ALBERT

Description: The Latest Danian Event (LDE; ~62.15 Ma) is a major double-spiked eccentricity-driven transient warming event and carbon cycle perturbation (hyperthermal) in the early Paleocene, which has received significantly less attention compared to the larger events of the late Paleocene–early Eocene. A better understanding of the nature of the LDE may broaden our understanding of hyperthermals more generally and improve our knowledge of Earth system responses to extreme climate states. Here we present planktic and benthic foraminiferal Mg/Ca and B/Ca records that shed new light on changes in South Atlantic temperature and carbonate chemistry during the LDE. Our planktic Mg/Ca record reveals a pulsed increase in sea surface temperature of at least ~1.5°C during the older carbon isotope excursion, and ~0.5°C during the younger isotope excursion. We observe drops in planktic and benthic B/Ca, synchronous with pronounced negative excursions in benthic δ13C, which suggest a shift in the carbonate system towards more acidic, dissolved inorganic carbon-rich conditions, in both the surface and deep ocean. Conditions remain more acidic following the LDE, which we suggest may be linked to an enhanced ocean alkalinity sink due to changes in the make-up of planktic calcifiers, hinting at a novel feedback between calcifier ecology and ocean-atmosphere CO2.

Description: Paired benthic foraminiferal trace metal and stable isotope records have been constructed from equatorial Pacific Ocean Drilling Program Site 1218. The records include the two largest abrupt (〈1 Myr) increases in the Cenozoic benthic oxygen isotope record: Oi‐1 in the earliest Oligocene (∼34 Ma) and Mi‐1 in the earliest Miocene (∼23 Ma). The paired Mg/Ca and oxygen isotope records are used to calculate seawater δ18O (δw). Calculated δw suggests that a large Antarctic ice sheet formed during Oi‐1 and subsequently fluctuated throughout the Oligocene on both short (〈0.5 Myr) and long (2–3 Myr) timescales, between about 50 and 100% of its maximum earliest Oligocene size. The magnitudes of these fluctuations are consistent with estimates of sea level derived from sequence stratigraphy. The transient expansion of the Antarctic ice sheet at Mi‐1 is marked in the benthic δ18O record by two positive excursions between 23.7 and 22.9 Ma, each with a duration of 200–300 kyr. Bottom water temperatures decreased by ∼2°C over the 150 kyr immediately prior to both rapid δ18O excursions. However, the onset of each of these phases of ice growth is synchronous, within the resolution of the records, with the onset of a 2°C warming over ∼150 kyr. We suggest that the warming during these glacial expansions reflect increased greenhouse forcing prompted by a sudden decrease in global chemical weathering rates as Antarctic basement silicate rocks became blanketed by an ice sheet. This represents a negative feedback process that might have operated during major abrupt growth phases of the Antarctic ice sheet.

Description: Current climate change may induce positive carbon cycle feedbacks that amplify anthropogenic warming on time scales of centuries to millennia. Similar feedbacks might have been active during a phase of carbon cycle perturbation and global warming, termed the Paleocene-Eocene Thermal Maximum (PETM, 56 million years ago). The PETM may help constrain these feedbacks and their sensitivity to warming. We present new high-resolution carbon isotope and sea surface temperature data from Ocean Drilling Project Site 959 in the Equatorial Atlantic. With these and existing data from the New Jersey shelf and Maud Rise, Southern Ocean, we quantify the lead-lag relation between PETM warming and the carbon input that caused the carbon isotope excursion. We show ~2 ºC of global warming preceded the CIE by millennia, strongly implicating CO2-driven warming triggered a positive carbon cycle feedback. We further compile new and published barium (Ba) records encompassing continental shelf, slope and deep-ocean settings. Based on this compilation, average Ba burial rates approximately tripled during the PETM, which may require an additional source of Ba to the ocean. Although the precipitation pathway is not well constrained, dissolved Ba stored in sulfate-depleted pore-waters below methane hydrates could represent an additional source. We speculate the most complete explanation for early warming and rise in Ba supply is that hydrate dissociation acted as a positive feedback and caused the CIE. This could imply hydrates are more temperature-sensitive than previously considered, and may warrant reconsideration of the political assignment of 2 °C warming as a safe future scenario.

Description: It contains three tables that correspond to the supplementary information of the article mentioned above. Tables S3 and S4 can be found within the Supplementary Information document. Table S1 contains high-resolution bulk and benthic carbon and oxygen stable isotope data from ODP Hole 702B across the Middle Eocene Climatic Optimum (40 Ma). Table S2 contains benthic foraminiferal data (relative abundance and ecology index) and accumulation rates from ODP Hole 702B across the Middle Eocene Climatic Optimum (40 Ma). Table S5 contains middle Eocene ODP Hole 702B XRF core scanning data, high-resolution bulk and benthic carbon and oxygen stable isotope data from ODP Site 1263 and age model correlation tie points between drill sites for ODP Sites 1263, 738 and 702B as well tie points for a detailed astronomical age model for ODP Site 1263 (La2010b solution).

Description: This paper introduces an integrated Neogene microfossil biostratigraphic chart developed within post-merger BP for the Gulf of Mexico Basin and is the first published industrial framework "fully-tuned" to orbital periodicities. Astronomical-tuning was accomplished through a 15-year research program on ODP Leg 154 sediments (offshore NE Brazil) with sampling resolution for calcareous nannofossils and planktonic foraminifera about 20 k.y. and 40 k.y. (thousand year), respectively. This framework extends from the Late Oligocene (25.05 Ma) to Recent at an average Chart Horizon resolution for the Neogene of 144 k.y., approximately double that of published Gulf of Mexico biostratigraphic charts and a five-fold increase over the highest resolution global calcareous microfossil biozonation. Such resolution approximates that of 4th to 5th order parasequences and is a critical component in the verification of seismic correlations between mini-basins in the deep-water Gulf of Mexico. Its utility in global time-scale construction and correlation has been proven, in part, by application of the scheme in full to internal research for the Oligocene-Miocene boundary interval on the Global Boundary Stratotype Section and Point (GSSP) in northern Italy and offshore wells in the eastern Mediterranean Sea. This step change in Neogene resolution, now at the level of cyclostratigraphy (the orbital periodicity of eccentricity) and the magnetostratigraphic chron, demonstrates the potential for calcareous microfossil biostratigraphy to more consistently reinforce correlations of these time scale parameters. The integration of microfossil disciplines, consistent taxonomies, and rigorous analytical methodologies are all critical to obtaining and reproducing this new level of biostratigraphic resolution.

Description: The Late Cretaceous-Early Paleogene is the most recent period of Earth history that experienced sustained global greenhouse warmth and was characterised by a dynamic carbon cycle. Yet, knowledge of ambient climate conditions and the evolution of atmospheric pCO2 at this time, along with their relation to forcing mechanisms, are still poorly constrained. Here we present an unprecedented 14.75 million year long high-resolution orbitally-tuned record of paired climate change and carbon-cycling (based on the oxygen and carbon isotope composition of benthic foraminiferal tests) compiled to date for the enigmatic Late Cretaceous to Early Eocene, and compare these records to the most up-to-date compilation of atmospheric pCO2 records for this time. We identify eccentricity as the dominant pacemaker of the observed climate and carbon cycle changes, through the modulation of precession. The carbon cycle (e.g., d13C) lagged changes in climate by ~22,800 years within the long eccentricity (405,000 year) band and ~3,000-4,500 years within the short eccentricity (100,000 year) band, suggesting that light carbon was released as a positive feedback to warming induced by small changes in orbital forcing. The majority of the hyperthermals of this time period occur during maxima in the long eccentricity cycle, with the exception of the Paleocene-Eocene Thermal Maximum and Late Maastrichtian warming event, which are likely to have been triggered by Large Igneous Province volcanism.

Description: Micropaleontological and geochemical analyses reveal distinct millennial-scale increases in carbonate preservation in the deep Southeast Atlantic (Cape Basin) during strong and prolonged Greenland interstadials that are superimposed on long-term (orbital-scale) changes in carbonate burial. These data suggest carbonate oversaturation of the deep Atlantic and a strengthened Atlantic Meridional Overturning Circulation (AMOC) during the most intense Greenland interstadials. However, proxy evidence from outside the Cape Basin indicate that AMOC changes also occurred during weaker and shorter Greenland interstadials. Here we revisit the link between AMOC dynamics and carbonate saturation in the deep Cape Basin over the last 400 kyr (sediment cores TN057-21, TN057-10 and ODP Site 1089) by reconstructing centennial changes in carbonate preservation using mm-scale X-ray fluorescence (XRF) scanning data. We observe close agreement between variations in XRF Ca/Ti, sedimentary carbonate content and foraminiferal shell fragmentation, reflecting a common control primarily through changing deep-water carbonate saturation. We suggest that the high-frequency (sub-orbital) component of the XRF Ca/Ti records indicates the fast and recurrent redistribution of carbonate ions in the Atlantic basin via the AMOC during both long/strong- and short/weak North Atlantic climate anomalies. In contrast, the low-frequency (orbital) XRF Ca/Ti component is interpreted to reflect slow adjustments through carbonate compensation, and/or changes in the deep-ocean respired carbon content. Our findings emphasize the recurrent influence of rapid AMOC variations on the marine carbonate system during past glacial periods, providing a mechanism for transferring the impacts of North Atlantic climate anomalies to the global carbon cycle via the Southern Ocean.

Description: The Paleocene - Eocene Thermal Maximum (PETM; 56 Ma) was a phase of rapid global warming associated with massive carbon input into the ocean-atmosphere system from a 13C-depleted reservoir. Many mid- and high-latitude sections have been studied and document changes in salinity, hydrology and sedimentation, deoxygenation, biotic overturning and migrations, but detailed records from tropical regions are lacking. Here, we study the PETM at Ocean Drilling Program (ODP) Site 959 in the equatorial Atlantic using a range of organic and inorganic proxies and couple these with dinoflagellate cyst (dinocyst) assemblage analysis. The PETM at Site 959 was previously found to be marked by a ~3.8 per mil negative carbon isotope excursion (CIE), and a ~4 ºC surface ocean warming from the uppermost Paleocene to peak PETM, of which ~1 ºC occurs before the onset of the CIE. We record upper Paleocene dinocyst assemblages that are similar to PETM assemblages as found in extra-tropical regions, confirming poleward migrations of ecosystems during the PETM. The early stages of the PETM are marked by a typical acme of the tropical genus Apectodinium, which reaches abundances of up to 95 %. Subsequently, dinocyst abundances diminish greatly, as do carbonate and pyritized silicate microfossils. The combined paleoenvironmental information from Site 959 and a close by shelf site in Nigeria implies the general absence of eukaryotic surface-dwelling microplankton during peak PETM warmth is most likely caused by heat stress. Crucially, abundant organic benthic foraminiferal linings imply sustained export production, likely driven by prokaryotes. In sharp contrast, the recovery of the CIE yields rapid (〈〈10 kyr) fluctuations in the abundance of several dinocyst groups, suggesting extreme ecosystem and environmental variability.

Description: The Western Equatorial Pacific (WEP) warm pool, with surface temperatures 〉28 °C and a relatively deep thermocline, is an important source of latent and sensible heat for the global climate system. Because the tropics are not sensitive to ice‐albedo feedbacks, the WEP's response to radiative forcing can be used to constrain a minimum estimate of Earth system sensitivity. Climate modeling of pCO2‐radiative warming projections shows little change in WEP variability; here we use temperature distributions of individual surface and subsurface dwelling fossil foraminifera to evaluate past variability and possible radiative and dynamic climate forcing over the Plio‐Pleistocene. We investigate WEP warm pool variability within paired glacial‐interglacial (G‐IG) intervals for four times: the Holocene‐Last Glacial Maximum, ~2 Ma, ~3 Ma, and ~ 4 Ma. Our results show that these surface and subsurface temperature distributions are similar for all G‐IG pairs, indicating no change in variability, even as pCO2‐radiative forcing and other boundary conditions changed on G‐IG timescales. Plio‐Pleistocene SST distributions are similar to those from the Holocene, indicating WEP SSTs respond to pCO2‐radiative forcing and associated feedbacks. In contrast, Plio‐Pleistocene subsurface temperature distributions suggest subsurface temperatures respond to changes in thermocline temperature and depth. We estimate tropical temperature sensitivity for the mid‐Pliocene (~3 Ma) using our individual foraminifera SST dataset and a previously published high‐resolution boron isotope based pCO2 reconstruction. We find tropical temperature sensitivity was equal to, or less than that of the Late Pleistocene.

Description: Strontium and calcium isotopic data for bulk carbonate solids and pore fluids from ODP Sites 1170 and 1171 are presented. Bulk carbonate and pore fluid samples from Ocean Drilling Program (ODP) Sites 1170A and 1171A were measured in this study. Both sites are located on the South TasmanRise; Site 1170A (47°09.0435°S; 146°02.9881°E) was drilled in 2704.7 m water depth and Site 1171A (48°29.99600S;149°06.69010E) was drilled in 2148.2 m water depth. The tables provide summarized data.

Description: The Mg and Sr isotopic compositions (d26Mg and87Sr/86Sr) of pore fluids and bulk carbonates from Ocean Drilling Project Site 1171 is located on the South Tasman Rise (48°29.996000S and 149°06.690100E) at a present-day waterdepth of 2148.2 m on a southwesterly dipping slope.

Description: The data is comprised of all the modern calibration environmental variables and coretop diatom species as well downcore diatom species for transfer function application

Description: We combine stable isotope, calcareous nannoplankton and benthic foraminiferal records for Ocean Drilling Program Sites 1262 (paleodepth ~ 3500 m) and 1263 (paleodepth ~ 1500 m) on Walvis Ridge (SE Atlantic), to document the marine biotic response to Eocene Thermal Maximum 3, in the early part of the Early Eocene Climate Optimum, ~3.1 myr after the Paleocene/Eocene Thermal Maximum (PETM). Bottom water warming may have decreased the vertical thermal gradient at both sites, but more at Site 1263 than at 1262. Floral and faunal changes were more muted at Site 1262 than at shallower Site 1263, indicating that carbonate dissolution was not the most important cause of biotic effects. Assemblage changes were more pronounced in benthos than in plankton. Calcareous nannofossils underwent minor ecological changes, possibly related to the presence of warmer waters, especially at Site 1263, and dissolution-resistant taxa increased in abundance. Benthic foraminiferal diversity decreased at both sites, but benthic foraminiferal accumulation rates (BFAR) declined dramatically at Site 1263, remaining stable at Site 1262. Ocean circulation may have changed during ETM3, resulting in the presence of a warmer (intermediate) water mass at Site 1263. More pronounced warming may have caused enhanced remineralization of organic matter, so less food reached the benthos. The biotic response to the X-event was less pronounced than that to earlier and more severe hyperthermal events, the PETM and Eocene Thermal Maximum 2. The extent of the biotic response reflects the severity of the environmental disturbance, but varies by location (e.g., paleodepth on Walvis Ridge).

Description: The late Miocene offers the opportunity to assess the sensitivity of the Earth's climate to orbital forcing and to changing boundary conditions, such as ice volume and greenhouse gas concentrations, on a warmer-than-modern Earth. Here we investigate the relationships between low- and high-latitude climate variability in an extended succession from the subtropical northwestern Pacific Ocean. Our high-resolution benthic isotope record in combination with paired mixed layer isotope and Mg/Ca-derived temperature data reveal that a long-term cooling trend was synchronous with intensification of the Asian winter monsoon and strengthening of the biological pump from ~7 Ma until ~5.5 Ma. The climate shift occurred at the end of a global δ13C decrease, suggesting that changes in the carbon cycle involving the terrestrial and deep ocean carbon reservoirs were instrumental in driving late Miocene climate cooling. The inception of cooler climate conditions culminated with ephemeral Northern Hemisphere glaciations between 6.0 and 5.5 Ma.

Description: We integrate micropaleontological and geochemical records (benthic stable isotopes, neodymium isotopes, benthic foraminiferal abundances and XRF-scanner derived elemental data) from well-dated Pacific Ocean successions(15-12.7Ma) to monitor circulation changes during the middle Miocene transition into a colder climate mode with permanent Antarctic ice cover. Together with previously published records, our results show improvement in deepwater ventilation and strengthening of the meridional overturning circulation following major ice expansion at 13.9 Ma. Neodymium isotope data reveal, however, that the provenance of intermediate and deepwater masses did not change markedly between 15 and 12.7 Ma. We attribute the increased d13C gradient between Pacific deep and intermediate water masses between 13.6 and 12.7 Ma to more vigorous entrainment of PacificCentral Water into the wind-driven ocean circulation due to enhanced production of intermediate and deep waters in the Southern Ocean. Prominent 100 kyr ventilation cycles after 13.9 Ma reveal that the deep Pacific remained poorly ventilated during warmer intervals at high eccentricity, whereas colder periods (low eccentricity) were characterized by a more vigorous meridional overturning circulation with enhanced carbonate preservation. The long-term d13C decline in Pacific intermediate and deepwater sites between 13.5 and 12.7 Ma reflects a global trend, probably related to a re-adjustment response of the global carbon cycle following the last 400 kyr carbon maximum (CM6) of the ''Monterey Excursion''.

Description: This dataset consists of organic biomarkers used to reconstruct the sea surface temperature and sea ice conditions in the Pliocene Nordic Seas. Specifically, it includes alkenone, IP25 and sterol data from the Pliocene of two Ocean Drilling Program sites, ODP Site 907 in the Iceland Sea and ODP Site 911 on the Yermak Plateau (Arctic Ocean).

Description: The Middle Eocene Climatic Optimum (MECO) was a warming event that interrupted the long-term Eocene cooling trend. While this event is well documented at high southern and mid-latitudes, it is poorly known from low latitudes and its timing and duration are not well constrained because of problems of hiati, microfossil preservation and weak magnetic polarity in key sedimentary sections. Here, we report the results of a study designed to improve the bio-, magneto- and chemostratigraphy of the MECO interval using high-resolution records from two low-latitude sections in the Atlantic Ocean, Ocean Drilling Program (ODP) Sites 1051 and 1260. We present the first detailed benthic foraminiferal stable isotope records of the MECO from the low latitudes as well as the biostratigraphic counts of Orbulinoides beckmanni and new magnetostratigraphic results. Our data demonstrate a ~ 750 kyr-long duration for the MECO characterized by increasing δ13C and decreasing δ18O, with minimum δ18O values lasting ~ 40 kyr at 40.1 Ma coincident with a short-lived negative δ13C excursion. Thereafter, δ18O and δ13C values recover rapidly. The shift to minimum δ18O values at 40.1 Ma is coincident with a marked increase in the abundance of the planktonic foraminifera O. beckmanni, consistent with its inferred warm-water preference. O. beckmanni is an important Eocene biostratigraphic marker, defining planktonic foraminiferal Zone E12 with its lowest and highest occurrences (LO and HOs). Our new records reveal that the LO of O. beckmanni is distinctly diachronous, appearing ~ 500 kyr earlier in the equatorial Atlantic than in the subtropics (40.5 versus 41.0 Ma). We also show that, at both sites, the HO of O. beckmanni at 39.5 Ma is younger than the published calibrations, increasing the duration of Zone E12 by at least 400 kyr. In accordance with the tropical origins of O. beckmanni, this range expansion to higher latitudes may have occurred in response to sea surface warming during the MECO and subsequently disappeared with cooling of surface waters.

Description: The TEX86 proxy, based on the distribution of isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) from planktonic Thaumarchaeota, is widely used to reconstruct sea surface temperature (SST). Recent observations of species-specific and regionally-dependent TEX86-SST relationships in cultures and the modern ocean raise the question of whether non-thermal factors may have impacted TEX86 paleorecords. Here we evaluate the effects of ecological changes on TEX86 using one Pliocene and two Pleistocene sapropels from the Mediterranean Sea. We find that TEX86-derived SSTs deviate from UK'37-derived SSTs before, during, and after each sapropel event. UK'37-derived SSTs vary by less than 6 °C, while TEX86-derived SSTs vary by up to 15 °C within a single record. Compound-specific carbon isotope compositions indicate minimal confounding influence on TEX86 from exogenous sources. Some of the variation can be accounted for by changes in nitrogen cycling intensity affecting thaumarchaeal iGDGT biosynthesis, as demonstrated by an inverse relationship between TEX86 and δ15N(TN). TEX86-derived SSTs also consistently show warm anomalies in the Pleistocene, while the Pliocene samples exhibit both warmer and cooler relative offsets. These anomalies result from systematic differences between Plio-Pleistocene iGDGT distributions and both modern Mediterranean and modern, globally-distributed core-top samples. Through characteristic GDGT distributions, we suggest the existence of three distinct endemic populations of Thaumarchaeota in the Pliocene, Pleistocene, and modern Mediterranean Sea, respectively. Importantly, these communities prevailed during both sapropel and oligotrophic conditions. Our results demonstrate that ecological and community-specific effects must be considered when applying the TEX86 proxy to paleorecords.

Description: During the late Miocene epoch, about seven million years ago, large areas of the continents experienced drying, enhanced seasonality, and a restructuring of terrestrial plant and animal communities. These changes are seen throughout the subtropics, but have typically been attributed to regional tectonic forcing. Here we present a set of globally distributed sea surface temperature records spanning the past 12 million years based on the alkenone unsaturation method. We find that a sustained late Miocene cooling occurred synchronously in both hemispheres, and culminated with ocean temperatures dipping to near-modern values between about 7 and 5.4 million years ago. The period of maximum cooling coincides with evidence for transient glaciations in the Northern Hemisphere and with a steepening of the pole-to-equator temperature gradient, as well. We thus infer that late Miocene aridity and terrestrial ecosystem changes occurred in a global context of increasing meridional temperature gradients. We conclude that a global forcing mechanism, such as the previously hypothesized decline in atmospheric CO2 levels between eight and six million years ago, is required to explain the late Miocene changes in temperature, climate and ecosystems.

Description: Pelagic sediments from the subtropical South Atlantic Ocean contain geographically extensive Oligocene ooze and chalk layers that consist almost entirely of the calcareous nannofossil Braarudosphaera. Poor recovery and the lack of precise dating of these horizons in previous studies has limited our understanding of the exact number of acmes, their timing and durations, and the causes of their recurrence. Here we present a high-resolution, astronomically tuned stratigraphy of Braarudosphaera oozes (29.5-27.9 Ma) from Ocean Drilling Program Site 1264 in the subtropical southeastern Atlantic Ocean. We identify seven acme events in the Braarudosphaera abundance record. The longest lasting acme event corresponds to a strong minimum in the ~2.4-My eccentricity cycle, and four acme events coincide with ~110-ky and 405-ky eccentricity maxima. We propose that eccentricity-modulated precession forcing of the freshwater budget of the South Atlantic Ocean resulted in the episodic formation of a shallow pycnocline and hyperstratification of the upper water column. We speculate that stratified surface water conditions may have served as a virtual sea floor, which facilitated the widespread Braarudosphaera acmes. This explanation reconciles the contrasting distribution patterns of Braarudosphaera in the modern ocean, limited largely to shallow water coastal settings, compared to their relatively brief and expanded oceanic distribution in the past.

Description: A consistent chronostratigraphic framework is required to understand the effect of major paleoclimate perturbations on both marine and terrestrial ecosystems. Transient global warming events in the early Eocene, 56-54 Ma ago, show the impact of large scale carbon input into the ocean-atmosphere system. Here we provide the first time-scale synchronization of continental and marine deposits spanning the Paleocene-Eocene Thermal Maximum (PETM) and the interval just prior to the Eocene Thermal Maximum 2 (ETM-2). Cyclic variations in geochemical data come from continental drill cores of the Bighorn Basin Coring Project (BBCP, Wyoming, USA) and from marine deep-sea drilling deposits retrieved by the Ocean Drilling Program (ODP). Both are dominated by eccentricity modulated precession cycles used to construct a common cyclostratigraphic framework. Integration of age models results in a revised astrochronology for the PETM in deep-sea records that is now generally consistent with independent 3He age models. The duration of the PETM is estimated at ~200 kyr for the CIE and ~120 kyr for the associated pelagic clay layer. A common terrestrial and marine age model shows a concurrent major change in marine and terrestrial biotas ~200 kyr before ETM-2. In the Bighorn Basin, the change is referred to as Biohorizon B, and represents a period of significant mammalian turnover and immigration, separating the upper Haplomylus-Ectocion Range Zone from the Bunophorus Interval Zone and approximating the Wa-4-Wa-5 land mammal zone boundary. In sediments from ODP Site 1262 (Walvis Ridge), major changes in the biota at this time are documented by the radiation of a "2nd generation" of apical spine-bearing sphenoliths species (e.g., S. radians and S. editus), the emergence of T. orthostylus, and the marked decline of D. multiradiatus.

Description: These files contain individual core images generated from core box photos using the Code for Ocean Drilling Data (CODD) software set. There are PNG images with mcd depth scales attached for use in graphics programs as well as scaled Igor binary images for use with CODD. MCD depths are from the offsets.

Description: Ocean Drilling Programme (ODP) Site 982 represents a key location for understanding the evolution of climate in the North Atlantic over the past 12 Ma. However, concerns exist about the validity and robustness of the underlying stratigraphy and astrochronology, which currently limits the adequacy of this site for high-resolution climate studies. To resolve this uncertainty, we verify and extend the early Pliocene to late Miocene shipboard composite splice at Site 982 using high-resolution XRF core scanning data and establish a robust high-resolution stable isotope stratigraphy and astrochronology between 4.5 and 8.0 Ma. Splice revisions and verifications resulted in ~11 m of gaps in the original Site 982 isotope stratigraphy. Our new stratigraphy reveals previously unseen benthic d18O excursions, particularly prior to 6.65 Ma. The benthic d18O record displays distinct, asymmetric cycles between 7.7 and 6.65 Ma, confirming that high-latitude climate is a prevalent forcing during this interval. An intensification of the 41-kyr beat in both the benthic d13C and d18O is also observed ~6.4 Ma, marking a strengthening in the cryosphere-carbon cycle coupling. A large ~0.7 per mil double excursion is revealed ~6.4-6.3 Ma, which also marks the onset an interval of average higher d18O and large precession and obliquity-dominated d18O excursions between 6.4-5.4 Ma, coincident with the culmination of the late Miocene cooling. The two largest benthic d18O excursions ~6.4-6.3 Ma and TG20/22 coincide with the coolest alkenone-derived SST estimates from Site 982, suggesting a strong connection between the late Miocene global cooling and deep-sea cooling and dynamic ice sheet expansion. The splice revisions and revised astrochronology resolve key stratigraphic issues that have hampered correlation between Site 982, the equatorial Atlantic and the Mediterranean. Comparisons of the revised Site 982 stratigraphy to high-resolution astronomically tuned benthic d18O stratigraphies from ODP Site 926 (equatorial Atlantic) and Ain el Beida (north western Morocco) show that prior inconsistencies in short-term excursions are now resolved. The identification of key new cycles at Site 982 further highlights the requirement for the current scheme for late Miocene marine isotope stages to be redefined. Our new integrated deep-sea benthic stable isotope stratigraphy and astrochronology from Site 982 will facilitate future high-resolution late Miocene to early Pliocene climate research.

Description: This is the full dataset for the manuscript Astronomical calibration of the Ypresian timescale: implications for seafloor spreading rates and the chaotic behavior of the solar system? by Westerhold, T., Röhl, U., Frederichs, T., Agnini, C., Raffi, I., Zachos, J. C., and Wilkens, R. H. published in Climate of the Past, 13, 1129-1152, https://doi.org/10.5194/cp-13-1129-2017, 2017. It contains 48 tables with XRF core scanning data, bulk and benthic stable isotope data compiled, raw inclination-declination-intensity data, Paleomagnetic interpretation, magnetostratigraphy, calcareous nanofossil events, mapping pairs for correlation of different hole in a drill site, tie points to correlated between drill sites for ODP Sites 1258, 1262, 1263, 1265, 1267 (Tables S1-44). Tables S45 to 48 contain a combined magnetostratigraphy, a 405-kyr tuning age model, tie points for a detailed astronomical age model, and comparison of magnetochron durations.

Description: The boron isotope composition (d11B) of planktic foraminiferal calcite, which reflects seawater pH, is a well-established proxy for reconstructing palaeo-atmospheric CO2 and seawater carbonate chemistry. However, to translate d11B measurements determined in calcareous fossils into pH we need to know the boron isotope composition of the parent seawater (d11Bsw). While a number of d11Bsw reconstructions exist, the discrepancies between them reveals uncertainties and deficiencies that need to be addressed. Here we present a new d11Bsw record based on the d11B difference between planktic and benthic foraminifera and an estimate of the pH gradient between surface and deep water. We then calculate d11Bsw two different ways. One variant of our method assumes that the pH gradient between surface and deep has remained the same as today over the past 23 Ma; the other uses the d13C gradient between surface and deep to represent change in the pH gradient through time. The results of these two methods of calculating d11Bsw are broadly consistency with each other, however, based on extensive carbon cycle modelling using CYCLOPS and GENIE we favour the d13C gradient method. In our favoured d11Bsw reconstruction, d11Bsw is around 2 per mil lower than today at ~37.5 per mil during the early and middle Miocene and increases to the modern value (39.61 per mil) by ~5 Ma. A similar pattern of change is evident in the seawater composition of three other stable isotope systems, Mg, Li and Ca. Concurrent shifts in the seawater isotopic composition of all four of these elements during the late Miocene, suggest a common forcing mechanism. We hypothesise the most likely cause of these shifts is a change in the isotopic composition of the riverine input, potentially driven by an increase in secondary mineral formation since ~15 Ma.

Description: This study reports neodymium isotopic (e-Nd) variability at a time resolution of 0.5 to 3 Ma since the Late Cretaceous as recorded in a marine sedimentary core from the Western Pacific (ODP 807; 3°36'N, 156°3?E; Ontong Java Plateau). Our core is mainly fine-grained and composed of continuous sequences of nannofossil oozes. The e-Nd measured in the carbonate fraction was used as a proxy of e-Nd of seawater of the Western Pacific. On a long term, our results indicate a general increase in e-Nd of seawater by 4.5 e-Nd units from the Late Cretaceous (e-Nd = - 6) to modern times (e-Nd = - 1.7). This pattern was related to the emergence of the West Pacific margin and the progressive isolation of the Pacific Ocean from the other oceanic basins, resulting in its progressive shift to more radiogenic values through the Cenozoic. This long-term pattern is in accordance with previously published Fe-Mn crusts data from the same study area. Nonetheless, by being at higher time resolution, our data records additional sharp and pseudo-cyclic variations (~ 7?11 Ma periods) superimposed on this long-term pattern from ~ 40 Ma to modern times. These oscillations might reflect the alternating dominance of the two main deep water masses (NPDW and UCDW) bathing our study area. In the same core, we also measured the e-Nd in the detrital fraction in order to trace back the local terrigenous inputs. The terrigenous record shows a significant variability up to + 12 e-Nd units. This was linked to the emergence of the west Pacific subduction zone ~ 50 Ma ago causing a higher input of radiogenic isotopes. In conclusion, the large variability observed in both seawater and detrital e-Nd records most probably result from a major tectonic and oceanic circulation reorganization of the Pacific Ocean.

Description: Determining the timing and amplitude of tropical sea surface temperature (SST) change is an important part of solving the puzzle of the Plio-Pleistocene ice ages. Alkenone-based tropical SST records from the major ocean basins show coherent glacial-interglacial temperature changes of 1° to 3°C that align with (but slightly lead) global changes in ice volume and deep ocean temperature over the past 3.5 million years. Tropical temperatures became tightly coupled with benthic d18O and orbital forcing after 2.7 million years. We interpret the similarity of tropical SST changes, in dynamically dissimilar regions, to reflect "top-down" forcing through the atmosphere. The inception of a strong carbon dioxide-greenhouse gas feedback and amplification of orbital forcing at ~2.7 million years ago connected the fate of Northern Hemisphere ice sheets with global ocean temperatures since that time.

Description: Geochemical and Sr-Nd-Pb isotopic compositions of the detrital sediments from ODP Hole 1202B and Taiwan rivers were measured in this study, aiming to reveal changes in sediment provenance in the southern Okinawa Trough (SOT) since 28 ka, and to examine the weathering and sediment transport processes in response to monsoon climate variability. Large variations in Sr-Nd-Pb isotopic ratios at 11?9 ka suggest changes in detrital sediment provenance in the SOT from a dominance of the paleo-Changjiang (Yangtze River) and/or continental shelf sediment during the late deglaciation and to west Taiwan rivers since 9.5 ka. Volcanic rocks and eastern Taiwan sediments have not significantly contributed to the SOT. The large shift in sediment provenance during the early Holocene marks a major change in oceanic circulation, mainly caused by the intrusion of the Kuroshio Current into the trough. Clay mineral and geochemical proxies suggest that the Taiwan-derived sediments accumulated during the early-mid ?Holocene climate optimum? (ca. 9.5-4 ka) might be tightly related to the reworking of older altered sediments from terraces and floodplains, rather than having experienced more intense silicate weathering than in the late Holocene (~ 4-0 ka). Overall, silicate weathering in Taiwan was greatly inhibited by accelerating sediment production and transfer from land to ocean caused by monsoon intensification in Holocene. Our study illustrates that the radiogenic isotopic and geochemical compositions of fine-grained detrital sediments are sensitive tools for fingerprinting sediment sources and for reconstructing changes in oceanic currents and monsoon climate in river-dominated East Asian continental margin.

Description: Sea ice is a critical component in the Arctic and global climate system, yet little is known about its extent and variability during past warm intervals, such as the Pliocene (5.33-2.58 Ma). Here, we present the first multi-proxy (IP25, sterols, alkenones, palynology) sea ice reconstructions for the Late Pliocene Iceland Sea (ODP Site 907). Our interpretation of a seasonal sea ice cover with occasional ice-free intervals between 3.50-3.00 Ma is supported by reconstructed alkenone-based summer sea surface temperatures. As evidenced from brassicasterol and dinosterol, primary productivity was low between 3.50 and 3.00 Ma and the site experienced generally oligotrophic conditions. The East Greenland Current (and East Icelandic Current) may have transported sea ice into the Iceland Sea and/or brought cooler and fresher waters favoring local sea ice formation. Between 3.00 and 2.40 Ma, the Iceland Sea is mainly sea ice-free, but seasonal sea ice occurred between 2.81 and 2.74 Ma. Sea ice extending into the Iceland Sea at this time may have acted as a positive feedback for the build-up of the Greenland Ice Sheet (GIS), which underwent a major expansion ~2.75 Ma. Thereafter, most likely a stable sea ice edge developed close to Greenland, possibly changing together with the expansion and retreat of the GIS and affecting the productivity in the Iceland Sea.

Description: new data on the main components of organic matter, inorganic geochemistry, and stable isotopes along a north-south transect from the Cretaceous Western Interior Seaway (Portland-1 Colorado; Iona-1; Innes-1; Well X; Bouldin Creek outcrop - Eagle Ford Group, SW Texas, USA) and to the equatorial western Atlantic (ODP Sites 1260 and 1261) and Southern Ocean (ODP Site 1138)

Description: Authigenic neodymium isotopes, benthic foraminiferal stable isotopes and radiocarbon dates from ODP 929 in the deep equatorial western Atlantic Ocean.

Description: Recognizing and deciphering transient global warming events triggered by massive release of carbon into Earth's ocean-atmosphere climate system in the past are important for understanding climate under elevated pCO2 conditions. Here we present new high-resolution geochemical records including benthic foraminiferal stable isotope data with clear evidence of a short-lived (30 kyr) warming event at 41.52 Ma. The event occurs in the late Lutetian within magnetochron C19r and is characterized by a ~2°C warming of the deep ocean in the southern South Atlantic. The magnitudes of the carbon and oxygen isotope excursions of the Late Lutetian Thermal Maximum are comparable to the H2 event (53.6 Ma) suggesting a similar response of the climate system to carbon cycle perturbations even in an already relatively cooler climate several million years after the Early Eocene Climate Optimum. Coincidence of the event with exceptionally high insolation values in the Northern Hemisphere at 41.52 Ma might indicate that Earth's climate system has a thermal threshold. When this tipping point is crossed, rapid positive feedback mechanisms potentially trigger transient global warming. The orbital configuration in this case could have caused prolonged warm and dry season leading to a massive release of terrestrial carbon into the ocean-atmosphere system initiating environmental change.

Description: A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Description: We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl 〉 + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Description: During the past five million yrs, benthic d18O records indicate a large range of climates, from warmer than today during the Pliocene Warm Period to considerably colder during glacials. Antarctic ice cores have revealed Pleistocene glacial-interglacial CO2 variability of 60-100 ppm, while sea level fluctuations of typically 125 m are documented by proxy data. However, in the pre-ice core period, CO2 and sea level proxy data are scarce and there is disagreement between different proxies and different records of the same proxy. This hampers comprehensive understanding of the long-term relations between CO2, sea level and climate. Here, we drive a coupled climate-ice sheet model over the past five million years, inversely forced by a stacked benthic d18O record. We obtain continuous simulations of benthic d18O, sea level and CO2 that are mutually consistent. Our model shows CO2 concentrations of 300 to 470 ppm during the Early Pliocene. Furthermore, we simulate strong CO2 variability during the Pliocene and Early Pleistocene. These features are broadly supported by existing and new d11B-based proxy CO2 data, but less by alkenone-based records. The simulated concentrations and variations therein are larger than expected from global mean temperature changes. Our findings thus suggest a smaller Earth System Sensitivity than previously thought. This is explained by a more restricted role of land ice variability in the Pliocene. The largest uncertainty in our simulation arises from the mass balance formulation of East Antarctica, which governs the variability in sea level, but only modestly affects the modeled CO2 concentrations.

Description: Pelagic ecosystem function is integral to global biogeochemical cycling, and plays a major role in modulating atmospheric CO2 concentrations (pCO2). Uncertainty as to the effects of human activities on marine ecosystem function hinders projection of future atmospheric pCO2. To this end, events in the geological past can provide informative case studies in the response of ecosystem function to environmental and ecological changes. Around the Cretaceous-Palaeogene (K-Pg) boundary, two such events occurred: Deccan large igneous province (LIP) eruptions and massive bolide impact at the Yucatan Peninsula. Both perturbed the environment, but only the impact coincided with marine mass extinction. As such, we use these events to directly contrast the response of marine biogeochemical cycling to environmental perturbation with and without changes in global species richness. We measure this biogeochemical response using records of deep-sea carbonate preservation. We find that Late Cretaceous Deccan volcanism prompted transient deep-sea carbonate dissolution of a larger magnitude and timescale than predicted by geochemical models. Even so, the effect of volcanism on carbonate preservation was slight compared with bolide impact. Empirical records and geochemical models support a pronounced increase in carbonate saturation state for more than 500 000 years following the mass extinction of pelagic carbonate producers at the K-Pg boundary. These examples highlight the importance of pelagic ecosystems in moderating climate and ocean chemistry.

Description: The long-term cooling trend of the Cenozoic is punctuated by shorter-term climatic events, such as the inception of permanent ice sheets on Antarctica at the Eocene-Oligocene Transition (~33.7 Ma). Taking advantage of the excellent state of preservation of coccolith calcite in equatorial Atlantic deep-sea cores, we unveil progressive tropical warming in the Atlantic Ocean initiated 4 million years prior to Antarctic glaciation. Warming preceding glaciation may appear counterintuitive, but we argue that this long-term climatic precursor to the EOT reinforced cooling of austral high latitudes via the redistribution of heat at the surface of the oceans. We discuss this new prominent paleoceanographic and climatic feature in the context of overarching pCO2 decline and the establishment of an Antarctic circumpolar current.

Description: The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Description: The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Description: In this study, new high-resolution XRF data from ODP Site 959 (3°37'N, 2°44'W) have been used to investigate the relationship between paleoenvironmental changes in West Africa and sedimentation in the tropical east Atlantic Ocean. Fe intensity data have been used to build a 91 meter composite depth record that has been astronomically tuned allowing the development of a detailed age model from 6.2 to 1.8 Ma. Based on this new stratigraphy we studied the variations of Ti/Al, Ti/Ca and Al/Si ratios, proxies for aeolian vs. fluvial supply, as dust indicator and fine vs. coarse grain size, respectively. We discuss sedimentation patterns at ODP Site 959 associated to the environmental changes from the late Miocene until the early Pleistocene. During the interval corresponding to the earlier stages of the Messinian Salinity Crisis our proxy records indicate enhanced run-off from the West African continent and major supply of fine material at ODP Site 959, suggesting a stronger monsoon and increased precipitation during eccentricity minima. A long-term decrease of river supply is documented after 5.4 Ma towards the early Pleistocene. From the increased values and variability of Ti/Al ratios we suggest that after 3.8 Ma dust started to reach the study site probably as a result of the southward shift of the Intertropical Convergence Zone during winter. Between 3.2 and 2.9 Ma ODP Site 959 Ti/Ca ratios exhibit three maxima corresponding to eccentricity maxima similarly to other dust records of northern Africa. This suggests continent-wide aridity or larger climate variability during that interval. Eccentricity forcing (405 kyr and 100 kyr) and precession frequencies are found in the entire studied interval. The variations of Ti/Al ratio suggest stronger seasonality between 5.8 and 5.5 Ma and after 3.2 Ma.

Description: Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to 〈 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to 〈 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at 〈 100 °C and carbonate formation at 〈 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.

Description: Oceanic sediments deposited at high rate close to continents are dominated by terrigenous material. Aside from dilution by biogenic components, their chemical compositions reflect those of nearby continental masses. This study focuses on oceanic sediments coming from the juvenile Canadian Cordillera and highlights systematic differences between detritus deriving from juvenile crust and detritus from old and mature crust. We report major and trace element concentrations for 68 sediments from the northernmost part of the Cascade forearc, drilled at ODP Sites 888 and 1027. The calculated weighted averages for each site can then be used in the future to quantify the contribution of subducted sediments to Cascades volcanism. The two sites have similar compositions but Site 888, located closer to the continent, has higher sandy turbidite contents and displays higher bulk SiO2/Al2O3 with lower bulk Nb/Zr, attributed to the presence of zircons in the coarse sands. Comparison with published data for other oceanic sedimentary piles demonstrates the existence of systematic differences between modern sediments deriving from juvenile terranes (juvenile sediments) and modern sediments derived from mature continental areas (cratonic sediments). The most striking systematic difference is for Th/Nb, Th/U, Nb/U and Th/Rb ratios: juvenile sediments have much lower ratios than cratonic sediments. The small enrichment of Th over Nb in cratonic sediments may be explained by intracrustal magmatic and metamorphic differentiation processes. In contrast, their elevated Th/U and Nb/U ratios (average values of 6.87 and 7.95, respectively) in comparison to juvenile sediments (Th/U ~ 3.09, Nb/U ~ 5.15) suggest extensive U and Rb losses on old cratons. Uranium and Rb losses are attributed to long-term leaching by rain and river water during exposure of the continental crust at the surface. Over geological times, the weathering effects create a slow but systematic increase of Th/U with exposure time.

Description: For paleoceanographic studies, it is important to understand the processes that influence the calcium (Ca) isotopic composition of foraminiferal calcite tests preserved in the sediment record. Seven species of planktonic foraminifera from coretop sediments collectively exhibited a Ca temperature dependent fractionation of 0.013 per mil per °C. This is in agreement with previously published estimates for most species of planktonic foraminifera as well as biogenic and inorganic calcite and aragonite. Four species of planktonic foraminifera collected from a sediment trap showed a considerable amount of scatter and no consistent temperature dependent fractionation. Analyzed size fractions of coretop samples show no significant relationship with d44/40Ca. However, preliminary results suggest that the symbiotic and spinose foraminifera G. sacculifer might exhibit a relationship between test size and d44/40Ca. A one-box model in which Ca isotopes are allowed to fractionate by Rayleigh distillation from a biomineralization reservoir (internal pool) was used to constrain the isotopic composition of the original biomineralization Ca reservoir, assuming around 85% of the Ca reservoir is precipitated and the fractionation factor during precipitation is 0.9985 + 0.00002(T ºC). To explain the foraminiferal Ca isotope data, this model indicates that the Ca isotopic composition of the biomineralization reservoir is offset from seawater (approximately -0.8per mil).

Description: Important insight into the relationship between de-oxygenation and warming can be obtained from the geological record, but evidence is limited because few ocean oxygenation records are available for past greenhouse climate conditions. We use I/Ca in benthic foraminifera to reconstruct late Paleocene through early Eocene bottom and pore-water redox conditions in the South Atlantic and Southern Indian Oceans, and compare our results with those derived from Mn speciation and the Ce anomaly in fish teeth.

Description: The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Description: Few astronomically calibrated high-resolution (〈=5 kyr) climate records exist that span the Oligocene?Miocene time interval. Notably, available proxy records show responses varying in amplitude at frequencies related to astronomical forcing, and the main pacemakers of global change on astronomical time-scales remain debated. Here we present newly generated X-ray fluorescence core scanning and benthic foraminiferal stable oxygen and carbon isotope records from Ocean Drilling Program Site 1264 (Walvis Ridge, southeastern Atlantic Ocean). Complemented by data from nearby Site 1265, the Site 1264 benthic stable isotope records span a continuous ~13-Myr interval of the Oligo-Miocene (30.1?17.1 Ma) at high resolution (~3.0 kyr). Spectral analyses in the stratigraphic depth domain indicate that the largest amplitude variability of all proxy records is associated with periods of ~3.4 m and ~0.9 m, which correspond to 405- and ~110-kyr eccentricity, using a magnetobiostratigraphic age model. Maxima in CaCO3 content, d18O and d13C are interpreted to coincide with ~110 kyr eccentricity minima. The strong expression of these cycles in combination with the weakness of the precession- and obliquity-related signals allow construction of an astronomical age model that is solely based on tuning the CaCO3 content to the nominal (La2011_ecc3L) eccentricity solution. Very long-period eccentricity maxima (~2.4-Myr) are marked by recurrent episodes of high-amplitude ~110-kyr d18O cycles at Walvis Ridge, indicating greater sensitivity of the climate/cryosphere system to short eccentricity modulation of climatic precession. In contrast, the responses of the global (high-latitude) climate system, cryosphere, and carbon cycle to the 405-kyr cycle, as expressed in benthic d18O and especially d13C signals, are more pronounced during ~2.4-Myr minima. The relationship between the recurrent episodes of high-amplitude ~110-kyr d18O cycles and the ~1.2-Myr amplitude modulation of obliquity is not consistent through the Oligo-Miocene. Identification of these recurrent episodes at Walvis Ridge, and their pacing by the ~2.4-Myr eccentricity cycle, revises the current understanding of the main climate events of the Oligo-Miocene.

Description: Modern global change threatens alpine ecosystems by forcing species to migrate to higher elevations and potentially eliminating alpine habitat altogether. Here we show that an analogous restriction of suitable habitat operates on submarine mountains. During the Paleocene–Eocene Thermal Maximum (PETM, ca. 55.96 Ma), ostracodes underwent local extinction on the crest of Allison Guyot in the central Pacific Ocean, which lost 64% of its ostracode species richness (14 species reduced to three species) and as much as 94% of ostracode abundance for ~1.1 m.y., before recolonization rebuilt biodiversity and abundance over the next 200 k.y. Biotic changes may reflect an increase in current speeds, acidification, and a decrease in food supply owing to a temperature-driven increase in metabolic rates. Notably, continental margin ostracodes also underwent extinction during the PETM (25%–38% loss) but, unlike Allison Guyot faunas, could quickly repopulate the continental slope. The absence of refugia for isolated seamounts prolonged the reduction in biodiversity initiated by the PETM, a pattern that may be expected for modern seamount faunas in an era of future global change.

Description: To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Description: Evolutionary prospection is the study of morphological evolution and speciation in calcareous plankton from selected time-slices and key sites in the world oceans. In this context, the Neogene menardiform globorotalids serve as study objects for morphological speciation in planktic foraminifera. A downcore investigation of test morphology of the lineage of G. menardii-limbata-multicamerata during the past 8 million years was carried out in the western tropical Atlantic ODP Hole 925B. A total of 4669 specimens were measured and analyzed from 38 stratigraphic levels and compared to previous studies from DSDP Sites 502 and 503. Collection of digital images and morphometric measurements from digitized outlines were achieved using a microfossil orientation and imaging robot called AMOR and software, which was especially developed for this purpose. Most attention was given to the evolution of spiral height versus axial length of tests in keel view, but other parameters were investigated as well. The variability of morphological parameters in G. menardii, G. limbata, and G. multicamerata through time are visualized by volume density diagrams. At Hole 925B results show gradual test size increase in G. menardii until about 3.2 Ma. The combination of taxonomic determination in the light microscope with morphometric investigations shows strong morphological overlap and evolutionary continuity from ancestral to extant G. menardii (4–6 chambers in the final whorl) to the descendent but extinct G. limbata (seven chambers in the final whorl) and to G. multicamerata (〉=8 chambers in the final whorl). In the morphospace defined by spiral height (dX) and axial length (dY) Globorotalia limbata and G. multicamerata strongly overlap with G. menardii. Distinction of G. limbata from G. menardii is only possible by slight differences in the number of chambers of the final whorl, nuances in spiral convexity, upper keel angles, radii of osculating circles, or by differences in reflectance of their tests. Globorotalia multicamerata can be distinguished from the other two forms by more than eight chambers in the final whorl. It appeared as two stratigraphically separate clusters during the Pliocene. Between 2.88 and 2.3 Ma G. menardii was severely restricted in size and abundance. Thereafter, it showed a rapid and prominent expansion of the upper test size extremes between 2.3 and 1.95 Ma persisting until present. The size-frequency distributions at Hole 925B are surprisingly similar to trends of menardiform globorotalids from Caribbean DSDP Site 502. There, the observations were explained as an adaptation to changes in the upper water column due to the emergence of the Isthmus of Panama. In light of more recent paleontological and geological investigations about the completion of the permanent land connection between North and South America since about 3 Ma the present study gives reason to suspect the sudden test size increase of G. menardii to reflect immigration of extra-large G. menardii from the Indian Ocean or the Pacific. It is hypothesized that during the Late Pliocene dispersal of large G. menardii into the southern to tropical Atlantic occurred during an intermittent episode of intense Agulhas Current leakage around the Cape of Good Hope and from there via warm eddy transport to the tropical Atlantic (Agulhas dispersal hypothesis).

Description: Milankovitch-scale alternations in Maastrichtian hemipelagic strata from Ocean Drilling Program Hole 1050C (Blake Nose) provide a natural experiment of paleoceanography and foraminiferal paleoecology in a tropical/subtropical greenhouse ocean. Cycles are 30-50 cm thick and thought to reflect the ~21 kyr precessional cycle. High planktic d18O values are correlated with high planktic but low benthic d13C values, indicating that cooler and/or more saline surface waters were associated with higher productivity. High-productivity intervals are also characterized by high Ca concentrations; enrichment in feldspar and kaolinite; and high relative abundance of Heterohelix spp., Globigerinelloides spp., and Laeviheterohelix glabrans. Conversely, low-productivity intervals have low planktic d18O values; high Fe and Ti concentrations; enrichment in quartz, illite, and chlorite; and relative increases in Globotruncana spp. and Pseudoguembelina spp. Potential forcing mechanisms for observed covariation include cyclic variation in water column stratification, variation in continental nutrient fluxes, and changes in the intensity of upwelling.

Description: Carbonates are invaluable archives of the past, and have been used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. Such archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the importance of diagenesis on proxy fidelity, the effects of diagenesis on the calcium isotopic composition (d44Ca) of carbonates are unclear. Accordingly, bulk carbonate d44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma). The d44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large (~0.8 per mil) variations in bulk carbonate d44Ca occur in the deeper site near the peak carbon isotope excursion, and are correlated with a large drop in carbonate weight percent. Such an effect is seen in neither the 1221 barite record nor the bulk carbonate record at the shallower, less dissolved Site 1212. We contend that ocean chemical changes associated with the abrupt and massive carbon release into the ocean-atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate d44Ca record via diagenesis in the sedimentary column. Such changes are considerable, and need to be taken into account when interpreting and modeling Ca isotope data over extreme climatic events associated with ocean chemical evolution.

Description: Ichthyolith abundances and accumulation rates for ODP 1209, ODP 1220, and ODP 1260. Ichthyolith morphotype relative abundances for ODP 1209, ODP 1220, and ODP 1260. Isotopic carbon data and ages for ODP 1209, ODP 1220, and ODP 1260

Description: Eocene Thermal Maximum 2 (ETM2) occurred ~1.8 Myr after the Paleocene Eocene Thermal Maximum (PETM) and, like the PETM, was characterized by a negative carbon isotope excursion coupled with warming. We combined benthic foraminiferal and sedimentological records for Southeast Atlantic Sites 1263 (1500 m paleodepth) and 1262 (3600 m paleodepth) to show that benthic foraminiferal diversity and accumulation rates declined more precipitously and severely at the shallower site during peak ETM2. The sites are in close proximity, so differences in surface productivity cannot have caused this differential effect. Instead, on the basis of an analysis of climate modelling experiments, we infer that changes in ocean circulation pattern across ETM2 may have resulted in more pronounced warming at intermediate depths (Site 1263). The effects of more pronounced warming include increased metabolic rates, leading to a decrease in effective food supply and increased deoxygenation, thus potentially explaining the more severe benthic impacts at Site 1263. In response to more severe benthic disturbance, bioturbation may have decreased at Site 1263 as compared to Site 1262, hence differentially affecting the bulk carbonate record. We use a sediment-enabled Earth system model to test whether a reduction in bioturbation and/or the likely reduced carbonate saturation of more poorly ventilated waters can explain the more extreme excursion in bulk d13C and sharper transition in wt% CaCO3 at Site 1263. We find that both enhanced acidification and reduced bioturbation during peak ELMO conditions are needed to account for the observed features. Our combined ecological and modelling analysis illustrates the potential role of ocean circulation changes in amplifying local environmental changes and driving temporary, but drastic, loss of benthic biodiversity and abundance.

Description: The grain size of deep-sea sediments provides an apparently simple proxy for current speed. However, grain size-based proxies may be ambiguous when the size distribution reflects a combination of processes, with current sorting only one of them. In particular, such sediment mixing hinders reconstruction of deep circulation changes associated with ice-rafting events in the glacial North Atlantic because variable ice-rafted detritus (IRD) input may falsely suggest current speed changes. Inverse modeling has been suggested as a way to overcome this problem. However, this approach requires high-precision size measurements that register small changes in the size distribution. Here we show that such data can be obtained using electrosensing and laser diffraction techniques, despite issues previously raised on the low precision of electrosensing methods and potential grain shape effects on laser diffraction. Down-core size patterns obtained from a sediment core from the North Atlantic are similar for both techniques, reinforcing the conclusion that both techniques yield comparable results. However, IRD input leads to a coarsening that spuriously suggests faster current speed. We show that this IRD influence can be accounted for using inverse modeling as long as wide size spectra are taken into account. This yields current speed variations that are in agreement with other proxies. Our experiments thus show that for current speed reconstruction, the choice of instrument is subordinate to a proper recognition of the various processes that determine the size distribution and that by using inverse modeling meaningful current speed reconstructions can be obtained from mixed sediments.

Description: Recent studies have shown that the Early Eocene Climatic Optimum (EECO) was preceded by a series of short-lived global warming events, known as hyperthermals. Here we present high-resolution benthic stable carbon and oxygen isotope records from ODP Sites 1262 and 1263 (Walvis Ridge, SE Atlantic) between ~54 and ~52 million years ago, tightly constraining the character, timing, and magnitude of six prominent hyperthermal events. These events, which include Eocene Thermal Maximum (ETM) 2 and 3, are studied in relation to orbital forcing and long-term trends. Our findings reveal an almost linear relationship between d13C and d18O for all these hyperthermals, indicating that the eccentricity-paced co-variance between deep-sea temperature changes and extreme perturbations in the exogenic carbon pool persisted during these events towards the onset of the EECO, in accord with previous observations for the Paleocene Eocene Thermal Maximum (PETM) and ETM2. The covariance of d13C and d18O during H2 and I2, which are the second pulses of the "paired" hyperthermal events ETM2-H2 and I1-I2, deviates with respect to the other events. We hypothesize that this could relate to a relatively higher contribution of an isotopically heavier source of carbon, such as peat or permafrost, and/or to climate feedbacks/local changes in circulation. Finally, the d18O records of the two sites show a systematic offset with on average 0.2 per mil heavier values for the shallower Site 1263, which we link to a slightly heavier isotopic composition of the intermediate water mass reaching the northeastern flank of the Walvis Ridge compared to that of the deeper northwestern water mass at Site 1262.

Description: During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (d44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater d44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater d44/40Ca shifts. This suggests that the response of seawater d44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms.

Description: Pliocene vegetation dynamics and climate variability in West Africa have been investigated through pollen and XRF-scanning records obtained from sediment cores of ODP Site 659 (18°N, 21°W). The comparison between total pollen accumulation rates and Ti/Ca ratios, which is strongly correlated with the dust input at the site, showed elevated aeolian transport of pollen during dusty periods. Comparison of the pollen records of ODP Site 659 and the nearby Site 658 resulted in a robust reconstruction of West African vegetation change since the Late Pliocene. Between 3.6 and 3.0 Ma the savannah in West Africa differed in composition from its modern counterpart and was richer in Asteraceae, in particular of the Tribus Cichorieae. Between 3.24 and 3.20 Ma a stable wet period is inferred from the Fe/K ratios, which could stand for a narrower and better specified mid-Pliocene (mid-Piacenzian) warm time slice. The northward extension of woodland and savannah, albeit fluctuating, was generally greater in the Pliocene. NE trade wind vigour increased intermittently around 2.7 and 2.6 Ma, and more or less permanently since 2.5 Ma, as inferred from increased pollen concentrations of trade wind indicators (Ephedra, Artemisia, Pinus). Our findings link the NE trade wind development with the intensification of the Northern Hemisphere glaciations (iNHG). Prior to the iNHG, little or no systematic relation could be found between sea surface temperatures of the North Atlantic with aridity and dust in West Africa.

Description: The shoaling and final closure of the Central American Seaway (CAS) resulted in a major change of the global ocean circulation and has been suggested as an essential driver for strengthening of Atlantic Meridional Overturning Circulation (AMOC). The exact timing of CAS closure is key to interpreting its importance. Here we present a reconstruction of deep and intermediate water Nd and Pb isotope compositions obtained from fossil fish teeth and the authigenic coatings of planktonic foraminifera in the eastern equatorial Pacific (Ocean Drilling Program (ODP) Site 1241) and the Caribbean (ODP Sites 998, 999, and 1000) covering the final stages of CAS closure between 5.6 and 2.2 Ma. The data for the Pacific site indicate no significant Atlantic/Caribbean influence over this entire period. The Caribbean sites show a continuous trend to less radiogenic Nd isotope compositions during the Pliocene, consistent with an enhancement of Upper North Atlantic Deep Water (UNADW) inflow and a strengthening of the AMOC. Superimposed onto this long-term trend, shorter-term changes of intermediate Caribbean Nd isotope signatures approached more UNADW-like values during intervals when published reconstructions of seawater salinity suggested complete closure of the CAS. The data imply that significant deep water exchange with the Pacific essentially stopped by 7 Ma and that shallow exchange, which still occurred at least periodically until approximately 2.5 Ma, may have been linked to the strength of the AMOC but did not have any direct effect on the intermediate and deep Caribbean Nd isotope signatures through mixing with Pacific waters.

Description: Seismicity patterns offshore Costa Rica (Central America) at the Middle America Trench have led to speculation that large (moment magnitude, Mw ~7.0) earthquakes are associated with subducting topographic highs. In areas of high basement topography, a regionally extensive nannofossil chalk unit is exposed at the seafl oor on the incoming plate, whereas in regions of low basement topography, hemipelagic clay-rich sediment is exposed. Because the entire sediment section is subducted at this margin, lithologic variation in the uppermost subducting sediments may control plate boundary fault behavior. Our laboratory experiments reveal that the chalk is frictionally strong (µ = 0.71-0.88) and characterized by velocity weakening and stick-slip behavior, notably at elevated temperature. In contrast, the hemipelagic sediment is weak (µ = 0.22-0.35) and in many cases velocity strengthening. We suggest that the presence of frictionally unstable carbonates at bathymetric highs may play a key, previously unrecognized, role in governing earthquake nucleation.

Description: The Late Paleocene and Early Eocene were characterised by warm greenhouse climates, punctuated by a series of rapid warming and ocean acidification events known as "hyperthermals", thought to have been paced or triggered by orbital cycles. While these hyperthermals, such as the Paleocene Eocene Thermal Maximum (PETM), have been studied in great detail, the background low-amplitude cycles seen in carbon and oxygen-isotope records throughout the Paleocene-Eocene have hitherto not been resolved. Here we present a 7.7 million year (myr) long, high-resolution, orbitally-tuned, benthic foraminiferal stable-isotope record spanning the late Paleocene and early Eocene interval (~52.5 - 60.5 Ma) from Ocean Drilling Program (ODP) Site 1262, South Atlantic. This high resolution (~2-4 kyr) record allows the changing character and phasing of orbitally-modulated cycles to be studied in unprecedented detail as it reflects the long-term trend in carbon cycle and climate over this interval. The main pacemaker in the benthic oxygen-isotope (d18O) and carbon-isotope (d13C) records from ODP Site 1262, are the long (405 kyr) and short (100 kyr) eccentricity cycles, and precession (21 kyr). Obliquity (41 kyr) is almost absent throughout the section except for a few brief intervals where it has a relatively weak influence. During the course of the Early Paleogene record, and particularly in the latest Paleocene, eccentricity-paced negative carbon-isotope excursions (d13C, CIEs) and coeval negative oxygen-isotope (d18O) excursions correspond to low carbonate (CaCO3) and coarse fraction (%CF) values due to increased carbonate dissolution, suggesting shoaling of the lysocline and accompanied changes in the global exogenic carbon cycle. These negative CIEs and d18O events coincide with maxima in eccentricity, with changes in d18O leading changes in d13C by ~6 (±5) kyr in the 405-kyr band and by ~3 (±1) kyr in the higher frequency 100-kyr band on average. However, these phase lags are not constant, with the lag in the 405-kyr band extending from ~4 (±5) kyr to ~21 (±2) kyr from the late Paleocene to the early Eocene, suggesting a progressively weaker coupling of climate and the carbon-cycle with time. The higher amplitude 405-kyr cycles in the latest Paleocene are associated with changes in bottom water temperature of 2-4ºC, while the most prominent 100 kyr-paced cycles can be accompanied by changes of up to 1.5ºC. Comparison of the 1262 record with a lower resolution, but orbitally-tuned benthic record for Site 1209 in the Pacific allows for verification of key features of the benthic isotope records which are global in scale including a key warming step at 57.7 Ma.

Description: The membrane lipids diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2G-GDGTs) in marine subsurface sediments are believed to originate from uncultivated benthic archaea, yet the production of 2G-GDGTs from subseafloor samples has not been demonstrated in vitro. In order to validate sedimentary biosynthesis of 2G-GDGTs, we performed a stable carbon isotope probing experiment on a subseafloor sample with six different 13C-labelled substrates (bicarbonate, methane, acetate, leucine, glucose and Spirulina platensis biomass). After 468 days of anoxic incubation, only glucose and S. platensis resulted in label uptake in lipid moieties of 2G-GDGTs, indicating incorporation of carbon from these organic substrates. The hydrophobic moieties of 2G-GDGTs showed minimal label incorporation, with up to 4 per mil 13C enrichment detected in crenarchaeol-derived tricyclic biphytane from the S. platensis-supplemented slurries. The 2G-GDGT-derived glucose or glycerol moieties also showed 13C incorporation (Dd13C = 18 - 38 per mil) in the incubations with glucose or S. platensis, consistent with a lipid salvage mechanism utilized by marine benthic archaea to produce new 2G-GDGTs. The production rates were nevertheless rather slow, even when labile organic matter was supplied. The 2G-GDGT turnover times of 1700 - 20 500 years were much longer than those estimated for subseafloor microbial communities, implying that sedimentary 2G-GDGTs as biomarkers of benthic archaea are cumulative records of past and present generations.

Description: Constraining the nature of Antarctic Ice Sheet (AIS) response to major past climate changes may provide a window onto future ice response and rates of sea level rise. One approach to tracking AIS dynamics, and differentiating whole system versus potentially heterogeneous ice sheet sector changes, is to integrate multiple climate proxies for a specific time slice across widely distributed locations. This study presents new iceberg-rafted debris (IRD) data across the interval that includes Marine Isotope Stage 31 (MIS 31: 1.081-1.062 Ma, a span of ~19 kyr; Lisiecki and Raymo, 2005), which lies on the cusp of the mid-Brunhes climate transition (as glacial cycles shifted from ~41,000 yr to ~100,000 yr duration). Two sites are studied - distal Ocean Drilling Program (ODP) Leg 177 Site 1090 (Site 1090) in the eastern subantarctic sector of the South Atlantic Ocean, and proximal ODP Leg 188 Site 1165 (Site 1165), near Prydz Bay, in the Indian Ocean sector of the Antarctic margin. At each of these sites, MIS 31 is marked by the presence of the Jaramillo Subchron (0.988-1.072 Ma; Lourens et al., 2004) which provides a time-marker to correlate these two sites with relative precision. At both sites, records of multiple climate proxies are available to aid in interpretation. The presence of IRD in sediments from our study areas, which include garnets indicating a likely East Antarctic Ice Sheet (EAIS) origin, supports the conclusion that although the EAIS apparently withdrew significantly over MIS 31 in the Prydz Bay region and other sectors, some sectors of the EAIS must still have maintained marine margins capable of launching icebergs even through the warmest intervals. Thus, the EAIS did not respond in complete synchrony even to major climate changes such as MIS 31. Further, the record at Site 1090 (supported by records from other subantarctic locations) indicates that the glacial MIS 32 should be reduced to no more than a stadial, and the warm interval of Antarctic ice retreat that includes MIS 31 should be expanded to MIS 33-31. This revised warm interval lasted about 52 kyr, in line with several other interglacials in the benthic d18O records stack of Lisiecki and Raymo (2005), including the super-interglacials MIS 11 (duration of 50 kyr) and MIS 5 (duration of 59 kyr). The record from Antarctica-proximal Site 1165, when interpreted in accord with the record from ANDRILL-1B, indicates that in these southern high latitude sectors, ice sheet retreat and the effects of warming lasted longer than at Site 1090, perhaps until MIS 27. In the current interpretations of the age models of the proximal sites, ice sheet retreat began relatively slowly, and was not really evident until the start of MIS 31. In another somewhat more speculative interpretation, ice sheet retreat began noticeably with MIS 33, and accelerated during MIS 31. Ice sheet inertia (the lag-times in the large-scale responses of major ice sheets to a forcing) likely plays an important part in the timing and scale of these events in vulnerable sectors of the AIS.

Description: A feature of Pliocene climate is the occurrence of "permanent El Niño-like" or "El Padre" conditions in the Pacific Ocean. From the analysis of sediment cores in the modern northern Benguela upwelling, we show that the mean oceanographic state off Southwest Africa during the warm Pliocene epoch was also analogous to that of a persistent Benguela "El Niño". At present these events occur when massive southward flows of warm and nutrient-poor waters extend along the coasts of Angola and Namibia, with dramatic effects on regional marine ecosystems and rainfall. We propose that the persistent warmth across the Pliocene in the Benguela upwelling ended synchronously with the narrowing of the Indonesian seaway, and the early intensification of the Northern Hemisphere Glaciations around 3.0-3.5 Ma. The emergence of obliquity-related cycles in the Benguela sea surface temperatures (SST) after 3 Ma highlights the development of strengthened links to high latitude orbital forcing. The subsequent evolution of the Benguela upwelling system was characterized by the progressive intensification of the meridional SST gradients, and the emergence of the 100 ky cycle, until the modern mean conditions were set at the end of the Mid Pleistocene transition, around 0.6 Ma. These findings support the notion that the interplay of changes in the depth of the global thermocline, atmospheric circulation and tectonics preconditioned the climate system for the end of the warm Pliocene epoch and the subsequent intensification of the ice ages.

Description: Sediment samples from both Site 165-999/165-1000 (Atlantic) and Site 202-1241 (Pacific) were chosen at 1Ma intervals over the period 0.3-9.3Ma. Samples were washed and sieved 〈150µm. Splits of the sediment fraction were picked completely to obtain, where possible, at least 30 specimens each of planktic foraminifer species Globigerinoides sacculifer and Globorotalia tumida, on which outline analysis (Fourier) was performed. Sea surface and thermocline temperatures were reconstructed from palaeoenvironmental proxies (UK37' and Tex86H respectively).

Description: A high-resolution stratigraphy is essential toward deciphering climate variability in detail and understanding causality arguments of events in earth history. Because the highly dynamic middle to late Eocene provides a suitable testing ground for carbon cycle models for a waning warm world, an accurate time scale is needed to decode climate-driving mechanisms. Here we present new results from ODP Site 1260 (Leg 207) which covers a unique expanded middle Eocene section (magnetochrons C18r to C20r, late Lutetian to early Bartonian) of the tropical western Atlantic including the chron C19r transient hyperthermal event and the Middle Eocene Climate Optimum (MECO). To establish a detailed cyclostratigraphy we acquired a distinctive iron intensity records by XRF scanning Site 1260 cores. We revise the shipboard composite section, establish a cyclostratigraphy and use the exceptional eccentricity modulated precession cycles for orbital tuning. The new astrochronology revises the age of magnetic polarity chrons C19n to C20n, validates the position of very long eccentricity minima at 40.2 and 43.0 Ma in the orbital solutions, and extends the Astronomically Tuned Geological Time Scale back to 44 Ma. For the first time the new data provide clear evidence for an orbital pacing of the chron C19r event and a likely involvement of the very long eccentricity cycle contributing to the evolution of the MECO.

Description: A high-resolution calcareous nannofossil analysis of the Danian/Selandian boundary was conducted at Site 1262 (Walvis Ridge, South Atlantic) to pinpoint the lowest occurrence of fasciculiths and to unravel the evolutionary trends throughout nannofossil Zone NP4. Using quantitative analyses, numerous primary and secondary bioevents were identified, improving the biostratigraphic resolution of this interval. The main events recorded at Site 1262 were also identified at the Zumaia section Global Stratotype Section and Point (GSSP) of the base of the Selandian and at the Qreiya section (Egypt). The lowest occurrence of fasciculiths (represented by the LO of Gomphiolithus magnicordis and Gomphiolithus magnus) was observed in the middle part of Chron C27r, above the LO of Toweius pertusus and prior to the LO of the genus Sphenolithus. The synchroneity of the LO of fasciculiths was also verified at various latitudes, such as DSDP Site 384 (NW Atlantic), ODP Site 761B (Indian Ocean) and DSDP Site 577A (Pacific Ocean). The first and second diversification events (Steurbaut and Sztrákos, 2008, doi:10.1016/j.marmicro.2007.08.004), or radiation events (Bernaola et al., 2009, doi:10.1344/105.000000272), of fasciculiths have been thoroughly discussed and well characterized by a succession of events. The occurrence of the Latest Danian Event (LDE) and several paleoenvironmental changes recognized during this time interval, coupled with an ecological competition with Sphenolithus, appear to be the probable causes of the First and Second Radiations and the fasciculith barren interval between them. The occurrence of new morphostructures and taxa suggests evolutionary trends and a strict link between morphological evolution and paleoclimate.

Description: Changes in the source of intermediate waters to the southern California margin may have caused variations in seafloor oxygen levels on stadial–interstadial time scales. We test this hypothesis using the Nd isotopic composition of benthic foraminifera and fossil fish debris from ODP Sites 893 and 1017 to track the composition of intermediate waters across interstadials 8-14 (~37-52 ka) during Marine Isotope Stage 3. The epsilon-Nd values of waters bathing the seafloor at Site 893 were typically ~-9 and those bathing Site 1017 were ~-7, both of which are significantly less radiogenic than waters that had originated in either the North Pacific or Southern Ocean (by the time such waters reached the southern California margin). Detrital silicate epsilon-Nd values of nearly -12 suggest that this offset toward lower epsilon-Nd values was likely caused by boundary scavenging that partially overprinted the water mass composition with local/regional fluvial Nd inputs. In spite of the evidence for boundary scavenging, the lack of systematic seawater Nd isotope changes on a stadial–interstadial basis suggests that the provenance of the intermediate waters did not change, and that the waters were derived from the Southern Ocean. Instead, changes in local/regional sea surface productivity may have caused the recorded changes in seafloor oxygenation.

Description: Magnetic properties and oxide petrography results are presented from dike samples recovered during Ocean Drilling Program Legs 137 and 140 at Hole 504B on the Costa Rica Rift. Although secondary magnetite is common, the most abundant magnetic phase is low-titanium magnetite produced during oxidation of primary (igneous) titanomagnetite. In general, titanomagnetite grains in the Leg 137/140 dike samples were observed to have experienced substantially higher degrees of high-temperature deuteric oxidation than the upper portion of the dike complex, suggesting a gradual decrease in the rate of cooling with depth. Paleomagnetic measurements indicate that samples recovered during Legs 137 and 140 acquired a component of drilling-induced remanent magnetization. However, stable magnetic inclinations determined after alternating-field demagnetization indicate the direction of the hardest component of magnetization is very near that predicted for this equatorial site (0°). The average intensity of natural remanent magnetization for the entire dike complex is 2.1 A/m, about half that observed for the overlying extrusive basalts. Room temperature rock magnetic measurements indicate that the effective magnetic grain size of the dike samples falls within the region described as pseudo-single domain. Together, these results suggest that the sheeted dike complex sampled at Hole 504B is capable of contributing to the anomaly observed at sea surface.

Description: We report relative paleointensity proxy records from four piston cores collected near the Agulhas Ridge and Meteor Rise (South Atlantic). The mean sedimentation rate of the cores varies from 24 cm/kyr to 11 cm/kyr. The two cores with mean sedimentation rates over 20 cm/kyr record positive remanence inclinations at 40-41 ka coeval with the Laschamp Event. Age models are based on oxygen isotope data from three of the cores, augmented by radiocarbon ages from nearby Core RC11-83, and by correlation of paleointensity records for the one core with no oxygen isotope data. The relative paleointensity proxy records are the first from the South Atlantic and from the high to mid-latitude southern hemisphere. Prominent paleointensity lows at ?40 ka and ?65 ka, as well as many other features, can be correlated to paleointensity records of comparable resolution from the northern hemisphere. The records are attributable, in large part, to the global-scale field, and therefore have potential for inter-hemispheric correlation at a resolution difficult to achieve with isotope data alone.

Description: 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 Ocean1. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean**2, 3, 4, 5, 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**2 (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**5, 6. 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.

Description: Calcareous nannoplankton assemblages and benthic d18O isotopes of Pliocene deep-sea sediments of ODP site 1172 (East of Tasmania) have been studied to improve our knowledge of the Southern Ocean paleoceanography. Our study site is located just north of the Subtropical Front (STF), an ideal setting to monitor migrations of the STF during our study period, between 3.45 and 2.45 Ma. The assemblage identified at ODP site 1172 has been interpreted as characteristic for the transitional zone water mass, located south of the STF, based on: (i) the low abundances (〈 1%) of subtropical taxa, (ii) relatively high percentages of Coccolithus pelagicus, a subpolar type species, (iii) abundances from 2-10% of Calcidiscus leptoporus, a species that frequently inhabits the zone south of the STF and (iv) the high abundances of small Noelaerhabdaceae which at present dominates the zone south of the STF. Across our interval the calcareous nannoplankton manifests glacial-interglacial variability. We have identified cold events, characterized by high abundances of C. pelagicus which coincide with glacial periods, except during G7. After 3.1 Ma cold events are more frequent, in concordance with global cooling trends. Around 2.75 Ma, the interglacial stage G7 is characterized by anomalous low temperatures which most likely are linked to definite closure of the Central American Seaway (CAS), an event that is believed to have had global consequences. A gradual increase of very small Reticulofenestra across our section marks a significant trend in the small Noelaerhabdaceae species group and has been linked to a general enhanced mixing of the water column in agreement with previous studies. It is suggested that a rapid decline of small Gephyrocapsa after isotopic stage G7 might be related to the cooling observed in our study site after the closure of the CAS.

Description: Predicting the impact of ongoing anthropogenic CO2 emissions on calcifying marine organisms is complex, owing to the synergy between direct changes (acidification) and indirect changes through climate change (e.g., warming, changes in ocean circulation, and deoxygenation). Laboratory experiments, particularly on longer-lived organisms, tend to be too short to reveal the potential of organisms to acclimatize, adapt, or evolve and usually do not incorporate multiple stressors. We studied two examples of rapid carbon release in the geological record, Eocene Thermal Maximum 2 (~53.2 Ma) and the Paleocene Eocene Thermal Maximum (PETM, ~55.5 Ma), the best analogs over the last 65 Ma for future ocean acidification related to high atmospheric CO2 levels. We use benthic foraminifers, which suffered severe extinction during the PETM, as a model group. Using synchrotron radiation X-ray tomographic microscopy, we reconstruct the calcification response of survivor species and find, contrary to expectations, that calcification significantly increased during the PETM. In contrast, there was no significant response to the smaller Eocene Thermal Maximum 2, which was associated with a minor change in diversity only. These observations suggest that there is a response threshold for extinction and calcification response, while highlighting the utility of the geological record in helping constrain the sensitivity of biotic response to environmental change.

Description: Subtropical Gyres are an important constituent of the ocean-atmosphere system due to their capacity to store vast amounts of warm and saline waters. Here we decipher the sensitivity of the (sub)surface North Atlantic Subtropical Gyre with respect to orbital and millennial scale climate variability between ~140 and 70 ka, Marine Isotope Stage (MIS) 5. Using (isotope)geochemical proxy data from surface and thermocline dwelling foraminifers from Blake Ridge off the west coast of North America (ODP Site 1058) we show that the oceanographic development at subsurface (thermocline) level is substantially different from the surface ocean. Most notably, surface temperatures and salinities peak during the penultimate deglaciation (Termination II) and early MIS 5e, implying that subtropical surface ocean heat and salt accumulation might have resulted from a sluggish northward heat transport. In contrast, maximum thermocline temperatures are reached during late MIS 5e when surface temperatures are already declining. We argue that the subsurface warming originated from intensified Ekman downwelling in the Subtropical Gyre due to enhanced wind stress. During MIS 5a-d a tight interplay of the subtropical upper ocean hydrography to high latitude millennial-scale cold events can be observed. At Blake Ridge, the most pronounced of these high latitude cold events are related to surface warming and salt accumulation in the (sub)surface. Similar to Termination II, heat accumulated in the Subtropical Gyre probably due to a reduced Atlantic Meridional Overturning Circulation. Additionally, a southward shift and intensification of the subtropical wind belts lead to a decrease of on-site precipitation and enhanced evaporation, coupled to intensified gyre circulation. Subsequently, the northward advection of these warm and saline water likely contributed to the fast resumption of the overturning circulation at the end of these high latitude cold events.

Description: The Pacific Ocean is the largest water body on Earth, and circulation in the Pacific contributed significantly to climate evolution in the latest Cretaceous, the culmination of a period of long-term cooling. Here, we present new high-resolution late Campanian to Maastrichtian benthic and planktic foraminiferal stable isotope data and a neodymium (Nd) isotope record obtained from sedimentary ferromanganese oxide coatings of Ocean Drilling Program Hole 1210B from the tropical Pacific Ocean (Shatsky Rise). These new records resolve 13 million years in the latest Cretaceous, providing insights into changes in surface and bottom water temperatures and source regions of deep to intermediate waters covering the carbon isotope excursions of the Campanian-Maastrichtian Boundary Event (CMBE) and the Mid-Maastrichtian event (MME). Our new benthic foraminiferal d18O and Nd isotope records together with published Nd isotope data show markedly parallel trends across the studied interval over a broad range of bathyal to abyssal water depths interpreted to reflect changes in the intensity of deep-ocean circulation in the tropical Pacific. In particular, we observe a three-million-year-long period of cooler conditions in the early Maastrichtian (72.5 to 69.5 Ma) when a concomitant change toward less radiogenic seawater Nd isotope signatures probably marks a period of enhanced admixture and northward flow of deep waters with Southern Ocean provenance. We suggest this change to have been triggered by intensified formation and convection of deep waters in the high southern latitudes, a process that weakened during the MME (69.5 to 68.5 Ma). The early Maastrichtian cold interval is closely related to the negative and positive carbon isotope trends of the CMBE and MME. The millions-of-years long duration of these carbon cycle perturbations suggests a tectonic forcing of climatic cooling, possibly related to changes in ocean basin geometry and bathymetry.

Description: We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Description: Cool tropical sea surface temperatures (SSTs) are reported for warm Paleogene greenhouse climates based on the d18O of planktonic foraminiferal tests. These results are difficult to reconcile with models of greenhouse gas-forced climate. It has been suggested that this "cool tropics paradox" arises from postdepositional alteration of foraminiferal calcite, yielding erroneously high d18O values. Recrystallization of foraminiferal tests is cryptic and difficult to quantify, and the compilation of robust d18O records from moderately altered material remains challenging. Scanning electron microscopy of planktonic foraminiferal chamber-wall cross sections reveals that the basal area of muricae, pustular outgrowths on the chamber walls of species belonging to the genus Morozovella, contain no mural pores and may be less susceptible to postdepositional alteration. We analyzed the d18O in muricae bases of morozovellids from the central Pacific (Ocean Drilling Program Site 865) by ion microprobe using 10 mm pits with an analytical reproducibility of ±0.34 per mil (2 standard deviations). In situ measurements of d18O in these domains yield consistently lower values than those published for conventional multispecimen analyses. Assuming that the original d18O is largely preserved in the basal areas of muricae, this new d18O record indicates Early Paleogene (~49-56 Ma) tropical SSTs in the central Pacific were 4°-8°C higher than inferred from the previously published d18O record and that SSTs reached at least ~33°C during the Paleocene-Eocene thermal maximum. This study demonstrates the utility of ion microprobe analysis for generating more reliable paleoclimate records from moderately altered foraminiferal tests preserved in deep-sea sediments.

Description: Modern savannah grasslands were established during the late Miocene and Pliocene (8-3 million years ago). In the tropics, grasslands are dominated by grasses that use the C4 photosynthetic pathway, rather than the C3 pathway. The C4 pathway is better adapted to warm, dry and low-CO2 conditions, leading to suggestions that declining atmospheric CO2 levels, increasing aridity and enhanced rainfall seasonality allowed grasses using this pathway to expand during this interval. The role of fire in C4 expansion may have been underestimated. Here we use analyses of pollen, microscopic charcoal and the stable isotopic composition of plant waxes from a marine sediment core off the coast of Namibia to reconstruct the relative timing of changes in plant composition and fire activity for the late Miocene and Pliocene. We find that in southwestern Africa, the expansion of C4 grasses occurred alongside increasing aridity and enhanced fire activity. During further aridification in the Pliocene, the proportion of C4 grasses in the grasslands increased, while the grassland contracted and deserts and semi-deserts expanded. Our results are consistent with the hypothesis that ecological disturbance by fire was an essential feedback mechanism leading to the establishment of C4 grasslands in the Miocene and Pliocene.

Description: The impact of an asteroid at the Cretaceous/Paleogene (K/Pg) boundary triggered dramatic biotic, biogeochemical and sedimentological changes in the oceans that have been intensively studied. Paleo-biogeographical differences in the biotic response to the impact and its environmental consequences, however, have been less well documented. We present a high-resolution analysis of benthic foraminiferal assemblages at Southern Ocean ODP Site 690 (Maud Rise, Weddell Sea, Antarctica). At this high latitude site, late Maastrichtian environmental variability was high, but benthic foraminiferal assemblages were not less diverse than at lower latitudes, in contrast to those of planktic calcifiers. Also in contrast to planktic calcifiers, benthic foraminifera did not suffer significant extinction at the K/Pg boundary, but show transient assemblage changes and decreased diversity. At Site 690, the extinction rate was even lower (~3%) than at other sites. The benthic foraminiferal accumulation rate varied little across the K/Pg boundary, indicating that food supply to the sea floor was affected to a lesser extent than at lower latitude sites. Compared to Maastrichtian assemblages, Danian assemblages have a lower diversity and greater relative abundance of heavily calcified taxa such as Stensioeina beccariiformis and Paralabamina lunata. This change in benthic foraminiferal assemblages could reflect post-extinction proliferation of different photosynthesizers (thus food for the benthos) than those dominant during the Late Cretaceous, therefore changes in the nature rather than in the amount of the organic matter supplied to the seafloor. However, severe extinction of pelagic calcifiers caused carbonate supersaturation in the oceans, thus might have given competitive advantage to species with large, heavily calcified tests. This indirect effect of the K/Pg impact thus may have influenced the deep-sea dwellers, documenting the complexity of the effects of major environmental disturbance.

Description: Many genera of modern planktic foraminifera are adapted to nutrient-poor (oligotrophic) surface waters by hosting photosynthetic symbionts, but it is unknown how they will respond to future changes in ocean temperature and acidity. Here we show that ca. 40 Ma, some fossil photosymbiont-bearing planktic foraminifera were temporarily 'bleached' of their symbionts coincident with transient global warming during the Middle Eocene Climatic Optimum (MECO). At Ocean Drilling Program (ODP) Sites 748 and 1051 (Southern Ocean and mid-latitude North Atlantic, respectively), the typically positive relationship between the size of photosymbiont-bearing planktic foraminifer tests and their carbon isotope ratios (d13C) was temporarily reduced for ~100 k.y. during the peak of the MECO. At the same time, the typically photosymbiont-bearing planktic foraminifera Acarinina suffered transient reductions in test size and relative abundance, indicating ecological stress. The coincidence of minimum d18O values and reduction in test size-d13C gradients suggests a link between increased sea-surface temperatures and bleaching during the MECO, although changes in pH and nutrient availability may also have played a role. Our findings show that host-photosymbiont interactions are not constant through geological time, with implications for both the evolution of trophic strategies in marine plankton and the reliability of geochemical proxy records generated from symbiont-bearing planktic foraminifera.

Description: Deciphering the driving mechanisms of Earth system processes, including the climate dynamics expressed as paleoceanographic events, requires a complete, continuous, and high-resolution stratigraphy that is very accurately dated. In this study, we construct a robust astronomically calibrated age model for the middle Eocene to early Oligocene interval (31-43 Ma) in order to permit more detailed study of the exceptional climatic events that occurred during this time, including the Middle Eocene Climate Optimum and the Eocene/Oligocene transition. A goal of this effort is to accurately date the middle Eocene to early Oligocene composite section cored during the Pacific Equatorial Age Transect (PEAT, IODP Exp. 320/321). The stratigraphic framework for the new time scale is based on the identification of the stable long eccentricity cycle in published and new high-resolution records encompassing bulk and benthic stable isotope, calibrated XRF core scanning, and magnetostratigraphic data from ODP Sites 171B-1052, 189-1172, 199-1218, and 207-1260 as well as IODP Sites 320-U1333, and -U1334 spanning magnetic polarity Chrons C12n to C20n. Subsequently we applied orbital tuning of the records to the La2011 orbital solution. The resulting new time scale revises and refines the existing orbitally tuned age model and the Geomagnetic Polarity Time Scale from 31 to 43 Ma. Our newly defined absolute age for the Eocene/Oligocene boundary validates the astronomical tuned age of 33.89 Ma identified at the Massignano (Italy) global stratotype section and point. Our compilation of geochemical records of climate-controlled variability in sedimentation through the middle-to-late Eocene and early Oligocene demonstrates strong power in the eccentricity band that is readily tuned to the latest astronomical solution. Obliquity driven cyclicity is only apparent during very long eccentricity cycle minima around 35.5 Ma, 38.3 Ma and 40.1 Ma.

Description: The largest increase in export production in the eastern Pacific of the last 5.3 Myr (million years) occurred between 2.2 and 1.6 Myr, a time of major climatic and oceanographic reorganization in the region. Here, we investigate the causes of this event using reconstructions of export production, nutrient supply and oceanic conditions across the Pliocene-Pleistocene in the eastern equatorial Pacific (EEP) for the last 3.2 Myr. Our results indicate that the export production peak corresponds to a cold interval marked by high nutrient supply relative to consumption, as revealed by the low bulk sedimentary 15N/14N (d15N) and alkenone-derived sea surface temperature (SST) values. This ~0.6 million year long episode of enhanced delivery of nutrients to the surface of the EEP was predominantly initiated through the upwelling of nutrient-enriched water sourced in high latitudes. In addition, this phenomenon was likely promoted by the regional intensification of upwelling in response to the development of intense Walker and Hadley atmospheric circulations. Increased nutrient consumption in the polar oceans and enhanced denitrification in the equatorial regions restrained nutrient supply and availability and terminated the high export production event.

Description: Salinity increase in the subtropical gyre system may have pre-conditioned the North Atlantic Ocean for a rapid return to stronger overturning circulation and high-latitude warming following meltwater events during the Last Glacial period. Here we investigate the Gulf Stream - subtropical gyre system properties over Dansgaard-Oeschger (DO) cycles 14 to 12, including Heinrich ice-rafting event 5. During the Holocene and Last Glacial Maximum a positive gradient in surface dwelling planktonic foraminifera d18O (Globigerinoides ruber) can be observed between the Gulf Stream and subtropical gyre, due to decreasing temperature, increasing salinity, and a change from summer to year-round occurrence of G. ruber. We assess whether this gradient was a common feature during stadial-interstadial climate oscillations of Marine Isotope Stage 3, by comparing existing G. ruber d18O from ODP Site 1060 (subtropical gyre location) and new data from ODP Site 1056 (Gulf Stream location) between 54 and 46 ka. Our results suggest that this gradient was largely absent during the period studied. During the major warm DO interstadials 14 and 12 we infer a more zonal and wider Gulf Stream, influencing both ODP Sites 1056 and 1060. A Gulf Stream presence during these major interstadials is also suggested by the large vertical d18O gradient between shallow dwelling planktonic foraminifera species, especially G. ruber, and the deep dwelling species Globorotalia inflata at site 1056, which we associate with strong summer stratification and Gulf Stream presence. A major reduction in this vertical d18O gradient from 51 ka until the end of Heinrich event 5 at 48.5 ka suggests site 1056 was situated within the subtropical gyre in this mainly cold period, from which we infer a migration of the Gulf Stream to a position nearer to the continental shelf, indicative of a narrower Gulf Stream with possibly reduced transport.

Description: The western Lau Basin, between the Central and Eastern Lau Spreading Centers and the Lau Ridge, contains several small, elongate, fault-bounded, partially sediment-filled sub-basins. Sites 834 and 835 were drilled in the oldest part of the Lau Basin in two of these small extensional basins close to the Lau Ridge, formed on late Miocene to early Pliocene oceanic crust. Both sites show a similar sediment sequence that consists of clayey nannofossil oozes and mixed sediments interbedded with epiclastic vitric sands and silts. The vitric sands and silts are largely restricted to the deeper part of the sediment column (early Pliocene-late Pliocene), and the upper part of the sediment column at both sites consists of a distinctive sequence of brown clayey nannofossil ooze, stained by iron and manganese oxyhydroxides (late Pliocene-Holocene). However, the clayey nannofossil ooze sequence at Site 835 is anomalously thick and contains several medium- to very thick beds of matrix-supported, mud-clast conglomerate (interpreted as muddy debris-flow deposits), together with large amounts of redeposited clayey nannofossil ooze and coherent rafted blocks of older hemipelagic material. Redeposited clayey nannofossil oozes can be distinguished from hemipelagic nannofossil oozes using several sedimentological criteria. These include variation in color hue and chroma, presence or absence of bioturbation, presence or absence of scattered foraminifers, grain-size characteristics, variability in calcium carbonate content, presence or absence of pumice clasts, and micropaleontology. Clayey nannofossil ooze turbidites and hemipelagites are also geochemically distinct, with the turbidites being commonly enriched in Mn, Ni, Pb, Zn, Cr, and P. The sediment sequence at Site 835 is dominated by allochthonous sediments, either muddy debris-flow deposits, coherent rafted blocks, or thick clayey nannofossil ooze turbidites. Since 2.9 Ma, only 25% of the 133 m of sediments deposited represents hemipelagic deposition, with an average sedimentation rate of 1.5 cm/k.y.. Allochthonous sediments were the main sediment type deposited during the Brunhes geomagnetic Epoch and make up 80% of the thickness of sediment deposited during this period. Short intervals of mainly hemipelagic deposition occurred from 0.4 to 0.9 Ma, 1.0 to 1.4 Ma, and 1.7 to 2.1 Ma. However, allochthonous sediments were again the dominant sediment type deposited between 2.1 and 2.5 Ma, with a large slide complex emplaced around 2.5 Ma. We conclude that the adjacent high ground, surrounding the basin in which Site 835 was drilled, was affected by marked instability throughout the late Pliocene and Pleistocene. In contrast, sedimentation at Site 834 during this period has been dominated by hemipelagic deposition, with redeposited sediments making up slightly less than 17% of the total thickness of sediment deposited since 2.3 Ma. However, there was a marked increase in frequency and magnitude of redeposited sediments at around 0.2 Ma at Site 834, which broadly corresponds to the onset of a major episode of turbidite and debris-flow emplacement beginning about 0.4 Ma at Site 835. This episode of instability at both sites may be the effect of the approach and passing of the Central Lau propagator at the latitude of Sites 834 and 835 at about 0.5 Ma.

Description: In addition to Oceanic Anoxic Event 2 (OAE2), other perturbations of the carbon cycle occurred during the Cenomanian and Turonian, of which the Middle Cenomanian Event (MCE) is the most prominent one. In palaeoecological publications, however, this event is strongly underrepresented in contrast to the well-studied OAE2. In order to fill this gap, we have studied Early Cenomanian to Late Turonian calcareous nannofossil and benthic foraminiferal assemblages of Ocean Drilling Program Site 1260 at Demerara Rise (western equatorial North Atlantic), in order to decipher biotic changes throughout this interval and especially across the MCE. Our data show distinctive changes in the relative abundance of certain calcareous nannofossil taxa and a drastic decrease in benthic foraminiferal diversities and abundances associated with the MCE. In the lower part of the studied section and prior to the MCE, a mixed water-column with high nutrient availability in the upper photic zone is suggested based on very high relative abundances of the mesotrophic/eutrophic nannofossil species Biscutum constans. Around the MCE interval, certain nannofossil taxa (e.g., Rhagodiscus asper) show a distinctive decrease in relative abundance while others become more dominant. Taxa which increase in relative abundance after the MCE (e.g., Eprolithus floralis) are interpreted as either having favoured less eutrophic surface-waters or having inhabited deeper parts of the photic zone in a well stratified water-column. This interpretation is supported by published oxygen isotope and TEX86 data, which suggest increased water-column stratification starting with the MCE and lasting to the end of the Cenomanian stage, as a result of the implementation of a saline intermediate- to deep-water mass during this interval. Our study shows that the MCE was a significant biotic event in the Cenomanian/Turonian equatorial Atlantic, characterised by a lasting change of surface- and bottom-water ecosystems.

Description: Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

Description: The role that meridional overturning circulation (MOC) patterns played in poleward heat transport during the extreme warmth of the Early to Late Cretaceous is a fundamental and unresolved question in climate dynamics. In order to address this question we must determine where deep waters formed, and how they may have circulated during periods of extreme warmth. Here we present late Albian through Maastrichtian (105 to 65 Ma) Nd isotope records from Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) sites in the proto-Indian Ocean and the tropical Pacific. Comparison of these data with previously published records indicates deep-water formation in the Indian sector of the Southern Ocean began at least ∼105 Ma, extending the record of high-latitude convection back into the Early Cretaceous prior to the peak warmth of the mid-Cretaceous. The growing body of data supports a mode of MOC in part characterized by high-latitude downwelling during the peak of greenhouse warmth of the Mesozoic and Cenozoic. However, this mode of MOC likely was characterized by numerous locations of deep convection that were regionally important, but not significant in terms of a globally overturning circulation due to paleogeographic and bathymetric barriers.

Description: Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -〉 D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Description: Barium concentrations were measured in pore fluids and sediments from the shallow forearc of the Costa Rica subduction zone to investigate the impact of progressive barite dissolution coupled to [SO4]2- depletion on the residual sediment Ba flux to the volcanic arc and mantle. At the Costa Rica subduction zone, the entire sediment section entering the trench is underthrust beneath the prism sediments of the overriding plate. Dissolved [SO4]2- concentrations measured in the reference sediment section in the incoming plate at ODP Site 1039/1253 vary between 13 and 29 mM. At ODP Site 1040/1254, 1.6 km arcward from the trench, [SO4]2- is depleted in the ~370 m of prism sediments as well as in the upper 30 m of the underthrust sediments. This suggests that, upon subduction, [SO4]2- diffusion from seawater into the underthrust sediment section ceases and the available pore fluid [SO4]2- at the top of the section is consumed by active microbial [SO4]2- reduction. Because the only remaining source of [SO4]2- is in the underthrust sediments, the depth of [SO4]2- depletion in the underthrust sediments must increase with distance from the trench. Dissolved Ba2+ concentrations in the uppermost underthrust sediments at Site 1040/1254 are several orders of magnitude greater than in the reference sediment section at Site 1039/1253, indicating intense barite dissolution coupled to [SO4]2- depletion. This is corroborated by a 50% decrease in the barite content within this unit. As a result of tectonic compaction, the dissolved Ba2+ released from barite dissolution is transported seaward and reprecipitated as barite when reaching [SO4]2- -rich fluids. As [SO4]2- depletion continues arcward, greater losses of sedimentary barite must occur in the subducting sediments. If all the barite is dissolved from the subducting sediment section, 60% of the incoming bulk sediment Ba will be distilled from the sediments in the shallow forearc. Balancing the Ba output flux with this lower input flux requires a much larger sediment component recycled to the volcanic arc than previously suggested. These results indicate that diagenetic mobilization of Ba from barite can have a profound impact on the chemical composition of sediments recycled to the arc and mantle, and should be considered in the global budget of subducted sediments.

Description: Spatiotemporal patterns of carbonate dissolution provide a critical constraint on carbon input during an ancient (~55.5 Ma) global warming event known as the Paleocene-Eocene thermal maximum (PETM), yet the magnitude of lysocline shoaling in the Southern Ocean is poorly constrained due to limited spatial coverage in the circum-Antarctic region. This shortcoming is partially addressed by comparing patterns of carbonate sedimentation at the Site 690 PETM reference section to those herein reconstructed for nearby Site 689. Biochemostratigraphic correlation of the two records reveals that the first ~36 ka of the carbon isotope excursion (CIE) signaling PETM conditions is captured by the Site 689 section, while the remainder of the CIE interval and nearly all of the CIE recovery are missing due to a coring gap. A relatively expanded stratigraphy and higher carbonate content at mid-bathyal Site 689 indicate that dissolution was less severe than at Site 690. Thus, the bathymetric transect delimited by these two PETM records indicates that the lysocline shoaled above Site 689 (~1,100 m) while the calcite compensation depth remained below Site 690 (~1,900 m) in the Weddell Sea region. The ensuing recovery of carbonate sedimentation conforms to a bathymetric trend best explained by gradual lysocline deepening as negative feedback mechanisms neutralized ocean acidification. Further, biochemostratigraphic evidence indicates the tail end of the CIE recovery interval at both sites has been truncated by a hiatus most likely related to vigorous production and advection of intermediate waters.

Description: We have analyzed the Nd isotopic composition of both ancient seawater and detrital material from long sequences of carbonated oozes of the South Indian Ocean which are ODP Site 756 (Ninety East Ridge (-30°S), 1518 m water depth) and ODP Site 762 (Northwest Australian margin, 1360 m water depth). The measurements indicate that the epsilon-Nd changes in Indian seawater over the last 35 Ma result from changes in the oceanic circulation, large volcanic and continental weathering Nd inputs. This highlights the diverse nature of those controls and their interconnections in a small area of the ocean. These new records combined with those previously obtained at the equatorial ODP Sites 757 and 707 in the Indian Ocean (Gourlan et al., 2008, doi:10.1016/j.epsl.2007.11.054) established that the distribution of intermediate seawater epsilon-Nd was uniform over most of the Indian Ocean from 35 Ma to 10 Ma within a geographical area extending from 40°S to the equator and from -60°E to 120°E. However, the epsilon-Nd value of Indian Ocean seawater which kept an almost constant value (at about -7 to -8) from 35 to 15 Ma rose by 3 epsilon-Nd units from 15 to 10 Ma. This sharp increase has been caused by a radiogenic Nd enrichment of the water mass originating from the Pacific flowing through the Indonesian Passage. Using a two end-members model we calculated that the Nd transported to the Indian Ocean through the Indonesian Pathway was 1.7 times larger at 10 Ma than at 15 Ma. The Nd isotopic composition of ancient seawater and that of the sediment detrital component appear to be strongly correlated for some specific events. A first evidence occurs between 20 and 15 Ma with two positive spikes recorded in both epsilon-Nd signals that are clearly induced by a volcanic crisis of, most likely, the St. Paul hot-spot. A second evidence is the very large epsilon-Nd decrease recorded at ODP Sites 756 and 762 during the past 10 Ma which has never been previously observed. The synchronism between the epsilon-Nd decrease in seawater from 10 to 5 Ma and evidences of desertification in the western part of the nearly Australian continent suggests enhanced weathering inputs in this ocean from this continent as a result of climatic changes.

Description: Geomagnetic excursions are recognized as intrinsic features of the Earth's magnetic field. High-resolution records of field behaviour, captured in marine sedimentary cores, present an opportunity to determine the temporal and geometric character of the field during geomagnetic excursions and provide constraints on the mechanisms producing field variability. We present here the highest resolution record yet published of the Blake geomagnetic excursion (~125 ka) measured in three cores from Ocean Drilling Program (ODP) Site 1062 on the Blake-Bahama Outer Ridge. The Blake excursion has a controversial structure and timing but these cores have a sufficiently high sedimentation rate (~10cm/ka) to allow detailed reconstruction of the field behaviour at this site during the excursion. Palaeomagnetic measurements of the cores reveal rapid transitions (〈500 yr) between the contemporary stable normal polarity and a completely reversed state of long duration which spans a stratigraphic interval of 0.7 m. We determine the duration of the reversed state during the Blake excursion using oxygen isotope stratigraphy, combined with 230Th excess measurements to assess variations in the sedimentation rates through the sections of interest. This provides an age and duration for the Blake excursion with greater accuracy and with constrained uncertainty. We date the directional excursion as falling between 129 and 122 ka with a duration for the deviation of 6.5±1.3 kyr. The long duration of this interval and the fully reversed field suggest the existence of a pseudo-stable, reversed dipole field component during the excursion and challenge the idea that excursions are always of short duration.

Description: The MBT-CBT proxy for the reconstruction of paleotemperatures and past soil pH is based on the distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids. The Methylation of Branched Tetraether (MBT) and the Cyclisation of Branched Tetraether (CBT) indices were developed to quantify these distributions, and significant empirical relations between these indices and annual mean air temperature (MAT) and/or soil pH were found in a large data set of soils. In this study, we extended this soil dataset to 278 globally distributed surface soils. Of these soils, 26% contains all nine brGDGTs, while in 63% of the soils the seven most common brGDGTs were detected, and the latter were selected for calibration purposes. This resulted in new transfer functions for the reconstruction of pH based on the CBT index: pH = 7.90-1.97 × CBT (r**2 = 0.70; RMSE = 0.8; n = 176), as well as for MAT based on the CBT index and methylation index based on the seven most abundant GDGTs (defined as MBT'): MAT = 0.81-5.67 × CBT + 31.0 × MBT' (r**2 = 0.59; RMSE = 5.0 °C; n = 176). The new transfer function for MAT has a substantially lower correlation coefficient than the original equation (r**2 = 0.77). To investigate possible improvement of the correlation, we used our extended global surface soil dataset to statistically derive the indices that best describe the relations of brGDGT composition with MAT and soil pH. These new indices, however, resulted in only a relatively minor increase in correlation coefficients, while they cannot be explained straightforwardly by physiological mechanisms. The large scatter in the calibration cannot be fully explained by local factors or by seasonality, but MAT for soils from arid regions are generally substantially (up to 20 °C) underestimated, suggesting that absolute brGDGT-based temperature records for these areas should be interpreted with caution. The applicability of the new MBT'-CBT calibration function was tested using previously published MBT-CBT-derived paleotemperature records covering the last deglaciation in Central Africa and East Asia, the Eocene-Oligocene boundary and the Paleocene-Eocene thermal maximum. The results show that trends remain similar in all records, but that absolute temperature estimates and the amplitude of temperature changes are lower for most records, and generally in better agreement with independent proxy data.

Description: In the New Jersey Coastal Plain, a silty to clayey sedimentary unit (the Marlboro Formation) represents deposition during the Paleocene-Eocene thermal maximum (PETM). This interval is remarkably different from the glauconitic sands and silts of the underlying Paleocene Vincentown and overlying Eocene Manasquan Formation. We integrate new and published stable isotope, biostratigraphic, lithostratigraphic and ecostratigraphic records, constructing a detailed time frame for the PETM along a depth gradient at core sites Clayton, Wilson Lake, Ancora and Bass River (updip to downdip). The onset of the PETM, marked by the base of the carbon isotope excursion (CIE), is within the gradual transition from glauconitic silty sands to silty clay, and represented fully at the updip sites (Wilson Lake and Clayton). The CIE "core" interval is expanded at the updip sites, but truncated. The CIE "core" is complete at the Bass River and Ancora sites, where the early part of the recovery is present (most complete at Ancora). The extent to which the PETM is expressed in the sediments is highly variable between sites, with a significant unconformity at the base of the overlying lower Eocene sediments. Our regional correlation framework provides an improved age model, allowing better understanding of the progression of environmental changes during the PETM. High-resolution benthic foraminiferal data document the change from a sediment-starved shelf setting to a tropical, river-dominated mud-belt system during the PETM, probably due to intensification of the hydrologic cycle. The excellent preservation of foraminifera during the PETM and the lack of severe benthic extinction suggest there was no extreme ocean acidification in shelf settings.

Description: The rate of uranium accumulation in oceanic sediments from seawater is controlled by bottom water oxygen concentrations and organic carbon fluxes-two parameters that are linked to deep ocean storage of CO2. To investigate glacial-interglacial changes in what is known as authigenic U, we have developed a rapid method for its determination as a simple addition to a procedure for foraminiferal trace element analysis. Foraminiferal calcite acts as a low U substrate (U/Ca 〈 15 nmol/mol) upon which authigenic U accumulates in reducing sediments. We measured a downcore record of foraminiferal U/Ca from ODP Site 1090 in the South Atlantic and found that U/Ca ratios increase by 70-320 nmol/mol during glacial intervals. There is a significant correlation between U/Ca records of benthic and planktonic foraminiferal species and between U/Ca and bulk sediment authigenic U. These results indicate that elevated U/Ca ratios are attributable to the accumulation of authigenic U coatings in sediments. Foraminiferal Mn/Ca ratios were lower during the glacial intervals, suggesting that the observed U accumulation on the shells is not directly linked to U incorporation into secondary manganese phases. Thus, foraminiferal U/Ca ratios may provide useful information on past changes in sediment redox conditions.

Description: This work presents the stratigraphic distribution of several species of calcareous nannofossil in the middle Eocene early-Oligocene from four Ocean Drilling Program (ODP) sites located between 60° and 65°S paleolatitude in the Southern Atlantic and Indian Oceans. Useful nannofossil datums that should facilitate construction of age-models and contribute to an integrated chronology for the upper Paleogene Southern Ocean sediments from ~42 to 33 Ma are summarized. The distribution patterns of calcareous nannofossils, studied by means of quantitative and semiquantitative methods, provide an improvement of the classical Southern Ocean biozonations, introducing new biostratigraphically useful biohorizons, and testing their reproducibility within and outside the region.

Description: Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Description: We present modern B/Ca core-top calibrations for the epifaunal benthic foraminifer Nuttallides umbonifera and the infaunal Oridorsalis umbonatus to test whether B/Ca values in these species can be used for the reconstruction of paleo-D[[CO3]2-]. O. umbonatus originated in the Late Cretaceous and remains extant, whereas N. umbonifera originated in the Eocene and is the closest extant relative to Nuttallides truempyi, which ranges from the Late Cretaceous through the Eocene. We measured B/Ca in both species in 35 Holocene sediment samples from the Atlantic, Pacific and Southern Oceans. B/Ca values in epifaunal N. umbonifera (~ 85-175 µmol/mol) are consistently lower than values reported for epifaunal Cibicidoides (Cibicides) wuellerstorfi (130-250 µmol/mol), though the sensitivity of D[[CO3]2-] on B/Ca in N. umbonifera (1.23 ± 0.15) is similar to that in C. wuellerstorfi (1.14 ± 0.048). In addition, we show that B/Ca values of paired N. umbonifera and its extinct ancestor, N. truempyi, from Eocene cores are indistinguishable within error. In contrast, both the B/Ca (35-85 µmol/mol) and sensitivity to D[[CO3]2-] (0.29 ± 0.20) of core-top O. umbonatus are considerably lower (as in other infaunal species), and this offset extends into the Paleocene. Thus the B/Ca of N. umbonifera and its ancestor can be used to reconstruct bottom water D[[CO3]2?], whereas O. umbonatus B/Ca appears to be buffered by porewater [[CO3]2-] and suited for constraining long-term drift in seawater B/Ca.

Description: Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/4He ratios from fluid inclusions within pyrite and anhydrite and the d18O signature of anhydrite. Depressed 3He/4He ratios of 0.2-6.91RA appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. d18O anhydrite ratios are 6.5 per mil to 11 per mil for Snowcap and 6.4 per mil to 11.9 per mil for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing d18O equilibration. By comparing new d18O values for anhydrite with corresponding published 87Sr/86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.