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Atmospheric carbon dioxide decline is hypothesized to drive the progressive cooling over the Cenozoic. However, at multimillion-year timescales during the Oligocene to Miocene time interval the existing reconstructions, most based on the phytoplankton carbon isotopic fractionation (εp) proxy, differ from what is expected to drive the climate observations. Here, we produce two new long-term records of εp over the Oligocene to early Miocene time interval from widely separated locations at IODP Site 1406 and ODP 1168 and increase the resolution of determinations at the equatorial Atlantic ODP 925. These new results confirm a global footprint of εp shift occurring during this interval. Abrupt 3 ‰ declines are found from 27 to 24.5 Ma and 24 to 22.5 Ma, and minimum εp is attained at 19 Ma. Between 28.7 and 29.7 Ma at IODP 1406, a higher resolution sampling reveals orbital scale 100 kyr cyclicity in εp. Making use of alkenone-based sea surface temperature (SST) estimates and benthic δ18O estimated extracted from the same samples, we perform a direct comparison with εp to evaluate the relationship with climate dynamics. We observe that across the long Oligocene to early Miocene interval the two sites' relationships contrast with what is expected if CO2 was the main driver of εp and average earth surface temperature evolution was registered at the local surface SST and global benthic δ18O. Moreover, at orbital timescale, εp and benthic δ18O appear to follow an inverse relationship, although located within the multimillion-year period with the strongest direct correlation between these variables (>25.5 Ma). To evaluate the physiological, non- CO2 influences on εp, we use modern cultures to evaluate the impact of changing cell size and growth rate on the trends in εp. Although at specific time intervals, those drivers seem to explain part of the εp divergence with SST or benthic δ18O, most periods remain largely divergent, particularly the late Oligocene warming. We infer that a common CO2 forcing is likely the dominant control on the coherent temporal trends in εp at widely separated sites, which experienced contrasting temperature evolution and likely experienced different variations in nutrient availability. While CO2 changes likely caused significant changes in radiative forcing, SST variation at the examined sites may have been conditioned by regional heat transport, and the relationship between benthic δ18O and εp could reflect variable phasing between ice growth and global temperature. [ABSTRACT FROM AUTHOR]

Numerous recent studies have tested the clumped isotope (Δ47) thermometer on a variety of biogenic carbonates such as foraminifera and bivalves and showed that most follow a common calibration. However, there may be a difference between biogenic-carbonate-based calibrations and the most recent inorganic carbonate calibrations that are assumed to have formed close to isotopic equilibrium. Biogenic calibrations such as those based on foraminifera from seafloor sediments suffer from uncertainties in the determination of the calcification temperatures. Therefore, well-constrained laboratory cultures without temperature uncertainty can help resolve these discrepancies. Although the sample size requirements for a reliable Δ47 measurement have decreased over the years, the availability and preservation of many biogenic carbonates are still limited and/or require substantial time to be extracted from sediments in sufficient amounts. Coccoliths, on the other hand, are abundant and often well-preserved in sediments, and they are a potential interesting target for palaeoceanography. We thus determined the Δ47 –temperature relationship for coccoliths due to their relative ease of growth in the laboratory. The carbon and oxygen isotopic compositions of coccolith calcite have limited use in palaeoenvironmental reconstructions due to physiological effects that cause variability in the carbon and oxygen isotopic fractionation during mineralization. However, the relatively limited data available suggest that clumped isotopes may not be significantly influenced by these effects. We cultured three species of coccolithophores under controlled carbonate system conditions with CO 2(aq) concentrations between 5 and 45 µM , pH between 7.9 and 8.6 units, and temperatures between 6 and 27 °C. Our well-constrained results agree with a previous culture study that there are no apparent species- or genus-specific vital effects on the Δ47 –temperature relationship in coccolithophores despite significant deviations from equilibrium in the C and O isotopic composition. We find that while varying environmental parameters other than temperature does not have a significant effect on Δ47 , changing the parameters yields coccolith Δ47 –temperature calibrations that agree within 1.2 ppm. Our coccolith-specific Δ47 –temperature calibration with well-constrained temperatures shows a consistent, positive offset of 2–3 °C to the inorganic carbonate calibrations, which point to as yet unknown coccolith-specific disequilibrium effects. Thus, we suggest the use of our coccolith-specific calibration for further coccolith palaeoceanographic studies and that calibrations derived from laboratory-grown biogenic carbonates are desirable to reinforce the confidence of clumped-isotope-based temperature reconstructions in palaeoceanography. [ABSTRACT FROM AUTHOR]

The full understanding of climate feedbacks responsible for the amplification of deglaciations requires robust chronologies for these climate transitions, but, in the case of marine records, radiocarbon chronologies are possible only for the last glacial termination. Although the assumed relationships between the marine isotopic record and the orbital parameters provide a first order chronology for the previous terminations, an independent chronological control allows the relationships between orbital forcing and the climate response to be assessed over multiple previous terminations. Here we present new geochemical records of Marine Isotope Stages 11 to 7 from a western Mediterranean speleothem, establishing a new long terrestrial climate record for this region. Its absolute U/Th dates provide an exceptional chronology for the glacial terminations IV, III, and III.a. The onset of these three glacial terminations was marked by rapid δ18O depletions, reflecting ocean freshening by ice melting, thus providing an excellent tie point for regional marine records also sensitive to such freshening. These new chronologies reveal an earlier onset of the deglacial melting for the TIV and TIII.a in contrast to the generally accepted marine chronologies and indicate that the duration of these deglaciations was variable, with TIV particularly longer (~20 kyr). This study also supports that the onset of deglacial melting always occurred during declining precession index while a nonunique relation occurred with the obliquity parameter. [ABSTRACT FROM AUTHOR]

Introduction: The stable carbon isotope ratio of long-chain alkenones produced by marine haptophyte phytoplankton has often been used to estimate past variations in atmospheric CO2 throughout the Cenozoic. However, previous experimental studies and surveys of alkenones from surface sediment and suspended particulate matter document additional environmental and physiological influences on carbon isotopic fractionation in alkenones. Methods: To clarify the non-CO2 effects on the alkenone carbon isotope fractionations, an important alkenone producer, Gephyrocapsa oceanica, was cultured in laboratory. To separate effects of different environment parameters, G. oceanica was grown in continuous cultures under a matrix of environmental conditions in order to explore the influence of temperature independently of CO2(aq). Through careful manipulation of the media carbon system, we can control the variation of the media CO2(aq) independently of temperature solubility. Carbon isotope fractionations from alkenones, coccolith, and particulate organic carbon were measured from this steady state system. Results and Discussion: We find εp in alkenones and particulate organic carbon inversely correlates with temperature, and temperature affects εp more strongly than CO2(aq). The magnitude of the temperature effect can be explained by higher growth rates at warmer temperatures with a similar growth rate dependence as observed in previous cultures in which growth rate was regulated by other factors. Where the past temperature influence on growth rate could be constrained using the UK37 alkenone index in the same samples, our finding offers an approach to deconvolve an important physiological factor affecting ancient alkenones ep, and may therefore improve past pCO2 estimates. [ABSTRACT FROM AUTHOR]

Hydrogen isotope ratios (δ²H) represent an important natural tracer of metabolic processes, but quantitative models of processes controlling H-fractionation in aquatic photosynthetic organisms are lacking. Here, we elucidate the underlying physiological controls of ²H/¹H fractionation in algal lipids by systematically manipulating temperature, light, and CO2(aq) in continuous cultures of the haptophyte Gephyrocapsa oceanica. We analyze the hydrogen isotope fractionation in alkenones (αalkenone), a class of acyl lipids specific to this species and other haptophyte algae. We find a strong decrease in the αalkenone with increasing CO2 (aq) and confirm αalkenone correlates with temperature and light. Based on the known biosynthesis pathways, we develop a cellular model of the δ²H of algal acyl lipids to evaluate processes contributing to these controls on fractionation. Simulations show that longer residence times of NADPH in the chloroplast favor a greater exchange of NADPH with ²H-richer intracellular water, increasing αalkenone. Higher chloroplast CO2(aq) and temperature shorten NADPH residence time by enhancing the carbon fixation and lipid synthesis rates. The inverse correlation of αalkenone to CO2(aq) in our cultures suggests that carbon concentrating mechanisms (CCM) do not achieve a constant saturation of CO2 at the Rubisco site, but rather that chloroplast CO2 varies with external CO2(aq). The pervasive inverse correlation of αalkenone with CO2(aq) in the modern and preindustrial ocean also suggests that natural populations may not attain a constant saturation of Rubisco with the CCM. Rather than reconstructing growth water, αalkenone may be a powerful tool to elucidate the carbon limitation of photosynthesis. [ABSTRACT FROM AUTHOR]

Palaeoclimate information on multiple climate variables at different spatiotemporal scales is becoming increasingly important to understand environmental and societal responses to climate change. A lack of high-quality reconstructions of past hydroclimate has recently been identified as a critical research gap. Speleothems, with their precise chronologies, widespread distribution, and ability to record changes in local to regional hydroclimate variability, are an ideal source of such information. Here, we present a new version of the Speleothem Isotopes Synthesis and AnaLysis database (SISALv3), which has been expanded to include trace element ratios and Sr isotopes as additional, hydroclimate-sensitive geochemical proxies. The oxygen and carbon isotope data included in previous versions of the database have been substantially expanded. SISALv3 contains speleothem data from 365 sites from across the globe, including 95 Mg/Ca , 85 Sr/Ca , 52 Ba/Ca , 25 U/Ca , 29 P/Ca , and 14 Sr-isotope records. The database also has increased spatiotemporal coverage for stable oxygen (892) and carbon (620) isotope records compared with SISALv2 (which consists of 673 and 430 stable oxygen and carbon records, respectively). Additional meta information has been added to improve the machine-readability and filtering of data. Standardized chronologies are included for all new entities along with the originally published chronologies. Thus, the SISALv3 database constitutes a unique resource of speleothem palaeoclimate information that allows regional to global palaeoclimate analyses based on multiple geochemical proxies, permitting more robust interpretations of past hydroclimate and comparisons with isotope-enabled climate models and other Earth system and hydrological models. The database can be accessed at 10.5287/ora-2nanwp4rk (Kaushal et al., 2024). [ABSTRACT FROM AUTHOR]

Speleothem fluorescence can provide insights into past vegetation dynamics and stalagmite chronology. However, its origin and especially the formation of fluorescent laminations in stalagmites are poorly understood. We conducted a year-long monthly monitoring of drip water fluorescence in La Vallina Cave (northern Iberian Peninsula) and compared the results to drip water chemistry and active speleothems from the same sites. Drip waters were analyzed using fluorescence spectroscopy and parallel factor analysis (PARAFAC). The resulting five-component model indicates contributions from vegetation, microbial activity, and bedrock. Intra-site fluorescence variability is mainly influenced by changes in overlying vegetation, water reservoir time, and respiration rates. Contrary to prevailing views, we find no systematic increase in drip water fluorescence during rainy conditions across drip sites and seasonal variations in drip water fluorescence are absent at a location where present-day speleothem layers form. Our findings challenge the notion of a higher abundance of humic-like fluorescence during the rainy season as the primary cause for layer formation and suggest additional controls on drip water fluorescence, such as bedrock interaction and microbial reprocessing. We also propose that growth rate may control the dilation of the fluorescence signal in stalagmites, indicating other potential mechanisms for fluorescent layer formation. [ABSTRACT FROM AUTHOR]

This study focuses on characterizing a discontinuity within the Seán stalagmite (4.75–7.75 cm) by means of two nondestructive techniques: (1) high-resolution micro-computed tomography (micro-CT) and (2) X-ray fluorescence (XRF) core scanning (XRFCS). Micro-CT was used to study the stalagmite density, and XRFCS was applied to obtain the qualitative elemental composition and colour measurements. The new data obtained from nondestructive techniques have been combined with previously published geochemical data and fabric determinations from the same stalagmite found in Sa Balma des Quartó cave in Mallorca. The two methodologies applied in the present study have improved the characterization of the distinctive horizon. The micro-CT images identified the layer as a minor event due the high air content. The distinctive horizon is characterized by a high Ti-content, indicating the arrival of terrigenous particles. Based on those observations, together with the fact that the micrite layer appears filling the gaps between the older columnar fabric, we argue that the micrite layer may represent a major flooding event inside the cave after the year 1616 ± 23 CE and before the year 1623 ± 28 CE, which can be related to an extreme rainfall event. This hypothesis is further supported by the observed cave flooding during the autumn of 2018. [ABSTRACT FROM AUTHOR]

Reconstructing of past hydroclimates at regional scales during the Common Era (CE) is necessary to place the current warming in the context of natural climate variability. Here we present a composite record of oxygen isotope variations during last 2500 years based on eight stalagmites from four caves in the central Pyrenees (NE Spain) dominated by temperature variations, with the amount of precipitation playing a minor role. The dataset is compared with other Iberian reconstructions that show a high degree of internal coherence with respect to variability at the centennial scale. The Roman Period (RP) (especially 0–200 CE), the Medieval Climate Anomaly (MCA), and part of the Little Ice Age (LIA) represent the warmest periods, while the coldest decades occurred during the Dark Ages (DA) and most of the LIA intervals (e.g., 520–550 CE and 1800–1850 CE). Importantly, the LIA cooling or the MCA warming were not continuous or uniform and exhibited high decadal variability. The Industrial Era (IE) shows an overall warming trend although with marked cycles and partial stabilization during the last 2 decades (1990–2010). The strong coherence between the speleothem data, European temperature reconstructions and global tree-ring data informs about the regional representativeness of this new record as Pyrenean past climate variations. Solar variability, likely through its impact on the North Atlantic Oscillation, and major volcanic eruptions appear to be the two main drivers of climate in southwestern Europe during the past 2.5 millennia. [ABSTRACT FROM AUTHOR]

The 87 Sr / 86 Sr of marine carbonates provides a key constraint on the balance of continental weathering and hydrothermal Sr fluxes to the ocean, and the mid-Oligocene to mid-Miocene period features the most rapid rates of increase in the 87 Sr / 86 Sr of the Cenozoic. Because previous records of the 87 Sr / 86 Sr increase with time were based on biostratigraphically defined age models in diverse locations, it was difficult to unambiguously distinguish million-year-scale variations in the rate of 87 Sr / 86 Sr change from variations in sedimentation rate. In this study, we produce the first 87 Sr / 86 Sr results from an Oligocene to early Miocene site with a precise age-model-derived orbital tuning of high-resolution benthic δ18 O at Equatorial Pacific Ocean Drilling Program (ODP) Site 1218. Our new dataset resolves transient decreases in 87 Sr / 86 Sr, as well as periods of relative stasis. These changes can be directly compared with the high-resolution benthic δ18 O at the same site. We find that slowing of the rate of 87 Sr / 86 Sr increase coincides with the onset of Antarctic ice expansion at the beginning of the mid-Oligocene glacial interval, and a rapid steeping in the 87 Sr / 86 Sr increase coincides with the benthic δ18 O evidence for rapid ice retreat. This pattern may reflect either northward shifts in the Intertropical Convergence Zone precipitation to areas of nonradiogenic bedrock and/or lowered weathering fluxes from highly radiogenic glacial flours on Antarctica. We additionally generate the first 87 Sr / 86 Sr data from ODP Site 1168 on the Tasman Rise and Integrated Ocean Drilling Program (IODP) Site 1406 of the Newfoundland Margin during the Oligocene to early Miocene to improve the precision of age correlation of these Northern Hemisphere and Southern Hemisphere midlatitude sites and to better estimate the duration of early Miocene hiatus and condensed sedimentation. [ABSTRACT FROM AUTHOR]

Numerous recent studies have tested the clumped isotope (Δ47) thermometer on a variety of biogenic carbonates such as foraminifera and bivalves and showed that all follow a common calibration. While the sample size requirements for a reliable Δ47 measurement have decreased over the years, the availability and preservation of many biogenic carbonates is still limited and/or require substantial time to be extracted from sediments in sufficient amounts. We thus determined the Δ47-temperature relationship for coccolith carbonate, which is abundant and often well-preserved in sediments. The carbon and oxygen isotopic compositions of coccolith calcite have limited use in palaeoenvironmental reconstructions due to physiological effects that cause variability in the carbon and oxygen isotopic values. However, the relatively limited data available suggest that clumped isotopes may not be influenced by these effects. We cultured three species of coccolithophores in well- constrained carbonate system conditions with a CO2(aq) between 5 and 45 ^M and temperatures between 6°C and 27°C. Our results agree with a previous culture study that there are no species- or genus-specific effects on the Δ47-temperature relationship in coccolithophores and find that varying environmental parameters other than temperature also do not have a significant effect. Our coccolith-specific Δ47-temperature calibration agrees within ±1°C of other biogenic carbonate calibrations yet all biogenic carbonate calibrations show a consistent offset of ≥2°C relative to the inorganic carbonate calibrations. Thus, all biogenic specific calibrations can be used interchangeably and must be used for the reconstruction of calcification temperatures in biogenic carbonates. [ABSTRACT FROM AUTHOR]

Paleoclimate information on multiple climate variables at different spatiotemporal scales is increasingly important to understand environmental and societal responses to climate change. A lack of high-quality reconstructions of past hydroclimate has recently been identified as a critical research gap. Speleothems, with their precise chronologies, widespread distribution, and ability to record changes in local to regional hydroclimate variability, are an ideal source of such information. Here we present a new version of the Speleothem Isotopes Synthesis and AnaLysis database (SISALv3), which has been expanded to include trace element ratios and Sr-isotopes as additional, hydroclimate-sensitive geochemical proxies. The oxygen and carbon isotope data included in previous versions of the database have been substantially expanded. SISALv3, contains speleothem data from 364 sites from across the globe, including 94 Mg/Ca, 83 Sr/Ca, 51 Ba/Ca, 25 U/Ca, 29 P/Ca and 14 Sr-isotope records. The database also has increased spatiotemporal coverage for stable oxygen (831) and carbon (588) isotope records compared to SISALv2. Additional meta information has been added to improve machine-readability and filtering of data. Standardized chronologies are included for all new entities together with the originally published chronologies. The SISALv3 database thus constitutes a unique resource of speleothem paleoclimate information that allows regional-to-global paleoclimate analyses based on multiple geochemical proxies, allowing more robust interpretations of past hydroclimate and comparisons with isotope-enabled climate models and other earth system and hydrological models. [ABSTRACT FROM AUTHOR]