Coupled Mg/Ca and Clumped Isotope Measurements Indicate Lack of Substantial Mixed Layer Cooling in the Western Pacific Warm Pool During the Last ∼5 Million Years

The Indo-Pacific Warm Pool (IPWP) plays a crucial role in influencing climate dynamics both in the tropics and globally. Yet, there is an ongoing controversy concerning the evolution of surface temperatures in the IPWP since the Pliocene, which is fueled by contradictory proxy evidence. Temperature reconstructions using TEX86 indicate a gradual cooling by ∼2°C from the Pliocene to today while Mg/Ca-based studies using planktonic foraminifera do not report any long-term trends. A bias in Mg/Ca records due to seawater chemistry changes has been suggested as an explanation for this proxy mismatch. Here, we present data from two independent foraminifera-based temperature proxies, Mg/Ca and clumped isotopes (Δ47), measured on the same samples from IODP Site U1488 in the IPWP. We reconstructed mixed layer and subsurface temperatures and find very good agreement among Mg/Ca and Δ47 when applying a minor correction for changing Mg/Ca ratios of seawater. Diagenetic effects could influence Δ47 but the evaluation of foraminifera preservation at Site U1488 suggests that this effect is unlikely to have masked a long-term trend in the data. While remaining uncertainties prevent us from fully ruling out particular hypotheses, our study adds evidence that mixed layer temperatures likely did not cool substantially, while subsurface temperatures cooled more strongly since the Pliocene. The substantial Pleistocene cooling previously observed in TEX86 data is consistent with this finding when interpreting it as a combined surface and subsurface signal.publishedVersio

Southern Ocean bottom-water cooling and ice sheet expansion during the middle Miocene climate transition

The middle Miocene climate transition (MMCT), around 14 Ma, was associated with a significant climatic shift, but the mechanisms triggering the event remain enigmatic. We present a clumped isotope (Δ47) bottom-water temperature (BWT) record from 16.0 to 12.2 Ma from Ocean Drilling Program (ODP) Site 747 in the Southern Ocean and compare it to existing BWT records from different latitudes. We show that BWTs in the Southern Ocean reached 8–10 ∘C during the Miocene climatic optimum. These high BWT values indicate considerably warmer bottom-water conditions than today. Nonetheless, bottom-water δ18O (calculated from foraminiferal δ18O and Δ47) suggests substantial amounts of land ice throughout the interval of the study. Our dataset further demonstrates that BWTs at Site 747 were variable with an overall cooling trend across the MMCT. Notably, a cooling of around 3–5 ∘C preceded the stepped main increase in benthic δ18O, interpreted as global ice volume expansion, and appears to have been followed by a transient bottom-water warming starting during or slightly after the main ice volume increase. We speculate that a regional freshening of the upper water column at this time may have increased stratification and reduced bottom-water heat loss to the atmosphere, counteracting global cooling in the bottom waters of the Southern Ocean and possibly even at larger scales. Feedbacks required for substantial ice growth and/or tectonic processes may have contributed to the observed decoupling of global ice volume and Southern Ocean BWT.publishedVersio

Sensitivity of clumped isotope temperatures in fossil benthic and planktic foraminifera to diagenetic alteration

Applying the clumped isotope (Δ47) thermometer to foraminifer microfossils offers the potential to significantly improve paleoclimate reconstructions, owing to its insensitivity to the isotopic composition of seawater (unlike traditional oxygen isotope (δ18O) analyses). However, the extent to which primary Δ47 signatures of foraminiferal calcites can be overprinted during diagenesis is not well known. Here, we present Δ47 data as well as high-resolution (∼10 kyr) δ18O and δ13C middle Eocene time series, measured on benthic and planktic foraminifera from ODP/IODP Sites 1408, 1409, 1410, 1050, 1260 and 1263 in the Atlantic Ocean. The sites examined span various oceanographic regimes, including the western tropical to mid-latitude North Atlantic, and the eastern mid-latitude South Atlantic. Comparing data from contemporaneous foraminifera with different preservation states, we test the effects of diagenetic alteration on paleotemperature reconstructions for the deep and surface ocean. We find that overall, primary Δ47 signatures appear similarly sensitive to diagenetic overprinting as δ18O, with differences in sensitivity depending on pore fluid chemistry and the amount of secondary calcite. Where planktic foraminifera are significantly altered, sea surface temperatures derived from Δ47 and δ18O values are biased towards cool temperatures. In comparison, Δ47 and δ18O values of benthic and well preserved planktic foraminifera are less affected by diagenesis and thus likely to yield robust foraminiferal calcification temperatures. With independent estimates of diagenetic calcite fractions, secondary overprints could be corrected for, using end-member modeling and Δ47-based temperatures from benthic foraminifera

Stable Biological Production in the Eastern Equatorial Pacific Across the Plio-Pleistocene Transition (∼3.35–2.0 Ma)

Upwelling within the Eastern Equatorial Pacific (EEP) Ocean is a key factor for the Earth's climate because it supports >10% of the present-day biological production. The dynamics of upwelling in the EEP across the Plio-Pleistocene transition—an interval particularly relevant for understanding near-future warming due to Anthropocene-like atmospheric carbon-dioxide levels—have been intensively studied for the region east of the East Pacific Rise. In contrast, changes of the equatorial upwelling regime in the open Pacific Ocean west of this oceanographic barrier have received markedly less attention. We therefore provide new proxy records from Ocean Drilling Program Site 849 located within the EEP open-ocean upwelling regime. Our target interval (∼3.35–2.0 Ma) covers the Plio-Pleistocene transition characterized by the intensification of Northern Hemisphere Glaciation (iNHG). We use benthic δ18O values to generate a new, high-resolution age model for Site 849, and sand-accumulation rates together with benthic δ13C values to evaluate net export production. Although showing temporary substantial glacial-interglacial variations, our records indicate stability in net export production on secular timescales across the iNHG. We suggest the following processes to have controlled the long-term evolution of primary productivity at Site 849. First, nutrient export from the high latitudes to the EEP; second, a successive shoaling of the Pacific nutricline during the studied interval; and third, a simultaneous reduction in dust-borne iron input.publishedVersio

Transformation of ENSO-related rainwater to dripwater δ^(18)O variability by vadose water mixing

Speleothem oxygen isotopes (δ^(18)O) are often used to reconstruct past rainfall δ^(18)O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ^(18)O time series from northern Borneo and compare them to local rainfall δ^(18)O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ^(18)O reflects amount-weighted rainfall δ^(18)O integrated over the previous 3–10 months. We document large interannual dripwater δ^(18)O variability related to the El Niño–Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ^(18)O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ^(18)O to aid interpretations of stalagmite δ^(18)O reconstructions

Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization

About a decade after its introduction, the field of carbonate clumped isotope thermometry is rapidly expanding because of the large number of possible applications and its potential to solve long‐standing questions in Earth Sciences. Major factors limiting the application of this method are the very high analytical precision required for meaningful interpretations, the relatively complex sample preparation procedures, and the mass spectrometric corrections needed. In this paper we first briefly review the evolution of the analytical and standardization procedures and discuss the major remaining sources of uncertainty. We propose that the use of carbonate standards to project the results to the carbon dioxide equilibrium scale can improve interlaboratory data comparability and help to solve long‐standing discrepancies between laboratories and temperature calibrations. The use of carbonates reduces uncertainties related to gas preparation and cleaning procedures and ensures equal treatment of samples and standards. We present a set of carbonate standards of diverse composition, discuss how they can be used to correct for mass spectrometric biases, and demonstrate that their use significantly improves the comparability among four laboratories. We propose that the use of these standards or of a similar set of carbonate standards will improve the comparability of data across laboratories.publishedVersio

North Atlantic Temperature Change Across the Eocene-Oligocene Transition From Clumped Isotopes

The Eocene-Oligocene transition (EOT) (∼34 Ma) is marked by the rapid development of a semi-permanent Antarctic ice-sheet, as indicated by ice-rafted debris and a 1–1.5‰ increase in deep sea δ18O. Proxy reconstructions indicate a drop in atmospheric CO2 and global cooling. How these changes affected surface ocean temperatures in the North Atlantic and ocean water stratification remains poorly constrained. In this study, we apply clumped-isotope thermometry to well-preserved planktonic foraminifera, that are associated with lower mixed-layer to subthermocline dwelling depths from the drift sediments at international ocean discovery program Site 1411, Newfoundland, across four intervals bracketing the EOT. The thermocline/lower mixed-layer dwelling foraminifera record a cooling of 1.9 ± 3.5 K (mean ± 95% CI) across the EOT. While the cooling amplitude is similar to previous sea surface temperature (SST) reconstructions, absolute temperatures (Eocene 20.0 ± 2.9°C, Oligocene 18.0 ± 2.2°C) appear colder than previous organic proxy reconstructions for the northernmost Atlantic extrapolated to this location. We discuss seasonal bias, recording depth, and appropriate consideration of paleolatitudes, all of which complicate the comparison between SST reconstructions and model output. Our subthermocline dwelling foraminifera record a larger cooling across the EOT (Eocene 19.0 ± 3.5°C, Oligocene 13.0 ± 3.2°C, cooling of 5.5 ± 4.6 K) than foraminifera from the thermocline/lower mixed-layer, consistent with global cooling and an increase in ocean stratification which may be related to the onset or intensification of the Atlantic meridional overturning circulation

Transformation of ENSO‐related rainwater to dripwater δ18O variability by vadose water mixing

Speleothem oxygen isotopes (δ18O) are often used to reconstruct past rainfall δ18O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ18O time series from northern Borneo and compare them to local rainfall δ18O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ18O reflects amount-weighted rainfall δ18O integrated over the previous 3–10 months. We document large interannual dripwater δ18O variability related to the El Niño–Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ18O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ18O to aid interpretations of stalagmite δ18O reconstructions

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