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The Agulhas Current in the southwest Indian Ocean is the strongest western boundary current on Earth. The major role of the Agulhas Current in driving significant heat and salt fluxes is well known, yet its biogeochemical fluxes remain largely uncharacterised. Here, we use nitrate isotopes (δ15N, δ18O, and Δ(15-18) = δ15N-δ18O) to evaluate nutrient supply mechanisms that ultimately support new production in the southwest Indian Ocean. Across the greater Agulhas region, thermocline nitrate-δ15N is lower (4.9-5.8‰) than the underlying Subantarctic Mode Water source (δ15N of 6.9‰) and the upstream source regions (where nitrate-δ15N ranges from 6.4-7.0‰), which we attribute to local N2 fixation. Using a one-box model to simulate the newly-fixed nitrate flux, we estimate a local N2 fixation rate of 7-25 Tg N.a-1, amounting to ~30-95% of the whole Indian Ocean nitrogen gain estimated by models. Thermocline and mixed-layer nitrate Δ(15-18) is also low, due to both N2 fixation and coupled partial nitrate assimilation and nitrification. This local nitrogen cycling imprints an isotopic signal on Indian Ocean nitrate that persists in Agulhas rings that “leak” into the South Atlantic and are subsequently transported northwards. If this signal is retained in calcifying organisms (e.g., foraminifera) deposited on the seafloor, it could be used to trace past Agulhas leakage, yielding quantitative insights into the strength of the Atlantic Meridional Overturning Circulation over time. In addition to local N2 fixation, the nitrate isotopes reveal three physical mechanisms of subsurface nitrate supply: i) inshore upwelling driven by the current and winds, ii) entrainment at the edges of a mesoscale eddy, and iii) density-driven overturning at the current edge induced by strong horizontal velocity and density shears. All these nitrate supply mechanisms are evident as incidences of relatively high-Δ(15-18) nitrate in the thermocline and surface yet the intensity and subsurface expression of some of them is not apparent in the physical data, highlighting the utility of the nitrate isotopes for exploring physical ocean processes. The high mesoscale variability that likely drives subsurface nitrate supply to Agulhas Current surface waters is common to all western boundary currents, implying that vertical nitrate entrainment is quantitatively significant in all such systems. We posit that along with N2 fixation, physical mechanisms of upward nitrate supply enhance ocean fertility and possibly carbon export in the South Indian Ocean. Higher rates of warming, and thus thermal stratification, are expected to decrease Indian Ocean productivity more rapidly in the future than that of other ocean basins. However, a coincident increase in eddy kinetic energy across boundary currents may enhance the upward nutrient supply, partially offsetting the stratification-driven decline in productivity.

The greater Agulhas Current region is an important component of the climate system, yet its influence on carbon and nutrient cycling is poorly understood. Here, we use nitrate isotopes (δ15N, δ18O, Δ(15–18) = δ15N–δ18O) to trace regional water mass circulation and investigate nitrogen cycling in the Agulhas Current and adjacent recirculating waters. The deep and intermediate waters record processes occurring remotely, including partial nitrate assimilation in the Southern Ocean and denitrification in the Arabian Sea. In the thermocline and surface, tropically sourced waters are biogeochemically distinct from adjacent subtropically sourced waters, confirming inhibited lateral mixing across the current core. (Sub)tropical thermocline nitrate δ15N is lower (4.9–5.8‰) than the sub-thermocline source, Subantarctic Mode Water (6.9‰); we attribute this difference to local N2 fixation. Using a one-box model to simulate the newly fixed nitrate flux, we estimate a local N2 fixation rate of 7–25 Tg N.a−1, with the upper limit likely biased high. In the mixed layer, nitrate δ15N and δ18O rise in unison, indicating that phytoplankton nitrate assimilation dominates in surface waters, with nitrification restricted to deeper waters. Because nitrate assimilation and nitrification are vertically decoupled, the rate of nitrate assimilation plus N2 fixation can be used to approximate carbon export. Thermocline and mixed-layer nitrate Δ(15–18) is low, due to both N2 fixation and coupled partial nitrate assimilation and nitrification. Similarly low-Δ(15–18) nitrate in Agulhas rings indicates leakage of low-δ15N nitrogen into the South Atlantic, which should be recorded in the organic matter sinking to the seafloor, providing a potential tracer of past Agulhas leakage.

The proposed Anthropocene Global Boundary Stratotype Section and Point (GSSP) candidate site of West Flower Garden Bank (27.8762°N, 93.8147°W) is an open ocean location in the Gulf of Mexico with a submerged coral reef and few direct human impacts. Corals contain highly accurate and precise (14C, 239+240Pu) have clear increases in this coral starting in 1957 for 14C and the first increase in 1956 for 239+240Pu (potential bases for the Anthropocene GSSP). Coral δ 13C declined especially after 1956 consistent with the Suess Effect resulting from the burning of fossil fuels. Coral skeletal δ 15N starts to increase in 1963 corresponding with the increase in agricultural fertilizers. Coral Hg concentrations (1933–1980) loosely track fluctuations in industrial pollution and coral Ba/Ca increases from 1965–1983 when offshore oil operations expand after 1947. Coral temperature proxies contain the 20th-century global warming trend whereas coral growth declines during this interval.

Corals are unique in the suite of proposed Anthropocene Global Boundary Stratotype Section and Point (GSSP) archives, as living organisms that produce aragonite exoskeletons preserved in the geological record that contain highly accurate and precise (, The Anthropocene Review, 10 (1), ISSN:2053-0196, ISSN:2053-020X

During glacial terminations, massive iceberg discharges and meltwater pulses in the North Atlantic triggered a shutdown of the Atlantic Meridional Overturning Circulation (AMOC). Speleothem calcium carbonate oxygen isotope records (δ18OCc) indicate that the collapse of the AMOC caused dramatic changes in the distribution and variability of the East Asian and Indian monsoon rainfall. However, the mechanisms linking changes in the intensity of the AMOC and Asian monsoon δ18OCc are not fully understood. Part of the challenge arises from the fact that speleothem δ18OCc depends on not only the δ18O of precipitation but also temperature and kinetic isotope effects. Here we quantitatively deconvolve these parameters affecting δ18OCc by applying three geochemical techniques in speleothems covering the penultimate glacial termination. Our data suggest that the weakening of the AMOC during meltwater pulse 2A caused substantial cooling in East Asia and a shortening of the summer monsoon season, whereas the collapse of the AMOC during meltwater pulse 2B (133,000 years ago) also caused a dramatic decrease in the intensity of the Indian summer monsoon. These results reveal that the different modes of the AMOC produced distinct impacts on the monsoon system., Nature Geoscience, 14 (12), ISSN:1752-0908, ISSN:1752-0894

The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10‰ increase in foraminifera-bound nitrogen isotopes (15N/14N) since the late Miocene (8 to 9 Mya), indicating large ODZs expansion. Coinciding with this change, we find a major increase in the nutrient content of the ocean, reconstructed from phosphorus and iron measurements of hydrothermal sediments at the same site. Whereas global warming studies cast seawater oxygen concentrations as mainly dependent on climate and ocean circulation, our findings indicate that modern ODZs are underpinned by historically high concentrations of seawater phosphate., Proceedings of the National Academy of Sciences of the United States of America, 119 (45), ISSN:0027-8424, ISSN:1091-6490

During the last ice age, the Northern Hemisphere experienced a series of abrupt millennial-scale climatic changes linked to variations in the strength of the Atlantic Meridional Overturning Circulation and sea-ice extent. However, our understanding of their impacts on decadal-scale climate variability in central Europe has been limited by the lack of high-resolution continental archives. Here, we present a near annual-resolution climate proxy record of central European temperature reconstructed from the Eifel maar lakes of Holzmaar and Auel in Germany, spanning the past 60,000 years. The lake sediments reveal a series of previously undocumented multidecadal climate cycles of around 20 to 150 years that persisted through the last glacial cycle. The periodicity of these cycles suggests that they are related to the Atlantic multidecadal climate oscillations found in the instrumental record and in other climate archives during the Holocene. Our record shows that multidecadal variability in central Europe was strong during all warm interstadials, but was substantially muted during all cold stadial periods. We suggest that this decrease in multidecadal variability was the result of the atmospheric circulation changes associated with the weakening of the Atlantic Meridional Overturning Circulation and the expansion of North Atlantic sea-ice cover during the coldest parts of the last ice age. Central European multidecadal climate variability was subdued during cold stadials through the last glacial cycle due to atmospheric and oceanic circulation shifts, according to almost annual-resolution terrestrial climate proxy records from varved maar lakes in Germany.

Salinity-driven density stratification of the upper Arctic Ocean isolates sea-ice cover and cold, nutrient-poor surface waters from underlying warmer, nutrient-rich waters. Recently, stratification has strengthened in the western Arctic but has weakened in the eastern Arctic; it is unknown if these trends will continue. Here we present foraminifera-bound nitrogen isotopes from Arctic Ocean sediments since 35,000 years ago to reconstruct past changes in nutrient sources and the degree of nutrient consumption in surface waters, the latter reflecting stratification. During the last ice age and early deglaciation, the Arctic was dominated by Atlantic-sourced nitrate and incomplete nitrate consumption, indicating weaker stratification. Starting at 11,000 years ago in the western Arctic, there is a clear isotopic signal of Pacific-sourced nitrate and complete nitrate consumption associated with the flooding of the Bering Strait. These changes reveal that the strong stratification of the western Arctic relies on low-salinity inflow through the Bering Strait. In the central Arctic, nitrate consumption was complete during the early Holocene, then declined after 5,000 years ago as summer insolation decreased. This sequence suggests that precipitation and riverine freshwater fluxes control the stratification of the central Arctic Ocean. Based on these findings, ongoing warming will cause strong stratification to expand into the central Arctic, slowing the nutrient supply to surface waters and thus limiting future phytoplankton productivity., Nature Geoscience, 14 (9), ISSN:1752-0908, ISSN:1752-0894

For times prior to those represented by the air trapped in Antarctic ice core records, the concentration of CO2 in the atmosphere must be reconstructed using geochemical proxies. The δ13C of particulate organic carbon (POC) produced in ocean surface waters has previously been observed to covary with the concentration of CO2 in the water. Relative to bulk sedimentary organic carbon, the minute quantity of organic matter trapped within the shell walls of planktonic foraminifera, “foraminifera-bound organic matter” (FBOM), has the potential advantage of being protected from diagenetic alteration and contamination by allochthonous organic matter. Here, with new protocols and instrumentation, FBOM-δ13C is investigated as a potential proxy for the aqueous CO2 concentration ([CO2(aq)]) and thus the partial pressure of CO2 (pCO2) in past surface waters. We achieve a full method precision for FBOM-δ13C of 0.4‰ (1SD) on sample sizes of 20 nanomole C by adding a cryofocus step, a helium sheath flow to the oxidation and reduction reactors, and other modifications to an elemental analyzer and by introducing new approaches to reduce contamination during sample preparation. FBOM-δ13C was analyzed in core-top sediments from the eastern tropical Pacific that span the equatorial maximum in surface water [CO2(aq)]. FBOM-δ13C is lower than predicted for marine phytoplankton, consistent with a substantial lipid component in FBOM. Anticorrelation is observed between FBOM-δ13C and climatological [CO2(aq)]; the relationship is statistically significant (P

Dissolved oxygen (O2) is essential for most ocean ecosystems, fuelling organisms’ respiration and facilitating the cycling of carbon and nutrients. Oxygen measurements have been interpreted to indicate that the ocean’s oxygen-deficient zones (ODZs) are expanding under global warming. However, models provide an unclear picture of future ODZ change in both the near term and the long term. The paleoclimate record can help explore the possible range of ODZ changes in warmer-than-modern periods. Here we use foraminifera-bound nitrogen (N) isotopes to show that water-column denitrification in the eastern tropical North Pacific was greatly reduced during the Middle Miocene Climatic Optimum (MMCO) and the Early Eocene Climatic Optimum (EECO). Because denitrification is restricted to oxygen-poor waters, our results indicate that, in these two Cenozoic periods of sustained warmth, ODZs were contracted, not expanded. ODZ contraction may have arisen from a decrease in upwelling-fuelled biological productivity in the tropical Pacific, which would have reduced oxygen demand in the subsurface. Alternatively, invigoration of deep-water ventilation by the Southern Ocean may have weakened the ocean’s ‘biological carbon pump’, which would have increased deep-ocean oxygen. The mechanism at play would have determined whether the ODZ contractions occurred in step with the warming or took centuries or millennia to develop. Thus, although our results from the Cenozoic do not necessarily apply to the near-term future, they might imply that global warming may eventually cause ODZ contraction., Nature, 609 (7925), ISSN:0028-0836, ISSN:1476-4687

Methods for reconstructing past temperatures from speleothems have only recently been developed. Advances in quantitative temperature proxies for speleothems are now allowing critical knowledge gaps to be filled, given the outstanding age control and wide geographical distribution of the speleothem archive. The methods of reconstructing temperatures from speleothems are diverse: they rely on concepts from geochemistry, biology, and physics, and are based on different aspects of speleothems, including water inclusions, calcite, and organic molecules. Combining the different approaches makes temperature reconstructions more robust, affords further insights into the methodologies, and provides constraints on other climate variables.

Trophic position is a fundamental characteristic of animals, yet it is unknown in many extinct species. In this study, we ground-truth the 15N/14N ratio of enameloid-bound organic matter (δ15NEB) as a trophic level proxy by comparison to dentin collagen δ15N and apply this method to the fossil record to reconstruct the trophic level of the megatooth sharks (genus Otodus). These sharks evolved in the Cenozoic, culminating in Otodus megalodon, a shark with a maximum body size of more than 15 m, which went extinct 3.5 million years ago. Very high δ15NEB values (22.9 ± 4.4‰) of O. megalodon from the Miocene and Pliocene show that it occupied a higher trophic level than is known for any marine species, extinct or extant. δ15NEB also indicates a dietary shift in sharks of the megatooth lineage as they evolved toward the gigantic O. megalodon, with the highest trophic level apparently reached earlier than peak size., Science Advances, 8 (25), ISSN:2375-2548

Historical coral skeleton (CS) δ18 O and δ15 N records were produced from samples recovered from sedimentary deposits, held in natural history museum collections, and cored into modern coral heads. These records were used to assess the influence of global warming and regional eutrophication, respectively, on the decline of coastal coral communities following the development of the Pearl River Delta (PRD) megacity, China. We find that, until 2007, ocean warming was not a major threat to coral communities in the Pearl River estuary; instead, nitrogen (N) inputs dominated impacts. The high but stable CS-δ15 N values (9‰-12‰ vs. air) observed from the mid-Holocene until 1980 indicate that soil and stream denitrification reduced and modulated the hydrologic inputs of N, blunting the rise in coastal N sources during the early phase of the Pearl River estuary urbanization. However, an unprecedented CS-δ15 N peak was observed from 1987 to 1993 (>13‰ vs. air), concomitant to an increase of NH4+ concentration, consistent with the rapid Pearl River estuary urbanization as the main cause for this eutrophication event. We suggest that widespread discharge of domestic sewage entered directly into the estuary, preventing removal by natural denitrification hotspots. We argue that this event caused the dramatic decline of the Pearl River estuary coral communities reported from 1980 to 2000. Subsequently, the coral record shows that the implementation of improved wastewater management policies succeeded in bringing down both CS-δ15 N and NH4+ concentrations in the early 2000s. This study points to the potential importance of eutrophication over ocean warming in coral decline along urbanized coastlines and in particular in the vicinity of megacities.

Predicted future climate scenarios share similar characteristics with the Eocene ‘greenhouse’ period. However, short-term Early Eocene terrestrial climate variability is still poorly constrained mainly due to the rarity of adequately resolved climate archives. This lack of information restricts not only the evaluation of past continental climate conditions but additionally limits regional climate modelling efforts but also the validation of model outputs. Here, we present highly-resolved biomarker-based (bacterial membrane lipid and leaf wax) paleoclimate data from the UNESCO World Heritage Site Messel Fossil Pit (Germany) that cover an interval of ca. 640 ka. The drilled Messel paleolake succession, characterized by finely laminated and frequently varved black pelites (referred to as ‘oil shale’) represent a regional climate and environmental archive from the latest Early to Middle Eocene (~48.0-47.4 Ma) of western Central Europe. Downcore mean annual air temperature (MAAT) reconstructions inferred from bacterial-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) show a long-term cooling trend and range from 14 to 22°C. High-resolution sampling within the basal and middle core interval reveal several short-term negative temperature excursions of 4-5°C, respectively. Moreover, we measured compound-specific δ2H and δ13C of excellently preserved odd carbon numbered mid- and long-chain leaf wax n-alkanes in order to estimate past regional hydroclimatic conditions. δ2H values of terrestrial long- and aquatic mid-chain n-alkanes show exceptional variations of up to 45‰ and 60‰, respectively. In contrast, δ13C values of long-chain n-alkanes are within 5‰ (-28‰ to -33‰) while mid-chain δ13C values vary by 11‰, ranging between -26‰ and -37‰. Our results indicate that the Early to Middle Eocene temperature history of central western Europe, particularly on short geological timescales was much more variable than previously assumed. We recognize two abrupt shifts in MAAT that coincide with lower δ2H values and therefore may point to either wetter climate conditions or changed atmospheric moisture trajectories. We emphasize that the long-term decline in estimated MAAT towards the top of the Messel section has to our best knowledge not been quantified from any time-equivalent terrestrial archive in Central Europe, but resembles Early Eocene cooling patterns well-documented from the global oceans.

Nitrogen isotoperatios (δ15N) are a well-established tool for investigating the dietary and trophic behavior of animals in terrestrial and marine food webs. To date, δ15N values in fossils have primarily been measured in collagen extracted from bone or dentin, which is susceptible to degradation and rarely preserved in deep time (>100,000 years). In contrast,tooth enamelorganic matter is protected from diagenetic alteration by the mineral structure of hydroxyapatite and thus is often preserved overgeological time. However, due to the low nitrogen content (isotopic compositionhas been prevented by the analytical limitations of traditional methods. Here, we present a novel application of the oxidation-denitrification method that allows measurement of δ15N values in tooth enamel (δ15Nenamel). This method involves the oxidation of nitrogen in enamel-bound organic matter to nitrate followed by bacterial conversion of nitrate to N2O, and requires ≥100 times less nitrogen than traditional approaches. To demonstrate that δ15Nenamelvalues record diet and trophic behavior, we conducted a controlled feeding experiment with rats and guinea pigs (n=37). We determined that nitrogen concentration in tooth enamel (x̄=5.0±1.0 nmol/mg) is sufficient for δ15Nenamelanalyses with ≥5 mg untreated enamel powder. The nitrogen isotope composition of enamel reflects diet with an enrichment (Δ15Nenamel-diet) of ca. 2–4‰. δ15Nenamelvalues differ significantly between dietary groups and clearly record a shift from pre-experimental to experimental diet. The small sample size required (≤5 mg) by this method permits analyses of sample size-limited, diagenetically robust tooth enamel, and, as such it represents a promising new dietary proxy for reconstructing food webs and investigating thetrophic ecologyof extant and extinct taxa.

Ocean circulation supplies the surface ocean with the nutrients that fuel global ocean productivity. However, the mechanisms and rates of water and nutrient transport from the deep ocean to the upper ocean are poorly known. Here, we use the nitrogen isotopic composition of nitrate to place observational constraints on nutrient transport from the Southern Ocean surface into the global pycnocline (roughly the upper 1.2 km), as opposed to directly from the deep ocean. We estimate that 62 ± 5% of the pycnocline nitrate and phosphate originate from the Southern Ocean. Mixing, as opposed to advection, accounts for most of the gross nutrient input to the pycnocline. However, in net, mixing carries nutrients away from the pycnocline. Despite the quantitative dominance of mixing in the gross nutrient transport, the nutrient richness of the pycnocline relies on the large-scale advective flow, through which nutrient-rich water is converted to nutrient-poor surface water that eventually flows to the North Atlantic., info:eu-repo/semantics/published

Background Cancerous cells can recycle metabolic ammonium for their growth. As this ammonium has a low nitrogen isotope ratio (15N/14N), its recycling may cause cancer tissue to have lower 15N/14N than surrounding healthy tissue. We investigated whether, within a given tissue type in individual mice, tumoral and healthy tissues could be distinguished based on their 15N/14N. Methods Micro-biopsies of murine tumors and adjacent tissues were analyzed for 15N/14N using novel high-sensitivity methods. Isotopic analysis was pursued in Nude and C57BL/6 mice models with mature orthotopic brain and head&neck tumors generated by implantation of H454 and MEERL95 murine cells, respectively. Results In the 7 mice analyzed, the brain tumors had distinctly lower 15N/14N than healthy neural tissue. In the 5 mice with head&neck tumors, the difference was smaller and more variable. This was at least partly due to infiltration of healthy head&neck tissue by tumor cells. However, it may also indicate that the 15N/14N difference between tumoral and healthy tissue depends on the nitrogen metabolism of the healthy organ in question. Conclusions The findings, coupled with the high sensitivity of the 15N/14N measurement method used here, suggest a new approach for micro-biopsy-based diagnosis of malignancy as well as an avenue for investigation of cancer metabolism.

The Indonesian Throughflow (ITF) controls the oceanic flux of heat and salt between the Pacific and Indian Oceans and therewith plays an important role in modulating the meridional overturning circulation and low latitude hydrological cycle. Here, we report new sea surface temperature and aridity records from the west coast of Australia (IODP Site U1460), which allow us to assess the sensitivity of the eastern Indian Ocean to the major reorganization of Earth’s climate that occurred during the Mid-Pleistocene Transition. Our records indicate glacial coolings at 1.55 and 0.65 million years ago that are best explained by a weakening of the ITF as a consequence of global sea level and tectonic changes. These coincide with the development of pronounced gradients in the carbon isotope composition of the different ocean basins and with substantial changes in regional aridity, suggesting that the restrictions of the ITF influenced both the evolution of global ocean circulation and the development of the modern hydrological cycle in Western Australia., Scientific Reports, 9 (1), ISSN:2045-2322

Circulation more than temperature Changes in continental configuration and sea level affected the ocean's oxygen levels and the rate of denitrification between 70 and 30 million years ago. That finding by Kast et al. shows a fundamental difference from the modern ocean, in which the extent of suboxia is controlled primarily by global temperature. Changes in the nitrogen isotopic composition of marine organic matter correlate with the collision of India and Asia and the circulation changes that occurred as a result. Later, isotopic composition changed further in response to a fall in sea level as global cooling caused ice sheets to grow. Science , this issue p. 386

Both the nitrogen (N) isotopic composition (d15N) of the nitrate source and the magnitude of isotope discrimination associated with nitrate assimilation are required to estimate the degree of past nitrate consumption from the d15N of organic matter in Southern Ocean sediments (e.g. preserved within diatom microfossils). It has been suggested that the amplitude of isotope discrimination (i.e. the isotope effect) correlates with mixed layer depth, driven by a physiological response of phytoplankton to light availability, which introduces complexity to the interpretation of sedimentary records. However, most of the isotope effect estimates that underpin this hypothesis derive from acid-preserved water samples, from which nitrite would have been volatilized and lost during storage. Nitrite d15N in Antarctic Zone surface waters is extremely low (61 ± 20‰), consistent with the expression of an equilibrium isotope effect associated with nitrate–nitrite interconversion. Its loss from the combinednitrate + nitrite pool would act to raise the d15N of nitrate, potentially yielding overestimation of the isotope effect. Here, we revisit the nitrate assimilation isotope effect in the Antarctic Zone with measurements of the d15N and concentration of nitrate with and without nitrite, using frozen sea water samples from 5 different cruises that collectively cover all sectors of the Southern Ocean. The N isotope effect estimated using nitrate + nitrite d15N is relatively constant (5.5 ± 0.6‰) across the Antarctic Zone, shows no relationship with mixed layer depth, and is in agreement with sediment trap d15N measurements. Estimates of the N isotope effect derived from nitrate-only d15N are higher and more variable (7.9 ± 1.5‰), consistent with an artifact from nitrate-nitrite isotope exchange. In the case of the Southern Ocean, we conclude that the d15N of nitrate + nitrite better reflects the isotope effect of nitrate assimilation. The stability of this isotope effect across the Antarctic Zone simplifies the effort to reconstruct the past degree of nitrate consumption., info:eu-repo/semantics/published

Bulk sediment δ N records from the eastern tropical Pacific (ETP) extending back to the last ice age most often show low glacial δ N, then a deglacial δ N maximum, followed by a gradual decline to a late Holocene δ N that is typically higher than that of the Last Glacial Maximum (LGM). The lower δ N of the LGM has been interpreted to reflect an ice age reduction in water column denitrification. We report foraminifera shell-bound nitrogen isotope (FB-δ N) measurements for the two species Neogloboquadrina dutertrei and Neogloboquadrina incompta over the last 35 ka in two sediment cores from the eastern equatorial Pacific (EEP), both of which have the typical LGM-to-Holocene increase in bulk sediment δ N. FB-δ N contrasts with bulk sediment δ N by not indicating a lower δ N during the LGM. Instead, the FB-δ N records are dominated by a deglacial δ N maximum, with comparable LGM and Holocene values. The lower LGM δ N of the bulk sediment records may be an artifact, possibly related to greater exogenous N inputs and/or weaker sedimentary diagenesis during the LGM. The new data raise the possibility that the previously inferred glacial reduction in ETP water column denitrification was incorrect. A review of reconstructed ice age conditions and geochemical box model output provides mechanistic support for this possibility. However, equatorial ocean circulation and nitrate-rich surface water overlying both core sites allow for other possible interpretations, calling for replication at non-equatorial ETP sites., Paleoceanography and Paleoclimatology, 36 (5), ISSN:2572-4525, ISSN:2572-4517

Downcore sediment grain-size records of mineral dust (2–10 μm) can provide key insights into changes in wind strength and source-area characteristics over glacial-interglacial timescales. However, so far, little is known about glacial-interglacial changes of dust grain size in the open Southern Ocean, which are potentially associated with changes in the strength and position of the southern westerly winds. Here, we analyzed the grain-size distributions of subantarctic deep-sea sediments from the Pacific (PS75/056–1) and Atlantic (ODP Site 1090) sectors of the Southern Ocean, downwind of the major Southern Hemisphere dust source regions. Dust mean grain sizes show opposite trends in the two Southern Ocean sectors. Larger glacial grain sizes are observed in the Pacific sector, while finer glacial grain sizes are observed in the Atlantic sector. In the South Pacific, larger mean dust grain sizes parallel higher Fe fluxes during glacials. In contrast, in the South Atlantic record increased glacial Fe fluxes coincide with a decrease in glacial mean dust grain sizes consistent with some Antarctic ice core records. Our results suggest that the opposing grain-size trends are the result of different responses to glacial conditions in the sources and of changing wind and transport patterns. For the South Pacific, a possible explanation of our results could be an intensification of wind strength over Australia enabling emission of larger dust particles. This strengthening would imply a northward shift of the westerlies which facilitated the transport of dust from enhanced and/or more Australian and New Zealand sources. For the Atlantic, the decreased glacial dust grain size could be the consequence of increased glacial activity in the Patagonian Andes, generating and supplying more and finer-grained dust from the exposed continental shelf to the South Atlantic. These findings indicate that more extensive studies of wind-blown sediment properties in the Southern Ocean can provide important insights on the timing and latitudinal extent of climatic changes in the sources and variations of transport to the Southern Ocean by the westerly winds. ISSN:0277-3791

Geochimica et cosmochimica acta 308, 326-352 (2021). doi:10.1016/j.gca.2021.06.012, Published by Elsevier, New York, NY [u.a.]

12 pages, 5 figures, supplementary material https://doi.org/10.1016/j.epsl.2020.116649, Over the last deglaciation there were two transient intervals of pronounced atmospheric CO rise; Heinrich Stadial 1 (17.5-15 kyr) and the Younger Dryas (12.9-11.5 kyr). Leading hypotheses accounting for the increased accumulation of CO in the atmosphere at these times invoke deep ocean carbon being released from the Southern Ocean and an associated decline in the global efficiency of the biological carbon pump. Here we present new deglacial surface seawater pH and CO records from the Sub-Antarctic regions of the Atlantic and Pacific oceans using boron isotopes measured on the planktic foraminifera Globigerina bulloides. These new data support the hypothesis that upwelling of carbon-rich water in the Sub-Antarctic occurred during Heinrich Stadial 1, and contributed to the initial increase in atmospheric CO. The increase in CO is coeval with a decline in biological productivity at both the Sub-Antarctic Atlantic and Pacific sites. However, there is no evidence for a significant outgassing of deep ocean carbon from the Sub-Antarctic during the rest of the deglacial, including the second period of atmospheric CO rise coeval with the Younger Dryas. This suggests that the second rapid increase in atmospheric CO is driven by processes operating elsewhere in the Southern Ocean, or another region, This project was supported by the Natural Environment Research Council [NE/L002531/1] to R.S. and [NE/J021075/1] to G.L.F., Spanish Ministry of Science and Innovation [CGL2015-68194-R] to E.C. and C.P., S.L.J. acknowledges financial support from the Swiss National Science Foundation (SNSF grant PP00P2_172915), and A.M.-G. acknowledges funding from the Max Planck Society. With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

The Southern Ocean is widely recognized as a potential cause of the lower atmospheric concentration of CO2 during ice ages, but the mechanism is debated. Focusing on the Southern Ocean surface, we review biogeochemical paleoproxy data and carbon cycle concepts that together favor the view that both the Antarctic and Subantarctic Zones (AZ and SAZ) of the Southern Ocean played roles in lowering ice age CO2 levels. In the SAZ, the data indicate dust-driven iron fertilization of phytoplankton growth during peak ice age conditions. In the ice age AZ, the area-normalized exchange of water between the surface and subsurface appears to have been reduced, a state that we summarize as “isolation” of the AZ surface. Under most scenarios, this change would have stemmed the leak of biologically stored CO2 that occurs in the AZ today. SAZ iron fertilization during the last ice age fits with our understanding of ocean processes as gleaned from modern field studies and experiments; indeed, this hypothesis was proposed prior to evidentiary support. In contrast, AZ surface isolation is neither intuitive nor spontaneously generated in climate model simulations of the last ice age. In a more prospective component of this review, the suggested causes for AZ surface isolation are considered in light of the subarctic North Pacific (SNP), where the paleoproxies of productivity and nutrient consumption indicate similar upper ocean biogeochemical changes over glacial cycles, although with different timings at deglaciation. Among the proposed initiators of glacial AZ surface isolation, a single mechanism is sought that can explain the changes in both the AZ and the SNP. The analysis favors a weakening and/or equatorward shift in the upwelling associated with the westerly winds, occurring in both hemispheres. This view is controversial, especially for the SNP, where there is evidence of enhanced upper water column ventilation during the last ice age. We offer an interpretation that may explain key aspects of the AZ and SNP observations. In both regions, with a weakening in westerly wind-driven upwelling, nutrients may have been “mined out” of the upper water column, possibly accompanied by a poleward “slumping” of isopycnals. In the AZ, this would have encouraged declines in both the nutrient content and the formation rate of new deep water, each of which would have contributed to the lowering of atmospheric CO2. Through several effects, the reduction in AZ upwelling may have invigorated the upwelling of deep water into the low latitude pycnocline, roughly maintaining the pycnocline’s supply of water and nutrients so as to (1) support the high productivity of the glacial SAZ and (2) balance the removal of water from the pycnocline by the formation of Glacial North Atlantic Intermediate Water. The proposed return route from the deep ocean to the surface resembles that of Broecker’s (1991) “global ocean conveyor,” but applying to the ice age as opposed to the modern ocean., Quaternary Science Reviews, 254, ISSN:0277-3791

Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean’s Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind–driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode—which arises from the meridional temperature gradient as affected by Earth’s obliquity (axial tilt)—can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles., info:eu-repo/semantics/published

Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean's Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind-driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode-which arises from the meridional temperature gradient as affected by Earth's obliquity (axial tilt)-can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles.

The shells of oysters (Family Ostreidae) are predominantly composed of two different calcite microstructures: A dense foliated structure consisting of sheet-like folia (“foliated” microstructure) and a more porous microstructure consisting of less well organized leaf-shaped crystals (“chalky” microstructure). These unique characteristics of oyster shells have been subject to a number of studies, with some authors hypothesizing that the chalky structures are mineralized by bacteria living in the shell (Vermeij, 2014). The formation of these microstructures is of great interest, because the phenomenon is unique in the mollusk phylum and because the shells of oysters are popular archives for paleoclimate and paleoenvironment reconstructions (e.g. Bougeois et al., 2018; de Winter et al., 2018). Previous authors have challenged the bacterially mediated mineralization hypothesis through microstructural observations of different parts of the oyster shell (Checa et al., 2018).Here, we expand on this structural evidence by adding detailed observations of differences in chemical composition between the foliated and chalky microstructures. We combine information on trace element concentrations with stable carbon, oxygen, nitrogen and sulfur isotope ratios as well as carbonate clumped isotope analyses of samples from foliated and chalky structures in multiple modern specimens of Magallana gigas, the Pacific oyster. These analyses shed light on the chemical variability within the oyster shell and how it relates to the occurrence of various calcite microstructures. Given the unique isotopic signature of bacterially mediated calcite, our isotopic analysis results allow us to definitively conclude whether the chalky shell structure in modern oysters was precipitated via symbiotic microbes. Furthermore, the degree of intra-shell chemical variability has implications for paleoclimate and paleoenvirionmental reconstructions from fossil oyster shells, for which the applied trace element and isotope systems function as important proxies. The results of this study therefore yield important recommendations for sampling fossil oyster shells for reconstructions, and provide a baseline for the investigation of chemical variability between shell microstructures throughout the Ostreidae family and the mollusk phylum. ReferencesBougeois, L., Dupont-Nivet, G., De Rafélis, M., Tindall, J. C., Proust, J.-N., Reichart, G.-J., de Nooijer, L. J., Guo, Z. and Ormukov, C.: Asian monsoons and aridification response to Paleogene sea retreat and Neogene westerly shielding indicated by seasonality in Paratethys oysters, Earth and Planetary Science Letters, 485, 99–110, 2018.Checa, A. G., Harper, E. M. and González-Segura, A.: Structure and crystallography of foliated and chalk shell microstructures of the oyster Magallana: the same materials grown under different conditions, Scientific reports, 8(1), 7507, 2018.Vermeij, G. J.: The oyster enigma variations: a hypothesis of microbial calcification, Paleobiology, 40(1), 1–13, 2014.de Winter, N., Vellekoop, J., Vorsselmans, R., Golreihan, A., Soete, J., Petersen, S., Meyer, K., Casadio, S., Speijer, R. and Claeys, P.: An assessment of latest Cretaceous Pycnodonte vesicularis (Lamarck, 1806) shells as records for palaeoseasonality: a multi-proxy investigation, Climate of the Past, 14(6), 725–749, 2018.

Available sea surface temperature (SST) records from the subantarctic SE Pacific reveal large amplitude changes at orbital time-scales. High sedimentation rates along the southern Chilean margin provided higher resolution records back to ~70 ka showing millennial-scale SST variations paralleling temperatures reconstructed in Antarctic ice-cores.Here we present high-resolution millennial-scale SST and subsurface temperature records based on core MR16-09 PC03 covering a complete glacial/interglacial cycle back to Marine Isotope Stage 6, including a high-resolution record of the Eemian. Located on the Chilean margin at the bifurcation of the Antarctic Circumpolar Current into the Peru-Chile Current to the North and the Cape Horn Current to the South, core MR16-09 PC03 is in an ideal position to study the continent-ocean interactions, including changes in water masses, ice sheet formation, precipitation and vegetation.We used alkenones and GDGTs to determine SST (UK’37) and subsurface temperatures (TEXH86; 0 - 200 m), and integrated these results with XRF core scanner and planktic δ18O data (G. bulloides). During the Eemian, SSTs and subsurface temperatures were ~2° C and ~4° C, higher than during the Holocene, respectively. The high Eemian temperatures at our site are roughly consistent with the few available subantarctic SST records. The large temperature difference in the subsurface water masses between the Eemian and the Holocene could be explained by a deeper thermocline during the Eemian. During the last glacial period, the strongly fluctuating temperatures averaged ~8° C at the surface and ~6° C in the subsurface. The relative amount of C37:4 alkenone (%C37:4) show a drastic increase during the glacial period, especially in Marine Isotope Stage 3 in concentration. High %C37:4 values suggest increased freshwater supply, which could be related to fluctuations of the Patagonian Ice sheet and/ or precipitation on the adjacent land. The sedimentation rate and other terrigenous proxies, e.g. Titanium, BIT, Iron and Alkanes, confirm such increased and highly variable terrestrial inputs.

We present the first nitrogen isotope (δ15N) measurements of planktic foraminifera, paleoceanographically important zooplankton, from the nutrient‐rich waters of the modern Southern Ocean. Foraminifera were collected from net tows in the Subantarctic and Polar Frontal Zones (SAZ and PFZ, respectively) south of Africa during winter 2015 and late summer 2016. In late summer, consistent with preferential uptake of 14N‐nitrate and the progressive, northward depletion of nitrate by phytoplankton across the Southern Ocean, foraminifer tissue and shell‐bound δ15N rise equatorward along with nitrate δ15N. However, foraminifer δ15N is ~3‰ lower than expected for heterotrophs relying on photosynthetic biomass generated directly from nitrate. This discrepancy appears to originate with the particulate organic N (PON) in late‐summer surface waters, the δ15N of which is lowered by ammonium recycling. In winter, when overall productivity and foraminifer production are reduced, foraminifer δ15N is higher (by 4.6 ± 0.8‰ for tissue and by 4.0 ± 1.5‰ for shell‐bound N compared to late summer) and exhibits no clear north‐south trend. These characteristics can also be explained by the feeding‐driven connection of foraminifera to PON, which is elevated in δ15N by net degradation in winter. Therefore, foraminifer δ15N is more closely tied to PON δ15N than to nitrate δ15N in the Southern Ocean mixed layer. Combining our isotope data with previously reported sediment trap fluxes from the western Pacific SAZ/PFZ suggests that, under modern conditions, the late‐summer ammonium recycling signal outweighs that of wintertime decomposition on the annually integrated δ15N of sinking foraminifera. ISSN:1525-2027

The middle Miocene climate transition (~14 million years ago) was characterized by a dramatic increase in the volume of the Antarctic ice sheet. The driving mechanism of this transition remains under discussion, with hypotheses including circulation changes, declining carbon dioxide in the atmosphere and orbital forcing. Southern Ocean records of planktic foraminiferal Mg/Ca have previously been interpreted to indicate a cooling of 6–7 °C and a decrease in salinity that preceded Antarctic cryosphere expansion by up to ~300,000 years. This interpretation has led to the hypothesis that changes in meridional heat and vapour transport along with an early thermal isolation of Antarctica from extrapolar climates played a fundamental role in triggering ice growth. Here we revisit the middle Miocene Southern Ocean temperature evolution using clumped isotope and lipid biomarker temperature proxies. Our records indicate that the Southern Ocean cooling and the associated salinity decrease occurred in phase with the expansion of the Antarctic ice sheet. We demonstrate that the timing and magnitude of the Southern Ocean temperature change seen in previous reconstructions can be explained if we consider pH as an additional, non-thermal, control on foraminiferal Mg/Ca ratios. Therefore, our new dataset challenges the view of a thermal isolation of Antarctica preceding ice sheet expansion, and suggests a strong coupling between Southern Ocean conditions and Antarctic ice volume in times of declining atmospheric carbon dioxide. Antarctic ice volume expansion in the middle Miocene coincides with Southern Ocean cooling, according to biomarker and clumped isotope temperature records from south of Tasmania.

In the Antarctic Zone of the Southern Ocean, the coupled observations of elevated diatom‐bound 15N/14N (δ15Ndb) and reduced export production during the ice ages indicates more complete nitrate (NO3−) consumption. This evidence points to an ice age decline in gross NO3− supply from the deep ocean to the surface wind‐mixed layer, which may help to explain the reduced CO2 levels of the ice age atmosphere. We use a seasonally resolved, two‐layer model of the N isotopes in the Antarctic Zone upper ocean to quantify the ice age decline in gross NO3− supply implied by the data. When model parameters are varied to reflect reduced gross NO3− supply, the concentration of wintertime upper ocean NO3− is lowered, but with a much weaker increase in NO3− δ15N than predicted by analytical models such as the Rayleigh and steady state models. Physical mixing is the dominant cause, with a modest contribution from foodweb dynamics. As a result, the observed δ15Ndb rise of ~3‰–4‰ must be explained mostly by a greater summertime increase in NO3− δ15N during the ice ages. The high degree of NO3− consumption required to generate this summertime δ15N rise indicates a >80% reduction in gross NO3− supply. Half or more of the modern gross NO3− supply is from wind‐forced Antarctic upwelling that drives the upper cell of Southern Ocean overturning. Thus, the decrease in NO3− supply cannot be achieved solely by a decline in vertical mixing or wintertime convection; rather, it requires an ice age weakening of the upper cell.