Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Stable isotope record of planktic foraminifera sampled by plankton haul and in surface sediments off North-West Africa

Foraminifera shells from modern sediments document the hydrography of the coastal upwelling region off Northwest-Africa (12-35° N) through the stable isotopic composition of their shells. Oxygen isotopes in planktonic foraminifers reflect sea surface temperatures (SST) during the main growing season of the differnt species: Globigerinoides ruber (pink and white) and G. sacculifer delineate the temperatures of the summer, Globorotalia inflata and Pulleniatina obliquiloculata those of the winter. Oxygen isotopes on Globigerina bulloides document temperature ranges of the upwelling seasons. d18O values in planktonic foraminifera from plankton hauls resemble those from the surface sediment samples, if the time of the plankton collection is identical with that of the main growing season of the species. The combined isotopic record of G. ruber (white) and G. inflata clearly reveals the latitudinal variations of the annual mean SST. The deviation of the d18O values from both species from their common mean is a scale for the seasonality, i.e. the maximum temperature range within one year. Thus in the summer upwelling region (north of 25° N) seasonality is relatively low, while it becomes high in the winter upwelling region south of 20° N. Furthermore, the winter upwelling region is characterized by relatively high d18O values - indicating low temperatures - in G. bulloides, the region of summer upwelling by relatively low d180 values compared with the constructed annual mean SST. Generally, carbon isotopes from the plankton hauls coincide with those from sediment surface samples. The enrichment of 13C isotopes in foraminifers from areas with high primary production can be caused by the removal of 12C from the total dissolved inorganic carbon during phytoplankton blooms. It is found that carbon isotopes from plankton hauls off Northwest-Africa are relatively enriched in 13C compared with samples from the western Atlantic Ocean. Also shells of G. ruber (pink and white) from upwelling regions are enriched in the heavier isotope compared with regions without upwelling. In the sediment, the enrichement of 13C due to high primary production can only be seen in G. bulloides from the high fertile upwelling region south of 20° N. North of this latitude values are relatively low. An enrichment of 12C is observed in shells of G. ruber (pink), G. inflata and P. obliquiloculata from summer-winter- and perennial upwelling regions respectively. Northern water masses can be distinguished from their southern counterparts by relatively high oxygen and carbon values in the "living" (=stained) benthic foraminifera Uvigerina sp. and Hoeglundina elegans. A tongue of the Mediterranean Outflow water can be identified far to the south (20° N) by 13C-enriched shells of these benthic foraminifera. A zone of erosion (15-25° N, 300-600 m) with a subrecent sediment surface can be mapped with the help of oxygen isotopes in "dead" benthic specimens. Comparison of d18O values in aragonitic and calcitic benthic foraminifers does not show a differential influence of temperature on the isotopic composition in the carbonate. However, carbon isotopes reflect slightly differences under the influence of temperature.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Grain size distribution, carbon content and wet bulk density of sediment cores in the equatorial Atlantic and the Norwegian Sea

Near-surface sediments from the equatorial east Atlantic and the Norwegian Sea exhibit pronounced shear strength maxima in profiles from the peak Holocene and Pleistocene. These semi-indurated layers start to occur at 8-102 cm below the sediment surface and can be explained neither by the modal composition nor by the effective overburden pressure of the sediments. However, scanning electron microscope and microprobe data exhibit micritic crusts and crystal carpets, which are clearly restricted to (undisturbed) samples from indurated layers and form a manifest explanation for their origin. The minerals precipitated comprise calcite, aragonite, and in samples more proximal to the African continent SiO2 needles, and needles of as yet unidentified K-Mg-Fe-Al silicates, crusts of which dominate the indurated layers in the Norwegian Sea. By their stratigraphic position in deep-sea sediments the carbonate-based shear strength maxima are tentatively ascribed to dissolved adjacent pteropod layers from the early Holocene and hence to short-lived no-analogue events of early diagenesis. Possibly, they have been controlled by a reduced organic carbon flux, leading to increased aragonite preservation in the deep sea.

Distribution of benthic foraminifera in surface sediments on the continental margin off North-West Africa

The benthic foraminiferal populations along three traverses across the Northwest African continental margin were analyzed on the base of ca. 60 surface sediment samples. Depth ranges of 213 species were established and the main trends of vertical distribution are compared with those known from adjacent regions. Main faunal breaks occure at 100/200 m and 1000/1500 m depth of water. Some species show latitudinal distribution boundaries and the same applies to population density (standing stock), reflecting the regional distribution of nutrients supply by river discharge and upwelling processes. - High proportions of Bolivina test at the lower slope indicate extended downslope transport.

Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.