Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

(Table 1) Age determination of stalagmites of the Marcello Arévalo Cave in Chile

Stalagmites are important palaeo-climatic archives since their chemical and isotopic signatures have the potential to record high-resolution changes in temperature and precipitation over thousands of years. We present three U/Th-dated records of stalagmites (MA1-MA3) in the superhumid southern Andes, Chile (53°S). They grew simultaneously during the last five thousand years (ka BP) in a cave that developed in schist and granodiorite. Major and trace elements as well as the C and O isotope compositions of the stalagmites were analysed at high spatial and temporal resolution as proxies for palaeo-temperature and palaeo-precipitation. Calibrations are based on data from five years of monitoring the climate and hydrology inside and outside the cave and on data from 100 years of regional weather station records. Water-insoluble elements such as Y and HREE in the stalagmites indicate the amount of incorporated siliciclastic detritus. Monitoring shows that the quantity of detritus is controlled by the drip water rate once a threshold level has been exceeded. In general, drip rate variations of the stalagmites depend on the amount of rainfall. However, different drip-water pathways above each drip location gave rise to individual drip rate levels. Only one of the three stalagmites (MA1) had sufficiently high drip rates to record detrital proxies over its complete length. Carbonate-compatible element contents (e.g. U, Sr, Mg), which were measured up to sub-annual resolution, document changes in meteoric precipitation and related drip-water dilution. In addition, these soluble elements are controlled by leaching during weathering of the host rock and soils depending on the pH of acidic pore waters in the peaty soils of the cave's catchment area. In general, higher rainfall resulted in a lower concentration of these elements and vice versa. The Mg/Ca record of stalagmite MA1 was calibrated against meteoric precipitation records for the last 100 years from two regional weather stations. Carbonate-compatible soluble elements show similar patterns in the three stalagmites with generally high values when drip rates and detrital tracers were low and vice versa. d13C and d18O values are highly correlated in each stalagmite suggesting a predominantly drip rate dependent kinetic control by evaporation and/or outgassing. Only C and O isotopes from stalagmite MA1 that received the highest drip rates show a good correlation between detrital proxy elements and carbonate-compatible elements. A temperature-related change in rainwater isotope values modified the MA1 record during the Little Ice Age (~0.7-0.1 ka BP) that was ~1.5 °C colder than today. The isotopic composition of the stalagmites MA2 and MA3 that formed at lower drip rates shows a poor correlation with stalagmite MA1 and all other chemical proxies of MA1. 'Hendy tests' indicate that the degassing-controlled isotope fractionation of MA2 and MA3 had already started at the cave roof, especially when drip rates were low. Changing pathways and residence times of the seepage water caused a non-climatically controlled isotope fractionation, which may be generally important in ventilated caves during phases of low drip rates. Our proxies indicate that the Neoglacial cold phases from ~3.5 to 2.5 and from ~0.7 to 0.1 ka BP were characterised by 30% lower precipitation compared with the Medieval Warm Period from 1.2 to 0.8 ka BP, which was extremely humid in this region.

Age profiles and isotopes d18O and d13C in Globigerina angiporoides and Oridorsalis umbonatus at DSDP Site 90-593 and Holes 12-111, 29-277 and 90-592

The late Eocene through earliest Miocene stable-isotope composition of southwest Pacific microfossils has been examined in a traverse of high-quality sedimentary sequences ranging from subantarctic (DSDP Site 277) through temperate regions (DSDP Sites 592 and 593). Changes in oxygen-isotope values, measured in benthic and planktonic foraminifers, document the Oligocene development and strengthening of latitudinal thermal zonation from water masses with broad temperature gradients during the Eocene to the steeper gradients and more distinct latitudinally distributed surface water-mass belts of the Neogene. The oxygen-isotope records can be divided into three intervals: late Eocene, early Oligocene, and middle to late Oligocene. Each interval represents a successive stage in the evolution of latitudinal thermal gradients between subantarctic and temperate regions in the Southern Hemisphere. During the late Eocene, oxygen-isotope values at subantarctic Site 277 were similar to those at temperate Sites 592 and 593. The isotope values suggest that, although the inferred paleotemperatures at Site 277 are slightly cooler on average than those at the temperate sites, there is no evidence for a major thermal boundary between the regions at this time. All three sites record the well-known oxygen-isotope enrichment of about 1 per mil in both planktonic and benthic foraminifers in close association with the Eocene/Oligocene boundary. In contrast to the earliest Oligocene enrichments in the planktonic and benthic oxygen-isotope composition at Site 277, more northern Sites 592 and 593 exhibit a depletion through the early-middle Oligocene. This documents the beginning of thermal segregation as subantarctic waters cooled relative to those at temperate latitudes. During the Oligocene, this surface-water differentiation continued, as measured by planktonic d18O values. The oxygen-isotope records of the benthic foraminifers also began to diverge in the earliest Oligocene. The most enriched oxygen-isotope values in all records cluster in the middle Oligocene, marked by oscillating episodes of enrichments >0.5 per mil occurring most prominently in the subantarctic record of Site 277. These values can be interpreted as recording either the coldest oceanic temperatures of the Paleogene and/or accumulations of Antarctic ice. After this interval, latitudinal thermal differentiation developed rapidly during the middle Oligocene, especially in the surface waters which actually warmed in temperate areas. If the enriched Oligocene oxygen-isotope values indicate that ice had accumulated, this ice must have disappeared by the early Miocene, when depleted oxygen-isotope values suggest very warm conditions. The data presented in this chapter document the progressive increase of latitudinal temperature gradients from the late Eocene through the late Oligocene. This pattern of increasing isotopic offset between latitudinally distributed southwest Pacific sites is linked to the establishment and strengthening of the Circum-Antarctic Current, previously considered to have developed during the middle to late Oligocene. The intensification of this current system progressively decoupled the warm subtropical gyres from cool polar circulation, in turn leading to increased Antarctic glaciation.

Stable hydrogen isotopic composition (dD) and stable carbon isotopic composition (d13C) of sediment core GeoB9508-5 off Senegal

To reconstruct variability of the West African monsoon and associated vegetation changes on precessional and millennial time scales, we analyzed a marine sediment core from the continental slope off Senegal spanning the past 44,000 years (44 ka). We used the stable hydrogen isotopic composition (dD) of individual terrestrial plant wax n-alkanes as a proxy for past rainfall variability. The abundance and stable carbon isotopic composition (d13C) of the same compounds were analyzed to assess changes in vegetation composition (C3/C4 plants) and density. The dD record reveals two wet periods that coincide with local maximum summer insolation from 38 to 28 ka and 15 to 4 ka and that are separated by a less wet period during minimum summer insolation. Our data indicate that rainfall intensity during the rainy season throughout both wet humid periods was similar, whereas the length of the rainy season was presumably shorter during the last glacial than during the Holocene. Additional dry intervals are identified that coincide with North Atlantic Heinrich stadials and the Younger Dryas interval, indicating that the West African monsoon over tropical northwest Africa is linked to both insolation forcing and high-latitude climate variability. The d13C record indicates that vegetation of the western Sahel was consistently dominated by C4 plants during the past 44 ka, whereas C3-type vegetation increased during the Holocene. Moreover, we observe a gradual ending of the Holocene humid period together with unchanging ratio of C3 to C4 plants, indicating that an abrupt aridification due to vegetation feedbacks is not a general characteristic of this time interval.

(Table 1) Oxygen and carbon isotopic values of benthic foraminifera from the Upper Maastrichtian interval of various DSDP and ODP sites

Stable isotopic data from benthic foraminifera indicate the occurrence of at least three deepwater masses in the late Maastrichtian ocean. Given mean oceanic d18Ow of -1.0 per mil, the temperature of the coolest intermediate-depth waters was 5°-7°C, that of the deepest waters was 10°C, and that of the warmest intermediate waters was 13°-15°C. The cool intermediate-depth water mass probably originated in the high-latitude Southern Ocean. The deepest waters originated at least partly in the northern Atlantic. The source region for the warmest intermediate-depth water mass is unknown. Although much of the late Maastrichtian deep water was probably preconditioned for winter sinking by low- or middle-latitude evaporation, no more than ~11% of late Maastrichtian deep water could have been directly actuated by low-latitude sea surface evaporation. At least in the southern Atlantic and Indian Oceans, heat transport by upwelling of deep water was not the primary cause of mild sea surface and coastal temperatures.

Fatty acid and stable isotope composition of calanoid copepods in the open eastern Atlantic Ocean during POLARSTERN cruise ANT-XXIX/1

The majority of global ocean production and total export production is attributed to oligotrophic oceanic regions due to their vast regional expanse. However, energy transfers, food-web structures and trophic relationships in these areas remain largely unknown. Regional and vertical inter- and intra-specific differences in trophic interactions and dietary preferences of calanoid copepods were investigated in four different regions in the open eastern Atlantic Ocean (38°N to 21°S) in October/November 2012 using a combination of fatty acid (FA) and stable isotope (SI) analyses. Mean carnivory indices (CI) based on FA trophic markers generally agreed with trophic positions (TP) derived from d15N analysis. Most copepods were classified as omnivorous (CI ~0.5, TP 1.8 to ~2.5) or carnivorous (CI >=0.7, TP >=2.9). Herbivorous copepods showed typical CIs of <=0.3. Geographical differences in d15N values of epi- (200-0 m) to mesopelagic (1000-200 m) copepods reflected corresponding spatial differences in baseline d15N of particulate organic matter from the upper 100 m. In contrast, species restricted to lower meso- and bathypelagic (2000-1000 m) layers did not show this regional trend. FA compositions were species-specific without distinct intra-specific vertical or spatial variations. Differences were only observed in the southernmost region influenced by the highly productive Benguela Current. Apparently, food availability and dietary composition were widely homogeneous throughout the oligotrophic oceanic regions of the tropical and subtropical Atlantic. Four major species clusters were identified by principal component analysis based on FA compositions. Vertically migrating species clustered with epi- to mesopelagic, non-migrating species, of which only Neocalanus gracilis was moderately enriched in lipids with 16% of dry mass (DM) and stored wax esters (WE) with 37% of total lipid (TL). All other species of this cluster had low lipid contents (< 10% DM) without WE. Of these, the tropical epipelagic Undinula vulgaris showed highest portions of bacterial markers. Rhincalanus cornutus, R. nasutus and Calanoides carinatus formed three separate clusters with species-specific lipid profiles, high lipid contents (>=41% DM), mainly accumulated as WE (>=79% TL). C. carinatus and R. nasutus were primarily herbivorous with almost no bacterial input. Despite deviating feeding strategies, R. nasutus clustered with deep-dwelling, carnivorous species, which had high amounts of lipids (>=37% DM) and WE (>=54% TL). Tropical and subtropical calanoid copepods exhibited a wide variety of life strategies, characterized by specialized feeding. This allows them, together with vertical habitat partitioning, to maintain high abundance and diversity in tropical oligotrophic open oceans, where they play an essential role in the energy flux and carbon cycling.

Shell size variation of Neogloboquadrina pachyderma sin. in the Norwegian-Greenland Sea during the last 1.3 Myr

We present measurements of the maximum diameter of the planktonic foraminifer Neogloboquadrina pachyderma sin. from six sediment cores (Ocean Drilling Program sites 643, 644, 907, 909, 985 and 987) from the Norwegian-Greenland Sea. Our data show a distinct net increase in mean shell size of N. pachyderma sin. at all sites during the last 1.3 Ma, with largest shell sizes reached after 0.4 Ma. External factors such as glacial-interglacial variability and carbonate dissolution alone cannot account for the observed variation in mean shell size of N. pachyderma sin. We consider the observed shell size increase to mirror an evolutionary trend towards better adaptation of N. pachyderma sin. to the cold water environment after 1.1-1.0 Ma. Probably, the Mid Pleistocene climate shift and the associated change of amplitude and frequency of glacial-interglacial fluctuations have triggered the evolution of this planktonic foraminifer. Oxygen and carbon stable isotope analyses of different shell size classes indicate that the observed shell size increase could not be explained by the functional concept that larger shells promote increasing sinking velocities during gametogenesis. For paleoceanographic reconstructions, the evolutionary adaptation of Neogloboquadrina pachyderma sin. to the cold water habitat has significant implications. Carbonate sedimentation in highest latitudes is highly dependent on the presence of this species. In the Norwegian-Greenland Sea, carbonate-poor intervals before 1.1 Ma are, therefore, not necessarily related to severe glacial conditions. They are probably attributed to the absence of this not yet polar-adapted species. Further, transfer function and modern analog techniques used for the reconstruction of surface water conditions in high latitudes could, therefore, contain a large range of errors if they were applied to samples older than 1.1-1.0 Myrs.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Determination of hydrocarbon gases in mud volcanoes in the Sorokin Trough

Hydrocarbon gases were determined in sediments from three mud volcanoes in the Sorokin Trough. In comparison to a reference station outside the mud volcano area, the deposits are characterized by an enrichment of high-molecular hydrocarbons (C2-C4), an absence of unsaturated homologues, a predominance of iso-butane in comparison with n-butane, and the presence of gas hydrate. The molecular composition of the hydrocarbon gases suggests their deep sources and thermogenic origin. In the pelagic sediments at the reference station, the methane concentration is relatively low (up to 49 ml/l); maximum concentrations are reached in deposits of the Dvurechenskii mud volcano (up to 400 ml/l). It was the first time that gas hydrate was sampled at the Dvurechenskii mud volcano. The gas extracted by dissociation of hydrate samples was dominated by methane (99.5%) with low amounts of ethane and propane (less than 0.5%). The isotopic composition of the methane varies between -62 and -66 per mill PDB in d13C, and between -185 and -209 per mill SMOW in dD, indicating a mainly biogenic origin with an admixture of thermogenic gas.

Sea surface temperature reconstruction of sediment core GeoB6518-1

Past hydrological changes in Africa have been linked to various climatic processes, depending on region and timescale. Long-term precipitation changes in the regions of northern and southern Africa influenced by the monsoons are thought to have been governed by precessional variations in summer insolation (Kutzbach and Liu, 1997, doi:10.1126/science.278.5337.440; Partridge et al., 1997, doi:10.1016/S0277-3791(97)00005-X). Conversely, short-term precipitation changes in the northern African tropics have been linked to North Atlantic sea surface temperature anomalies, affecting the northward extension of the Intertropical Convergence Zone and its associated rainbelt (Hastenrath, 1990, doi:10.1002/joc.3370100504, Street-Perrott and Perrott, 1990, doi:10.1038/343607a0). Our knowledge of large-scale hydrological changes in equatorial Africa and their forcing factors is, however, limited (Gasse, 2000, doi:10.1016/S0277-3791(99)00061-X). Here we analyse the isotopic composition of terrigenous plant lipids, extracted from a marine sediment core close to the Congo River mouth, in order to reconstruct past central African rainfall variations and compare this record to sea surface temperature changes in the South Atlantic Ocean. We find that central African precipitation during the past 20,000 years was mainly controlled by the difference in sea surface temperatures between the tropics and subtropics of the South Atlantic Ocean, whereas we find no evidence that changes in the position of the Intertropical Convergence Zone had a significant influence on the overall moisture availability in central Africa. We conclude that changes in ocean circulation, and hence sea surface temperature patterns, were important in modulating atmospheric moisture transport onto the central African continent.