Thorium and Uranium analyses of sediment core GIK12310-4, NW African continental margin (Table 1,2)

The Th content of the sediment samples from "Meteor" core GIK12310-4 (3080 m water depth, off NW Africa) on a carbonate-free basis lies around the average of 12.4 ppm and is similar to the average content of the earth crust. On the contrary, uranium was found to be up to 3.5-fold enriched in the core section between 60 and 330 cm (within the Wuerm Glacial) where reducing conditions occur, due to deposition of authigenic uranium (9 µg/cm**2 1000 yrs.). The authigenic uranium content is correlated to the organic matter content (U/Corg ratio = 6 * 10**4). On the basis of the uranium content of the oxidized section uranium was split into a detritic and an authigenic component and the amount of supported ionium was calculated. From the profile of the specific Io-cxcess activity (= Io-total - Io-supported) with depth, average sedimentation rates of 3.3 ± 0.6 cm/1000 yrs. for the warmer stages and of 5 ± 1 cm/l000 yrs. for the cooler periods were estimated.

(Table 1) N-isotope record of planktonc foraminifera of sediment core MD02-2550C2

Constraining variations in marine N2-fixation over glacial-interglacial timescales is crucial for determining the role of the marine nitrogen cycle in modifying ocean productivity and climate, yet paleo-records from N2-fixation regions are sparse. Here we present new nitrogen isotope (d15N) records of bulk sediment and foraminifera test-bound (FB) nitrogen extending back to the last ice age from the oligotrophic Gulf of Mexico (GOM). Previous studies indicate a substantial terrestrial input during the last ice age and early deglacial, for which we attempt to correct the bulk sediment d15N using its observed relationship with the C/N ratio. Both corrected bulk and FB-d15N reveal a substantial glacial-to-Holocene decrease of d15N toward Holocene values of around 2.5 per mil, similar to observations from the Caribbean. This d15N change is most likely due to a glacial-to-Holocene increase in regional N2-fixation. A deglacial peak in the FB-d15N of thermocline dwelling foraminifera Orbulina universa probably reflects a whole ocean increase in the d15N of nitrate during deglaciation. The d15N of the surface dwelling foraminifera Globigerinoides ruber and the corrected bulk d15N show little sign of this deglacial peak, both decreasing from last glacial values much earlier than does the d15N of O. universa; this may indicate that G. ruber and bulk N reflect the euphotic zone signal of an early local increase in N2-fixation. Our results add to the evidence that, during the last ice age, the larger iron input from dust did not lead to enhanced N2-fixation in this region. Rather, the glacial-to-Holocene decrease in d15N is best explained by a response of N2-fixation within the Atlantic to the deglacial increase in global ocean denitrification.

Analyses of benthic and planktonic foraminifera during Marine Isotope Stage 5 of ODP Hole 172-1058C

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.

Radionuclides in sediment cores from the higher latitudes

In this thesis it is shown that the cosmogenic radionuclide 10Be proved to be a sensitive stratigraphic tool for sediment cores from the Arctic Ocean with low or negligible content of biogenic carbonate, impeding a reliable 0180 stratigraphy. 10Be enables a stratigraphy of Arctic sediments comparable to the d18O stratigraphy Imbrie et al. [1984] in that high concentration of 10Be are related to interglacial stages in contrast to lower values during glacial periods. To use the °Be profile as dating tool it is necessary to investigate the sources and sinks as well as the pathways of this radiotracer. 10Be is produced in the upper atmosphere and transfered to the earth's surface by dry and wet deposition. Besides the atmospheric component there is an important input of 10Be with the rivers to the Arctic Ocean. I determined depositional 10Be fluxes in the shelf area of the Laptev Sea, which is characterized by a huge input of river water, the continental slope of the Laptev Sea, the central Arctic Ocean and the Norwegian- and Greenland Sea. The depositional 10Be fluxes of (20 ± 5) x 10**6 atoms/cm**2/a in the shelf area of the Laptev Sea are by two orders of magnitude higher than the recent atmospheric input (0.2 - 0.5) x 10**6 atoms/cm**2/a in Greenland. while the fluxes in the central Arctic Ocean are in the same range. Further I developed a model to reconstruct the pathways of radionuclides 230Th, 231Pa and 10Be in high northern latitudes. The modelling results were compared with the measured concentrations in the water column and the recent depositional fluxes. These results show that the recent pathways of these nuclides can be rebuild by this model. Thus we can apply this model to earlier oxygen isotope stages to find out which predominate conditions lead to the determined depositional fluxes.

Carbon and oxygen isotope ratios, and geochemistry of the Precambrian-Cambrian Sukharikha River section, northwestern Siberian platform

A high-resolution carbon isotope profile through the uppermost Neoproterozoic-Lower Cambrian part of the Sukharikha section at the northwestern margin of the Siberian platform shows prominent secular oscillations of d13C with peak-to-peak range of 6-10 ?. There are six minima, 1n-6n, and seven maxima 1p-7p, in the Sukharikha Formation and a rising trend of d13C from the minimum 1n of -8.6 ? to maximum 6p of +6.4 ?. The trough 1n probably coincides with the isotopic minimum at the Precambrian-Cambrian boundary worldwide. Highly positive d13C values of peaks 5p and 6p are typical of the upper portion of the Precambrian-Cambrian transitional beds just beneath the Tommotian Stage in Siberia. A second rising trend of d13C is observed through the Krasnoporog and lower Shumny formations. It consists of four excursions with four major maxima that can be cor related with Tommotian-Botomian peaks II, IV, V, and VII of the reference profile from the southeastern Siberian platform. According to the chemostratigraphic cor relation, the first appearances of the index forms of archaeocyaths are earlier in the Sukharikha section than in the Lena-Aldan region.

Chemical composition of tephra from the Greenland-Iceland-Norwegian-Sea

Explosive ocean island volcanism in the Greenland-Iceland-Norwegian Sea (GIN Sea) is indicated by marine tephra layers at 10-300 ka. Peaks of explosive volcanism occurred in oxygen isotope stages 8, 7, 5 and 1. The depositional age of the tephra was estimated using the oxygen isotope stratigraphy and dating of marine records. Geochemical analyses of the tephra layers show that all originate from Iceland. Here we report the characteristics of tephra from these major Icelandic events in 30 deep-sea cores from the GIN Sea. Our findings provide constraints on the distribution of tephra from the eruption source. For the Vedde Ash (oxygen isotope stage 1) we estimate a minimum fallout area of 2*10**5 km**2, stretching from central Greenland in the west and southern Sweden in the east, to 71°N in the GIN Sea. The magnitude of the eruption and the regional wind conditions controlled the extent and concentrations of these ash fallout events. Oceanic circulation and differential settling may have affected the distribution and final deposition of ash particles such as bubble wall shards.

Chemical and isotopic composition of carbonate veins from ODP Leg 209

Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T > 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.

Victoria Land Antarctica Pb and Ba concentrations and Pb isotope ratios 1872-1994 CE

Pb and Ba concentrations and Pb isotopic compositions are reported for firn core and snow pit samples from Victoria Land, Antarctica, dating from 1872 AD to 1994 AD. From variations in Pb/Ba ratios and Pb isotopic compositions, two periods of major Pb enhancements were identified, from 1891 to 1908 AD and from 1948 to 1994 AD. The earlier pollution event is attributed to Pb emissions from non-ferrous metal production and coal combustion in the Southern Hemisphere and is in excellent agreement with coincident pollution inputs reported in firn/ice cores from two other regions of Antarctica, at Coats Land and Law Dome. Using Pb isotopic systematics, it was calculated that ~50% of Pb deposited in Victoria Land in 1897 originated from anthropogenic emission sources. The more recent period of Pb enhancements, from 1948 to 1994 AD, corresponds to the introduction and widespread use of gasoline alkyl Pb additives in automobiles in the Southern Hemisphere, with anthropogenic Pb inputs averaging 60% of total Pb but with large uncertainty. Intra- and inter-annual variations in Pb concentrations and isotopic compositions were evaluated in snow pits samples corresponding to the period 1991-1994. Substantial variations in Pb/ Ba and 206Pb/207Pb ratios were detected but the absence of a regular seasonal pattern for these parameters suggests that the transport and deposition of aerosols to the Antarctic ice sheet are complex and vary from year to year.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.

Geochemistry, carbon isotope ratio and radiocarbon ages of sediment core GIK1093-2 from Bornholm Basin, Baltic Sea

Concentrations of Cd, Pb, Zn, Cu, Co, Ni, Fe, and Al203, water content, the amounts of organic carbon, the ratio of 13C/12C and the 14C-activity of the organic fraction were determined with sediment depth from a 34 cm long box-core from the Bornholm Basin (Baltic Sea). The average sedimentation rate was 2.4 mm/yr. The upper portion of the core contained increasing amounts of 14C-inactive organic carbon, and above 3 cm depth, man-made 14C from atomic bomb tests. The concentrations of the heavy metals Cd, Pb, Zn, and Cu increase strongly towards the surface, while other metals, as Fe, Ni and Co remain almost unchanged. This phenomenon is attributed to anthropogenic influences. A comparison of the Kieler Bucht, the Bornholm and the Gotland Basins shows that today the anthropogenic addition of Zn is about 100 mg/m**2 yr in all three basins. The beginning of this excess of Zn, however, is delayed by about 20 years in, the Bornholm Basin and by about 40 years in the Gotland Basin. It is suggested that SW-NE transport of these anthropogenically mobilized metals may be related to periodic bottom water renewal in the Baltic Sea sedimentary basins.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.

Geochemistry of basalts from the Caribbean Large Igneous Province

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ~3*10**6 km**2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96+/-0.16, n=64 out of 79 samples, 2sigma) and initial Nd-Pb isotopic compositions (e.g. 143Nd/144Ndin=0.51291+/-3, epsilon-Nd i=7.3+/-0.6, 206Pb/204Pbin=18.86+/-0.12, n=54 out of 66, 2sigma). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/4He in olivines of enriched picrites at Quepos are ~12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been <=500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.