Stable carbon and oxygen isotope compositions of Eocene benthic foraminifera from ODP Site 207-1258

'Hyperthermals' are intervals of rapid, pronounced global warming known from six episodes within the Palaeocene and Eocene epochs (~65-34 million years (Myr) ago) (Zachos et al., 2005, doi:10.1126/science.1109004; 2008, doi:10.1038/nature06588; Roehl et al., 2007, doi:10.1029/2007GC001784; Thomas et al., 2000; Cramer et al., 2003, doi:10.1029/2003PA000909; Lourens et al., 2005, doi:10.1038/nature03814; Petrizzo, 2005, doi:10.2973/odp.proc.sr.198.102.2005; Sexton et al., 2006, doi:10.1029/2005PA001253; Westerhold et al., 2007, doi:10.1029/2006PA001322; Edgar et al., 2007, doi:10.1038/nature06053; Nicolo et al., 2007, doi:10.1130/G23648A.1; Quillévéré et al., 2008, doi:10.1016/j.epsl.2007.10.040; Stap et al., 2010, doi:10.1130/G30777.1). The most extreme hyperthermal was the 170 thousand year (kyr) interval (Roehl et al., 2007) of 5-7 °C global warming (Zachos et al., 2008) during the Palaeocene-Eocene Thermal Maximum (PETM, 56 Myr ago). The PETM is widely attributed to massive release of greenhouse gases from buried sedimentary carbon reservoirs (Zachos et al., 2005; 2008; Lourenbs et al., 2005; Nicolo et al., 2007; Dickens et al., 1995, doi:10.1029/95PA02087; Dickens, 2000; 2003, doi:10.1016/S0012-821X(03)00325-X; Panchuk et al., 2008, doi:10.1130/G24474A.1) and other, comparatively modest, hyperthermals have also been linked to the release of sedimentary carbon (Zachos et al., 2008, Lourens et al., 2005; Nicolo et al., 2007; Dickens, 2003; Panchuk et al., 2003). Here we show, using new 2.4-Myr-long Eocene deep ocean records, that the comparatively modest hyperthermals are much more numerous than previously documented, paced by the eccentricity of Earth's orbit and have shorter durations (~40 kyr) and more rapid recovery phases than the PETM. These findings point to the operation of fundamentally different forcing and feedback mechanisms than for the PETM, involving redistribution of carbon among Earth's readily exchangeable surface reservoirs rather than carbon exhumation from, and subsequent burial back into, the sedimentary reservoir. Specifically, we interpret our records to indicate repeated, large-scale releases of dissolved organic carbon (at least 1,600 gigatonnes) from the ocean by ventilation (strengthened oxidation) of the ocean interior. The rapid recovery of the carbon cycle following each Eocene hyperthermal strongly suggests that carbon was resequestered by the ocean, rather than the much slower process of silicate rock weathering proposed for the PETM (Zachos et al., 2005; 2003). Our findings suggest that these pronounced climate warming events were driven not by repeated releases of carbon from buried sedimentary sources (Zachos et al., 2008, Lourens et al., 2005; Nicolo et al., 2007; Dickens, 2003; Panchuk et al., 2003) but, rather, by patterns of surficial carbon redistribution familiar from younger intervals of Earth history.

(Table S1) Age determination of ODP Site 202-1240

Interannual-decadal variability in the equatorial Pacific El Niño-Southern Oscillation (ENSO) induces climate changes at global scale, but its potential influence during past global climate change is not yet well constrained. New high-resolution eastern equatorial Pacific proxy records of thermocline conditions present new evidence of strong orbital control in ENSO-like variability over the last 275,000 years. Recurrent intervals of saltier thermocline waters are associated with the dominance of La Niña-like conditions during glacial terminations, coinciding with periods of low precession and high obliquity. The parallel dominance of d13C-depleted waters supports the advection of Antarctic origin waters toward the tropical thermocline. This "oceanic tunneling" is proposed to have reinforced orbitally induced changes in ENSO-like variability, composing a complex high- and low-latitude feedback during glacial terminations.

Calculation of paleoproductivity during the Eocene-Oligocene transition of ODP Site 113-689

High-resolution records of carbon and oxygen isotopes and benthic foraminiferal accumulation rates for the Eocene-Oligocene section at Ocean Drilling Program Site 689 (Maud Rise, Weddell Sea; paleodepth about 1500 m) were used to infer variations in paleoproductivity in relation to changes in climate and ventilation of the deeper-water column. The benthic foraminiferal abundance and isotope records show short-term fluctuations at periodicities of 100 and 400 ka, implying orbitally driven climatic variations. Both records suggest that intermediate-depth water chemistry and primary productivity changed in response to climate. During the Eocene, productivity increased during cold periods and during cold-to-warm transitions, possibly as a result of increased upwelling of nutrient-rich waters. In the Oligocene, in contrast, productivity maxima occurred during intervals of low delta18O values (presumably warmer periods), when a proto-polar front moved to the south of the location of Site 689. This profound transition in climate-productivity patterns occurred around 37 Ma, coeval with rapid changes toward increasing variability of the oxygen and carbon isotope and benthic abundance records and toward larger-amplitude delta18O fluctuations. Therefore, we infer that, at this time, temperature fluctuations increased and a proto-polar front formed in conjunction with the first distinct pulsations in size of the Antarctic ice sheet. We speculate that this major change might have resulted from an initial opening of the Drake Passage at 37 Ma, at least for surface- and intermediate-water circulation.

Geochemistry of Baltic Sea sediments and porewaters

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link between iron oxyhydroxide dissolution and release of P from Baltic Sea sediments, we show that preferential remineralization of P with respect to carbon (C) and nitrogen (N) during degradation of organic matter plays a key role in determining the surplus of bioavailable P in the water column. Preferential remineralization of P takes place both in the water column and upper sediments and its rate is shown to be redox-dependent, increasing as reducing conditions become more severe at greater water-depth in the deep basins. Existing Redfield-based biogeochemical models of the Baltic may therefore underestimate the imbalance between N and P availability for primary production, and hence the vulnerability of the Baltic to sustained eutrophication via the fixation of atmospheric N. However, burial of organic P is also shown to increase during multidecadal intervals of expanded hypoxia, due to higher net burial rates of organic matter around the margins of the deep basins. Such intervals may be characterized by basin-scale acceleration of all fluxes within the P cycle, including productivity, regeneration and burial, sustained by the relative accessibility of the water column P pool beneath a shallow halocline.

Physical properties of sediment core AND-2A

Whole-core measurements of Wet Bulk Density (WBD), compressional (P)-wave velocity (Vp), and Magnetic Susceptibility were measured at a sampling interval of 1 or 2 centimetres (cm) throughout the AND-2A drill core for initial core characterisation and on-site correlation with seismic modeling to predict target-reflector depth. Measurements were made using a GEOTEK (Multi-Sensor-Core-Logger MSCL). Density and velocity standards were measured together with core runs of 3-6 metres (m) (and occasionally up to 18 m) throughout the entire depth range to monitor data quality. Drift of the magnetic susceptibility sensor was also monitored and corrected where necessary. These physical properties show a large range of values, reflecting the different nature of the various lithologies including extremely high velocity and density values in individual clasts, and the effects of cementation on porosity. A downcore increase in WBD and Vp occurs in the upper 200 m, however, no systematic trend exists at greater depths although large fluctuations on a m-decimetre- (dm) scale occur. Magnetic susceptibility is generally low (<100 x 10-5 SI), however, four intervals of high (>600 x 10-5 SI) susceptibility occur at 560, 800, 980 and 1 080 mbsf, indicating a relatively greater contribution of volcanic-derived material to the core site in the lower half of the AND-2A core.

Core correlation data and revised composite depth scale of Exp302 (ACEX) cores

Expedition 302 of the Integrated Ocean Drilling Program (IODP), also known as the Arctic Coring Expedition (ACEX), successfully penetrated a sequence of Cenozoic sediments draping the crest of the Lomonosov Ridge in the central Arctic Ocean. The cumulative sedimentary record spans the last 57 m.y. and was recovered from three sites located within 15 km of each other. Merging the recovered cores onto a common depth scale that accurately reflects their stratigraphic placement below the seafloor is a fundamental step toward interpreting this unique sedimentary record. However, the lack of overlapping recovery in adjacent holes and intervals of high core disturbance complicated traditional methods of stratigraphic correlation. Here we present a revised composite depth scale for the ACEX sediments, generated in part by performing a regional stratigraphic correlation with sediments recovered from previous expeditions to the Lomonosov Ridge. The revised depth scale also reassesses the offsets for cores in the upper 55 meters below seafloor, where no overlapping recovery was acquired, and proposes modifications to these depths.

Magnetostratigraphy of DSDP Leg 94 sediments

The primary objective of DSDP Leg 94 was to obtain continuous paleoclimatic records along a roughly north-south transect in the North Atlantic. The magnetostratigraphy of 21 holes at 6 sites cored with the hydraulic piston corer and extended-core-barrel corer is presented here and establishes an independent chronology for these sediments. Nearly complete records were obtained for the last 2.5 m.y.; in addition, deeper drilling at three sites to satisfy tectonic and paleoceanographic objectives produced older sections suitable for magnetostratigraphic study, allowing first-order correlations of the polarity sequences with calcareous and siliceous micro fossil events. The sections with high sediment accumulation rates yielded very detailed records of polarity history and allowed three short normal-polarity zones within the Matuyama Chronozone to be detected, in addition to the Jaramillo and Olduvai subchronozones. A short reversed-polarity zone also occurs, within the upper intervals of the Gauss Chronozone. These short zones are present in multiple holes, ruling out the possibility that they might be of local origin. Correlation of these short zones with radiometrically dated polarity zones in igneous rocks strongly supports the interpretation of these polarity zones as records of true geomagnetic polarity chrons.

High resolution geochemical analyses of ODP Leg 119 samples

Higher resolution pore-water samples were recovered at intervals of 0.3 to 3 m from selected cores during Leg 119 in order to identify zones where active geochemical reactions were occurring. In addition to shipboard measurements, solid- and dissolved-phase samples were analyzed at my shore-based laboratory. Solid-phase samples were analyzed for redox conditions, carbon, total metals, and leachable metals. Pore-water samples were analyzed for ammonia, silica, sulfate, and major cations. Data are presented in tables for 400 samples from Site 739 in Prydz Bay, East Antarctica, and Sites 736, 737, 738, 744, 745, and 746 at the Kerguelen Ridge, South Indian Ocean.

Stable oxygen isotope records of different benthic foraminiferal species of core GeoB3004-1 from the western Arabian Sea

The stable isotope composition of one epifaunal and three infaunal benthic foraminiferal species of a sediment core from 1800 m water depth of the western Arabian Sea was determined to evaluate deepwater oxygenation, organic matter remineralization, and early diagenetic processes during the past 190,000 years. The d18O records reveal species-specific metabolic effects, susceptibility to changes in carbonate ion concentration, and supralysoclinal calcite dissolution. The foraminiferal d13C records reveal changes in the stable carbon isotope gradients of pore water dissolved inorganic carbon (d13CDIC) and in the microhabitat depth of infaunal species. Maximum d13CDIC offsets between bottom and pore waters ranged between mean values of 0.8 and 1.2% corresponding to estimates of deepwater oxygen concentration between approximately 1 and 2.7 ml/l. Intervals of improved deepwater oxygenation coincided with high benthic foraminiferal diversity and indicate the admixture of well-oxygenated deepwater masses during interglacials. During interglacial maxima the d13C difference between epifauna and shallow infauna indicates highest organic matter remineralization rates at times of maximum organic matter fluxes.

Calcareous nannofossils of ODP Sites 149-897 and 149-901

Mesozoic calcareous nannofossil assemblages recovered during Ocean Drilling Program Leg 149 from the Iberia Abyssal Plain off the coast of Portugal were examined to determine the age of the rifting processes that affected the western Iberia Margin. Dark carbonaceous claystones (black shales) recovered from Site 901 contain highly diverse and abundant Tithonian calcareous nannofossil assemblages. Careful examination and documentation of this material has extended the ranges of numerous Jurassic and Cretaceous species and detailed a significant Late Jurassic assemblage turnover observed in the calcareous nannofossil record. The Lower Cretaceous sequence consists of intervals of serpentinized peridotite intercalated between various breccias and dark claystones. With the exception of a few samples, calcareous nannofossils are few and moderately preserved. The age of nannofossils within these varied sedimentary lithologies ranges from the late Barremian to the late Aptian. Eight new species are described: Ansulasphaera covingtonii, Clepsilithus meniscus, Conusphaera sinespina, Crepidolithus parvulus, Diazomatholithus galicianus, Percivalia arata, Rotelapillus pleoseptatus, and Tranolithus incus. Also proposed are five new combinations.

(Table 2) Stable carbon and oxygen isotope record of benthic foraminifera of eastern Mediterranean Sea sediment cores

The paleoproductivity, paleo-oxygenation, and paleohydrographic configuration of the southeastern Mediterranean during the late Holocene was reconstructed on the basis of the isotopic composition of the epibenthic Heterolepa floridana, shallow-endobenthic Uvigerina mediterranea, and the deeper endobenthic Bulimina inflata from two high-resolution cores GA-112 (470 m) and GA-110 (670 m). The Delta d13C between H. floridana and U. mediterranea reveals four intervals of enhanced productivity, from 3.3-2.6, 2.3-1.9, 1.5-1.1, and 0.8-0.4 kyr BP, coinciding with increased nutrient supply by the Nile River. The entire basin was well aerated, with oxygen consumption varying between 1.0 and 3.5 mL O2/L. Oxygen consumption increases toward present day, probably because of higher accumulation of total organic carbon at 1.7 kyr BP, coinciding with the appearance of the mesotropic benthic species. The hydrographic configuration of the basin has changed during the course of the last 3.75 kyr. The Levantine Intermediate Water (LIW) deepens below 470 m between 3.3 and 2.0 kyr, and especially between 2.5 and 2.0 kyr. During the last 1.5 kyr, the LIW becomes shallower than 470 m, similar to the present day. The change in the hydrographic configuration reflects changes in evaporation/precipitation ratio and in temperature.

Geochemistry and lithology of clayey nannofossil ooze turbidites and hemipelagites at ODP Holes 135-834A and 135-835A

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.

Mineral and foraminifer composition of sediments across the Paleocene/Eocene Thermal Maximum from ODP Leg 198 sites

The Paleocene/Eocene Thermal Maximum (PETM) was a transient interval of global warming ~55 m.y. ago associated with transformation of ecosystems and changes in carbon cycling. The event was caused by the input of massive amounts of CO2 or CH4 to the ocean-atmosphere system. Rapid shoaling of the lysocline and calcite compensation depth (CCD) is a predicted response of CO2 or CH4 input; however, the extent of this shoaling is poorly constrained. Investigation of Ocean Drilling Program (ODP) Sites 1209-1212 at Shatsky Rise, which lies along a depth transect, suggests a minimum lysocline shoaling of ~500 m in the tropical Pacific Ocean during the PETM. The sites also show evidence of CaCO3 dissolution within the sediment column, carbonate "burn-down" below the level of the carbon isotope excursion, and a predicted response to a rapid change in deepwater carbonate saturation. Close examination of several foraminiferal preservation proxies (i.e., fragmentation, benthic/planktonic foraminiferal ratios, coarse fraction, and CaCO3 content) and observations of foraminifers reveal that increased fragmentation levels most reliably predict intervals with visually impoverished foraminiferal preservation as a result of dissolution. Low CaCO3 content and high benthic/planktonic ratios also mirror intervals of poorest preservation.

(Table 1) Oxygen isotoic composition of interstitial watres from ODP Sites 128-798 and 128-799

Oxygen isotope compositions of the interstitial waters have been measured for 21 samples taken from the depth intervals of 1.5 to 398.9 mbsf at Site 798 (Oki Ridge) and 16.5 to 435.6 mbsf at Site 799 (Kita-Yamato Trough) in Japan Sea. The d18O values decrease with depth from -0.49 to -3.38 per mil (SMOW) at Site 798 and from -0.71 to -4.36 per mil (SMOW) at Site 799 corresponding to an average depletion gradient of -0.8 per mil per 100 m. Material balance calculations reveal that the d18O-variations at Sites 798 and 799 were principally controlled by low-temperature alteration of basement basalt and andesite, resulting in negative shifts in pore water d18O values, and by the polymorphic transformations of biogenic opal-A to opal-CT and opal-CT to microquartz, which tend to increase d18O of interstitial waters. Carbonate diagenesis and ash alteration also caused weakly negative shifts in pore water d18O values.

Polarity chron boundaries and foraminiferal 87Sr/86Sr ratios of ODP Sites 162-986 and 162-987

Cores recovered at Sites 986 and 987 comprise glacial fan sedimentation associated with the Svalbard-Barents Sea and Greenland Ice Sheets, respectively. At Site 986, the top 150 m and the basal 250 m yielded interpretable magnetic stratigraphies. The record from the intervening 550 m is compromised by drilling-related core deformation, poor recovery, and numerous debris flows. The uppermost 150 m appears to record the Brunhes/Matuyama boundary and the Jaramillo Subchron. The base of the drilled section (at ~950 meters below seafloor [mbsf]) is interpreted to lie within the Matuyama Chron (age <2.58 Ma) with an apparent normal polarity interval in the ~730-750 mbsf interval. Dinoflagellate cyst biostratigraphy and Sr isotopic ratios are consistent with a Matuyama age for the base of the drilled section and with the normal polarity interval as the Olduvai Subchron. On the other hand, the last occurrence of Neogloboquadrina atlantica (sinistral) and the last common occurrence of the warm-dwelling Globigerina bulloides at 647-650 mbsf in Hole 986D indicate an age for this level of ~2.3 Ma, inconsistent with the designation of the Olduvai Subchron in the ~730-750 mbsf interval. If the age at 647-650 mbsf in Hole 986D is taken as 2.3 Ma and the base of the hole lies within the Matuyama Chron, then the sedimentation rate in the basal 300 m of the cored section averages 1 m/k.y. At Site 987, the magnetic stratigraphy is fairly unambiguous throughout the section and yields an age of 7.5 Ma (Chron 4n) for the base of the drilled section. The paucity of calcareous and siliceous microfossils precludes biostratigraphic corroboration of the magnetostratigraphic interpretation, although dinoflagellate cysts provide general support, particularly at the base of the section. The age model indicates relatively low sedimentation rates (~5 cm/k.y.) at the base of the section with rates at least four to five times greater during intervals of debris flows at ~5-4.6 and ~2.6 Ma.