Sediment and organic matter properties, and molecular formula from sampling locations in the Northern Black Sea

Remineralization of organic matter in reactive marine sediments releases nutrients and dissolved organic matter (DOM) into the ocean. Here we focused on the molecular-level characterization of DOM by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sediment pore waters and bottom waters from contrasting redox regimes in the northern Black Sea with particular emphasis on nitrogen-bearing compounds to derive an improved understanding of the molecular transformations involved in nitrogen release. The number of nitrogen-bearing molecules is generally higher in pore waters than in bottom waters. This suggests intensified degradation of nitrogen-bearing precursor molecules such as proteins in anoxic sediments: No significant difference was observed between sediments deposited under oxic vs anoxic conditions (average O/C ratios of 0.55) suggesting that the different organic matter quality induced by contrasting redox conditions does not impact protein diagenesis in the subseafloor. Compounds in the pore waters were on average larger, less oxygenated, and had a higher number of unsaturations. Applying a mathematical model, we could show that the assemblages of nitrogen-bearing molecular formulas are potential products of proteinaceous material that was transformed by the following reactions: (a) hydrolysis and deamination, both reducing the molecular size and nitrogen content of the products and intermediates; (b) oxidation and hydration of the intermediates; and (c) methylation and dehydration.

Chemistry of Late Quaternary sediments and their interstitial waters of sediment cores from the Nort-West African continental margin

In the sediments of the NW African continental margin the mainly biogenic carbonate constituents become increasingly diluted with terrigenous material as one approaches the coast, as indicated by the carbonate-CO2 content, the Al2O3/SiO2-ratios, and the presence of ammonia fixed to alumino-silicates, predominantly to illites. In the norther area of the investigation - off Cape Blanc and Cape Bojador . the terrigenous constituents are mainly quartz from the Sahara Desert, whereas in the south - off Senegal - more alumino-silicates as clay minerals are admixed with the carbonate constituents. The organic carbon content of the continental slope sediments off Senegal is higher than in samples of the continental rise or of the preservation of organic matter as a result of high production and relatively rapid sedimentation. The zone of manganese-oxide enrichment follows the redox potential of + 330 mV from the surface (0-5 cm) into the sediments (20-30 cm deep) at 2000--3000 m and 3700 m of water depths, respectively. At shallower water depths, low redox potentials preclude deposition of manganese oxides and cause their mobilization from the sediments. About 1/3 of the total sedimentary Zn and 1/4 of the Cu is associated with the carbonate mineral fraction, probably in calcium phosphate overgrowths as a result of the mineralization of phosphorus-containing organic matter. Besides the precipitation of calcium phosphate, the mineralization of organic matter mediated by bacterial sulfate reduction also results in calcium carbonate precipitation and the exchange of ammonia for potassium on illites. Because of these simultaneous reactions, the depth distribution of all mineralization constituents in the interstitial water can be determined using the actual molar carbon-to-nitrogen-to phosphorus ratios of the sedimentary organic matter. The amount of sulfide sulfur in this process indicates the predominance of bacterial sulfate reduction in the sediments off NW Africa. This process also preferentially decomposes nitrogen- and phosphorus-containing organic compounds so organic matter deficient in these elements is characteristic for the rapidly accumulating sediments than today, indicating there was increased production of organic carbon compounds and more favorable conditions of their preservations. During the last interglacial times conditions were similar to those to today. This differentiation with time has also been observed in sediments from the Argentine Basin and from slope off South India indicating perhaps world-wide environmental changes throughout Late Quaternary times.

Pollen profile of sediment core Dethlingen, Germany

To better understand the environmental variability during the Holsteinian interglacial, we have palynologically analyzed a new core from Dethlingen, northern Germany, at a decadal resolution. Our data provide insights into the vegetation dynamics and thus also climate variability during the meso- to telocratic forest phases of the interglacial. Temperate mixed forests dominated the regional landscape throughout the Holsteinian. However, changes in the forest composition during the younger stages of the interglacial suggest a climatic transition towards milder conditions in winter. The strong presence of boreal floral elements during the older stages of the Holsteinian interglacial suggests a high seasonality. In contrast, during the younger stages the development of sub-Atlantic and Atlantic floral elements suggests increasingly warm and humid climatic conditions. Peak warming during the younger stage of the Holsteinian is marked by the maximum pollen abundances of Buxus, Abies, and Quercus. Although the vegetation dynamics suggest a general warming trend throughout the Holsteinian interglacial, abrupt as well as gradual changes in the relative abundances of temperate plants indicate considerable climatic variability. In particular, two marked declines in temperate taxa leading to the transient development of boreal and sub-temperate forests indicate short-term climatic oscillations that occurred within full interglacial conditions. The palynological signatures of these two regressive phases in vegetation development differ with regard to the expansion of pioneer trees, the abundances and rates of change of temperate taxa, and the presence of frost-sensitive taxa. These differences point to different mechanisms responsible for the individual regressive phases. Assuming a correlation of the interglacial at Dethlingen with Marine Isotope Stage (MIS) 11, our data suggest that temperate forests prevailed in northern Germany during the younger parts of MIS 11c.

Sedimentology of the southern Bellingshausen Sea

A major trough ('Belgica Trough') eroded by a palaeo-ice stream crosses the continental shelf of the southern Bellingshausen Sea (West Antarctica) and is associated with a trough mouth fan ('Belgica TMF') on the adjacent continental slope. Previous marine geophysical and geological studies investigated the bathymetry and geomorphology of Belgica Trough and Belgica TMF, erosional and depositional processes associated with bedform formation, and the temporal and spatial changes in clay mineral provenance of subglacial and glaciomarine sediments. Here, we present multi-proxy data from sediment cores recovered from the shelf and uppermost slope in the southern Bellingshausen Sea and reconstruct the ice-sheet history since the last glacial maximum (LGM) in this poorly studied area of West Antarctica. We combined new data (physical properties, sedimentary structures, geochemical and grain-size data) with published data (shear strength, clay mineral assemblages) to refine a previous facies classification for the sediments. The multi-proxy approach allowed us to distinguish four main facies types and to assign them to the following depositional settings: 1) subglacial, 2) proximal grounding-line, 3) distal sub-ice shelf/subsea ice, and 4) seasonal open-marine. In the seasonal open-marine facies we found evidence for episodic current-induced winnowing of near-seabed sediments on the middle to outer shelf and at the uppermost slope during the late Holocene. In addition, we obtained data on excess 210Pb activity at three core sites and 44 AMS 14C dates from the acid-insoluble fraction of organic matter (AIO) and calcareous (micro-)fossils, respectively, at 12 sites. These chronological data enabled us to reconstruct, for the first time, the timing of the last advance and retreat of the West Antarctic Ice Sheet (WAIS) and the Antarctic Peninsula Ice Sheet (APIS) in the southern Bellingshausen Sea. We used the down-core variability in sediment provenance inferred from clay mineral changes to identify the most reliable AIO 14C ages for ice-sheet retreat. The palaeo-ice stream advanced through Belgica Trough after ~36.0 corrected 14C ka before present (B.P.). It retreated from the outer shelf at ~25.5 ka B.P., the middle shelf at ~19.8 ka B.P., the inner shelf in Eltanin Bay at ~12.3 ka B.P., and the inner shelf in Ronne Entrance at ~6.3 ka B.P.. The retreat of the WAIS and APIS occurred slowly and stepwise, and may still be in progress. This dynamical ice-sheet behaviour has to be taken into account for the interpretation of recent and the prediction of future mass-balance changes in the study area. The glacial history of the southern Bellingshausen Sea is unique when compared to other regions in West Antarctica, but some open questions regarding its chronology need to be addressed by future work.

Humic acids in bottom sediments of the Western Pacific

Elemental composition, functional groups, and molecular mass distribution were determined in humic acids from the Western Pacific abyssal and coastal bottom sediments. Humic acid structure was studied by oxidative degradation with alkaline nitrobenzene and potassium permanganate, p-coumaric, guaiacilic, and syringilic structural units typical for lignin of terrestrial plants were identified in humic acids by chromatographic analysis of oxidation products. Polysubstituted and polycondensed aromatic systems with minor proportion of aliphatic structures were basic structural units of humic acids in abyssal sediments.

Water chemistry and fluffy layer geochemistry and mineral content at four sites in the western Baltic Sea

The fluffy layer was sampled repeatedly during nine expeditions between October 1996 and December 1998 at four stations situated along a S-N-transect from the Oder Estuary to the Arkona Basin. Geochemical and mineralogical analyses of the fluff show regional differences (trends) in composition, attributed to provenance and to hydrographical conditions along their transport pathways. Temporal variability is very high at the shallow water station of the estuary, and decreases towards the deeper stations in the north. In the shallow water area, intensive resuspension of the fluff due to wind-driven waves and currents leads to an average residence time of only one to two days. Near-bottom lateral transport of the fluff is the main process that transfers the fine grained material, containing both nutrients and contaminants, from the coastal zone into the deeper basins of the Baltic Sea. Seasonal effects (e.g. biogenic production in relation to trace metal variation) are observed at the Tromper Wiek station, where the residence time of the fluffy material is in the scale of seasons. Thus, the fluffy layer offers suitable material for environmental monitoring programs.

Permafrost cores and active layer pits on Herschel Island: core attributes

Twelve permafrost cores and active layer pits were drilled/dug on Herschel Island in order to estimate the soil organic carbon and total nitrogen contents in the first 30, 100 and 200 cm of ground. The data are the core information obtained during sampling.

Late pleistocene and holocene sedimentation in the central and eastern Persian Gulf

The sandfraction of the sediment was analysed in five cores, taken from 65 m water depth in the central and eastern part of the Persian Gulf. The holocene marls are underlayn by aragonite muds, which are probably 10-11,000 years old. 1. The cores could be subdivided into coarse grained and fine grained layers. Sorting is demonstrated by the following criteria: With increasing median values of the sandfraction - the fine grained fraction decreases within each core; - the median of each biogenic component, benthonic as well as planktonic, increases; - the median of the relict sediment, which in core 1179 was carried upward into the marl by bioturbation, increases; - the percentages of pelecypods, gastropods, decapods and serpulid worms in the sandfraction increase, the percentages of foraminifera and ostracods decrease; - the ratios of pelecypods to foraminifera and of decapods to ostracods increase; - the ratios of benthonic molluscs to planktonic molluscs (pteropods) and of benthonic foraminifera to planktonic foraminifera increase (except in core 1056 and 1179); - the ratio of planktonic molluscs (pteropods) to planktonic foraminifera increases; - the globigerinas without orbulinas increase, the orbulinas decrease in core 1056. Different settling velocities of these biogenic particles help in better understanding the results : the settling velocities, hence the equivalent hydrodynamic diameters, of orbulinas are smaller than those of other globigerinas, those of planktonic foraminifera are smaller than those of planktonic molluscs, those of planktonic molluscs are smaller than those of benthonic molluscs, those of pelecypods are smaller than those of gastropods. Bioturbation could not entirely distroy this "grain-size-stratification". Sorting has been stronger in the coarse layers than in the finer ones. As a cause variations in the supply of terrigenous material at constant strength of tidal currents is suggested. When much terrigenous material is supplied (large contents of fine grained fraction) the sedimentation rates are high: the respective sediment surface is soon covered and removed from the influence of tidal currents. When, however, the supply of terrigenous material is small, more sandy material is taken away in all locations within the influence of terrigenous supply. Thus the biogenic particles in the sediment do not only reflect the organic production, but also the influence of currents. 2. There is no parameter present in all cores that is independently variable from grain size and can be used for stratigraphic correlation. The two cores from the Strait of Hormus were correlated by their sequences of coarse and fine grained layers. 3. The sedimentation rates of terrigenous material, of total planktonic and benthonic organisms and of molluscs, foraminifera, echinoids and ophiuroids are shown in table 1 (total sediment 6.3-75.5 cm/1000 yr, biogenic carbonate 1.9-3.6 cm/1000 yr). The sedimentation rates of benthonic organisms are nearly the same in the cores of the Strait of Hormus, whereas near the Central Swell they are smaller. In the upper parts of the two cores of the Strait of Hormus sedimentation rates are higher than in the deeper parts, where higher median values point to stronger reworking. 4. The sequence of coarse and fine grained intervals in the two cores of the Hormus Strait, attributed to variations in climate, as well as the increase of terrigenous supply from the deeper to the upper parts of the cores, agrees with the descriptions in the literature of the post Pleistocene climate as becoming more humid. The rise of sea level is sedimentologically not measurable in the marly sediments - except perhaps for the higher content of echinoids in the lower part of core 1056. These may be attributed to the influence of a migrating wave-base. 5. The late Pleistocene aragonite mud is very fine grained (> 50%< 2 p) and poor in fossils (0.5-1.8%) biogenic particles of total sediment. The sand fraction consists almost entirely of white clumps, c. 0.1 mm in diameter (1177), composed of aragonite needles and of detrital minerals with the same size (1201). The argonite mud was probably not formed in situ, because the water depth at time of formation was at most 35 m at least 12 m. The sorting of the sediment (predominance of the fine grained sand), the absence of larger biogenic components and of pellets, c. 0.2-0.5 mm in diameter, which are typical for Recent and Pleistocene locations of aragonite formation, as well as the sedimentological conditions near the sampling points, indicate rather a transport of aragonite mud from an area of formation in very shallow waters. Sorting as well as lenticular fabric in core 1201 point to sedimentation within the influence of currents. During alternating sedimentation - and reworking processes the aragonitic matrix was separated from the silt - and sand-sized minerals. The lenses grade into touches because of bioturbation. 6. In core 1056 D2 from Hormus Bay the percentages of organic carbon, total nitrogen and total carbonate were determined. With increasing amounts of smaller grain sizes the content of organic matter increases, whereas the amount of carbonate decreases. The amounts of organic carbon and of nitrogen decrease with increasing depth, probably due to early-diagenetic decomposition processes. Most of the total nitrogen is of organic origin, only about 10% may well be inorganically fixed as ammonium-nitrogen. In the upper part of the core the C/N-ratio increases with increasing depth. This may be connected with a stronger decomposition of nitrogen-containing organic compounds. The general decrease of the C/N-ratios in the lower part of the core may be explained by the relative increase of inorganically fixed ammonium-nitrogen with decreasing content of organic matter.

Geochemistry, fatty acid content and phylogenetic affiliation of soil samples from Livingston Island, South Shetland Archipelago, Antarctica

Microorganisms inhabit very different soil habitats in the ice-free areas of Antarctica, playing a major role in nutrient cycling in cold environments. We studied the soil characteristics and the dominant bacterial composition from nine different soil profiles located on Livingston Island (maritime Antarctica). The total carbon (TC) and total nitrogen (TN) values were high for the vegetated soils, decreasing with depth, whereas the values for the mineral soils were generally low. Soil pH was more acidic for moss-covered soils and neutral to alkaline for mineral soils. Numbers of culturable heterotrophic bacteria were higher at vegetated sites, but significant numbers were also detectable in carbon-depleted soils. Patterns of denaturing gradient gel electrophoresis (DGGE) revealed a highly heterogeneous picture throughout the soil profiles. Subsequent sequencing of DGGE bands revealed in total 252 sequences that could be assigned to 114 operational taxonomic units, showing the dominance of members of the Bacteroidetes and Acidobacteria. The results of phospholipid fatty acid analysis showed a lack of unsaturated fatty acids for most of the samples. Samples with a prevalence of unsaturated over saturated fatty acids were restricted to several surface samples. Statistical analysis showed that the dominant soil bacterial community composition is most affected by TC and TN contents and soil physical factors such as grain size and moisture, but not pH. Keywords