(Table 3) Relative depth and age, CaCO3, d18O, d13C and Sr/Ca analysis from ODP Leg 130, 154 and 138

Interpretations of calcite strontium/calcium records in terms of ocean history and calcite diagenesis require distinguishing the effects on deep-sea calcite sediments of changes in ocean chemistry, of different mixes of calcite-depositing organisms as sediment contributors through time and space, and of the loss of Sr during diagenetic calcite recrystallization. In this paper Sr/Ca and d18O values of bulk calcium carbonate sediments are used to estimate the relative extent of calcite recrystallization in samples from four time points (core tops, 5.6, 9.4, and 37.1 Ma) at eight Ocean Drilling Program sites in the equatorial Atlantic (Ceara Rise) and equatorial Pacific (Ontong Java Plateau and two eastern equatorial Pacific sites). The possibility that site-to-site differences in calcite Sr/Ca at a given time point originated from temporal variations in ocean chemistry was eliminated by careful age control of samples for each time point, with sample ages differing by less than the oceanic residence times of Sr and Ca. The Sr/Ca and d18O values of 5.6- and 9.4-Ma samples from the less-carbonate-rich eastern equatorial Pacific sites and Ceara Rise Site 929 appear to be less diagenetically altered than the Sr/Ca and d18O values of contemporaneous samples from the more carbonate-rich sites. It is evident from these data that both Sr/Ca and d18O in bulk calcite have been diagenetically altered in some samples 5.6 Ma and older. These data indicate that noncarbonate sedimentary components, like clay and biogenic silica, have partially suppressed recrystallization at the lower carbonate sites. Sr/Ca data from the less altered, carbonate-poor sites indicate higher oceanic Sr/Ca relative to today at 5.6 and 9.4 Ma.

Isotopic data of atmospheric methane from EDML and Vostok ice cores over a full glacial cycle

The response of natural CH4 sources to climate changes will be an important factor to consider as concentrations of this potent greenhouse gas continue to increase. Polar ice cores provide the means to assess this sensitivity in the past and have shown a close connection between CH4 levels and northern hemisphere temperature variability over the last glacial cycle. However, the contribution of the various CH4 sources and sinks to these changes is still a matter of debate. Contemporaneous stable CH4 isotope records in ice cores provide additional boundary conditions for assessing changes in the CH4 sources and sinks. Here we present new ice core CH4 isotope data covering the last 160,000 years, showing a clear decoupling between CH4 loading and carbon isotopic variations over most of the record. We suggest that d13CH4 variations were not dominated by a change in the source mix but rather by climate- and CO2-related ecosystem control on the isotopic composition of the methane precursor material, especially in seasonally inundated wetlands in the tropics. In contrast, relatively stable d13CH4 intervals occurred during large CH4 loading changes concurrently with past climate changes implying that most CH4 sources (most notably tropical wetlands) responded simultaneously.

(Table 2) Petrophysical, petrological, and geochemical characteristics of ODP Hole 163-990A sediments

Ocean Drilling Program Hole 990A penetrated 131 m of subaerially emplaced Paleocene flood basalts on the Southeast Greenland margin with a recovery of 74%. Shipboard P-wave velocity (Vp), density, and magnetic susceptibility were measured with 2- to 15-cm intervals on the core. Individual flow units were divided into four zones based on the observed petrophysical characteristics. From the top, these are Zone I (<7 m thick with a Vp of ~2.5 km/s), Zone II (3-5 m thick with a strongly increasing Vp from 2.5 to 5.5 km/s), Zone III (up to 20 m thick with a Vp of ~5.5-6.0 km/s), and Zone IV (<2 m thick with a strongly decreasing Vp from 6.0 to 2.5 km/s). Eighteen samples were selected from three of the fourteen penetrated basalt units for geochemical, petrological, and petrophysical studies focusing on the altered, low-velocity upper lava Zones I and II. Zone I is strongly altered to >50% clay minerals (smectite) and iron hydroxides, and the petrophysical properties are primarily determined by the clay properties. Zone II is intermediately altered with 5%-20% clay minerals, where the petrophysical properties are a function of both the degree of alteration and porosity variations. Shipboard and shore-based measurements of the same samples show that storage permanently lowers the elastic moduli of basalt from Zones I to III. This is related to the presence of even small quantities of swelling clays. The data show that alteration processes are important in determining the overall seismic properties of flood basalt constructions. The degree and depth of alteration is dependent on the primary lava flow emplacement structures and environment. Thus, the interplay of primary emplacement and secondary alteration structures determine the elastic properties of basalt piles. Rock property theories for sand-clay systems are further used to model the physical property variations in these altered crystalline rocks.

Sea surface temperatures reconstructed from alkenones of surface sediment samples of the Argentine Basin at stations GeoB1501-1 to GeoB2830-1

We analysed the alkenone unsaturation ratio (UK'37) in 87 surface sediment samples from the western South Atlantic (5°N-50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured UK'37 ratios were converted into temperature using the global core-top calibration of Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by -2° to -6°C are found in the regions of the Brazil-Malvinas Confluence (35-39°S) and the Malvinas Current (41-48°S). From the oceanographic evidence these low UK'37 values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating UK'37 temperatures. In this way, particles and sediments carrying a cold water UK'37 signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.

(Table 1) Sample locations and clay mineral data of sediment surface samples from the Barents Sea region

A new surface sediment sample set gained in the western Barents Sea by the MAREANO program has been analysed for basic clay mineral assemblages. Distribution maps including additional samples from earlier German research cruises to and off Svalbard are compiled. Some trends in the clay mineral assemblages are related to the sub-Barents Sea geology because the Quaternary sediment cover is rather thin. Additionally, land masses like Svalbard and northern Scandinavia dominate the clay mineral signal with their erosional products. Dense bottom water, very often of brine origin, that flows within deep troughs, such as the Storfjorden or Bear Island Trough, transport the clay mineral signal from their origin to the Norwegian-Greenland Sea.

Stable carbon isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

The sediment cores 225514 and 225510 were recovered from 420 and 285 m water depth, respectively. They were investigated for their benthic foraminiferal delta13C during the last 500 years. Both cores were recovered from the southern flank of the Skagerrak. The delta13C values of Uvigerina mediterranea and other shallow infaunal species in both cores indicate that organic matter rain rates to the seafloor varied around a mean value until approximately AD 1950 after which they increased. This increase might result from changes in the North Atlantic Current System and a co-occurring persistently high North Atlantic Oscillation index state in the 1980s to 1990s, rather than from anthropogenic eutrophication. Using delta13C mean values of multiple species, we reconstruct delta13C gradients of dissolved inorganic carbon (DIC) within pore waters for the time periods AD 1500 to 1950 and AD 1950 to 2000. The calculated delta13CDIC ranges, interpreted as indicating total organic matter remineralization due to respiration, are generally bigger in Core 225514 than in Core 225510. Since mean delta13C values of U. mediterranea suggest that organic matter rain rates were similar at both locations, differences in total organic matter remineralization are attributed to differing oxygen availability. However, oxygen concentrations in the overlying bottom water masses are not likely to have differed significantly. Thus, we suggest that organic matter remineralization was controlled by oxygen availability within the sediments, reflecting strong differences in sedimentation rates at the two investigated core sites. Based on the assumptions that tests of benthic foraminiferal species inhabiting the same microhabitat depth should show equal delta13C values unless they are affected by vital effects and that Globobulimina turgida records pore water delta13CDIC, we estimate microhabitat-corrected vital effects for several species with respect to G. turgida: >0.7 per mil for Cassidulina laevigata, >1.3 per mil for Hyalinea balthica, and >0.7 per mil for Melonis barleeanus. Melonis zaandami seems to closely record pore water delta13CDIC.

Stable oxygen isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

Benthic foraminiferal tests of a sediment core from southwestern Skagerrak (northeastern North Sea, 420 m water depth) were investigated for their ratio of stable oxygen isotopes. During modern times sudden drops in temperature and salinity of Skagerrak deep waters point to advection-induced cascades of colder and denser central North Sea waters entering the Skagerrak. These temperature drops, which are recorded in benthic foraminiferal tests via the stable oxygen isotopic composition, were used to reconstruct deep-water renewal in the Skagerrak. In a second step we will show that, at least during the last 1200 years, Skagerrak deep-water renewal is triggered by the negative phase of the North Atlantic Oscillation (NAO). The NAO exerts a strong influence on the climate of northwestern Europe. It is currently under debate if the long-term variability of the NAO is capable of influencing Northern Hemisphere climate on long timescales. The data presented here cannot reinforce these speculations. Our data show that most of the 'Little Ice Age' was dominated by comparably warm deep-water temperatures. However, we did find extraordinary strong temperature differences between central North Sea waters and North Atlantic water masses during this time interval.

Radiocarbon ages and 230Th data of five sediment cores from the Björn and Gardar Drift, North Atlantic

In locations of rapid sediment accumulation receiving substantial amounts of laterally transported material the timescales of transport and accurate quantification of the transported material are at the focus of intense research. Here we present radiocarbon data obtained on co-occurring planktic foraminifera, marine haptophyte biomarkers (alkenones) and total organic carbon (TOC) coupled with excess Thorium-230 (230Thxs) measurements on four sediment cores retrieved in 1649-2879 m water depth from two such high accumulation drift deposits in the Northeast Atlantic, Björn and Gardar Drifts. While 230Thxs inventories imply strong sediment focussing, no age offsets are observed between planktic foraminifera and alkenones, suggesting that redistribution of sediments is rapid and occurs soon after formation of marine organic matter, or that transported material contains negligible amounts of alkenones. An isotopic mass balance calculation based on radiocarbon concentrations of co-occurring sediment components leads us to estimate that transported sediment components contain up to 12% of fossil organic matter that is free of or very poor in alkenones, but nevertheless appears to consist of a mixture of fresh and eroded fossil material. Considering all available constraints to characterize transported material, our results show that although focussing factors calculated from bulk sediment 230Thxs inventories may allow useful approximations of bulk redeposition, they do not provide a unique estimate of the amount of each laterally transported sediment component. Furthermore, our findings provide evidence that the occurrence of lateral sediment redistribution alone does not always hinder the use of multiple proxies but that individual sediment fractions are affected to variable extents by sediment focussing.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.