Geochemical and palynological measurements from the ODP Leg 189 at Site 1172 on the East Tasman Plateau

A brief (~150 kyr) period of widespread global average surface warming marks the transition between the Paleocene and Eocene epochs, ~56 million years ago. This so-called "Paleocene-Eocene thermal maximum" (PETM) is associated with the massive injection of 13C-depleted carbon, reflected in a negative carbon isotope excursion (CIE). Biotic responses include a global abundance peak (acme) of the subtropical dinoflagellate Apectodinium. Here we identify the PETM in a marine sedimentary sequence deposited on the East Tasman Plateau at Ocean Drilling Program (ODP) Site 1172 and show, based on the organic paleothermometer TEX86, that southwest Pacific sea surface temperatures increased from ~26 °C to ~33°C during the PETM. Such temperatures before, during and after the PETM are >10 °C warmer than predicted by paleoclimate model simulations for this latitude. In part, this discrepancy may be explained by potential seasonal biases in the TEX86 proxy in polar oceans. Additionally, the data suggest that not only Arctic, but also Antarctic temperatures may be underestimated in simulations of ancient greenhouse climates by current generation fully coupled climate models. An early influx of abundant Apectodinium confirms that environmental change preceded the CIE on a global scale. Organic dinoflagellate cyst assemblages suggest a local decrease in the amount of river run off reaching the core site during the PETM, possibly in concert with eustatic rise. Moreover, the assemblages suggest changes in seasonality of the regional hydrological system and storm activity. Finally, significant variation in dinoflagellate cyst assemblages during the PETM indicates that southwest Pacific climates varied significantly over time scales of 103 - 104 years during this event, a finding comparable to similar studies of PETM successions from the New Jersey Shelf.

Global compilation of last glacial maximum oxygen isotopic ratios for planktonic and benthic foraminifera

We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 yr). By using a model that is able to explicitly simulate the sensor (d18O), results can be directly compared with data from climatic archives in the different realms. Our results indicate that iLOVECLIM reproduces well the main feature of the LGM climate in the atmospheric and oceanic components. The annual mean d18O in precipitation shows more depleted values in the northern and southern high latitudes during the LGM. The model reproduces very well the spatial gradient observed in ice core records over the Greenland ice-sheet. We observe a general pattern toward more enriched values for continental calcite d18O in the model at the LGM, in agreement with speleothem data. This can be explained by both a general atmospheric cooling in the tropical and subtropical regions and a reduction in precipitation as confirmed by reconstruction derived from pollens and plant macrofossils. Data-model comparison for sea surface temperature indicates that iLOVECLIM is capable to satisfyingly simulate the change in oceanic surface conditions between the LGM and present. Our data-model comparison for calcite d18O allows investigating the large discrepancies with respect to glacial temperatures recorded by different microfossil proxies in the North Atlantic region. The results argue for a trong mean annual cooling between the LGM and present (>6°C), supporting the foraminifera transfer function reconstruction but in disagreement with alkenones and dinocyst reconstructions. The data-model comparison also reveals that large positive calcite d18O anomaly in the Southern Ocean may be explained by an important cooling, although the driver of this pattern is unclear. We deduce a large positive d18Osw anomaly for the north Indian Ocean that contrasts with a large negative d18Osw anomaly in the China Sea between the LGM and present. This pattern may be linked to changes in the hydrological cycle over these regions. Our simulation of the deep ocean suggests that changes in d18Osw between the LGM and present are not spatially homogenous. This is supported by reconstructions derived from pore fluids in deep-sea sediments. The model underestimates the deep ocean cooling thus biasing the comparison with benthic calcite d18O data. Nonetheless, our data-model comparison support a heterogeneous cooling of few degrees (2-4°C) in the LGM Ocean.

Upwelling and isolation in oxygen-depleted anticyclonic modewater eddies and implications for nitrate cycling

The physical (temperature, salinity, velocity) and biogeochemical (oxygen, nitrate) structure of an oxygen depleted coherent, baroclinic, anticyclonic mode-water eddy (ACME) is investigated using high-resolution autonomous glider and ship data. A distinct core with a diameter of about 70 km is found in the eddy, extending from about 60 to 200 m depth and. The core is occupied by fresh and cold water with low oxygen and high nitrate concentrations, and bordered by local maxima in buoyancy frequency. Velocity and property gradient sections show vertical layering at the flanks and underneath the eddy characteristic for vertical propagation (to several hundred-meters depth) of near inertial internal waves (NIW) and confirmed by direct current measurements. A narrow region exists at the outer edge of the eddy where NIW can propagate downward. NIW phase speed and mean flow are of similar magnitude and critical layer formation is expected to occur. An asymmetry in the NIW pattern is seen that possible relates to the large-scale Ekman transport interacting with ACME dynamics. NIW/mean flow induced mixing occurs close to the euphotic zone/mixed layer and upward nutrient flux is expected and supported by the observations. Combing high resolution nitrate (NO3-) data with the apparent oxygen utilization (AOU) reveals AOU:NO3- ratios of 16 which are much higher than in the surrounding waters (8.1). A maximum NO3- deficit of 4 to 6 µmol kg-1 is estimated for the low oxygen core. Denitrification would be a possible explanation. This study provides evidence that the recycling of NO3-, extracted from the eddy core and replenished into the core via the particle export, may quantitatively be more important. In this case, the particulate phase is of keys importance in decoupling the nitrogen from the oxygen cycling.

Geochemistry and isotopic ratios of basalts from ODP Leg 163 sites

Voluminous, subaerial magmatism resulted in the formation of extensive seaward-dipping reflector sequences (SDRS) along the Paleogene Southeast Greenland rifted margin. Drilling during Leg 163 recovered basalts from the SDRS at 66ºN (Site 988) and 63ºN (Sites 989 and 990). The basalt from Site 988 is light rare-earth-element (REE) enriched (La(n)/Yb(n) = 3.4), with epsilon-Nd(t=60) = 5.3, 87Sr/86Sr = 0.7034, and 206Pb/204Pb = 17.98. It is similar to tholeiites recovered from the Irminger Basin during Leg 49 and to light-REE-enriched tholeiites from Iceland. Drilling at Site 989, the innermost of the sites on the 63ºN transect, was proposed to extend recovery of the earliest part of the SDRS initiated during Leg 152. These basalts are, however, younger than those from Site 917 and are compositionally similar to basalts from the more seaward Sites 990 and 915. Many of the basalts from Sites 989 and 990 show evidence of contamination by continental crust (e.g., epsilon-Nd(t=60) extends down to -3.7, 206Pb/204Pb extends down to 15.1). We suggest that the contaminant is a mixture of Archean granulite and amphibolite and that the most contaminated basalts have assimilated ~5% of crust. Uncontaminated basalts are isotopically similar to basalts from Site 918, on the main body of the SDRS, and are light-REE depleted. Consistent with previous models of the development of this margin, we show that at the time of formation of the basalts from Sites 989 and 990 (1) melting was at relatively shallow levels in a fully-fledged rift zone; (2) fragments of continental crust were present in the lithosphere above the zones of melt generation; and (3) the sublithospheric mantle was dominated by a depleted Icelandic plume component.

(Table 1) Dissolved Hafnium and Neodymium in the South Atlantic measured on water bottle samples during POLARSTERN cruise ANT-XXIV/3

We present the first combined dissolved hafnium (Hf) and neodymium (Nd) concentrations and isotope compositions of deep water masses from the Atlantic sector of the Southern Ocean. Eight full depth profiles were analyzed for Hf and twelve for Nd. Hafnium concentrations are generally depleted in the upper few hundred meters ranging between 0.2 pmol/kg and 0.4 pmol/kg and increase to relatively constant values of around 0.6 pmol/kg in the deeper water column. At the stations north of the Polar Front (PF), Nd concentrations increase linearly from about 10 pmol/kg at depths of ~ 200 m to up to 31 pmol/kg close to the bottom indicating particle scavenging and release. Within the Weddell Gyre (WG), however, Nd concentrations are essentially constant at 25 pmol/kg at depths greater than ~ 1000 m. The distributions of both elements show a positive correlation with dissolved silicon implying a close linkage to diatom biogeochemistry. Hafnium essentially shows invariant isotope compositions with values averaging at epsilon-Hf = +4.6, whereas Nd isotopes mark distinct differences between water masses, such as modified North Atlantic Deep Water (NADW, epsilon-Nd = -11 to -10) and Antarctic Bottom Water (AABW, epsilon-Nd = -8.6 to -9.6), but also waters locally advected via the Agulhas Current can be identified by their unradiogenic Nd isotope compositions. Mixing calculations suggest that a small fraction of Nd is removed by particle scavenging during mixing of water masses north of the PF. Nevertheless, the Nd isotope composition has apparently not been significantly affected by uptake and release of Nd from particles, as indicated by mixing calculations. A mixing envelope of an approximated North Pacific and a North Atlantic end-member shows that Nd isotope and concentration patterns in the Lower Circumpolar Deep Water (LCDW) can be fully explained by ~ 30:70 percentage contributions of these respective end-members.

Sedimentology of cores from the Iberian margin

Bioturbation in marine sediments has basically two aspects of interest for palaeo-environmental studies. First, the traces left by the burrowing organisms reflect the prevailing environmental conditions at the seafloor and thus can be used to reconstruct the ecologic and palaeoceanographic situation. Traces have the advantage over other proxies of practically always being preserved in situ. Secondly, for high- resolution stratigraphy, bioturbation is a nuisance due to the stirring and mixing processes that destroy the stratigraphic record. In order to evaluate the applicability of biogenic traces as palaeoenvironmental indicators, a number of gravity cores from the Portuguese continental slope, covering the period from the last glacial to the present were investigated through X-ray radiographs. In addition, physical and chemical parameters were determined to define the environmental niche in each core interval. A number of traces could be recognized, the most important being: Thalassinoides, Planolites, Zoophycos, Chondrites, Scolicia, Palaeophycus, Phycosiphon and the generally pyritized traces Trichichnus and Mycellia. The shifts between the different ichnofabrics agree strikingly well with the variations in ocean circulation caused by the changing climate. On the upper and middle slope, variations in current intensity and oxygenation of the Mediterranean Outflow Water were responsible for shifts in the ichnofabric. Larger traces such as Planolites and Thalassinoides dominated in coarse, well oxygenated intervals, while small traces such as Chondrites and Trichichnus dominated in fine grained, poorly oxygenated intervals. In contrast, on the lower slope where calm steady sedimentation conditions prevail, changes in sedimentation rate and nutrient flux have controlled variations in the distribution of larger traces such as Planolites, Thalassinoides, and Palaeophycus. Additionally, distinct layers of abundant Chondrites correspond to Heinrich events 1, 2, and 4, and are interpreted as a response to incursions of nutrient rich, oxygen depleted Antarctic waters during phases of reduced thermohaline circulation. The results clearly show that not one single factor but a combination of several factors is necessary to explain the changes in ichnofabric. Furthermore, large variations in the extent and type of bioturbation and tiering between different settings clearly show that a more detailed knowledge of the factors governing bioturbation is necessary if we shall fully comprehend how proxy records are disturbed. A first attempt to automatize a part of the recognition and quantification of the ichnofabric was performed using the DIAna image analysis program on digitized X-ray radiographs. The results show that enhanced abundance of pyritized microburrows appears to be coupled to organic rich sediments deposited under dysoxic conditions. Coarse grained sediments inhibit the formation of pyritized burrows. However, the smallest changes in program settings controlling the grey scale threshold and the sensitivity resulted in large shifts in the number of detected burrows. Therefore, this method can only be considered to be semi-quantitative. Through AMS-^C dating of sample pairs from the Zoophycos spreiten and the surrounding host sediment, age reversals of up to 3,320 years could be demonstrated for the first time. The spreiten material is always several thousands of years younger than the surrounding host sediment. Together with detailed X-ray radiograph studies this shows that the trace maker collects the material on the seafloor, and then transports it downwards up to more than one meter in to the underlying sediment where it is deposited in distinct structures termed spreiten. This clearly shows that age reversals of several thousands of years can be expected whenever Zoophycos is unknowingly sampled. These results also render the hitherto proposed ethological models proposed for Zoophycos as largely implausible. Therefore, a combination of detritus feeding, short time caching, and hibernation possibly combined also with gardening, is suggested here as an explanation for this complicated burrow.

(Table 1) Uranium at DSDP Hole 69-504B pore water

Basalt formation waters collected from Hole 504B at sub-basement depths of 194, 201, 365, and 440 meters show inverse linear relationships between 87Sr/86Sr and Ca, 87Sr/86Sr and Sr, and K and Ca. If the Ca content of a fully reacted formation water end-member is assumed to be 1340 ppm, the K, Sr, and 87Sr/86Sr values for the end-member are 334 ppm, 7.67 ppm, and 0.70836, respectively. With respect to contemporary seawater at Hole 504B, K is depleted by 13%, Sr is enriched by 2.7%, and 87Sr/86Sr is depleted by 0.8%. The Sr/Ca ratio of the formation water (0.0057) is much lower than that of seawater (0.018) but is similar to the submarine hot spring waters from the Galapagos Rift and East Pacific Rise and to geothermal brines from Iceland. At the intermediate temperatures represented by the Hole 504B formation waters (70°-105°C), the interaction between seawater and the ocean crust produces large solution enrichments in Ca, the addition of a significant basalt Sr isotope component accompanied by only a minor elemental Sr component, and the removal from solution of seawater K. The Rb, Cs, and Ba contents of the formation waters appear to be affected by contamination, possibly from drilling muds.

Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.