North Atlantic surface ocean warming and salinization in response to middle Eocene greenhouse warming.

Quantitative reconstructions of hydrological change during ancient greenhouse warming events provide valuable insight into warmer-than-modern hydrological cycles but are limited by paleoclimate proxy uncertainties. We present sea surface temperature (SST) records and seawater oxygen isotope (δ18Osw) estimates for the Middle Eocene Climatic Optimum (MECO), using coupled carbonate clumped isotope (Δ47) and oxygen isotope (δ18Oc) data of well-preserved planktonic foraminifera from the North Atlantic Newfoundland Drifts. These indicate a transient ~3°C warming across the MECO, with absolute temperatures generally in accordance with trace element (Mg/Ca)-based SSTs but lower than biomarker-based SSTs for the same interval. We find a transient ~0.5‰ shift toward higher δ18Osw, which implies increased salinity in the North Atlantic subtropical gyre and potentially a poleward expansion of its northern boundary in response to greenhouse warming. These observations provide constraints on dynamic ocean response to warming events, which are consistent with theory and model simulations predicting an enhanced hydrological cycle under global warming.

Evolution of tropical land temperature across the last glacial termination.

The tropical West Pacific hosts the warmest part of the surface ocean and has a considerable impact on the global climate system. Reconstructions of past temperature in this region can elucidate climate connections between the tropics and poles and the sensitivity of tropical temperature to greenhouse forcing. However, existing data are equivocal and reliable information from terrestrial archives is particularly sparse. Here we constrain the magnitude and timing of land temperature change in the tropical West Pacific across the last deglaciation using an exceptionally precise paleothermometer applied to a well-dated stalagmite from Northern Borneo. We show that the cave temperature increased by 4.4 ± 0.3 °C (2 SEM) from the Last Glacial Maximum to the Holocene, amounting to 3.6 ± 0.3 °C (2 SEM) when correcting for sea-level induced cave altitude change. The warming closely follows atmospheric CO2 and Southern Hemisphere warming. This contrasts with hydroclimate, as reflected by drip water δ18O, which responds to Northern Hemisphere cooling events in the form of prominent drying, while temperature was rising. Our results thus show a close response of tropical temperature to greenhouse forcing, independent of shifts in the tropical circulation patterns.

Cenozoic evolution of deep ocean temperature from clumped isotope thermometry.

Characterizing past climate states is crucial for understanding the future consequences of ongoing greenhouse gas emissions. Here, we revisit the benchmark time series for deep ocean temperature across the past 65 million years using clumped isotope thermometry. Our temperature estimates from the deep Atlantic Ocean are overall much warmer compared with oxygen isotope-based reconstructions, highlighting the likely influence of changes in deep ocean pH and/or seawater oxygen isotope composition on classical oxygen isotope records of the Cenozoic. In addition, our data reveal previously unrecognized large swings in deep ocean temperature during early Eocene acute greenhouse warmth. Our results call for a reassessment of the Cenozoic history of ocean temperatures to achieve a more accurate understanding of the nature of climatic responses to tectonic events and variable greenhouse forcing.

InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards.

Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth-system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47 and Δ47 values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ47 (I-CDES) values for Intercarb-Carbon Dioxide Equilibrium Scale.

Long-term performance of the Kiel carbonate device with a new correction scheme for clumped isotope measurements.

RATIONALE: Carbonate clumped isotope thermometry is a powerful new technique increasingly used in many fields in earth science. Recently, it has been shown that clumped isotope measurements can be performed with a Kiel carbonate preparation device and micro-volume analyses, allowing measurements of small (1.5-2 mg) carbonate samples. However, common data correction schemes rely on measurements of gases prepared offline, potentially leading to unrecognized biases in the results. METHODS: We propose a new correction scheme for the Kiel device method including: (1) A pressure-sensitive baseline correction (PBL) of the raw beam signals; (2) Transfer of data to the absolute reference frame; (3) Correction for acid fractionation; (4) Correction for average standard offsets; (5) When necessary, correction for Δ47 scale compression based on offsets among standards with different ordering state. The long-term performance of the new scheme was tested with a large set of standard measurements (N = 432) obtained over the course of 15 months. RESULTS: The PBL correction reliably removes composition-dependent artifacts, which are commonly corrected for with gas measurements, and offsets observed in micro-volume measurements when ion beams are imbalanced. We show that the shape of the PBL can vary strongly and needs to be properly characterized. Combined PBL and standard correction resulted in long-term stability with standard deviations in Δ47 of 0.012-0.016 ‰ for the five standards over the whole period, close to the average error of 0.011 ‰ observed for individual measurements consisting of 10 replicate analyses. CONCLUSIONS: Our correction scheme eliminates the need for routine gas measurements, allowing for equal treatment of samples and standards with the Kiel device setup. While the PBL and standard data obtained over 15 months reveal variable mass spectrometer behavior, they provide a robust means of correction, yielding reproducible results from small carbonate samples in the long term.

Changes in North Atlantic nitrogen fixation controlled by ocean circulation.

In the ocean, the chemical forms of nitrogen that are readily available for biological use (known collectively as 'fixed' nitrogen) fuel the global phytoplankton productivity that exports carbon to the deep ocean. Accordingly, variation in the oceanic fixed nitrogen reservoir has been proposed as a cause of glacial-interglacial changes in atmospheric carbon dioxide concentration. Marine nitrogen fixation, which produces most of the ocean's fixed nitrogen, is thought to be affected by multiple factors, including ocean temperature and the availability of iron and phosphorus. Here we reconstruct changes in North Atlantic nitrogen fixation over the past 160,000 years from the shell-bound nitrogen isotope ratio ((15)N/(14)N) of planktonic foraminifera in Caribbean Sea sediments. The observed changes cannot be explained by reconstructed changes in temperature, the supply of (iron-bearing) dust or water column denitrification. We identify a strong, roughly 23,000-year cycle in nitrogen fixation and suggest that it is a response to orbitally driven changes in equatorial Atlantic upwelling, which imports 'excess' phosphorus (phosphorus in stoichiometric excess of fixed nitrogen) into the tropical North Atlantic surface. In addition, we find that nitrogen fixation was reduced during glacial stages 6 and 4, when North Atlantic Deep Water had shoaled to become glacial North Atlantic intermediate water, which isolated the Atlantic thermocline from excess phosphorus-rich mid-depth waters that today enter from the Southern Ocean. Although modern studies have yielded diverse views of the controls on nitrogen fixation, our palaeobiogeochemical data suggest that excess phosphorus is the master variable in the North Atlantic Ocean and indicate that the variations in its supply over the most recent glacial cycle were dominated by the response of regional ocean circulation to the orbital cycles.

Deglacial pulses of deep-ocean silicate into the subtropical North Atlantic Ocean.

Growing evidence suggests that the low atmospheric CO2 concentration of the ice ages resulted from enhanced storage of CO2 in the ocean interior, largely as a result of changes in the Southern Ocean. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean, but the mechanism connecting the North Atlantic and the Southern Ocean remains unclear. Biogenic opal export in the low-latitude ocean relies on silicate from the underlying thermocline, the concentration of which is affected by the circulation of the ocean interior. Here we report a record of biogenic opal export from a coastal upwelling system off the coast of northwest Africa that shows pronounced opal maxima during each glacial termination over the past 550,000 years. These opal peaks are consistent with a strong deglacial reduction in the formation of silicate-poor glacial North Atlantic intermediate water (GNAIW). The loss of GNAIW allowed mixing with underlying silicate-rich deep water to increase the silicate supply to the surface ocean. An increase in westerly-wind-driven upwelling in the Southern Ocean in response to the North Atlantic change has been proposed to drive the deglacial rise in atmospheric CO2 (refs 3, 4). However, such a circulation change would have accelerated the formation of Antarctic intermediate water and sub-Antarctic mode water, which today have as little silicate as North Atlantic Deep Water and would have thus maintained low silicate concentrations in the Atlantic thermocline. The deglacial opal maxima reported here suggest an alternative mechanism for the deglacial CO2 release. Just as the reduction in GNAIW led to upward silicate transport, it should also have allowed the downward mixing of warm, low-density surface water to reach into the deep ocean. The resulting decrease in the density of the deep Atlantic relative to the Southern Ocean surface promoted Antarctic overturning, which released CO2 to the atmosphere.

Interglacial hydroclimate in the tropical West Pacific through the Late Pleistocene.

Records of atmospheric carbon dioxide concentration (P(CO(2))) and Antarctic temperature have revealed an intriguing change in the magnitude of interglacial warmth and P(CO(2)) at around 430,000 years ago (430 ka), but the global climate repercussions of this change remain elusive. Here, we present a stalagmite-based reconstruction of tropical West Pacific hydroclimate from 570 to 210 ka. The results suggest similar regional precipitation amounts across the four interglacials contained in the record, implying that tropical hydroclimate was insensitive to interglacial differences in P(CO(2)) and high-latitude temperature. In contrast, during glacial terminations, drying in the tropical West Pacific accompanied cooling events in northern high latitudes. Therefore, the tropical convective heat engine can either stabilize or amplify global climate change, depending on the nature of the climate forcing.

Foraminiferal isotope evidence of reduced nitrogen fixation in the ice age Atlantic Ocean.

Fixed nitrogen (N) is a limiting nutrient for algae in the low-latitude ocean, and its oceanic inventory may have been higher during ice ages, thus helping to lower atmospheric CO2 during those intervals. In organic matter within planktonic foraminifera shells in Caribbean Sea sediments, we found that the 15N/14N ratio from the last ice age is higher than that from the current interglacial, indicating a higher nitrate 15N/14N ratio in the Caribbean thermocline. This change and other species-specific differences are best explained by less N fixation in the Atlantic during the last ice age. The fixation decrease was most likely a response to a known ice age reduction in ocean N loss, and it would have worked to balance the ocean N budget and to curb ice age-interglacial change in the N inventory.