Radiogenic isotopes in the Mediterranean Sea: water mass exchange and precessional variability during the Messinian

During the late Miocene, exchange between the Mediterranean Sea and Atlantic Ocean changed dramatically, culminating in the Messinian Salinity Crisis (MSC). Understanding Mediterranean-Atlantic exchange at that time could answer the enigmatic question of how so much salt built up within the Mediterranean, while furthering the development of a framework for future studies attempting to understand how changes may have impacted global thermohaline circulation. Due to their association with specific water masses at different scales, radiogenic Sr, Pb, and Nd isotope records were generated from various archives contained within marine deposits to endeavour to understand better late Miocene Mediterranean-Atlantic exchange. The archives used include foraminiferal calcite (Sr), fish teeth and bone (Nd), dispersed authigenic ferromanganese oxyhydroxides (Nd, Pb), and a ferromanganese crust (Pb). The primary focus is on sediments preserved at one end of the Betic corridor, a gateway that once connected the Mediterranean to the Atlantic through southern Spain, although other locations are investigated. The Betic gateway terminated within several marginal sub-basins before entering the Western Mediterranean; one of these is the Sorbas Basin, a well-studied location whose sediments have been astronomically tuned at high temporal resolution, providing the necessary age control for sub-precessional resolution records. Since the climatic history of the Mediterranean is strongly controlled by precessional changes in regional climate, the aim was to produce records at high (sub-precessional) temporal resolution, to be able to observe clearly any precessional cyclicity driven by regional climate which could be superimposed over longer trends. This goal was achieved for all records except the ferromanganese crust record. The 87Sr/86Sr isotope record (Ch. 3) shows precessional frequency excursions away from the global seawater curve. As precessional frequency oscillations are unexpected for this setting, a numerical box model was used to determine the mechanisms causing the excursions. To enable parameterisation of model variables, regional Sr characteristics, data from general circulation model HadCM3L, and new benthic foraminiferal assemblage data are employed. The model results imply that the Sorbas Basin likely had a positive hydrologic budget in the late Miocene, very different to that of today. Moreover, the model indicates that the mechanism controlling the Sr isotope ratio of Sorbas Basin seawater was not restriction, but a lack of density-driven exchange with the Mediterranean. Beyond improving our understanding of how marginal Mediterranean sub-basins may evolve different isotope signatures, these results have implications for astronomical tuning and stratigraphy in the region, findings which are crucial considering the geological and climatic history of the late Miocene Mediterranean is based entirely on marginal deposits. An improved estimate for the Nd isotope signature of late Miocene Mediterranean Outflow (MO) was determined by comparing Nd isotope signatures preserved in the deeper Alborán Sea at ODP Site 978 with literature data as well as the signature preserved in the Sorbas Basin (Ch. 4; -9.34 to -9.92 ± 0.37 εNd(t)). It was also inferred that it is unlikely that Nd isotopes can be used reliably to track changes in circulation within the shallow settings characteristic of the Mediterranean-Atlantic connections; this is significant in light of a recent publication documenting corridor closure using Nd isotopes. Both conclusions will prove useful for future studies attempting to understand changes in Mediterranean-Atlantic exchange. Excursions to high values, with precessional frequency, are also observed in the radiogenic Pb isotope record for the Sorbas Basin (Ch. 5). Widening the scope to include locations further away from the gateways, records were produced for late Miocene sections on Sicily and Northern Italy, and similar precessional frequency cyclicity was observed in the Pb isotope records for these sites as well. Comparing these records to proxies for Saharan dust and available whole rock data indicates that, while further analysis is necessary to draw strong conclusions, enhanced dust production during insolation minima may be driving the observed signal. These records also have implications for astronomical tuning; peaks in Pb isotope records driven by Saharan dust may be easier to connect directly to the insolation cycle, providing improved astronomical tuning points. Finally, a Pb isotope record derived using in-situ laser ablation performed on ferromanganese crust 3514-6 from the Lion Seamount, located west of Gibraltar within the MO plume, has provided evidence that plume depth shifted during the Pliocene. The record also suggests that Pb isotopes may not be a suitable proxy for changes in late Miocene Mediterranean-Atlantic exchange, since the Pb isotope signatures of regional water masses are too similar. To develop this record, the first published instance of laser ablation derived 230Thexcess measurements are combined with 10Be dating

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

Coupled Southern Ocean cooling and Antarctic ice sheet expansion during the middle Miocene

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.acceptedVersio

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

Coupled Southern Ocean cooling and Antarctic ice sheet expansion during the middle Miocene

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

Warm Middle Miocene Indian Ocean Bottom Water Temperatures: Comparison of Clumped Isotope and Mg/Ca‐Based Estimates

The middle Miocene is an important analogue for potential future warm climates. However, few independent deep ocean temperature records exist, though these are important for climate model validation and estimates of changes in ice volume. Existing records, all based on the foraminiferal Mg/Ca proxy, suggest that bottom water temperatures were 5–8°C warmer than present. In order to improve confidence in these bottom water temperature reconstructions, we generated a new record using carbonate clumped isotopes (Δ47) and compared our results with Mg/Ca‐based estimates for the Indian Ocean at ODP Site 761. Our results indicate temperatures of 11.0 ± 1.7°C during the middle Miocene Climatic Optimum (MCO, 14.7–17 Ma) and 8.1 ± 1.9°C after the middle Miocene Climate Transition (MCT, 13.0–14.7 Ma), values 6 to 9°C warmer than present. Our record also indicates cooling across the MCT of 2.9 ± 2.5°C (uncertainties 95% confidence level). The Mg/Ca record derived from the same samples indicates temperatures well within uncertainty of Δ47. As the two proxies are affected by different non‐thermal biases, the good agreement provides confidence in these reconstructed temperatures. Our Δ47 temperature record implies a ~0.6‰ seawater δ18O change over the MCT, in good agreement with previously published values from other sites. Our data furthermore confirm overall high seawater δ18O values across the middle Miocene, at face value suggesting ice volumes exceeding present‐day despite the warm bottom water temperatures. This finding suggests previously underappreciated additional influences on seawater δ18O and/or a decoupling of ice volume and ocean temperature

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