysulfide and aqueous sulfide are probably restricted to the surface of the solid-phase sulfur and iron-sulfur aggregates. Although pyrite is growing throughout the uppermost sediment column, the pyrite at depth has a sulfur isotopic composition similar to that of pyrite formed near the sediment surface. To understand the isotopic discrepancy between pyrite and aqueous sulfide in the deeper sediments, we developed a simple diagenetic model, which reproduces the observed sulfur isotopic composition of pyrite well. Our results suggest that much of the pyrite is rapidly formed near the sediment–water interface, and its δ34S is not as influenced by the 34S-enriched pool of aqueous sulfide in the deeper part of the sediment, allowing 32S-enriched pyrite to be preserved in deeper sediments. This near-surface diagenesis and the associated isotopic pattern are possibly of relevance for many marine sediments with high organic matter content, and high aqueous sulfide but low reactive iron availability. Moreover, our sulfur isotopic data demonstrate that extremely slow pyritization is ongoing in the deep lacustrine clay sediments. These results have implications for the interpretation of sulfur–iron geochemical data in both modern and ancient settings as well as for improving reconstructions of ancient depositional environments and a better understanding of the marine sulfur cycle throughout Earth's history.

Bursts of carbon dioxide, released into the atmosphere and occurring on centennial time scales, were seen during the cold periods of the last glacial cycle but not in older or warmer conditions. Nehrbass-Ahles et al. present a record of atmospheric carbon dioxide concentrations retrieved from the European Project for Ice Coring in Antarctica Dome C ice core showing that these carbon dioxide jumps occurred during both cold and warm periods between 330,000 and 450,000 years ago. They relate these pulses to disruptions of the Atlantic meridional overturning circulation caused by freshwater discharge from ice sheets. Such rapid carbon dioxide increases could occur in the future if global warming also disrupts this ocean circulation pattern.Science, this issue p. 1000Pulse-like carbon dioxide release to the atmosphere on centennial time scales has only been identified for the most recent glacial and deglacial periods and is thought to be absent during warmer climate conditions. Here, we present a high-resolution carbon dioxide record from 330,000 to 450,000 years before present, revealing pronounced carbon dioxide jumps (CDJ) under cold and warm climate conditions. CDJ come in two varieties that we attribute to invigoration or weakening of the Atlantic meridional overturning circulation (AMOC) and associated northward and southward shifts of the intertropical convergence zone, respectively. We find that CDJ are pervasive features of the carbon cycle that can occur during interglacial climate conditions if land ice masses are sufficiently extended to be able to disturb the AMOC by freshwater input.

The Last Interglacial (LIG), a warmer period 130,000–116,000 years before present, is a potential analogue for future climate change. Stronger LIG summertime insolation at high northern latitudes drove Arctic land summer temperatures 4–5 °C higher than in the pre-industrial era. Climate model simulations have previously failed to capture these elevated temperatures, possibly because they were unable to correctly capture LIG sea-ice changes. Here, we show that the latest version of the fully coupled UK Hadley Center climate model (HadGEM3) simulates a more accurate Arctic LIG climate, including elevated temperatures. Improved model physics, including a sophisticated sea-ice melt-pond scheme, result in a complete simulated loss of Arctic sea ice in summer during the LIG, which has yet to be simulated in past generations of models. This ice-free Arctic yields a compelling solution to the long-standing puzzle of what drove LIG Arctic warmth and supports a fast retreat of future Arctic summer sea ice. Arctic climate in the Last Interglacial (LIG)—a warm period 130,000–116,000 years ago—is poorly simulated by modern climate models. A model with improved sea-ice melt-pond physics reproduces LIG Arctic temperatures, suggests an ice-free Arctic during this period and predicts the same by 2035.

The Kutch Basin is unique among the western Indian sedimentary basins because of its near‐complete sequence of post‐Palaeozoic rocks. Due to extensive marine influence, the Oligocene–Early Miocene formations of the basin, namely Maniyara Fort, Khari Nadi and Chhasra, contain numerous shellbeds. Although age assignments of these formations exist based on foraminiferal biostratigraphy, detailed numerical age of the lithounits are yet to be established. We have identified a total of eleven distinct shellbeds (oldest SB 01 to youngest SB11) from this interval primarily containing bivalve fossils. Using 87Sr/86Sr of selected oyster and pectinid shells with pristine shell characteristics, we report the age of four shellbeds. The ages of SB 01, SB 04, SB 06 and SB 10 are 24.37, 17.31, 16.85 and 15.38 Ma, respectively. Our dates suggest a Chattian (24.37 Ma) age for SB 01 from the Bermoti Member, validating the previous biostratigraphical estimates from the Maniyara Fort Formation. The Chhasra Formation, however, shows a younger range of ages (17.31–15.38 Ma) characterized by a transition from the Burdigalian (SB 04–SB 06) to the Langhian (SB 10) stages. These dates have important implications in the study of sequence stratigraphy, Palaeobiogeography and tectonic history of the Kutch Basin. A surface with subaerial exposure is found in SB 08 (between 16.85 and 15.38 Ma) that corresponds to a global eustatic sea‐level decrease (Mi2). Our new dates will also help evaluate the response of marine fauna to the closure of the Tethyan seaway around 19 Ma due to the formation of ‘Gomphotherium Landbridge’. The dated shellbeds enable us to identify pre‐ and post‐closure fauna and assess the effect of biogeographical separation on these fauna. These dates have important implications in evaluating the regional geological record of western India in the context of various global events.

We employ complementary field and laboratory‐based incubation techniques to explore the geochemical environment where siderite concretions are actively forming and growing, including solid‐phase analysis of the sediment, concretion, and associated pore fluid chemistry. These recently formed siderite concretions allow us to explore the geochemical processes that lead to the formation of this less common carbonate mineral. We conclude that there are two phases of siderite concretion growth within the sediment, as there are distinct changes in the carbon isotopic composition and mineralogy across the concretions. Incubated sediment samples allow us to explore the stability of siderite over a range of geochemical conditions. Our incubation results suggest that the formation of siderite can be very rapid (about two weeks or within 400 hr) when there is a substantial source of iron, either from microbial iron reduction or from steel material; however, a source of dissolved iron is not enough to induce siderite precipitation. We suggest that sufficient alkalinity is the limiting factor for siderite precipitation during microbial iron reduction while the lack of dissolved iron is the limiting factor for siderite formation if microbial sulfate reduction is the dominant microbial metabolism. We show that siderite can form via heated transformation (at temperature 100°C for 48 hr) of calcite and monohydrocalcite seeds in the presence of dissolved iron. Our transformation experiments suggest that the formation of siderite is promoted when carbonate seeds are present.

Marine radiocarbon dates, corrected for ocean‐atmosphere reservoir age offsets (R‐ages), are widely used to constrain marine chronologies. R‐ages also represent the surface boundary condition that links the ocean interior radiocarbon distribution (i.e., “radiocarbon ventilation ages”) to the ocean's large‐scale overturning circulation. Understanding how R‐ages have varied over time is therefore essential both for accurate dating and for investigations into past ocean circulation/carbon cycle interactions. A number or recent studies have shed light on surface reservoir age changes over the last deglaciation; however, a clear picture of global/regional spatiotemporal patterns of variability has yet to emerge. Here we combine new and existing reservoir age estimates to show coherent but distinct regional reservoir age trends in the subpolar North Atlantic and Southern Ocean. It can be further shown that similar but lower amplitude changes occurred at midlatitudes in each hemisphere. An apparent link between regional patterns of reservoir age variability and the “thermal bipolar seesaw” suggests a causal link with changes in ocean circulation, mixed‐layer depth, and/or sea ice dynamics. A further link to atmospheric CO2 is also apparent and underlines a potentially dominant role for changes in the ocean's “disequilibrium carbon” pool, rather than changes in ocean transport, in deglacial CO2 change. The existence of significant R‐age variability over the last deglaciation poses a problem for marine radiocarbon age calibrations. However, its apparent regional consistency also raises the prospect of developing region‐specific marine calibration curves for radiocarbon‐dating purposes.

Quaternary interglacials provide key observations of the Earth system's responses to orbital and greenhouse gas forcing. They also inform on the capabilities of Earth system models, used for projecting the polar ice-sheet and sea-level responses to a regional warmth comparable to that expected by 2100 C.E. However, a number of uncertainties remain regarding the processes and feedbacks linking climate, ice-sheet and sea-level changes during past warm intervals. Here, we delineate the major research questions that need to be resolved and future research directions that should be taken by the paleoclimate, sea-level and ice-sheet research communities in order to increase confidence in the use of past interglacial climate, ice-sheet and sea-level reconstructions to constrain future predictions. These questions were formulated during a joint workshop held by the PAGES-INQUA PALSEA (PALeo constraints on SEA level rise) and the PAGES-PMIP QUIGS (QUaternary InterGlacialS) Working Groups in September 2018.

Constraining the response time of the climate system to changes in North Atlantic Deep Water (NADW) formation is fundamental to improving climate and Atlantic Meridional Overturning Circulation predictability. Here we report a new synchronization of terrestrial, marine, and ice-core records, which allows the first quantitative determination of the response time of North Atlantic climate to changes in high-latitude NADW formation rate during the last deglaciation. Using a continuous record of deep water ventilation from the Nordic Seas, we identify a ∼400-year lead of changes in high-latitude NADW formation ahead of abrupt climate changes recorded in Greenland ice cores at the onset and end of the Younger Dryas stadial, which likely occurred in response to gradual changes in temperature- and wind-driven freshwater transport. We suggest that variations in Nordic Seas deep-water circulation are precursors to abrupt climate changes and that future model studies should address this phasing., The response time of North Atlantic climate to changes in high-latitude deep-water formation during the last deglaciation is still unclear. Here the authors show that gradual changes in Nordic Seas deep-water circulation systematically lead ahead of abrupt regional climate shifts by ~400 years.

The boron concentration (B/Ca ratio) and isotopic composition (δ11B) of biogenic calcite are widely applied to reconstruct past changes in seawater carbonate chemistry. Knowledge of B incorporation pathways into calcite is critical for these applications and for improving the theoretical basis of B proxies. While the canonical interpretation of δ11B holds that B in calcite predominantly derives from dissolved borate anion in seawater, recent studies of the B content, coordination, and isotopic composition in calcite suggest more complex B incorporation pathways. To provide new insights into these pathways, here we present δ11B of inorganic calcite precipitated from saline solutions of varying pH, calcium and dissolved inorganic carbon (DIC) concentration for which B/Ca data were previously reported by Uchikawa et al. (2015). Results show that calcite δ11B significantly increases with increasing pH and decreases with increasing [Ca2+] and [DIC]. In combination, these experiments show that the difference in δ11B between solid calcite and aqueous borate linearly decreases with increasing calcite precipitation rate. To interpret these data, we present the first application of surface kinetic modeling (SKM) to boron incorporation. The SKM can simultaneously explain rate-dependent B/Ca and δ11B patterns observed in our and previously published inorganic calcite precipitation experiments when both aqueous borate and boric acid contribute to boron in inorganic calcite. If the B incorporation mechanism shown here for inorganic calcite is applicable to biogenic calcite, precipitation rate variations could modify δ11B patterns by changing the contributions of aqueous boric acid and borate to boron in calcite. However, better knowledge of biogenic calcite precipitation mechanisms and rates is needed to assess the importance of this effect for applications of B proxies in biogenic carbonates.

RATIONALE\ud Oxygen and hydrogen isotopes are important tools for studying modern and past hydrological cycle. Previous evaporation experiments use episodic measurement of liquid and/or vapor or have not measured all isotopologues of water. Here, we describe an evaporation experimental system that allows all isotopologues of liquid and water vapor to be measured simultaneously and near‐continuously at high‐precision using cavity ring‐down laser spectroscopy (CRDS).\ud \ud METHODS\ud Evaporating liquid is periodically sampled from a closed recirculating loop by a syringe pump that delivers a constant supply of water to the vaporizer, achieving a water vapor concentration of 20,000 ppmV H2O (±132, 1σ). Vapor is sampled directly from the evaporation chamber. Isotope ratios are measured simultaneously with a Picarro L2140‐I CEDS instrument.\ud \ud RESULTS\ud For liquid measurements, Allan variance analysis indicates an optimum data collection window of 34 minutes for oxygen isotopes and 27 minutes for hydrogen isotopes. During these periods, the mean standard error is ±0.0081 ‰ for δ17O values, ±0.0081 ‰ for δ18O values, and ±0.019 ‰ for δ2H values. For the derived parameters 17O‐excess and d‐excess, the standard error of the mean is 5.8 per meg and 0.07 ‰, respectively. For the vapor phase a 12.5‐minute data window for all isotopologues results in a mean standard error of ±0.012 ‰ for δ17O values, ±0.011 ‰ for δ18O values, and ±0.023 ‰ for δ2H values. For the derived parameters, the standard error of the mean is 9.2 per meg for 17O‐excess and 0.099 ‰ for d‐excess. These measurements result in consistently narrow 95% confidence limits for the slopes of ln(δ17O+1) vs ln(δ18O+1) and ln(δ2H +1) vs ln(δ18O+1).\ud \ud CONCLUSIONS\ud The experimental method permits measurement of fractionation of triple‐oxygen and hydrogen isotopes of evaporating water under varying controlled conditions at high precision. Application of this method will be useful for testing theoretical models of evaporation and conducting experiments to simulate evaporation and isotopic equilibration in natural systems.

International audience; Changes in ocean ventilation, controlled by both overturning rates and air‐sea gas exchange, are thought to have played a central role in atmospheric CO2 rise across the last deglaciation. Here, we constrain the nature of Atlantic Ocean ventilation changes over the last deglaciation using radiocarbon and stable carbon isotopes from two depth transects in the Atlantic basin. Our findings broadly cohere with the established pattern of deglacial Atlantic overturning change, and underline the existence of active northern sourced deep‐water export at the Last Glacial Maximum (LGM). We find that the western Atlantic was less affected by incursions of southern‐sourced deep water, as compared to the eastern Atlantic, despite both sides of the basin being strongly influenced by the air‐sea equilibration of both northern and southern deep‐water end‐members. Ventilation at least as strong as modern is observed throughout the Atlantic during the Bølling‐Allerød (BA), implying a “flushing” of the entire Atlantic water column that we attribute to the combined effects of Atlantic meridional overturning circulation (AMOC) reinvigoration and increased air‐sea equilibration of southern sourced deep‐water. This ventilation “overshoot” may have counteracted a natural atmospheric CO2 decline during interstadial conditions, helping to make the BA a “point of no return” in the deglacial process. While the collected data emphasize a predominantly indirect AMOC contribution to deglacial atmospheric CO2 rise, via far field impacts on convection in the Southern Ocean and/or North Pacific during Heinrich Stadial 1 and the Younger Dryas, the potential role of the AMOC in centennial CO2 pulses emerges as an important target for future work.

While traditional microbiological freshwater tests focus on the detection of specific bacterial indicator species, including pathogens, direct tracing of all aquatic DNA through metagenomics poses a profound alternative. Yet, in situ metagenomic water surveys face substantial challenges in cost and logistics. Here, we present a simple, fast, cost-effective and remotely accessible freshwater diagnostics workflow centred around the portable nanopore sequencing technology. Using defined compositions and spatiotemporal microbiota from surface water of an example river in Cambridge (UK), we provide optimised experimental and bioinformatics guidelines, including a benchmark with twelve taxonomic classification tools for nanopore sequences. We find that nanopore metagenomics can depict the hydrological core microbiome and fine temporal gradients in line with complementary physicochemical measurements. In a public health context, these data feature relevant sewage signals and pathogen maps at species level resolution. We anticipate that this framework will gather momentum for new environmental monitoring initiatives using portable devices., eLife digest Many water-dwelling bacteria can cause severe diseases such as cholera, typhoid or leptospirosis. One way to prevent outbreaks is to test water sources to find out which species of microbes they contain, and at which levels. Traditionally, this involves taking a water sample, followed by growing a few species of ‘indicator bacteria’ that help to estimate whether the water is safe. An alternative technique, called metagenomics, has been available since the mid-2000s. It consists in reviewing (or ‘sequencing’) the genetic information of most of the bacteria present in the water, which allows scientists to spot harmful species. Both methods, however, require well-equipped laboratories with highly trained staff, making them challenging to use in remote areas. The MinION is a pocket-sized device that – when paired with a laptop or mobile phone – can sequence genetic information ‘on the go’. It has already been harnessed during Ebola, Zika or SARS-CoV-2 epidemics to track the genetic information of viruses in patients and environmental samples. However, it is still difficult to use the MinION and other sequencers to monitor bacteria in water sources, partly because the genetic information of the microbes is highly fragmented during DNA extraction. To address this challenge, Urban, Holzer et al. set out to optimise hardware and software protocols so the MinION could be used to detect bacterial species present in rivers. The tests focussed on the River Cam in Cambridge, UK, a waterway which faces regular public health problems: local rowers and swimmers often contract waterborne infections, sometimes leading to river closures. For six months, Urban, Holzer et al. used the MinION to map out the bacteria present across nine river sites, assessing the diversity of species and the presence of disease-causing microbes in the water. In particular, the results showed that optimising the protocols made it possible to tell the difference between closely related species – an important feature since harmful and inoffensive bacteria can sometimes be genetically close. The data also revealed that the levels of harmful bacteria were highest downstream of urban river sections, near a water treatment plant and river barge moorings. Together, these findings demonstrate that optimising MinION protocols can turn this device into a useful tool to easily monitor water quality. Around the world, climate change, rising urbanisation and the intensification of agriculture all threaten water quality. In fact, access to clean water is one of the United Nations sustainable development goals for 2030. Using the guidelines developed by Urban, Holzer et al., communities could harness the MinION to monitor water quality in remote areas, offering a cost-effective, portable DNA analysis tool to protect populations against deadly diseases.

International audience; Radiocarbon dates and marine tephra suggest that the upper 10 m of core MD99-2274 off North Iceland extends from ∼0 to ∼65 ka BP. A multi-proxy sediment and biomarker study at a ∼0.5 ky resolution is used to derive a paleoclimate scenario for this area of the southwestern Nordic Seas, which during the Holocene had intermittent excursions of icebergs and a seasonal cover of drifting sea ice across the site. The sortable silt mean size (S̅S̅) suggests a bottom current (1000 m depth) flow speed maximum to minimum range of ∼8 cm/s during Marine Isotope Stages 2–3, but the data are unreliable for the Holocene. Slow-down in flow speeds may be associated with massive ice and water discharges linked to the Hudson Strait ice stream (H-events) and to melt of icebergs from Greenland in the Nordic seas where convection would have been suppressed. Five pulses of sediment with a distinct felsic component are associated with iceberg transport from E/NE Greenland. Sea ice, open water and sea surface temperature (SST) biomarker proxies (i.e. IP25, HBI III, brassicasterol and alkenones) all point towards near-perennial sea ice cover during MIS 3 and 2, rather than seasonal sea ice or open water conditions. Indeed, our biomarker and sediment data require that the seas north of Iceland experienced a nearly continuous cover of sea ice, together with icebergs calved from ice stream termini, which drifted southward. The cross-correlation of the quartz % records between MD99-2274 and the well-dated core PS2644 in Blosseville Basin indicates significant coherence in the records at a multi-millennial (∼8 ky) timescale. A transition to open ocean conditions is evident from the early Holocene onwards, albeit with the occurrence of some drift ice and icebergs.

Core MD99-2323 was extracted from the Snorri Drift at a water depth of 1062 m, just south of the Denmark Strait, and ~120 km from the Last Glacial Maximum (LGM) margins of the Iceland and East Greenland Ice Sheets. The core chronology (~7.5 to 240 cal ka) is derived from radiocarbon dates, marker tephra, paleomagnetic excursion, and correlation with North Atlantic δ18O records on Neogloboquadrina pachyderma (δ18ONp). Sedimentation averaged ~7.5 cm/kyr. Records of proxy flow speed, ice rafted debris (IRD) and oxygen isotopes show that many IRD abundance peaks represent winnowing of the fine fraction by faster flows rather than pulses of increased IRD flux. The overall pattern of flow speed does not resemble the classic fast interglacial/slow glacial pattern seen in records of Nordic Sea overflow, rather the current record is suggested to be partly controlled by the production of brine-driven gravity flows from adjacent ice fronts, especially during cold periods. On a smaller scale the usual glacial/slow – interglacial/fast pattern appears to be the case during ~5 kyr oscillations during Marine Isotope Stage (MIS) 6 where periodic low flow speed is matched by high values of planktonic oxygen isotope ratios. Eight peaks in quartz wt% reflect increased contributions from glacial erosion of Precambrian and Caledonian bedrock from E and NE Greenland; peaks in dolomite may reflect glacial-marine transport from the Laurentide Ice Sheet. Cross wavelet analysis of the δ18ONp versus sortable silt and quartz records indicate significant precession and obliquity periodicities, but with little temporal correlations due to leads and lags in responses.

The modeling of paleoclimate, using physically based tools, is increasingly seen as a strong out-of-sample test of the models that are used for the projection of future climate changes. New to the Coupled Model Intercomparison Project (CMIP6) is the Tier 1 Last Interglacial experiment for 127 000 years ago (lig127k), designed to address the climate responses to stronger orbital forcing than the midHolocene experiment, using the same state-of-the-art models as for the future and following a common experimental protocol. Here we present a first analysis of a multi-model ensemble of 17 climate models, all of which have completed the CMIP6 DECK (Diagnostic, Evaluation and Characterization of Klima) experiments. The equilibrium climate sensitivity (ECS) of these models varies from 1.8 to 5.6 ∘C. The seasonal character of the insolation anomalies results in strong summer warming over the Northern Hemisphere continents in the lig127k ensemble as compared to the CMIP6 piControl and much-reduced minimum sea ice in the Arctic. The multi-model results indicate enhanced summer monsoonal precipitation in the Northern Hemisphere and reductions in the Southern Hemisphere. These responses are greater in the lig127k than the CMIP6 midHolocene simulations as expected from the larger insolation anomalies at 127 than 6 ka. New synthesis for surface temperature and precipitation, targeted for 127 ka, have been developed for comparison to the multi-model ensemble. The lig127k model ensemble and data reconstructions are in good agreement for summer temperature anomalies over Canada, Scandinavia, and the North Atlantic and for precipitation over the Northern Hemisphere continents. The model–data comparisons and mismatches point to further study of the sensitivity of the simulations to uncertainties in the boundary conditions and of the uncertainties and sparse coverage in current proxy reconstructions. The CMIP6–Paleoclimate Modeling Intercomparison Project (PMIP4) lig127k simulations, in combination with the proxy record, improve our confidence in future projections of monsoons, surface temperature, and Arctic sea ice, thus providing a key target for model evaluation and optimization.

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ34S and δ18O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ34S and δ18O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ34S and δ18O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.

Plain Language Summary\ud Modeling of future climate suggests that California may experience increased frequency of both extremely wet and extremely dry periods in the 21st century, leading to the emergence of “climate whiplash” phenomena which would significantly stress the state's water‐sensitive infrastructure. Understanding hydroclimate changes in California's past can help planners prepare for extremes that may be more severe than those of the historical record. However, existing paleoclimate records are often limited to qualitative interpretations of hydroclimate change, restricting their usefulness. We present new calcium isotope measurements from a California stalagmite that grew from 6,900 to 8,600 years ago, revealing variability in rainfall amounts on the California coast during and surrounding the 8.2 kyr event, an abrupt cold snap noted in other global paleoclimate records 8,200 years ago. We generate semiquantitative estimates of annual rainfall rates during the 8.2 kyr event period and compare them with modern annual rainfall amounts, finding that the magnitude of rainfall variability during and surrounding the 8.2 kyr event approaches and in some cases exceeds that of California today. This work indicates that California may have experienced even more intense “climate whiplash” phenomena in the past than during recent decades, suggesting that future planning may need to consider greater wet and dry extremes.\ud Abstract\ud A multiproxy record from a fast‐growing stalagmite reveals variable hydroclimate on the California coast across the 8.2 kyr event and a precursor event likely caused by initial drainage of proglacial Lake Agassiz. Using speleothem δ44Ca, we develop the first semiquantitative estimates of paleorainfall variability for California through calibration with measurements of the modern climate and cave environment. We find that the magnitude of rainfall variability during the 8.2 kyr event approached the multiyear variability observable in the recent past (1950–2019) and the magnitude of variability during the precursor event likely exceeded this range. Additionally, we observe other instances of multidecadal variability comparable in magnitude to the precursor event during the record. Our work suggests that speleothem calcium isotope ratios are a powerful semiquantitative means to reconstruct paleorainfall, although numerous factors must be assessed in each cave system before applying this approach.

The southwest Atlantic gyre connects several distinct water masses, which means that this oceanic region is characterized by a complex frontal system and enhanced water mass modification. Despite its significance, the distribution and variability of vertical mixing rates have yet to be determined for this system. Specifically, potential conditioning of mixing rates by frontal structures, in this location and elsewhere, is poorly understood. Here, we analyze vertical seismic (i.e., acoustic) sections from a three-dimensional survey that straddles a major front along the northern portion of the Brazil-Falkland Confluence. Hydrographic analyses constrain the structure and properties of water masses. By spectrally analyzing seismic reflectivity, we calculate spatial and temporal distributions of the dissipation rate of turbulent kinetic energy, ε, of diapycnal mixing rate, K, and of vertical diffusive heat flux, FH. We show that estimates of ε, K, and FH are elevated compared to regional and global mean values. Notably, cross-sectional mean estimates vary little over a 6 week period whilst smaller scale thermohaline structures appear to have a spatially localized effect upon ε, K, and FH. In contrast, a mesoscale front modifies ε and K to a depth of 1 km, across a region of O(100) km. This front clearly enhances mixing rates, both adjacent to its surface outcrop and beneath the mixed layer, whilst also locally suppressing ε and K to a depth of 1 km. As a result, estimates of FH increase by a factor of two in the vicinity of the surface outcrop of the front. Our results yield estimates of ε, K and FH that can be attributed to identifiable thermohaline structures and they show that fronts can play a significant role in water mass modification to depths of 1 km.

Rivers carry the dissolved and solid products of silicate mineral\ud weathering, a process that removes CO2 from the atmosphere and\ud provides a key negative climate feedback over geological timescales.\ud Here we show that in some river systems, a reactive exchange pool\ud on river suspended particulate matter, bonded weakly to mineral\ud surfaces, increases the mobile cation flux by 50%. The chemistry\ud of both river waters and the exchange pool demonstrate exchange\ud equilibrium, confirmed by Sr isotopes. Global silicate weathering\ud fluxes are calculated based on riverine dissolved sodium (Na+) from\ud silicate minerals. The large exchange pool supplies Na+ of non-\ud silicate origin to the dissolved load, especially in catchments with\ud widespread marine sediments, or where rocks have equilibrated with\ud saline basement fluids. We quantify this by comparing the riverine\ud sediment exchange pool and river water chemistry. In some basins,\ud cation exchange could account for the majority of sodium in the\ud river water, significantly reducing estimates of silicate weathering.\ud At a global scale, we demonstrate that silicate weathering fluxes\ud are over-estimated by 12-28%. This over-estimation is greatest in\ud regions of high erosion and high sediment loads where the negative\ud climate feedback has a maximum sensitivity to chemical weathering\ud reactions. In the context of other recent findings that reduce the\ud net CO2 consumption through chemical weathering, the magnitude\ud of the continental silicate weathering fluxes and its implications for\ud solid Earth CO2 degassing fluxes needs to be further investigated.

Permafrost thaw in Arctic watersheds threatens to mobilize hitherto sequestered carbon. We examine the radiocarbon activity (F14C) of dissolved organic carbon (DOC) in the northern Mackenzie River basin. From 2003–2017, DOC‐F14C signatures (1.00 ± 0.04; n = 39) tracked atmospheric 14CO2, indicating export of “modern” carbon. This trend was interrupted in June 2018 by the widespread release of aged DOC (0.85 ± 0.16, n = 28) measured across three separate catchment areas. Increased nitrate concentrations in June 2018 lead us to attribute this pulse of 14C‐depleted DOC to mobilization of previously frozen soil organic matter. We propose export through lateral perennial thaw zones that occurred at the base of the active layer weakened by preceding warm summer and winter seasons. Although we are not yet able to ascertain the broader significance of this “anomalous” mobilization event, it highlights the potential for rapid and large‐scale release of aged carbon from permafrost., Key Points A widespread pulse of aged dissolved organic carbon (DOC) occurred in the Mackenzie River and its tributaries in June 2018Export of aged DOC is consistent with a prolonged warming period and the formation of supra‐permafrost taliksMobilization of aged DOC and nitrate suggests percolation of supra‐permafrost groundwater through previously frozen soil layers

Chemical weathering plays an important role in sequestering atmospheric CO2, but its potential influence on global climate over geological timescales remains debated. To some extent, this uncertainty arises from the difficulty in separating the respective contribution of sedimentary and crystalline silicate rocks to past weathering rates in the geological record; two types of rocks having presumably different impact on the long-term carbon cycle. In this study, we investigate the use of rare earth element (REE) and neodymium isotopes (εNd) in leached iron oxide fractions of river sediments for tracing the origin of weathered rocks on continents. A new index, called ‘concavity index’ (CI), is defined for measuring the degree of mid-REE enrichment in geological samples, which enables the determination of the source of iron oxides in sediments, such as seawater-derived Fe-oxyhydroxide phases, ancient marine Fe oxides derived from the erosion of sedimentary rocks, and recent secondary oxides formed in soils via alteration of crystalline silicate rocks or pyrite oxidation. Using this index, we demonstrate that the εNd difference between paired Fe-oxide and detrital fractions in river sediments (defined here as ∆εNd Feox-Det) directly reflects the relative contribution of sedimentary versus crystalline silicate rocks during weathering. While rivers draining old cratons and volcanic provinces display near-zero ∆εNd Feox-Det values indicative of dominant silicate weathering (0.5 ± 1.1; n = 30), multi-lithological catchments hosting sedimentary formations yield systematically higher values (2.7 ± 1.2; n = 44), showing that sedimentary rock weathering can be traced by the occurrence of riverine Fe oxides having more radiogenic Nd isotope signatures compared to detrital fractions. This assumption is reinforced by the evidence that calculated ∆εNd Feox-Det values agree well with previous estimates for carbonate and silicate weathering rates in large river basins. Examining the influence of climate and tectonics on measured Nd isotopic compositions, we find that ∆εNd Feox-Det is strongly dependent on temperature in lowlands, following an Arrhenius-like relationship that reflects enhanced alteration of silicate rocks and formation of secondary Fe oxides in warmer climates. In contrast, in high-elevation catchments, ∆εNd Feox-Det defines striking correlation with maximum basin elevation, which we also interpret as reflecting the intensification of silicate weathering and associated Fe oxide formation as elevation decreases, due to the combined effects of thicker soils and warmer temperature. Overall, our new findings are consistent with previous assertions that the alteration of sedimentary rocks prevails in high-elevation environments, while silicate weathering dominates in floodplains. This novel approach combining REE and Nd isotopes opens new perspectives for disentangling the weathering signals of sedimentary and crystalline silicate rocks in the geologic record, which could be used in future studies to reassess the causal relationships between mountain uplift, erosion and climate throughout Earth's history.

The record of past climate highlights recurrent and intense millennial anomalies, characterised by a distinct pattern of inter-polar temperature change, termed the ‘thermal bipolar seesaw’, which is widely believed to arise from rapid changes in the Atlantic overturning circulation. By forcing a suppression of North Atlantic convection, models have been able to reproduce many of the general features of the thermal bipolar seesaw; however, they typically fail to capture the full magnitude of temperature change reconstructed using polar ice cores from both hemispheres. Here we use deep-water temperature reconstructions, combined with parallel oxygenation and radiocarbon ventilation records, to demonstrate the occurrence of enhanced deep convection in the Southern Ocean across the particularly intense millennial climate anomaly, Heinrich Stadial 4. Our results underline the important role of Southern Ocean convection as a potential amplifier of Antarctic warming, and atmospheric CO2 rise, that is responsive to triggers originating in the North Atlantic. Antarctic warming and the rise of atmospheric CO2 levels during Heinrich Stadial 4 were amplified by enhanced convection and air-sea gas and heat exchange in the Southern Ocean, according to an analysis of deep water ventilation and temperature proxies

Many geographically dispersed records from across the globe reveal the occurrence of abrupt climate changes, called interstadial events, during the last glacial period. These events appear to have happened at the same time, but the difficulty of determining absolute dates in many of the records have made that proposition difficult to prove. Corrick et al. present results from 63 precisely dated speleothems that confirm the synchrony of those interstadial events. Their results also provide a tool with which to validate model simulations of abrupt climate change and calibrate other time series such as ice-core chronologies.Science, this issue p. 963Abrupt climate changes during the last glacial period have been detected in a global array of palaeoclimate records, but our understanding of their absolute timing and regional synchrony is incomplete. Our compilation of 63 published, independently dated speleothem records shows that abrupt warmings in Greenland were associated with synchronous climate changes across the Asian Monsoon, South American Monsoon, and European-Mediterranean regions that occurred within decades. Together with the demonstration of bipolar synchrony in atmospheric response, this provides independent evidence of synchronous high-latitude–to-tropical coupling of climate changes during these abrupt warmings. Our results provide a globally coherent framework with which to validate model simulations of abrupt climate change and to constrain ice-core chronologies.

Chemical weathering of volcanic rocks in warm and humid climates contributes disproportionately to global solute fluxes. Geochemical signatures of solutes and solids formed during this process can help quantify and reconstruct weathering intensity in the past. Here, we measured silicon (Si) and germanium (Ge) isotope ratios of the soils, clays, and fluids from a tropical lowland rainforest in Costa Rica. The bulk topsoil is intensely weathered and isotopically light (mean±1σ: δ 30Si = –2.1 ± 0.3‰, δ 74Ge = –0.13 ± 0.12‰) compared to the parent rock (δ 30Si = –0.11 ± 0.05‰, δ 74Ge = 0.59 ± 0.07‰). Neoforming clays have even lower values (δ 30Si = –2.5 ± 0.2‰, δ 74Ge = –0.16 ± 0.09‰), demonstrating a whole-system isotopic shift in extremely weathered systems. The lowland streams represent mixing of dilute local fluids (δ 30Si = 0.2 – 0.6‰, δ 74Ge = 2.2 – 2.6‰) with solute-rich interbasin groundwater (δ 30Si = 1.0±0.2‰, δ 74Ge = 4.0‰). Using a Ge-Si isotope mass balance model, we calculate that 91 ± 9% of Ge released via weathering of lowland soils is sequestered by neoforming clays, 9 ± 9% by vegetation, and only 0.2 ± 0.2% remains dissolved. Vegetation plays an important role in the Si cycle, directly sequestering 39 ± 14% of released Si and enhancing clay neoformation in surface soils via the addition of amorphous phytolith silica. Globally, volcanic soil δ 74Ge closely tracks the depletion of Ge by chemical weathering (τGe), whereas δ 30Si and Ge/Si both reflect the loss of Si (τSi). Because of the different chemical mobilities of Ge and Si, a δ 74Ge-δ 30Si multi-proxy system is sensitive to a wider range of weathering intensities than each isotopic system in isolation.

The abrupt nature of warming events recorded in Greenland ice-cores during the last glacial has generated much debate over their underlying mechanisms. Here, we present joint marine and terrestrial analyses from the Portuguese Margin, showing a succession of cold stadials and warm interstadials over the interval 35–57 ka. Heinrich stadials 4 and 5 contain considerable structure, with a short transitional phase leading to an interval of maximum cooling and aridity, followed by slowly increasing sea-surface temperatures and moisture availability. A climate model experiment reproduces the changes in western Iberia during the final part of Heinrich stadial 4 as a result of the gradual recovery of the Atlantic meridional overturning circulation. What emerges is that Greenland ice-core records do not provide a unique template for warming events, which involved the operation of both fast and slow components of the coupled atmosphere–ocean–sea-ice system, producing adjustments over a range of timescales., We thank Russell Drysdale and Eric Wolff for comments on specific aspects of the paper. Financial support was provided by Natural Environment Research Council grants NE/C514758/1 (to P.C.T., held at the University of Leeds) and NE/J00653X/1 (to D.A.H.), and Australian Research Council grant FT180100606 (to L.M.). E.C. acknowledges financial support from the ChronoClimate project, funded by the Carlsberg Foundation and MME from the Research Council of Norway and from COFUND – Marie Skłodowska-Curie Actions FP7, project numbers 274429 and 223259. B.M. acknowledges support from the CSIC Ramón y Cajal postdoctoral programme RYC-2013-14073 and LINKA20102. We wish to acknowledge use of the Ferret program for generating the maps in Fig. 7 and Supplementary Fig. 2 in this paper. Ferret is a product of NOAA’s Pacific Marine Environmental Laboratory (information is available at http://ferret.pmel.noaa.gov/Ferret/).

T.J. Heaton is supported by a Leverhulme Trust Fellowship RF-2019-140\9, “Improving the Measurement of Time Using Radiocarbon”. M Butzin is supported by the German Federal Ministry of Education and Research (BMBF), as Research for Sustainability initiative (FONA); www.fona.de through the PalMod project (grant numbers: 01LP1505B, 01LP1919A). E. Bard is supported by EQUIPEX ASTER-CEREGE and ANR CARBOTRYDH. Meetings of the IntCal Marine Focus group have been supported by Collège de France. The concentration of radiocarbon (14C) differs between ocean and atmosphere. Radiocarbon determinations from samples which obtained their 14C in the marine environment therefore need a marine-specific calibration curve and cannot be calibrated directly against the atmospheric-based IntCal20 curve. This paper presents Marine20, an update to the internationally agreed marine radiocarbon age calibration curve that provides a non-polar global-average marine record of radiocarbon from 0–55 cal kBP and serves as a baseline for regional oceanic variation. Marine20 is intended for calibration of marine radiocarbon samples from non-polar regions; it is not suitable for calibration in polar regions where variability in sea ice extent, ocean upwelling and air-sea gas exchange may have caused larger changes to concentrations of marine radiocarbon. The Marine20 curve is based upon 500 simulations with an ocean/atmosphere/biosphere box-model of the global carbon cycle that has been forced by posterior realizations of our Northern Hemispheric atmospheric IntCal20 14C curve and reconstructed changes in CO2 obtained from ice core data. These forcings enable us to incorporate carbon cycle dynamics and temporal changes in the atmospheric 14C level. The box-model simulations of the global-average marine radiocarbon reservoir age are similar to those of a more complex three-dimensional ocean general circulation model. However, simplicity and speed of the box model allow us to use a Monte Carlo approach to rigorously propagate the uncertainty in both the historic concentration of atmospheric 14C and other key parameters of the carbon cycle through to our final Marine20 calibration curve. This robust propagation of uncertainty is fundamental to providing reliable precision for the radiocarbon age calibration of marine based samples. We make a first step towards deconvolving the contributions of different processes to the total uncertainty; discuss the main differences of Marine20 from the previous age calibration curve Marine13; and identify the limitations of our approach together with key areas for further work. The updated values for ΔR, the regional marine radiocarbon reservoir age corrections required to calibrate against Marine20, can be found at the data base http://calib.org/marine/. Publisher PDF

Funder: German Research Foundation (DFG) SFB-TRR 170 "Late Accretion onto Terrestrial Planets" (subprojects C5, C6) and projects Ts 17/2-1 and NO 1324/2-1, Funder: Swiss National Foundation under grant PZ00P2 174028 and the National Center for Competence in Research PlanetS, Volcanic degassing of planetary interiors has important implications for their corresponding atmospheres. The oxidation state of rocky interiors affects the volatile partitioning during mantle melting and subsequent volatile speciation near the surface. Here we show that the mantle redox state is central to the chemical composition of atmospheres while factors such as planetary mass, thermal state, and age mainly affect the degassing rate. We further demonstrate that mantle oxygen fugacity has an effect on atmospheric thickness and that volcanic degassing is most efficient for planets between 2 and 4 Earth masses. We show that outgassing of reduced systems is dominated by strongly reduced gases such as [Formula: see text], with only smaller fractions of moderately reduced/oxidised gases ([Formula: see text], [Formula: see text]). Overall, a reducing scenario leads to a lower atmospheric pressure at the surface and to a larger atmospheric thickness compared to an oxidised system. Atmosphere predictions based on interior redox scenarios can be compared to observations of atmospheres of rocky exoplanets, potentially broadening our knowledge on the diversity of exoplanetary redox states.

Arctic fjord sediments of Svalbard receive terrestrial material from glacial runoff and organic matter from marine primary productivity. Organic carbon mineralization proceeds primarily through sulfate and iron reduction in the fjord sediment. The ongoing retreat of glaciers in the high Arctic is altering the input of glacial material to the fjords, with unknown consequences for the iron and sulfur cycles in the fjord sediments. We measured sulfate reduction rates in sediment cores and analyzed porewater geochemistry, then compared these results to long-term sediment incubations to determine the rates of iron reduction and sulfide oxidation in three glacially influenced fjords on the west coast of Spitsbergen, Svalbard. Despite an abundance of glacially-sourced Fe(III)-oxide minerals, active sulfate reduction took place throughout the sediment. Analyses of the sulfur and oxygen isotopic composition of porewater sulfate and sulfate concentrations suggest that sulfide produced from biological sulfate reduction is reoxidized to sulfate. Long-term sediment incubations indicated sulfide oxidation at all three stations. The rate of sulfide oxidation was controlled by both the rate of sulfate reduction and the quantity and reactivity of Fe(III)-oxides. In our experimental incubations, we detected a decrease in Fe(III) content of the 0.5 M HCl and ascorbate-extractable fractions, but not in the 6 M HCl fraction, indicating that the highly reactive Fe(III) fraction is utilized by microorganisms and serves as the oxidant for sulfide oxidation. Our results show that sulfide oxidation in glacially-influenced fjord sediments is a wide-spread geochemical process. Further warming will drive glacial retreat onto land, where sediment-laden glacial meltwater will be altered during flow through proglacial streams and lakes before entering the marine environment. Fjord sediments will likely become more sulfidic, as glaciers deliver less particulate, highly-reactive metal oxides to the marine environment.

The North Atlantic subpolar gyre (SPG) connects tropical and high latitude waters, playing a leading role in deep‐water formation, propagation of Atlantic water into the Arctic, and as habitat for many ecosystems. Instrumental records spanning recent decades document significant decadal variability in SPG circulation, with associated hydrographic and ecological changes. Emerging longer‐term records provide circumstantial evidence that the North Atlantic also experienced centennial trends during the 20th century. Here, we use marine sediment records to show that there has been a long‐term change in SPG circulation during the industrial era, largely during the 20th century. Moreover, we show that the shift and late 20th century SPG configuration were unprecedented in the last 10,000 years. Recent SPG dynamics resulted in an expansion of subtropical ecosystems into new habitats and likely also altered the transport of heat to high latitudes.

Volcanic eruptions are thought to be a key driver of rapid climate perturbations over geological time, such as global cooling, global warming, and changes in ocean chemistry. However, identification of stratospheric volcanic eruptions in the geological record and their causal link to the mass extinction events during the past 540 million years remains challenging. Here we report unexpected, large mass-independent sulphur isotopic compositions of pyrite with Δ33S of up to 0.91‰ in Late Ordovician sedimentary rocks from South China. The magnitude of the Δ33S is similar to that discovered in ice core sulphate originating from stratospheric volcanism. The coincidence between the large Δ33S and the first pulse of the Late Ordovician mass extinction about 445 million years ago suggests that stratospheric volcanic eruptions may have contributed to synergetic environmental deteriorations such as prolonged climatic perturbations and oceanic anoxia, related to the mass extinction., Identification of stratospheric volcanic eruptions in the geological record and their link to mass extinction events during the past 540 million years remains challenging. Here, the authors report unexpected, large mass-independent sulphur isotopic compositions of pyrite in Late Ordovician sedimentary rocks, which they suggest originates from stratospheric volcanism linked to the first pulse of the Late Ordovician mass extinction.

Reconstructing changes in the calcium isotopic composition (δ44Ca) of the ocean over Earth history has been challenging. This difficulty is due to the large range of calcium isotope fractionation factors during mineral precipitation and the potential for overwriting the initial δ44Ca of minerals during shallow marine diagenesis. We present a new δ44Ca record measured in carbonate hardground cements, an inorganic carbonate-mineral precipitate that rapidly forms at or near the sediment-water interface. The range in the δ44Ca for any particular carbonate hardground cements is between 0.05 and 0.56‰. In some cases, the progressive increase in the δ44Ca during precipitation can be observed, consistent with precipitation in a ‘closed-system’. Our data show an average calcium isotope fractionation during carbonate hardground cement precipitation that is −0.57 ± 0.27‰, similar to the calcium isotope fractionation factor for inorganic calcite precipitates in previous laboratory and modelling studies, and closer to what is considered a kinetic end member calcium isotope fractionation than growth at equilibrium. This is consistent with the rapid carbonate mineral precipitation expected for carbonate hardground cements. Our δ44Ca record over the Phanerozoic is similar to other calcium-bearing mineral records over the same time interval, with average δ44Ca becoming lower going back in time by about 0.5 to 0.7‰. Our results add further support for the evolution of seawater δ44Ca over time, and we discuss the possible causes of these changes with suggestions for future studies.

Calcium is an essential element in the biogeochemical cycles that regulate the long-term climate state of Earth. The removal of CO2 from the ocean-atmosphere system is controlled by the burial of carbonate sediments (CaCO3), ultimately linking the global calcium and carbon cycles. This fundamental link has driven the development of the stable calcium isotope proxy with application to both ancient skeletal and non-skeletal bulk carbonate sediments. Calcium isotope ratios (δ44/40Ca) have been used to track long-term changes in seawater chemistry (e.g., aragonite vs. calcite seas) and to elucidate short-term climatic perturbations associated with mass extinction events. However, developments in the calcium isotope proxy have shown that δ44/40Ca values in carbonate minerals also are sensitive to changes in precipitation rates, mineralogy and diagenesis, thereby complicating the application of the proxy to the reconstruction of global cycles. First, inorganic carbonate precipitation experiments have demonstrated that carbonate δ44/40Ca values are sensitive to precipitation rates with higher rates generally leading to larger fractionation. Second, δ44/40Ca values are sensitive to carbonate mineralogy with inorganic aragonite and calcite being on average ~ 1.5‰ and ~ 0.9‰ depleted relative to contemporaneous seawater, respectively. The effects of both changes in carbonate mineralogy and precipitation rates affect primary and secondary minerals, but are particularly pronounced during carbonate diagenesis where relatively slow rates of recrystallization and neomorphism can lead to significant changes in bulk sediment δ44/40Ca values. Third, changes in faunal composition expressed in skeletal fossil archives can lead to large changes in carbonate δ44/40Ca values that are decoupled from changes in global cycles. Nevertheless, when these factors are appropriately considered the application of calcium isotopes in ancient carbonate sediments becomes a powerful tool for understanding biogeochemical processes that operate over many scales; from diagenetic changes within the sediment pore-space, to regional changes across ancient carbonate platforms, and to global changes in seawater chemistry through time. Importantly, the processes that contribute to variability in carbonate δ44/40Ca values are likely to impact other carbonate-bound proxies, highlighting the potential for calcium isotopes as a tool to better understand the variability of other isotope systems.

Magnesium and lithium stable isotope ratios (δ26Mg and δ7Li) have shown promise as tools to elucidate biogeochemical processes both at catchment scales and in deciphering global climate processes. Nevertheless, the controls on riverine Mg and Li isotope ratios are often difficult to determine as a myriad of factors can cause fractionation from bulk rock values such as secondary mineral formation and preferential weathering of isotopically distinct mineral phases. Quantifying the relative contribution from carbonate and silicate minerals to the dissolved load of glacierized catchments is particularly crucial for determining the role of chemical weathering in modulating the carbon cycle over glacial-interglacial periods. In this study we report Mg and Li isotope data for water, river sediment, rock, and mineral separates from the Leverett Glacier catchment, West Greenland. We assess whether the silicate mineral contributions to the dissolved load, previously determined using radiogenic Sr, Ca, Nd, and Hf isotopes, are consistent with dissolved Mg and Li isotope data, or whether a carbonate contribution is required as inferred previously for this region. For δ7Li, the average dissolved river water value (+19.2 ± 2.5h, 2SD) was higher than bedrock, river sediment, and mineral δ7Li values, implying a fractionation process. For δ26Mg, the average dissolved river water value (−0.30 ± 0.14h, 2SD) was within error of bedrock and river sediment and within the range of mineral δ26Mg values (−1.63 to +0.06h). The river δ26Mg values are consistent with the mixing of Mg derived from the same mineral phases previously identified from radiogenic isotope measurements as controlling the dissolved load chemistry. Glacier fed rivers previously measured in this region had δ26Mg values ∼0.80h lower than those measured in the Leverett River which could be caused by a larger contribution from garnet (−1.63h) dissolution compared to Leverett. This study highlights that dissolved Mg and Li isotope ratios in the Leverett River are affected by different processes (mixing and fractionation), and that since variations in silicate mineral δ26Mg values exist, preferential weathering of individual silicate minerals should be considered in addition to carbonate when interpreting dissolved δ26Mg values., Frontiers in Earth Sciences, 7, ISSN:1863-4621, ISSN:1863-463X

Two consecutive cruises in the Weddell Sea, Antarctica, in winter 2013 provided the first direct observations of sea salt aerosol (SSA) production from blowing snow above sea ice, thereby validating a model hypothesis to account for winter time SSA maxima in the Antarctic. Blowing or drifting snow often leads to increases in SSA during and after storms. For the first time it is shown that snow on sea ice is depleted in sulfate relative to sodium with respect to seawater. Similar depletion in bulk aerosol sized ∼0.3–6 µm above sea ice provided the evidence that most sea salt originated from snow on sea ice and not the open ocean or leads, e.g. >90 % during the 8 June to 12 August 2013 period. A temporally very close association of snow and aerosol particle dynamics together with the long distance to the nearest open ocean further supports SSA originating from a local source. A mass budget estimate shows that snow on sea ice contains even at low salinity ( psu) more than enough sea salt to account for observed increases in atmospheric SSA during storms if released by sublimation. Furthermore, snow on sea ice and blowing snow showed no or small depletion of bromide relative to sodium with respect to seawater, whereas aerosol was enriched at 2 m and depleted at 29 m, suggesting that significant bromine loss takes place in the aerosol phase further aloft and that SSA from blowing snow is a source of atmospheric reactive bromine, an important ozone sink, even during winter darkness. The relative increase in aerosol concentrations with wind speed was much larger above sea ice than above the open ocean, highlighting the importance of a sea ice source in winter and early spring for the aerosol burden above sea ice. Comparison of absolute increases in aerosol concentrations during storms suggests that to a first order corresponding aerosol fluxes above sea ice can rival those above the open ocean depending on particle size. Evaluation of the current model for SSA production from blowing snow showed that the parameterizations used can generally be applied to snow on sea ice. Snow salinity, a sensitive model parameter, depends to a first order on snowpack depth and therefore was higher above first-year sea ice (FYI) than above multi-year sea ice (MYI). Shifts in the ratio of FYI and MYI over time are therefore expected to change the seasonal SSA source flux and contribute to the variability of SSA in ice cores, which represents both an opportunity and a challenge for the quantitative interpretation of sea salt in ice cores as a proxy for sea ice.

This study combines high-resolution records of nannofossil abundances, oxygen and carbon stable isotopes, core scanning X-ray fluorescence (XRF), and ice rafted debris (IRD) to assess the paleoceanographic changes that occurred during the last deglaciation on the SW Iberian Margin. Our results reveal parallel centennial-scale oscillations in coccolithophore productivity, nutricline depth and upwelling phenomena not previously observed, explained by means of arrival of iceberg-melting waters, iceberg-induced turbulent conditions, SST changes and riverine discharges. On millennial time-scales, higher primary productivity (PP), shallower nutricline, and upwelling occurrence/invigoration are observed for the Last Glacial Maximum (LGM) and Bølling-Allerød (B/A). The opposite scenario (i.e., lower productivity, deeper nutricline and upwelling weakening/absence) is linked to cold spells such as Heinrich Stadials 2 and 1 (HS2 and HS1) and the Younger Dryas (YD). Such paleoproductivity variations are attributed to latitudinal migrations of the thermal fronts associated with oceanic gyres in the North Atlantic, in parallel to oscillations in the strength of the Atlantic Meridional Overturning Circulation (AMOC). Moderate-to-high PP during the Holocene is ascribed to the development of the modern seasonal surface hydrography, with a more persistent Iberian Poleward Current (IPC) and seasonal wind-induced upwelling. ISSN:0277-3791

Analysis of 87Sr/86Sr ratios and modelling of formation water, injection water and produced water compositions from the CO2CRC Otway Research Facility in Victoria, Australia are used to test tracer behaviour and response in push-pull experiments. Such experiments are an essential pre-requisite to understanding the controls imposed by reservoir heterogeneities on CO2 dissolution rates which may be an important stabilising mechanism for geological carbon storage. The experiments (Otway stage 2B extension in 2014) comprised two sequential tests in which ~ 100 tonnes of CO2-saturated water was injected with combinations of Sr and Br or Li and Fluorescein tracers, each injection being followed by two staged extractions of ~ 10 tons and a final extraction of ~ 50 tons all spaced at ~ 10 day intervals. Analysis of the 87Sr/86Sr ratios of the produced fluids from the first injection, spiked with SrCl2 and NaBr, is consistent with Sr behaving conservatively. This contrasts with previous interpretations in which Br was argued to have behaved conservatively while Sr, which dilutes ~ three times as fast as Br, was thought to be lost to a mineral phase. Such Sr-loss cannot explain the evolution of 87Sr/86Sr ratios. The analysis of 87Sr/86Sr ratios in the waters produced after the second injection episode, spiked with LiCl and Fluorescein tracers, allows calculation of the fractions of the formation waters and the injection waters from both tests 1 and 2. The Sr, Li and SO4 tracers (the later formed by oxidation of formation sulphide) all indicate similar rates of dilution that is consistent with conservative behaviour. The results of the two injection episodes with spaced extractions are compared with two subsequent push-pull injections in which the produced waters, spiked with methanol, were extracted continuously. These continuous extraction experiments exhibited significantly less dilution over the same range of produced to injected water volumes (upto only ~ 0.6) than the earlier experiments with spaced extractions. This implies that some process related to the pauses in extraction enhances mixing of injected and formation waters. Achieving the objective of using push-pull experiments to assess reservoir heterogeneities and CO2 dissolution rates will require better assessment of the various tracers to establish which behave conservatively followed a proper understanding of the causes of the variations in mixing as fluids are extracted from the formations.

The stable isotopes of sulfate, nitrate, and phosphate are frequently used to study geobiological processes of the atmosphere, ocean, as well as land. Conventionally, the isotopes of these and other oxyanions are measured by isotope-ratio sector mass spectrometers after conversion into gases. Such methods are prone to various limitations on sensitivity, sample throughput, or precision. In addition, there is no general tool that can analyze several oxyanions or all the chemical elements they contain. Here, we describe a new approach that can potentially overcome some of these limitations based on electrospray hyphenated with Quadrupole Orbitrap mass spectrometry. This technique yields an average accuracy of 1–2‰ for sulfate δ³⁴S and δ¹⁸O and nitrate δ¹⁵N and δ¹⁸O, based on in-house and international standards. Less abundant variants such as δ¹⁷O, δ³³S, and δ³⁶S, and the ³⁴S–¹⁸O “clumped” sulfate can be quantified simultaneously. The observed precision of isotope ratios is limited by the number of ions counted. The counting of rare ions can be accelerated by removing abundant ions with the quadrupole mass filter. Electrospray mass spectrometry (ESMS) exhibits high-throughput and sufficient sensitivity. For example, less than 1 nmol sulfate is required to determine ¹⁸O/³⁴S ratios with 0.2‰ precision within minutes. A purification step is recommended for environmental samples as our proposed technique is susceptible to matrix effects. Building upon these initial provisions, new features of the isotopic anatomy of mineral ions can now be explored with ESMS instruments that are increasingly available to bioanalytical laboratories.

A large portion of freshwater and sediment is exported to the ocean by a small number of major rivers. Many of these megarivers are subject to substantial anthropogenic pressures, which are having a major impact on water and sediment delivery to deltaic ecosystems. Due to hydrodynamic sorting, sediment grain size and composition vary strongly with depth and across the channel in large rivers, complicating flux quantification. To account for this, we modified a semi‐empirical Rouse model, synoptically predicting sediment concentration, grain‐size distribution, and organic carbon (%OC) concentration with depth and across the river channel. Using suspended sediment depth samples and flow velocity data, we applied this model to calculate sediment fluxes of the Irrawaddy (Ayeyarwady) and the Salween (Thanlwin), the last two free‐flowing megarivers in Southeast Asia. Deriving sediment‐discharge rating curves, we calculated an annual sediment flux of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0001 Mt/year for the Irrawaddy and urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0002 Mt/year for the Salween, together exporting 46% as much sediment as the Ganges‐Brahmaputra system. The mean flux‐weighted sediment exported by the Irrawaddy is significantly coarser (D84 = 193 ± 13 μm) and OC‐poorer (0.29 ± 0.08 wt%) compared to the Salween (112 ± 27 μm and 0.59 ± 0.16 wt%, respectively). Both rivers export similar amounts of particulate organic carbon, with a total of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0003 Mt C/year, 53% as much as the Ganges‐Brahmaputra. These results underline the global significance of the Irrawaddy and Salween rivers and warrant continued monitoring of their sediment flux, given the increasing anthropogenic pressures on these river basins.

International audience; Past millennial-scale changes in atmospheric CO2 (CO2,atm) concentrations have often been attributed to variations in the overturning timescale of the ocean that result in changes in the marine carbon inventory. Yet, there remains a paucity of proxy evidence that documents changes in marine carbon storage globally, and that links them to abrupt climate variability in the northern hemisphere associated with perturbations of the Atlantic Meridional Overturning Circulation (AMOC). The last two glacial periods were suggested to differ in the spatial extent of the AMOC and its sensitivity to perturbations. This provides an opportunity to compare the nature of marine carbon cycle-climate feedbacks between them. Here, we reconstruct variations in respired carbon storage (via oxygenation) and the AMOC “geometry” (via carbonate ion saturation) in the deep South Atlantic. We infer decreases in deep South Atlantic respired carbon levels at times of weakened AMOC and rising CO2,atm concentrations during both glacial periods. These findings suggest a consistent pattern of increased Southern Ocean convection and/or air-sea CO2 fluxes during northern-hemisphere stadials accompanying AMOC perturbations and promoting a rise in CO2,atm levels. We find that net ocean carbon loss, and hence the magnitude of CO2,atm rise, is largely determined by the stadial duration. North Atlantic climate anomalies therefore affect Southern Ocean carbon cycling in a consistent manner, through oceanic (e.g., ventilation seesaw) and/or atmospheric processes (e.g., Ekman pumping).

Radiometric dating of glacial terminations over the past 640,000 years suggests pacing by Earth’s climatic precession, with each glacial-interglacial period spanning four or five cycles of ~20,000 years. However, the lack of firm age estimates for older Pleistocene terminations confounds attempts to test the persistence of precession forcing. We combine an Italian speleothem record anchored by a uranium-lead chronology with North Atlantic ocean data to show that the first two deglaciations of the so-called 100,000-year world are separated by two obliquity cycles, with each termination starting at the same high phase of obliquity, but at opposing phases of precession. An assessment of 11 radiometrically dated terminations spanning the past million years suggests that obliquity exerted a persistent influence on not only their initiation but also their duration. We acknowledge financial support from Australian Research Council Discovery Project grants 0664621 (to J.D.W.), 110102185 (to R.N.D., J.D.W., J.C.H., E.W., A.E.F., and S.F.), and 160102969 (to R.N.D., J.D.W., G.Z., E.W., and P.F.). We thank the Gruppo Speleologico Lucchese and the Federazione Speleologica Toscana for logistic and funding support. The SUERC contribution to this study falls within the framework of the Scottish Alliance for Geoscience, Environment and Society (SAGES). P.B. was the recipient of a University of Melbourne International Postgraduate Research Scholarship and Postgraduate Writing-Up Award supported by the Albert Shimmins Fund. J.C.H. was the recipient of an Australian Research Council Future Fellowship (FT130100801). P.F. acknowledges support from the European Union through a Marie-Curie Reintegration grant (PERG-GA-2010-272134 - MILLEVARIABILI). D.H. acknowledges support from the UK Natural Environmental Research Council. E.W. is supported by a Royal Society Professorship. A.H.L.V. and T.R. received financial support from Fundação para a Ciência e a Tecnologia (FCT, Portugal) projects MOWCADYN (PTDC/MAR-PRO/3761/2012), WarmWorld (PTDC/CTA-GEO/29897/2017), and CCMAR (UID/ Multi/04326/2019). Samples from the marine sites were provided by the Integrated Ocean Drilling Program to D.H., A.H.L.V., and T.R. info:eu-repo/semantics/publishedVersion

Geology is the science of how the Earth functions and has evolved and, as such, it can contribute to our understanding of the climate system and how it responds to the addition of carbon dioxide (CO2) to the atmosphere and oceans. Observations from the geological record show that atmospheric CO2 concentrations are now at their highest levels in at least the past 3 million years. Furthermore, the current speed of human-induced CO2 change and warming is nearly without precedent in the entire geological record, with the only known exception being the instantaneous, meteorite-induced event that caused the extinction of non-bird-like dinosaurs 66 million years ago. In short, whilst atmospheric CO2 concentrations have varied dramatically during the geological past due to natural processes, and have often been higher than today, the current rate of CO2 (and therefore temperature) change is unprecedented in almost the entire geological past.\ud \ud The geological record shows that changes in temperature and greenhouse gas concentrations have direct impacts on sea-level, the hydrological cycle, marine and terrestrial ecosystems, and the acidification and oxygen depletion of the oceans. Important climate phenomena, such as the El Niño–Southern Oscillation (ENSO) and the monsoons, which today affect the socio-economic stability and food and water security of billions of people, have varied markedly with past changes in climate.\ud Climate reconstructions from around the globe show that climate change is not globally uniform, but tends to exhibit a consistent pattern, with changes at the poles larger than elsewhere. This polar amplification is seen in ancient warmer-than-modern time intervals like the Eocene epoch, about 50 million years ago and, more recently, in the Pliocene, about 3 million years ago. The warmest intervals of the Pliocene saw the disappearance of summer sea ice from the Arctic. The loss of ice cover during the Pliocene was one of the many rapid climate changes observed in the record, which are ften called climate tipping points. The geological record can be used to calculate a quantity called Equilibrium Climate Sensitivity, which is the amount of warming caused by a doubling of atmospheric CO2, after various processes in the climate system have reached equilibrium. Recent estimates suggest that global mean climate warms between 2.6 and 3.9°C per doubling of CO2 once all slow Earth system processes have reached equilibrium.\ud The geological record provides powerful evidence that atmospheric CO2 concentrations drive climate change, and supports multiple lines of evidence that greenhouse gases emitted by human activities are altering the Earth’s climate. Moreover, the amount of anthropogenic greenhouse gases already in the atmosphere means that Earth is committed to a certain degree of warming. As the Earth’s climate changes due to the burning of fossil fuels and changes in land-use, the planet we live on will experience further changes that will have increasingly drastic effects on human societies. An assessment of past climate changes helps to inform policy decisions regarding future climate change. Earth scientists will also have an important role to play in the delivery of any policies aimed at limiting future climate change.

Much of our understanding of Earth's past climate comes from the measurement of oxygen and carbon isotope variations in deep-sea benthic foraminifera. Yet, long intervals in existing records lack the temporal resolution and age control needed to thoroughly categorize climate states of the Cenozoic era and to study their dynamics. Here, we present a new, highly resolved, astronomically dated, continuous composite of benthic foraminifer isotope records developed in our laboratories. Four climate states-Hothouse, Warmhouse, Coolhouse, Icehouse-are identified on the basis of their distinctive response to astronomical forcing depending on greenhouse gas concentrations and polar ice sheet volume. Statistical analysis of the nonlinear behavior encoded in our record reveals the key role that polar ice volume plays in the predictability of Cenozoic climate dynamics.

The Last Interglacial (129–116 thousand years ago (ka)) represents one of the warmest climate intervals of the past 800,000 years and the most recent time when sea level was metres higher than today. However, the timing and magnitude of the peak warmth varies between reconstructions, and the relative importance of individual sources that contribute to the elevated sea level (mass gain versus seawater expansion) during the Last Interglacial remains uncertain. Here we present the first mean ocean temperature record for this interval from noble gas measurements in ice cores and constrain the thermal expansion contribution to sea level. Mean ocean temperature reached its maximum value of 1.1 ± 0.3 °C warmer-than-modern values at the end of the penultimate deglaciation at 129 ka, which resulted in 0.7 ± 0.3 m of thermosteric sea-level rise relative to present level. However, this maximum in ocean heat content was a transient feature; mean ocean temperature decreased in the first several thousand years of the interglacial and achieved a stable, comparable-to-modern value by ~127 ka. The synchroneity of the peak in mean ocean temperature with proxy records of abrupt transitions in the oceanic and atmospheric circulation suggests that the mean ocean temperature maximum is related to the accumulation of heat in the ocean interior during the preceding period of reduced overturning circulation. Rapid oceanic and atmospheric circulation shifts led to a transient peak in the mean temperature of the ocean at the start of the Last Interglacial, according to noble gas isotope records from an Antarctic ice core.

Ocean dynamics served an important role during past dramatic climate changes via impacts on deep-ocean carbon storage. Such changes are recorded in sedimentary proxies of hydrographic change on continental margins, which lie at the ocean–atmosphere–earth interface. However, interpretations of these records are challenging, given complex interplays among processes delivering particulate material to and from ocean margins. Here we report radiocarbon (14C) signatures measured for organic carbon in differing grain-size sediment fractions and foraminifera in a sediment core retrieved from the southwest Iberian margin, spanning the last ~25,000 yr. Variable differences of 0–5000 yr in radiocarbon age are apparent between organic carbon in differing grain-sizes and foraminifera of the same sediment layer. The magnitude of 14C differences co-varies with key paleoceanographic indices (e.g., proximal bottom-current density gradients), which we interpret as evidence of Atlantic–Mediterranean seawater exchange influencing grain-size specific carbon accumulation and translocation. These findings underscore an important link between regional hydrodynamics and interpretations of down-core sedimentary proxies., Marine sedimentary records and the proxies within play a central role in unlocking our understanding of past climates, yet interpreting the signals they contain can be complex. Here, the authors reveal and discuss the complex effects of hydrodynamics on carbon accumulation in the sediments off the Iberian margin.

This special issue of Geochimica et Cosmochemica Acta is dedicated to our friend and colleague Harry Elderfield (1943–2016) who transformed the field of ocean geochemistry and palaeochemistry (Fig. 1). His passion for understanding the behavior of trace elements and their isotopes in modern seawater and how they are imprinted in the sediment record has advanced our understanding of geochemical cycling in the oceans. The special issue is aptly titled “Chemistry of oceans past and present” to reflect Harry’s contributions to both modern and ancient geochemical processes.

We present calcium isotope data from pore fluids and solids from Ocean Drilling Program Leg 175: Sites 1081 and 1086 (off the coast of West Africa). These sites are similar with respect to geographic location, sediment age (from modern to 8 Myr), and water depth (800 m), but Site 1081 is carbonate-poor, whereas Site 1086 is carbonate-rich. Therefore, these sites are suited for the exploration of the influence of sediment type on carbonate dissolution, precipitation, and recrystallization. We use two numerical modelling approaches to explore the rates of carbonate dissolution and precipitation in the sediment column. The first is the standard diffusion-reaction approach, using the strontium concentration within the pore fluid to ascertain a dissolution rate for the carbonate, which is then applied to a second model of calcium isotopes within the pore fluid to calculate precipitation rates. Given the high sedimentation rates we also apply an advection-reaction model (Huber et al., 2017) which results in the same depth distribution of carbonate precipitation but significantly higher overall rates, which is discussed. Calcium isotope ratios in pore fluid calcium increase in zones where our model predicts carbonate precipitation, and approach isotopic equilibrium with the solid in zones where our model predicts equivalent rates of dissolution and precipitation, similar to previous findings. Contrary to previous findings in marine sediments, our model requires a calcium isotope fractionation on carbonate precipitation to fit the data, as there is an offset between the δ44Ca of the fluid and the solid. Using the zones of carbonate precipitation determined from the models and previously published carbon isotope profiles of the dissolved inorganic carbon from these sites, we suggest that the δ13C of the authigenic carbonate is uniformly lower than biogenic carbonate but by a wider range than was previously suggested.

Circulation changes have been suggested to play an important role in the sequestration of atmospheric CO2 in the glacial ocean. However, previous studies have resulted in contradictory results regarding the strength of the Atlantic Meridional Overturning Circulation (AMOC) and three-dimensional, quantitative reconstructions of the glacial ocean constrained by multiple proxies remain scarce. Here we simulate the modern and glacial ocean using a coupled physical-biogeochemical, global, three-dimensional model constrained simultaneously by δ 13 C, radiocarbon, and δ 15 N to explore the effects of AMOC differences and Southern Ocean iron fertilization on the distributions of these isotopes and ocean carbon storage. We show that δ 13 C and radiocarbon data sparsely sampled at the locations of existing glacial sediment cores can be used to reconstruct the modern AMOC accurately. Applying this method to the glacial ocean we find that a surprisingly weak (6–9 Sv or about half of today's) and shallow AMOC maximizes carbon storage and best reproduces the sediment isotope data. Increasing the atmospheric soluble iron flux in the model's Southern Ocean intensifies export production, carbon storage, and further improves agreement with δ 13 C and δ 15 N reconstructions. Our best fitting simulation is a significant improvement compared with previous studies, and suggests that both circulation and export production changes were necessary to maximize carbon storage in the glacial ocean.