(Table 1) Geochemistry of Sapropels of the Mediterranean Sea

Sapropels -organic-matter rich layers- are common in Neogene sediments of the eastern Mediterranean Sea. The formation of these layers has been attributed to climate-related increases in organic-matter production (Calvert et al., 1992, doi:10.1038/359223a0; Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X) and increased organic-matter preservation due to oxygen depletion in more stagnant bottom waters (Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X). Here we report that eastern Mediterranean Pliocene sapropels (Emeis et al., 1996, doi:10.2973/odp.proc.ir.160.102.1996) contain molecular fossils of a compound (isorenieratene) known to be synthesized by photosynthetic green sulphur bacteria, suggesting that sulphidic (euxinic) -and therefore anoxic- conditions prevailed in the photic zone of the water column. These sapropels also have a high trace-metal content, which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column. The abundance and sulphur-isotope composition of pyrite are consistent with iron sulphide formation in the water column. We conclude that basin-wide water-column euxinia occurred over substantial periods during Pliocene sapropel formation in the eastern Mediterranean Sea, and that the ultimate degradation of the increased organic-matter production was strongly influential in generating and sustaining the euxinic conditions.

Chemical concentrations and fluxes from EPICA ice cores EDML and EDC

Continuous sea salt and mineral dust aerosol records have been studied on the two EPICA (European Project for Ice Coring in Antarctica) deep ice cores. The joint use of these records from opposite sides of the East Antarctic plateau allows for an estimate of changes in dust transport and emission intensity as well as for the identification of regional differences in the sea salt aerosol source. The mineral dust flux records at both sites show a strong coherency over the last 150 kyr related to dust emission changes in the glacial Patagonian dust source with three times higher dust fluxes in the Atlantic compared to the Indian Ocean sector of the Southern Ocean (SO). Using a simple conceptual transport model this indicates that transport can explain only 40% of the atmospheric dust concentration changes in Antarctica, while factor 5-10 changes occurred. Accordingly, the main cause for the strong glacial dust flux changes in Antarctica must lie in environmental changes in Patagonia. Dust emissions, hence environmental conditions in Patagonia, were very similar during the last two glacials and interglacials, respectively, despite 2-4 °C warmer temperatures recorded in Antarctica during the penultimate interglacial than today. 2-3 times higher sea salt fluxes found in both ice cores in the glacial compared to the Holocene are difficult to reconcile with a largely unchanged transport intensity and the distant open ocean source. The substantial glacial enhancements in sea salt aerosol fluxes can be readily explained assuming sea ice formation as the main sea salt aerosol source with a significantly larger expansion of (summer) sea ice in the Weddell Sea than in the Indian Ocean sector. During the penultimate interglacial, our sea salt records point to a 50% reduction of winter sea ice coverage compared to the Holocene both in the Indian and Atlantic Ocean sector of the SO. However, from 20 to 80 ka before present sea salt fluxes show only very subdued millennial changes despite pronounced temperature fluctuations, likely due to the large distance of the sea ice salt source to our drill sites.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.