ALBERT

Description: 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.

Description: Accumulation rates of Mg, Al, Si, Mn, Fe, Ni, Cu, Zn, opal, and calcium carbonate have been calculated from their concentrations in samples from equatorial Deep Sea Drilling Project sites. Maps of element accumulation rates and of Q-mode factors derived from raw data indicate that the flux of trace metals to equatorial Pacific sediments has varied markedly through time and space in response to changes in the relative and absolute influence of several depositional influences: biogenic, detrital, authigenic, and hydrothermal sedimentation. Biologically derived material dominates the sediment of the equatorial Pacific. The distributions of Cu and Zn are most influenced by surface-water biological activity, but Ni, Al, Fe, and Mn are also incorporated into biological material. All of these elements have equatorial accumulation maxima similar to those of opal and calcium carbonate at times during the past 50 m.y. Detritus distributed by trade winds and equatorial surface circulation contributes Al, non-biogenic Si, Fe, and Mg to the region. Detrital sediment is most important in areas with a small supply of biogenic debris and low bulk-accumulation rates. Al accumulation generally increases toward the north and east, indicating its continental source and distribution by the northeast trade winds. Maxima in biological productivity during middle Eocene and latest Miocene to early Pliocene time and concomitant well-developed surface circulation contributed toward temporal maxima in the accumulation rates of Cu, Zn, Ni, and Al in sediments of those ages. Authigenic material is also important only where bulk-sediment accumulation rates are low. Ni, Cu, Zn, and sometimes Mn are associated with this sediment. Fe is almost entirely of hydrothermal origin. Mn is primarily hydrothermal, but some is probably scavenged from sea water by amorphous iron hydroxide floes along with other elements concentrated in hydrothermal sediments, Ni, Cu, and Zn. During the past 50 m.y. all of these elements accumulated over the East Pacific Rise at rates nearly an order of magnitude higher than those at non-rise-crest sites. In addition, factor analysis indicates that some of this material is carried substantial distances to the west of the rise crest. Accumulation rates of Fe in basal metalliferous sediments indicate that the hydrothermal activity that supplied amorphous Fe oxides to the East Pacific Rise areas was most intense during middle Eocene and late Miocene to early Pliocene time.

Description: Pliocene and Pleistocene planktonic foraminiferal biogeography and paleoceanography have been examined in Deep Sea Drilling Project (DSDP) sites of the Panama Basin (Pacific Ocean) and Colombian and Venezuelan Basins (Atlantic Ocean) to determine the timing of the isolation of Atlantic and Pacific tropical planktonic faunas resulting from the development of the Central American isthmus. Previous studies have suggested a late Miocene to middle Pliocene occurrence of this event. The Panama Basin (DSDP site 157) and the Colombian Basin (DSDP site 154A) share two early Pliocene biogeographic events: (1) great abundance of sinistral coiling Neogloboquadrina pachyderma at 4.3 m.y. ago at site 157 and 0.7 m.y. later at site 154A, and (2) a sinistral-to-dextral change in the coiling-direction preference in Pulleniatina 3.5 m.y. ago at both locations. Identification of these events farther to the east in the Venezuelan Basin (DSDP site 148) is complicated by insufficient lower Pliocene core recovery, but abundant sinistral N. pachydcrma appear to have extended far to the east in the Caribbean 3.6 m.y. ago; perhaps the early Pliocene abundance of this form is not indicative of cool water. The coiling-direction history and stratigraphic ranges of Pulleniatina became different in the Atlantic and Pacific Oceans during the early Pliocene; this is inferred to result from geographic isolation of the assemblages. Saito (1976) used the temporary disappearance of this genus from Atlantic waters at 3.5 m.y. ago to mark the closure of the Isthmus of Panama, but I show that in the Colombian Basin (site 154A) its disappearance was closer to 3.1 m.y. ago. This suggests the possibility of surface-water communication between the Atlantic and Pacific until that time.

Description: The marine ecosystem on the eastern shelf of the Antarctic Peninsula was surveyed 5 and 12 years after the climate-induced collapse of the Larsen A and B ice shelves. An impoverished benthic fauna was discovered, that included deep-sea species presumed to be remnants from ice-covered conditions. The current structure of various ecosystem components appears to result from extremely different response rates to the change from an oligotrophic sub-ice-shelf ecosystem to a productive shelf ecosystem. Meiobenthic communities remained impoverished only inside the embayments. On local scales, macro- and mega-epibenthic diversity was generally low, with pioneer species and typical Antarctic megabenthic shelf species interspersed. Antarctic Minke whales and seals utilised the Larsen A/B area to feed on presumably newly established krill and pelagic fish biomass. Ecosystem impacts also extended well beyond the zone of ice-shelf collapse, with areas of high benthic disturbance resulting from scour by icebergs discharged from the Larsen embayments.

Description: Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. d18O of chert ranges between 27 and 39%. relative to SMOW, d18O of porcellanite - between 30 and 42%. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases. d18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975; http://www.deepseadrilling.org/32/volume/dsdp32_15.pdf) indicates the possibility of d18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of d18O values, increasing diagenesis being reflected in a lowering of d18O. Drusy quartz has the lowest d18O values. On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts. Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. dD of this water ranges between -78 and -95%. and is not a function of d18O of the cherts (or the temperature of their formation).

Description: Near-shore waters along the northwest African margin are characterized by coastal upwelling and represent one of the world's major upwelling regions. Sea surface temperature (SST) records from Moroccan sediment cores, extending back 2500 years, reveal anomalous and unprecedented cooling during the 20th century, which is consistent with increased upwelling. Upwelling-driven SSTs also vary out of phase with millennial-scale changes in Northern Hemisphere temperature anomalies (NHTAs) and show relatively warm conditions during the Little Ice Age and relatively cool conditions during the Medieval Warm Period. Together, these results suggest that coastal upwelling varies with NHTAs and that upwelling off northwest Africa may continue to intensify as global warming and atmospheric CO2 levels increase.

Description: A high-resolution sea surface temperature and paleoproductivity reconstruction on a sedimentary record collected at 36°S off central-south Chile (GeoB 7165-1, 36°33'S, 73°40'W, 797 m water depth, core length 750 cm) indicates that paleoceanographic conditions changed abruptly between 18 and 17 ka. Comparative analysis of several cores along the Chilean continental margin (30°-41°S) suggests that the onset and the pattern of deglacial warming was not uniform off central-south Chile due to the progressive southward migration of the Southern Westerlies and local variations in upwelling. Marine productivity augmented rather abruptly at 13-14 ka, well after the oceanographic changes.We suggest that the late deglacial increase in paleoproductivity off central-south Chile reflects the onset of an active upwelling system bringing nutrient-rich, oxygen-poor Equatorial SubsurfaceWater to the euphotic zone, and a relatively higher nutrient load of the Antarctic Circumpolar Current. During the Last Glacial Maximum, when the Southern Westerlies were located further north, productivity off central-south Chile, in contrast to off northern Chile, was reduced due to direct onshore-blowing winds that prevented coastal upwelling and export production.

Description: The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Description: Low-temperature rock magnetic measurements have distinct diagnostic value. However, in most bulk marine sediments the concentration of ferrimagnetic and antiferromagnetic minerals is extremely low, so even sensitive instrumentation often responds to the paramagnetic contribution of the silicate matrix in the residual field of the magnetometer. Analysis of magnetic extracts is usually performed to solve the problems raised by low magnetic concentrations. Additionally magnetic extracts can be used for several other analyses, for example electron microscopy or X-ray diffraction. The magnetic extraction technique is generally sufficient for sediments dominated by magnetite. In this study however, we show that high-coercivity components are rather underrepresented in magnetic extracts of sediments with a more complex magnetic mineralogy. We test heavy liquid separation, using hydrophilic sodium polytungstenate solution Na6[H2W12O40], to demonstrate the efficiencies of both concentration techniques. Low-temperature cycling of zero-field-cooled, field-cooled and saturation isothermal remanent magnetization acquired at room temperature was performed on dry bulk sediments, magnetic extracts, and heavy liquid separates of clay-rich pelagic sediments originating from the Equatorial Atlantic. The results of the thermomagnetic measurements clarify that magnetic extraction favours components with high spontaneous magnetization, such as magnetite and titanomagnetite. The heavy liquid separation is unbiased with respect to high- and low-coercive minerals, thus it represents the entire magnetic assemblage.

Description: We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios 〈35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.