Search

The Indian Ocean provides a source of salt for North Atlantic deep-water convection sites, via the Agulhas Leakage, and may thus drive changes in the ocean’s overturning circulation1–3. However, little is known about the salt content variability of Indian Ocean and Agulhas Leakage waters during past glacial cycles and how this may influence circulation. Here we show that the glacial Indian Ocean surface salt budget was notably different from the modern, responding dynamically to changes in sea level. Indian Ocean surface salinity increased during glacial intensification, peaking in glacial maxima. We find that this is due to rapid land exposure in the Indonesian archipelago induced by glacial sea-level lowering, and we suggest a mechanistic link via reduced input of relatively fresh Indonesian Throughflow waters into the Indian Ocean. Using climate model results, we show that the release of this glacial Indian Ocean salinity via the Agulhas Leakage during deglaciation can directly impact the Atlantic Meridional Overturning Circulation and global climate.

Funding: This research has been supported by the Leverhulme Trust (grant RPG-2015-246), by a Royal Society Professorship (grant no. RP/R/180003), and by a Marie Curie Career Integration Grant (CIG14-631752). Volcanic eruptions are the dominant cause of natural variability in climate forcing on timescales up to multidecadal. Large volcanic eruptions lead to global-scale climate effects and influence the carbon cycle on long timescales. However, estimating the frequency of eruptions is challenging. Here we assess the frequency at which eruptions with particular deposition fluxes are observed in the EPICA Dome C ice core over the last 200 kyr. Using S isotope analysis we confirm that most of the largest peaks recorded at Dome C are from stratospheric eruptions. The cumulative frequency through 200 kyr is close to linear, suggesting an approximately constant rate of eruptions. There is no evidence for an increase in the rate of events recorded in Antarctica at either of the last two deglaciations. Millennial variability is at the level expected from recording small numbers of eruptions, while multimillennial variability may be partly due to changes in transport efficiency through the Brewer–Dobson circulation. Our record of events with sulfate deposition rates > 20 and >50 mg m−2 contains 678 and 75 eruptions, respectively, over the last 200 kyr. Calibration with data on historic eruptions and analysis of a global Quaternary dataset of terrestrial eruptions indicates that sulfate peaks with deposition rates > 20 and >50 mg m−2 correspond to explosive eruptions of magnitude ≥ 6.5 and ≥7, respectively. The largest recorded eruption deposited just over 300 mg m−2. Publisher PDF

Funding was provided by the University of Edinburgh, the Royal Society (grant NIF\R1\191527), National Science Foundation (grants DEB 1654949 and EAR 1654952), European Research Council (ERC) starting grants (nos. 756226 and 805246) under the European Union’s Horizon 2020 Research and Innovation Programme, a Philip Leverhulme Prize and a SNSF Mobility Fellowship (grant P2EZP2_199923). After the end-Cretaceous extinction, placental mammals quickly diversified , occupied key ecological niches and increased in size , but this last was not true of other therians. The uniquely extended gestation of placental young may have factored into their success and size increase, but reproduction style in early placentals remains unknown. Here we present the earliest record of a placental life history using palaeohistology and geochemistry, in a 62 million-year-old pantodont, the clade including the first mammals to achieve truly large body sizes. We extend the application of dental trace element mapping by 60 million years, identifying chemical markers of birth and weaning, and calibrate these to a daily record of growth in the dentition. A long gestation (approximately 7 months), rapid dental development and short suckling interval (approximately 30-75 days) show that Pantolambda bathmodon was highly precocial, unlike non-placental mammals and known Mesozoic precursors. These results demonstrate that P. bathmodon reproduced like a placental and lived at a fast pace for its body size. Assuming that P. bathmodon reflects close placental relatives, our findings suggest that the ability to produce well-developed, precocial young was established early in placental evolution, and that larger neonate sizes were a possible mechanism for rapid size increase in early placentals. Postprint

Throughout Earth's history, CO2 is thought to have exerted a fundamental control on environmental change. Here we review and revise CO2 reconstructions from boron isotopes in carbonates and carbon isotopes in organic matter over the Cenozoic—the past 66 million years. We find close coupling between CO2 and climate throughout the Cenozoic, with peak CO2 levels of ∼1,500 ppm in the Eocene greenhouse, decreasing to ∼500 ppm in the Miocene, and falling further into the ice age world of the Plio–Pleistocene. Around two-thirds of Cenozoic CO2 drawdown is explained by an increase in the ratio of ocean alkalinity to dissolved inorganic carbon, likely linked to a change in the balance of weathering to outgassing, with the remaining one-third due to changing ocean temperature and major ion composition. Earth system climate sensitivity is explored and may vary between different time intervals. The Cenozoic CO2 record highlights the truly geological scale of anthropogenic CO2 change: Current CO2 levels were last seen around 3 million years ago, and major cuts in emissions are required to prevent a return to the CO2 levels of the Miocene or Eocene in the coming century. ▪ CO2 reconstructions over the past 66 Myr from boron isotopes and alkenones are reviewed and re-evaluated. ▪ CO2 estimates from the different proxies show close agreement, yielding a consistent picture of the evolution of the ocean-atmosphere CO2 system over the Cenozoic. ▪ CO2 and climate are coupled throughout the past 66 Myr, providing broad constraints on Earth system climate sensitivity. ▪ Twenty-first-century carbon emissions have the potential to return CO2 to levels not seen since the much warmer climates of Earth's distant past.

Key Points: - High resolution carbonate chemistry, δ13C-DIC, and particle flux measurements in the NE Pacific sheds light on the upper oceancalcium carbonate and alkalinity cycles. - Based on this sampling campaign, there isevidence for substantial CaCO3 dissolution in the mesopelagic zone above the saturation horizon. - Dissolution experiments, observations, and modeling suggest that shallow CaCO3 dissolutionis coupled to the consumption of organic carbon, through a combination of zooplankton grazing and oxic respiration within particle microenvironments. The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situcoccolith and foraminiferal calcite dissolution rates.We combine these rates with solid phase fluxes,dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean.The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution ratesof all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods)aretoo slow to explainthe patternsofboth CaCO3sinking fluxand alkalinity regenerationin the NorthPacific.Usinga combination of dissolved and solid-phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3dissolutionwith acombination of ambient saturation state and oxygen consumption simultaneously explainssolid-phase CaCO3flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. Wedo not need to invokethe presence ofcarbonate phases with higher solubilities.Instead, biomineralization and metabolic processesintimately associatethe acid (CO2) and the base (CaCO3) in the same particles,driving the coupled shallow remineralization of organic carbonand CaCO3.The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration withindegrading particle aggregates.The coupling of these cyclesacts as a major filter on the export of both organic and inorganic carbon to the deep ocean.

Funding was provided by an Antarctic Bursary awarded to J.A.S., ERC and NERC grants awarded to L.F.R. (278705, NE/S001743/1, NE/R005117/1) and L.F.R. and J.W.B.R. (NE/N003861/1). The Antarctic Cold Reversal (ACR; 14.7 to 13 thousand years ago; ka) phase of the last deglaciation saw a pause in the rise of atmospheric CO2 and Antarctic temperature, that contrasted with warming in the North. A re-expansion of sea ice and a northward shift in the position of the westerly winds in the Southern Ocean are well-documented, but the response of deep-sea biota and the primary drivers of habitat viability remain unclear. Here we present a new perspective on ecological changes in the deglacial Southern Ocean, including multi-faunal benthic assemblage (foraminifera and cold-water corals) and coral geochemical data (Ba/Ca and δ11B) from the Drake Passage. Our records show that, during the ACR, peak abundances of thick-walled benthic foraminifera Uvigerina bifurcata and corals are observed at shallow depths in the sub-Antarctic (∼300 m), while coral populations at greater depths and further south diminished. Our ecological and geochemical data indicate that habitat shifts were dictated by (i) a northward migration of food supply (primary production) into the Subantarctic Zone and (ii) poorly oxygenated seawater at depth during this Antarctic cooling interval. Publisher PDF

The ∼74 ka Toba eruption was one of the largest volcanic events of the Quaternary. There is much interest in determining the impact of such a large event, particularly on the climate and hominid populations at the time. Although the Toba eruption has been identified in both land and marine archives as the Youngest Toba Tuff, its precise place in the ice core record is ambiguous. Several volcanic sulfate signals have been identified in both Antarctic and Greenland ice cores and span the Toba eruption 40Ar/39Ar age uncertainty. Here, we measure sulfur isotope compositions in Antarctic ice samples from the Dome C (EDC) and Dronning Maud Land (EDML) ice cores at high temporal resolution across 11 of these potential Toba sulfate peaks to identify candidates with sulfur mass-independent fractionation (S-MIF), indicative of an eruption whose plume reached altitudes at or above the stratospheric ozone layer. Using this method, we identify several candidate sulfate peaks that contain stratospheric sulfur. We further narrow down potential candidates based on the isotope signatures by identifying sulfate peaks that are due to a volcanic event at tropical latitudes. In one of these sulfate peaks at 73.67 ka, we find the largest ever reported magnitude of S-MIF in volcanic sulfate in polar ice, with a Δ33S value of −4.75 ‰. As there is a positive correlation between the magnitude of the S-MIF signal recorded in ice cores and eruptive plume height, this could be a likely candidate for the Toba super-eruption, with a plume top height in excess of 45 km. These results support the 73.7±0.3 ka (1σ) 40Ar/39Ar age estimate for the eruption, with ice core ages of our candidates with the largest magnitude S-MIF at 73.67 and 73.74 ka. Finally, since these candidate eruptions occurred on the transition into Greenland Stadial 20, the relative timing suggests that Toba was not the trigger for the large Northern Hemisphere cooling at this time although we cannot rule out an amplifying effect.

Ocean acidification typically reduces the calcification rates of massive Porites spp. corals, but increasing seawater temperatures (below the stress and bleaching threshold) can offset this effect. Here, we use δ11B to reconstruct the pH of the calcification media (pHECM) used to precipitate the skeleton in poritid corals cultured over a range of seawater pCO2 and at 25 °C and 28 °C. Increasing temperature had no significant effect on pHECM at high pCO2 although corals increased their calcification rates. pHECM was reduced at 28 °C compared to 25 °C at low seawater pCO2, although calcification rates remained constant. Increasing calcification rates could reflect the positive influence of temperature on aragonite precipitation rate, an increase in calcification media saturation state or a change in the concentration/behaviour of the skeletal organic matrix. The two temperatures utilized in this study were within the seasonal range at the coral collection site and do not represent a heat stress scenario. Increasing seawater temperatures may promote calcification in some corals in the future but are unlikely to benefit the majority of corals, which are already living close to their maximum thermal tolerance limits.

This work was supported bythe Korea Ministry of Science and ICT (GP2020-038), by the Korea Ministry of Oceans and Fisheries (NP2011-040 and 1525011795), and by the Korea Polar Research Institute (Grants No. PE20350). W.-L.H. acknowledges the supports from the ArcticSGD, a project supported by the Norway Grants and the EEA Grants (2019/34/H/ST10/00645). Additional funds were contributed by the AWI Research Program PACES-II Workpackage 3.1 and 3.2. The response of Arctic Ocean biogeochemistry to subsurface flow driven by permafrost thaw is poorly understood. We present dissolved chloride and water isotopic data from the Chukchi Sea Shelf sediments that reveal the presence of a meteoric subsurface flow enriched in cations with a radiogenic Sr fingerprint. This subsurface fluid is also enriched in dissolved inorganic carbon and methane that bear isotopic compositions indicative of a carbon reservoir modified by reactions in a closed system. Such fluid characteristics are in stark contrast with those from other sites in the Chukchi Sea where the pore water composition shows no sign of meteoric input, but reflect typical biogeochemical reactions associated with early diagenetic sequences in marine sediment. The most likely source of the observed subsurface flow at the Chukchi Sea Shelf is from the degradation of permafrost that had extended to the shelf region during the Last Glacial Maximum. Our data suggest that the permafrost-driven subsurface flow most likely took place during the 2-3 oC warming in the Early Holocene Thermal Maximum (EHTM). This time scale is supported by numerical simulation of pore fluid profiles, which indicate that a minimum of several thousand years must have passed since the cessation of the subsurface methane-bearing fluid flow. Publisher PDF

Funder: Tromsø Research Foundation : A31720, The Fram Strait is the only deep gateway between the Arctic Ocean and the Nordic Seas and thus is a key area to study past changes in ocean circulation and the marine carbon cycle. Here, we study deep ocean temperature, δ18O, carbonate chemistry (i.e., carbonate ion concentration [CO32−]), and nutrient content in the Fram Strait during the late glacial (35,000–19,000 years BP) and the Holocene based on benthic foraminiferal geochemistry and carbon cycle modeling. Our results indicate a thickening of Atlantic water penetrating into the northern Nordic Seas, forming a subsurface Atlantic intermediate water layer reaching to at least ∼2,600 m water depth during most of the late glacial period. The recirculating Atlantic layer was characterized by relatively high [CO32−] and low δ13C during the late glacial, and provides evidence for a Nordic Seas source to the glacial North Atlantic intermediate water flowing at 2,000–3,000 m water depth, most likely via the Denmark Strait. In addition, we discuss evidence for enhanced terrestrial carbon input to the Nordic Seas at ∼23.5 ka. Comparing our δ13C and qualitative [CO32−] records with results of carbon cycle box modeling suggests that the total terrestrial CO2 release during this carbon input event was low, slow, or directly to the atmosphere.

Cruise MSM57-1/-2 was funded by the German Research Foundation ( DFG ), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE. This work is partly supported by the Research Council of Norway (RCN) through Petromaks2-NORCRUST (project number 255150 ) and the Centre of Excellence funding scheme for CAGE (project number 223259 ). APF’s contribution was part of the SEAMSTRESS project supported by starting grants from the Tromsø Research Foundation and the Research Council of Norway (grant nr. 2878659 ). Seafloor seepage sites along the Vestnesa Ridge off west-Svalbard have been, for decades, a natural laboratory for the studies of fluid flow and gas hydrate dynamics along passive continental margins. The lack of ground truth evidence for fluid composition and gas hydrate abundance deep in the sediment sequence however prohibits us from further assessing the current model of pockmark evolution from the region. A MARUM-MeBo 70 drilling cruise in 2016 aims to advance our understanding of the system by recovering sediments tens of meters below seafloor from two active pockmarks along Vestnesa Ridge. We report pore fluid composition data focusing on dissolved chloride, stable isotopes of water (δ18O and δD), and the isotopic composition of dissolved boron (δ11B). From one of the seepage sites, we detect a saline formation water with two layers where gas hydrates were recovered. This saline formation pore fluid is characterized by elevated chloride concentrations (up to 616 mM), high B/Cl ratios (9 × 10−4 mol/mol), high δ18O and δD isotopic signatures (+0.6‰ and +3.8‰, respectively) and low δ11B signatures (+35.0‰), which collectively hint to a high temperature modification at great depths. Based on the dissolved chloride concentration profiles, we estimated up to 47% of pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. The observation of bubble fabric in the recovered gas hydrates suggests formation during past periods of intensive gaseous methane seepage. The presence of these gas hydrates without associated positive anomalies in dissolved chloride concentrations however suggests that the decomposition of gas hydrate is as fast as its formation. Such a state of gas hydrates can be attributed to a relatively low methane supply transported by the saline formation water at present. Our findings based on pore fluid composition corroborate previous inferences along Vestnesa Ridge that fluids sustaining seepage have migrated from great depths and that the variable gaseous and aqueous phases through the gas hydrate stability zone control the distributions of authigenic carbonates and gas hydrates. Publisher PDF

The ~74ka Toba eruption in Indonesia was one of the largest volcanic events of the Quaternary and loaded an estimated 100 million tonnes of H2SO4 into the atmosphere. Understanding the precise timing of this colossal eruption is vital to unravelling the climatic and environmental impacts of the largest volcanic events on Earth. Sulfur aerosols injected into the stratosphere following large volcanic events scatter incoming radiation and lead to global cooling, and in the case of Toba it has been suggested that it led to cooling of 1 – 5°C and extinctions of some local hominin populations. One of the most enigmatic features of the Toba eruption is that the S peak has yet to be identified in the ice core records, although numerous candidate sulfate peaks have been identified in both Arctic and Antarctic ice cores. To address this, we analysed the sulfur isotope fingerprint (δ34S and Δ33S) of 11 Toba candidates from two Antarctic ice cores by multi-collector inductively coupled plasma mass spectrometry. This approach allows us to evaluate injection altitudes and to distinguish large tropical eruptions from proximal eruptions because stratospheric sulfur aerosols undergo UV photochemical reactions that impart a sulfur mass-independent isotopic fractionation (S-MIF). In contrast, tropospheric sulfur aerosols do not exhibit S-MIF because they are shielded from the relevant UV radiation by the ozone layer.We identify three stratospheric, tropical eruption candidates with two recording the largest Δ33S signals measured to date in the ice core archives. The largest of these Δ33S signals is >2 ‰ more negative than previous measurements of the 1257 Samalas eruption (the largest eruption of the last 2000 years), despite having a similar integrated sulfate flux for this event to the ice core. These three candidates are within uncertainly of the Ar40/Ar39 age estimates for the Toba eruption and when considered with other paleoclimate proxies place the event during the transition into Greenland Stadial 20. Finally, we further analyse the relationship between the Toba eruption candidates and these proxies to determine the precise timing and potential climatic impacts of one of the largest eruptions of the Quaternary period.

A conservative element in seawater, uranium is readily incorporated into the aragonitic skeletons of scleractinian corals, making them an important paleoclimate archive that can be absolutely dated with U-Th techniques. In addition, uranium concentrations (U/Ca ratios) in corals have been suggested to be influenced by the temperature and/or carbonate ion concentration of the ambient seawater based on empirical calibrations. Microsampling techniques have revealed strong heterogeneities in U/Ca within individual specimens in both surface and deep-sea corals, suggesting a biological control on the U incorporation into the skeletons. Here we further explore the mechanism of uranium incorporation in coral skeletons with the deep-sea species Desmophyllum dianthus, an ideal test organism for the biomineralization processes due to its relatively constant growth environment. We find a negative correlation between bulk coral U/Ca and temperature as well as ambient pH and [CO32–] that is consistent with previous studies. By sampling the growth bands of individual corals, we also find a twofold change in U/Ca within individual corals that is strongly correlated with the δ18O, δ13C, and other Me/Ca ratios of the bands. A similar correlation between U/Ca and stable isotopes as well as other Me/Ca ratios are observed in bulk deep-sea coral samples. With a numerical coral calcification model, we interpret the U/Ca-stable isotope correlation as a result of changes in uranium speciation in response to internal pH elevations in the extracellular calcifying fluid (ECF) of the corals, and suggest that the Ca2UO2(CO3)3(aq) complex, the dominant U species in seawater, may be the major species incorporated into the coral skeleton. Therefore, the correlation between U/Ca and ambient [CO32–] is likely a result of the response of the biomineralization process, especially the magnitude of internal pH elevation, to the growth environment of the corals. Our data suggest overall lower alkalinity pump rates in corals from low saturation seawater compared to those from high saturation seawater, and possible increases in Ca2+ supply from active pumping relative to seawater transport in response to the environmental stress of low saturation.

The Indian Ocean has been proposed as an important source of salt for North Atlantic deep-water convection sites, via the Agulhas Leakage, and may thus drive changes in the ocean’s overturning circulation. However, while past changes in Agulhas leakage volume have been explored, little is known about this water’s salt content, representing a major gap in our understanding of Agulhas salinity supply. Here, we present new planktonic foraminiferal Mg/Ca-derived sea surface temperatures (SST) and stable isotope-derived salinity reconstructions for the last 1.2Ma from the western Indian Ocean source waters of the Agulhas Leakage to investigate glacial-interglacial changes in surface water properties. We find that SST and relative salinity both increase during glaciation, leading to high salinity and SST during glacial maxima. We show that the onset of surface salinification and warming in the Indian Ocean occurs during a phase of rapid land-bridge exposure in the Indonesian archipelago induced by sea level lowering. We link these findings to new global climate model results which show that the export of salt from the Indian Ocean via the Agulhas Leakage can directly impact the deglacial Atlantic meridional overturning circulation and therefore global climate.

Enhanced overturning circulation in the glacial North Pacific caused warming, nutrient limitation, and lower atmospheric CO2., Although the Pacific Ocean is a major reservoir of heat and CO2, and thus an important component of the global climate system, its circulation under different climatic conditions is poorly understood. Here, we present evidence that during the Last Glacial Maximum (LGM), the North Pacific was better ventilated at intermediate depths and had surface waters with lower nutrients, higher salinity, and warmer temperatures compared to today. Modeling shows that this pattern is well explained by enhanced Pacific meridional overturning circulation (PMOC), which brings warm, salty, and nutrient-poor subtropical waters to high latitudes. Enhanced PMOC at the LGM would have lowered atmospheric CO2—in part through synergy with the Southern Ocean—and supported an equable regional climate, which may have aided human habitability in Beringia, and migration from Asia to North America.

Boron isotopes and trace element content measurements were funded by: the French National Research Agency projects ANR CARBORIC (Grant No. ANR-13-BS06-0013-04) and ANR HAMOC (Grant No. ANR-13-BS06-0003-02) at LSCE; NERC NE/N003861/1 & NE/S001743/1 at Bristol; NERC NE/N011716/1 at the University of St Andrews. The boron isotopic (δ11BSRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, comparability of results between laboratories requires carbonate reference materials. Here we report results of an inter‐laboratory comparison study to both assign δ11BSRM951 and trace element compositions to new marine carbonate reference materials (RM), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess analytical variability among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ11BSRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information values among laboratories (e.g., Mg/Ca ± 5%) was often greater than analytical precision (% RSD) within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes. Publisher PDF

Absolutely dated deep-sea coral ∆14C, δ11B, and δ15N records reveal Southern Ocean’s role in rapid deglacial carbon cycle events., The Southern Ocean plays a crucial role in regulating atmospheric CO2 on centennial to millennial time scales. However, observations of sufficient resolution to explore this have been lacking. Here, we report high-resolution, multiproxy records based on precisely dated deep-sea corals from the Southern Ocean. Paired deep (∆14C and δ11B) and surface (δ15N) proxy data point to enhanced upwelling coupled with reduced efficiency of the biological pump at 14.6 and 11.7 thousand years (ka) ago, which would have facilitated rapid carbon release to the atmosphere. Transient periods of unusually well-ventilated waters in the deep Southern Ocean occurred at 16.3 and 12.8 ka ago. Contemporaneous atmospheric carbon records indicate that these Southern Ocean ventilation events are also important in releasing respired carbon from the deep ocean to the atmosphere. Our results thus highlight two distinct modes of Southern Ocean circulation and biogeochemistry associated with centennial-scale atmospheric CO2 jumps during the last deglaciation.

This study was funded by the European Research Council, the Natural Environment Research Council (NE/S001743/1; NE/N011716/1), the Philip Leverhulme Trust, the Strategic Priority Research Program of Chinese Academy of Sciences (XDB40010200), the National Natural Science Foundation of China (41822603), the US National Science Foundation (OCE-0926637, OCE-10309040 and OCE-0926491), a Marie Curie Reintegration Grant and the NOAA (National Oceanic and Atmospheric Administration) Ocean Exploration Trust. During the last deglaciation (~18–11 thousand years ago), existing radiocarbon (14C) reconstructions of intermediate waters in the mid- to low-latitude oceans show widely diverging trends, with some broadly tracking the atmosphere and others suggesting extreme depletions. These discrepancies cloud our understanding of the deglacial carbon cycle because of the diversity of hypotheses needed to explain these diverging records, for example, injections of 14C-dead geological carbon, mixing of extremely isolated waters from the abyssal ocean or changes in sites of deep-water ventilation. Here we present absolutely dated deglacial deep-sea coral 14C records of intermediate waters from the Galápagos Platform—close to the largest reported deglacial 14C depletions—together with data from the low-latitude Atlantic. Our records indicate coherent, well-equilibrated intermediate-water 14C ventilation in both oceans relative to the atmosphere throughout the deglaciation. The observed overall trend towards 14C-enriched signatures in our records is largely due to enhanced air–sea carbon isotope exchange efficiency under increasing atmospheric pCO2. These results suggest that the 14C-depleted signatures from foraminifera are likely sedimentary rather than water mass features, and provide tight 14C constraints for modelling changes in circulation and carbon cycle during the last deglaciation. Postprint

JWBR received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 805246) and from the Natural Environmental Research Council (NERC) grant NE/N011716/1. Boron isotopes in marine carbonates are increasingly used to reconstruct seawater pH and atmospheric pCO2 through Earth’s history. While isotope ratio measurements from individual laboratories are often of high quality, it is important that records generated in different laboratories can equally be compared. Within this Boron Isotope Intercomparison Project (BIIP), we characterised the boron isotopic composition (commonly expressed in δ11B) of two marine carbonates: Geological Survey of Japan carbonate reference materials JCp‐1 (coral Porites) and JCt‐1 (giant clam Tridacna gigas). Our study has three foci: (a) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ11B; (b) to determine to what degree the chosen analytical approach may affect the resultant δ11B; and (c) to provide well‐constrained consensus δ11B values for JCp‐1 and JCt‐1. The resultant robust mean and associated robust standard deviation (s*) for un‐oxidised JCp‐1 is 24.36 ± 0.45‰ (2s*), compared with 24.25 ± 0.22‰ (2s*) for the same oxidised material. For un‐oxidised JCt‐1, respective compositions are 16.39 ± 0.60‰ (2s*; un‐oxidised) and 16.24 ± 0.38‰ (2s*; oxidised). The consistency between laboratories is generally better if carbonate powders were oxidatively cleaned prior to purification and measurement. Publisher PDF

Gas hydrate dynamics and the fluid flow systems from two active pockmarks along Vestnesa Ridge (offshore west Svalbard) were investigated through the pore fluid geochemistry obtained during the 2016 MARUM-MeBo 70 drilling cruise. Based on the pore water chloride concentration profiles from Lunde and Lomvi pockmarks, we estimated up to 47% pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. These gas hydrates were formed during periods of gaseous methane seepage, but are now in a state of dynamic equilibrium sustained by a relatively low methane supply at present. We detect a saline formation pore fluid around nine meters below seafloor from one of the seepage sites in Lunde pockmark. This formation pore fluid has elevated dissolved chloride concentrations and B/Cl ratios, higher δO and δD isotopic signatures of water and lower δB signatures, which collectively hint to a high temperature modification of this fluid at great depths. By integrating our findings with the previous work from Vestnesa Ridge, we show that the variable fluid phases (gaseous vs. aqueous fluid) and migration pathways are controlled by the sediment properties, such as buried carbonate crusts, and the state of fluid reservoirs.

Paleoclimate records from the North Atlantic show some of the most iconic signals of abrupt climate change during the ice ages. Here we use radiocarbon as a tracer of ocean circulation and air-sea gas exchange to investigate potential mechanisms for the abrupt climate changes seen in the North Atlantic over the last deglaciation. We have created a stack of North Atlantic surface radiocarbon reservoir ages over the past 20,000 years, using new synchronized age models from thirteen sediment cores refined with thorium normalization between tie-points. This stack shows consistent and large reservoir age increases of more than 1000 years from the LGM into HS1, dropping abruptly back to approximately modern reservoir ages before the onset of the Bolling-Allerod. We use the intermediate complexity earth system model cGENIE to investigate the potential drivers of these reservoir age changes. We find that sea ice, circulation and CO2 all play important roles in setting the reservoir age. We use these coherently dated records to revisit the sequence and timing of climatic events during HS1 and the last deglaciation, and show that Laurentide Heinrich Events are a response to stadial conditions, rather than their root cause.

The North Pacific has been thought of as a sleeping giant in Earth’s climate system. Despite being a major reservoir of heat, nutrients, and carbon, the lack of deep water formation in this region today limits the exchange of these properties. Here, using a variety of new and published sediment core data, alongside Earth system modeling, we provide evidence that the North Pacific giant is in fact a dynamic player in Earth’s climate system, with active PMOC during the LGM and deep water formation during HS1. We also demonstrate a persistent Atlantic-Pacific seesaw in deep water formation during rapid climate change events, and discuss the impact of these changes on regional climate and global CO2.

Perhaps the most important feedback to orbital climate change is CO2 storage in the deep ocean. By regulating atmospheric CO2, ocean carbon storage synchronizes glacial climate in both hemispheres, and drives the full magnitude of glacial-interglacial climate change. However few data exist that directly track the deep ocean’s carbon chemistry over a glacial cycle. Here, we present geochemical reconstructions of deep ocean circulation, redox, and carbon chemistry from sediment cores making up a detailed depth profile in the South Atlantic, alongside a record of Southern Ocean surface water CO2, spanning the last glacial cycle. These data indicate that initial glacial CO2 drawdown is associated with a major increase in surface ocean pH in the Antarctic Zone of the Southern Ocean, cooling at depth, enhanced deep ocean stratification, and carbon storage. Deep ocean carbon storage and deep stratification are further enhanced when CO2 falls at the onset of Marine Isotope Stage 4, and are also pronounced during the LGM, illustrating a link between orbital scale climate stages and deep ocean carbon. However our data also illustrate non-linear feedbacks to orbital forcing during glacial terminations, which show abrupt decreases in pH in Southern Ocean surface and subsurface waters, as CO2 is rapidly expelled from the deep ocean at the end of the last ice age.

Indian Ocean surface salinity dynamics are thought to play an important role in shaping glacial-interglacial climate through controlling Agulhas leakage efficiency. It is proposed that a strong Agulhas leakage supplies warm and salty Indian ocean surface waters to Atlantic surface currents influencing convective potential at North Atlantic deep-water formation sites. Here, we present new planktonic foraminiferal Mg/Ca and stable isotope-derived salinity reconstructions for the last 1.2Ma from the northern Mozambique channel. We find salinity increases well before terminations, followed by early decrease before glacial inception. We present a possible link between the hydrography in the northern Mozambique channel and whole ocean salinity changes due to unique surface circulation in the Indian ocean. Despite being a mostly tropical and subtropical ocean, salinity in the modern tropical Indian Ocean is fresher than at comparable latitudes in the Atlantic or Pacific. This is due to the inflow of freshwater from the Indonesian throughflow and recycling via an active Agulhas leakage. We show that salinity in the glacial western Indian Ocean was significantly higher due to a reduced ITF and a weaker Agulhas leakage. We hypothesise that opening and closing of these two gateways influences the development/diminishment of a strong subtropical Indian Ocean gyre which controls sea surface salinity and temperature of tropical Indian Ocean water masses and subsequently the efficiency of the Agulhas Leakage.

International audience; North Pacific atmospheric and oceanic circulations are key missing pieces in our understanding of the reorganization of the global climate system since the Last Glacial Maximum. Here, using a basin-wide compilation of planktic foraminiferal δ 18 O, we show that the North Pacific subpolar gyre extended~3°further south during the Last Glacial Maximum, consistent with sea surface temperature and productivity proxy data. Climate models indicate that the expansion of the subpolar gyre was associated with a substantial gyre strengthening, and that these gyre circulation changes were driven by a southward shift of the midlatitude westerlies and increased wind stress from the polar easterlies. Using single-forcing model runs, we show that these atmospheric circulation changes are a nonlinear response to ice sheet topography/albedo and CO 2. Our reconstruction indicates that the gyre boundary (and thus westerly winds) began to migrate northward at~16.5 ka, driving changes in ocean heat transport, biogeochemistry, and North American hydroclimate. Plain language summary Despite the North Pacific's importance in the global climate system, changes in the circulation of this region since the last ice age are poorly understood. Today, the North Pacific Ocean has distinct properties north and south of~40°N: To the south, the warm surface waters form a circulation cell that moves clockwise (the subtropical gyre); to the north, the cold surface waters form a circulation cell that moves anticlockwise (the subpolar gyre). This difference in surface ocean circulation north and south of~40°N is determined by the wind patterns. Here, using a compilation of oxygen isotopes measured in the carbonate shells of fossil plankton from sediment cores across the basin, which tracks changes in the spatial pattern of temperature, we reconstruct how the position of the boundary between the gyres changed since the last ice age. Our results show that the boundary between the gyres was shifted southward by~3°during the last ice age; this indicates that the westerly winds were also shifted southward at this time. Using numerical simulations of the climate, we find that this ice age shift in the westerly winds is primarily due to the presence of a large ice sheet over North America.

REZ is grateful to Lance Agavulin and Glen Morangie for their spiritual support. JWBR was supported by the European Research Council (ERC Grant 805246) and the Natural Environment Research Council (NERC grant NE/N011716/1). The aqueous boric, hydrofluoric, and fluoroboric acid systems are key to a variety of applications, including boron measurements in marine carbonates for CO2 system reconstructions, chemical analysis and synthesis, polymer science, sandstone acidizing, fluoroborate salt manufacturing, and more. Here we present a comprehensive study of chemical equilibria and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. We work out the chemical speciation of the various dissolved compounds over a wide range of pH, total fluorine (FT), and total boron (BT) concentrations. We show that at low pH (0 ≤ pH ≤ 4) and FT ≫ BT, the dominant aqueous species is BF4−, a result relevant to recent advances in high precision measurements of boron concentration and isotopic composition. Using experimental data on kinetic rate constants, we provide estimates for the equilibration time of the slowest reaction in the system as a function of pH and [HF], assuming FT ≫ BT. Furthermore, we present the first quantum-chemical (QC) computations to determine boron isotope fractionation in the fluoroboric acid system. Our calculations suggest that the equilibrium boron isotope fractionation between BF3 and BF4− is slightly smaller than that calculated between B(OH)3 and B(OH)4−. Based on the QC methods X3LYP/6-311+G(d,p) (X3LYP+) and MP2/aug-cc-pVTZ (MP2TZ), α(BF3−BF4−) ≃ 1.030 and 1.025, respectively. However, BF4− is enriched in 11B relative to B(OH)4−, i.e., α(BF4−−B(OH)4−) ≃ 1.010 (X3LYP+) and 1.020 (MP2TZ), respectively. Selection of the QC method (level of theory and basis set) represents the largest uncertainty in the calculations. The effect of hydration on the calculated boron isotope fractionation turned out to be minor in most cases, except for BF4− and B(OH)3. Finally, we provide suggestions on best practice for boric acid–hydrofluoric acid applications in geochemical boron analyses. Postprint

Funding was provided through a NERC Research Training Support Grant awarded NE/L002590/1 to Ben Taylor and NERC grant NE/N011716/1 awarded to James Rae and Andrea Burke. Planktic foraminifera census data have been used to reconstruct past temperatures through transfer functions, as well as changes in ocean ecosystems, chemistry and circulation. Here we present new multinet, plankton net and core-top census data from 20 sites in the Subpolar North Pacific. We combine these with previous data to provide an up to date compilation of North Pacific planktic foraminifera assemblage data. Our compilation is used to define 6 faunal zones: the subpolar zone; transitional zone; upwelling zone; subtropical zone; east equatorial zone; west equatorial zone; based on the distribution of 10 major species of planktic foraminifera. Two species of planktic foraminifera Neogloboquadrina pachyderma and Globigerina bulloides provide the basis for many subpolar paleo-reconstructions. Through the analysis of new multinet and CTD data we find that G. bulloides and N. pachyderma are predominantly found within 0–50 m of the water column and coincide with high food availability. N. pachyderma also shows a strong temperature control and can thrive in food poor waters where temperatures are low. Both species bloom seasonally, particularly during the spring bloom of March to June, with G. bulloides exhibiting greater seasonal variation. We suggest that percentage abundance of N. pachyderma in paleo-assemblages can be used to assess relative changes in past temperature, with G. bulloides abundance more likely to reflect changes in food availability. By comparing our core-top and multinet data, we also find a dissolution bias of G. bulloides over N. pachyderma in the North Pacific, which may enrich assemblages in the latter species. Postprint

Wally Broecker acknowledges funding from the Comer Science and Education Foundation. James W. B. Rae acknowledges funding from NERC standard grants NE/N003861/1 and NE/N011716/1, and support from the School of Earth and Environmental Sciences at the University of St Andrews during Wally Broecker’s visit, which sparked the discussions that led to this paper. In this contribution we explore constraints on the fractions of deep water present in the Indian and Pacific oceans which originated in the northern Atlantic and in the Southern Ocean. Based on PO4* we show that if ventilated Antarctic shelf waters characterize the Southern contribution, then the proportions could be close to 50–50. If instead a Southern Ocean bottom water value is used, the Southern contribution is increased to 75 %. While this larger estimate may best characterize the volume of water entering the Indo-Pacific from the Southern Ocean, it contains a significant portion of entrained northern water. We also note that ventilation may be highly tracer dependent: for instance Southern Ocean waters may contribute only 35 % of the deep radiocarbon budget, even if their volumetric contribution is 75 %. In our estimation, the most promising approaches involve using CFC-11 to constrain the amount of deep water formed in the Southern Ocean. Finally, we highlight the broad utility of PO4* as a tracer of deep water masses, including descending plumes of Antarctic Bottom Water and large-scale patterns of deep ocean mixing, and as a tracer of the efficiency of the biological pump. Publisher PDF

The B/Ca ratio of planktic foraminiferal calcite, a proxy for the surface ocean carbonate system, displays large negative excursions during the Paleocene-Eocene Thermal Maximum (PETM, 55.9 Ma), consistent with rapid ocean acidification at that time. However, the B/Ca excursion measured at the PETM exceeds a magnitude that modern pH calibrations can explain. Numerous other controls on the proxy have been suggested, including foraminiferal growth rate and the total concentration of dissolved inorganic carbon (DIC). Here we present new calibrations for B/Ca versus the combined effects of pH and DIC in the symbiont-bearing planktic foraminifer Orbulina universa, grown in culture solutions with simulated Paleocene seawater elemental composition (high [Ca], low [Mg], and low total boron concentration ([B]_T). We also investigate the isolated effects of low seawater [B]_T, high [Ca], reduced symbiont photosynthetic activity, and average shell growth rate on O. universa B/Ca in order to further understand the proxy systematics and to determine other possible influences on the PETM records. We find that average shell growth rate does not appear to determine B/Ca in high calcite saturation experiments. In addition, our “Paleocene” calibration shows higher sensitivity than the modern calibration at low [B(OH)_4−]/DIC. Given a large DIC pulse at the PETM, this amplification of the B/Ca response can more fully explain the PETM B/Ca excursion. However, further calibrations with other foraminifer species are needed to determine the range of foraminifer species-specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations.

Significance Debate lingers over what caused the last mass extinction 66 million years ago, with intense volcanism and extraterrestrial impact the most widely supported hypotheses. However, without empirical evidence for either’s exact environmental effects, it is difficult to discern which was most important in driving extinction. It is also unclear why recovery of biodiversity and carbon cycling in the oceans was so slow after an apparently sudden extinction event. In this paper, we show (using boron isotopes and Earth system modeling) that the impact caused rapid ocean acidification, and that the resulting ecological collapse in the oceans had long-lasting effects for global carbon cycling and climate. Our data suggest that impact, not volcanism, was key in driving end-Cretaceous mass extinction., Mass extinction at the Cretaceous–Paleogene (K-Pg) boundary coincides with the Chicxulub bolide impact and also falls within the broader time frame of Deccan trap emplacement. Critically, though, empirical evidence as to how either of these factors could have driven observed extinction patterns and carbon cycle perturbations is still lacking. Here, using boron isotopes in foraminifera, we document a geologically rapid surface-ocean pH drop following the Chicxulub impact, supporting impact-induced ocean acidification as a mechanism for ecological collapse in the marine realm. Subsequently, surface water pH rebounded sharply with the extinction of marine calcifiers and the associated imbalance in the global carbon cycle. Our reconstructed water-column pH gradients, combined with Earth system modeling, indicate that a partial ∼50% reduction in global marine primary productivity is sufficient to explain observed marine carbon isotope patterns at the K-Pg, due to the underlying action of the solubility pump. While primary productivity recovered within a few tens of thousands of years, inefficiency in carbon export to the deep sea lasted much longer. This phased recovery scenario reconciles competing hypotheses previously put forward to explain the K-Pg carbon isotope records, and explains both spatially variable patterns of change in marine productivity across the event and a lack of extinction at the deep sea floor. In sum, we provide insights into the drivers of the last mass extinction, the recovery of marine carbon cycling in a postextinction world, and the way in which marine life imprints its isotopic signal onto the geological record.

J. Shao and L.D. Stott were supported by an NSF grant (MG&G 1558990). W. R. Gray and R. Greenop were supported by NERC grants NE/N011716/1 and NE/N011716/1 to J.W.B. Rae. I. Pecher, H.L. Neil, and B. Davy were supported by RSNZ Marsden Fund grant UOA1022. R. Coffin was supported by a DOE-NETL contract to NRL subcontract to TAMUCC (#601970). Identifying processes within the Earth System that have modulated atmospheric pCO2 during each glacial cycle of the late Pleistocene stands as one of the grand challenges in climate science. The growing array of surface ocean pH estimates from the boron isotope proxy across the last glacial termination may reveal regions of the ocean that influenced the timing and magnitude of pCO2 rise. Here we present two new boron isotope records from the subtropical‐subpolar transition zone of the Southwest Pacific that span the last 20 kyr, as well as new radiocarbon data from the same cores. The new data suggest this region was a source of carbon to the atmosphere rather than a moderate sink as it is today. Significantly higher outgassing is observed between ~16.5‐14 kyrBP, associated with increasing δ13C and [CO3]2‐ at depth, suggesting loss of carbon from the intermediate ocean to the atmosphere. We use these new boron isotope records together with existing records to build a composite pH/pCO2 curve for the surface oceans. pH disequilibrium/CO2 outgassing was widespread throughout the last deglaciation, likely explained by upwelling of CO2 from the deep/intermediate ocean. During the Holocene, a smaller outgassing peak is observed at a time of relatively stable atmospheric CO2, which may be explained by regrowth of the terrestrial biosphere countering ocean CO2 release. Our stack is likely biased toward upwelling/CO2 source regions. Nevertheless, the composite pCO2 curve provides robust evidence that various parts of the ocean were releasing CO2 to the atmosphere over the last 25 kyr. Publisher PDF

The work is supported by the Research Council of Norway (RCN) through Petromaks2- NORCRUST (project number: 255150) and its Centre of Excellence funding scheme for CAGE (project number: 223259). J.-H. K. is supported by the project "Development on Geochemical Proxies of Isotope and Trace Element for Understanding of Earth and Universe Evolution Processes (GP2017-018)" funded by the Korea Ministry of Science and ICT (MSIT). Svalbard fjord cruise in 2016 with RV Helmer Hanssen for Science Research Program to S.-I.N. is fully supported by MSIT (NRF-2015M1A5A1037243, PN19090). Submarine groundwater discharge could impact the transport of critical solutes to the ocean. However, its driver(s), significance over geological time scales, and geographical coverage are poorly understood. We characterize a submarine groundwater seep from the continental slope off northern Norway where substantial amount of meteoric water was detected. We reconstruct the seepage history from textural relationships and U-Th geochronology of authigenic minerals. We demonstrate how glacial-interglacial dynamics promoted submarine groundwater circulation more than 100 km offshore and resulted in high fluxes of critical solutes to the ocean. This cryosphere-hydrosphere coupling is likely common in the circum-Arctic implying that future decay of glaciers and permafrost in a warming Arctic is expected to attenuate such a coupled process and thus decrease the export of critical solutes. Publisher PDF