Age models, ostracods and trace elements of five gravity cores from the NW Black Sea

New Mg/Ca, Sr/Ca, and published stable oxygen isotope and 87Sr/86Sr data obtained on ostracods from gravity cores located on the northwestern Black Sea slope were used to infer changes in the Black Sea hydrology and water chemistry for the period between 30 to 8 ka B.P. (calibrated radiocarbon years). The period prior to 16.5 ka B.P. was characterized by stable conditions in all records until a distinct drop in d18O values combined with a sharp increase in 87Sr/86Sr occurred between 16.5 and 14.8 ka B.P. This event is attributed to an increased runoff from the northern drainage area of the Black Sea between Heinrich Event 1 and the onset of the Bølling warm period. While the Mg/Ca and Sr/Ca records remained rather unaffected by this inflow; they show an abrupt rise with the onset of the Bølling/Allerød warm period. This rise was caused by calcite precipitation in the surface water, which led to a sudden increase of the Sr/Ca and Mg/Ca ratios of the Black Sea water. The stable oxygen isotopes also start to increase around 15 ka B.P., although in a more gradual manner, due to isotopically enriched meteoric precipitation. While Sr/Ca remains constant during the following interval of the Younger Dryas cold period, a decrease in the Mg/Ca ratio implies that the intermediate water masses of the Black Sea temporarily cooled by 1-2°C during the Younger Dryas. The 87Sr/86Sr values drop after the cessation of the water inflow at 15 ka B.P. to a lower level until the Younger Dryas, where they reach values similar to those observed during the Last Glacial Maximum. This might point to a potential outflow to the Mediterranean Sea via the Sea of Marmara during this period. The inflow of Mediterranean water started around 9.3 ka B.P., which is clearly detectable in the abruptly increasing Mg/Ca, Sr/Ca, and 87Sr/86Sr values. The accompanying increase in the d18O record is less pronounced and would fit to an inflow lasting ~100 a.

Dissolved organic carbon in waters of the Okhotsk and Bering Seas

A comparison was made of capability of two methods: photochemical oxidation and high-temperature catalytic combustion - to oxidize organic carbon in organic substances different in their element composition and in their degree of complexity. Results of measurements of dissolved organic carbon obtained by both of these methods in waters of the Black, Bering and Okhotsk Seas are presented. Varying oxidation degree of organic matter was shown to be dependent on the region and depth. A conclusion was made that the high-temperature catalytic combustion method was to be preferred for dissolved organic carbon determination due to its easier standardization, while values obtained by the wet-oxidation method may be influenced by a great number of factors that are difficult to be controlled.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Hydrate abundances at the high-flux Batumi seep area in the southeastern Black Sea

Submarine gas hydrates are a major global reservoir of the potent greenhouse gas methane. Since current assessments of worldwide hydrate-bound carbon vary by one order of magnitude, new technical efforts are required for improved and accurate hydrate quantifications. Here we present hydrate abundances determined for surface sediments at the high-flux Batumi seep area in the southeastern Black Sea at 840 m water depth using state-of-the art autoclave technology. Pressure sediment cores of up to 2.65 m in length were recovered with an autoclave piston corer backed by conventional gravity cores. Quantitative core degassing yielded volumetric gas/bulk sediment ratios of up to 20.3 proving hydrate presence. The cores represented late glacial to Holocene hemipelagic sediments with the shallowest hydrates found at 90 cmbsf. Calculated methane concentrations in the different cores surpassed methane equilibrium concentrations in the two lowermost lithological Black Sea units sampled. The results indicated hydrate fractions of 5.2% of pore volume in the sapropelic Unit 2 and mean values of 21% pore volume in the lacustrine Unit 3. We calculate that the studied area of ~ 0.5 km**2 currently contains about 11.3 kt of methane bound in shallow hydrates. Episodic detachment and rafting of such hydrates is suggested by a rugged seafloor topography along with variable thicknesses in lithologies. We propose that sealing by hydrate precipitation in coarse-grained deposits and gas accumulation beneath induces detachment of hydrate/sediment chunks. Floating hydrates will rapidly transport methane into shallower waters and potentially to the sea-atmosphere boundary. In contrast, persistent in situ dissociation of shallow hydrates appears unlikely in the near future as deep water warming by about 1.6 °C and/or decrease in hydrostatic pressure corresponding to a sea level drop of about 130 m would be required. Because hydrate detachment should be primarily controlled by internal factors in this area and in similar hydrated settings, it serves as source of methane in shallow waters and the atmosphere which is mainly decoupled from external forcing.

Chemical composition of ferromanganese concretions and host bottom sediments from the Black Sea

Ferromanganese concretions spread out on the bottom of the shallow northwest part of the Black Sea are mainly represented by Fe and Mn nodules on shells and substituted worm tubes. Element composition of these formations was measured by methods of chemical, atomic absorbtion, neutron activation, and ICP-MS analyses. It was established that Fe and Mn contents and Mn/Fe ratio in the concretions varied considerably and which controlled occurrence of several associated metals and minor elements; some of them have not been studied in Black Sea concretions before.

Composition of organic matter from black shales drilled in the Cape Verde Basin in DSDP Hole 41-367

Results of geochemical studies of organic matter in black shales from the Cape Verde Basin are reported. Based on these results, in combination with data of petrographic analysis, conclusions are made about sapropelic nature of their organic matter and low degree of its coalification. It corresponds to the proto-catagenetic substage of sedimentary rocks. Black shales of the Cape Verde Basin are classified as potential oil source strata.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

(Table 2) Plankton biomass and production in the Burgas Bay, Black Sea

Distribution of mesoplankton in the Burgas Bay in 53 bottle samples taken in October-November 1982 is discussed. Decrease in total biomass of zooplankton from north to south can be traced at the northern meridional section (Cape Krotiriya to Cape Kaliakra), probably resulting from decrease in eutrophicating effect of the Danube River in this direction. Plankton off the Bulgarian coast was in typical autumn condition. In the southern part of the Burgas Bay, where there is discharge current carrying eutrophicated sewage from the city of Burgas, various stages in development of the community, from a young community in the inner end of the bay to a mature one at its outlet, were observed.