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.

Age models and sea-surface paleotemperature reconstruction of sediment cores from the eastern equatorial Atlantic

Based on the faunal record of planktonic foraminifers in three long gravity sediment cores from the eastern equatorial Atlantic, the sea-surface temperature history ove the last 750,000 years was studied at a resolution of 3,000 to 10,000 years. Detailed oxygen-isotope and paleomagnetic stratigraphy helped to identify the following major faunal events: Globorotaloides hexagonus and Globorotalia tumida flexuosa became extinct in the eastern tropical Atlantic at the isotope stage 4/5 boundary, now dated at 68,000 years B.P. The persistent occurrence of the pink variety of Globigerinoides ruber started during the late stage 12 at 410,000 years B.P. CARTUNE-age. This datum may provide an easily detectible faunal stratigraphic marker for the mid-Brunhes Chron. The updated scheme of the Ericson zones helped the recognition of a hiatus at the northwestern slope of the Sierra Leone Basin covering oxygen-isotope stages 10 to 12. Classifying the planktonic foraminifer counts into six faunal assemblages, according to the factor analysis derived model of Pflaumann (1985), the tropical and the tropical-upwelling communities account for 57 % at Site 16415, and 86 % at Site 13519, respectively of the variance of the faunal record. A largely continuous paleotemperature record for both winter and summer seasons was obtained from the top of the Sierra Leone Rise with the winter temperatures ranging between 20 and 25 °C, and the summer ones between 24 and 30 °C. The record of cores from greater water depths is frequently interrupted by samples with no-analogue faunal communities and/or poor preservation. Based on the seasonality signal, during cold periods the termal equator shifted to a geographically mnore asymmetrical northern position. Dissolution altering the faunal communities becomes stronger with greater water depth, the estimated mean minimum loss of specimens increases from 70 % to 80 % between 2,860 and 3,850 water depth although some species will be more susceptible than others. Enhanced dissolution occured during stage 4 but also during cold phases in the warm stage 7 and 9. Correlations between the Foraminiferal Dissolution Index and the estimated sea-surface temperatures are significant. Foraminiferal flux rates, negatively correlated to the flux rates of organic carbon and of diatoms, may be a result of enhanced dissolution during cold stages, destroying still more of the faunal signal than indicated by the calculated minimum loss. The fluctuations of the oxygen-isotope curves and the hibernal sea-surfave temperatures are fairly coherent. During warm oxygen-isotope stages the temperature maxima lag often by 5 to 15 ka behind the respective sotope minima. During cold stages, sea-surface temperature changes are partly out of phase and contain additional fluctuations.

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.

Controls of sediment dynamics on the Galician slope reconstructed from three sediment cores (GeoB11035-1, GeoB130206-1, GeoB13071-1)

Controls of sediment dynamics at the Galician continental slope (NW Iberia) during the past 30 ka were reconstructed from three new gravity cores (GeoB11035-1, 130206-1, 13071-1) based on sedimentological (e.g. sortable silt, IRD), micropalaeontological (e.g. coccoliths), geochemical (AMS 14C, XRF) and geophysical (e.g. magnetic susceptibility) diagnostics. The data are consistent with existing regional knowledge that, during marine isotope stages 3-1, variations in detrital input, marine productivity and sea level were the essential drivers of sediment availability on the slope, whereas deep-water current velocities controlled sediment deposition: (1) the period prior to 30 cal ka BP is characterized by minor but systematic variations in various proxies which can be associated with D-O cycles; (2) between 30 and 18 cal ka BP, high detrital input and steady slope-parallel currents led to constant sedimentation; (3) from the LGM until 10 cal ka BP, the shelf-transgressive sea-level rise increased the detrital particle flux; sedimentation was influenced by significantly enhanced deep-water circulation during the Bølling/Allerød, and subsequent slowing during the Younger Dryas; (4) an abrupt and lasting change to hemipelagic sedimentation at ca. 10 cal ka BP was probably due to Holocene warming and decelerated transgression; (5) after 5 cal ka BP, additional input of detrital material to the slope is plausibly linked to the evolution of fine-grained depocentres on the Galician shelf, this being the first report of this close shelf-slope sedimentary linkage off NW Iberia. Furthermore, there is novel evidence of the nowadays strong outer shelf Iberian Poleward Current becoming established at about 15.5 cal ka BP. The data also demonstrate that small-scale morphologic features and local pathways of sediment export from the neighbouring shelf play an important role for sediment distribution on the NW Iberian slope, including a hitherto unknown sediment conduit off the Ría de Arousa. By implication, the impact of local morphology on along- and down-slope sediment dynamics is more complex than commonly considered, and deserves future attention.

Ikaite of sediment cores from the Zaire deep-sea fan

Most concentration profiles of sulfate in continental margin sediments show constant or continuously increasing gradients from the benthic boundary layer down to the deep sulfate reduction zone. However, a very marked change in this gradient has been observed several meters below the surface at many locations, which has been attributed to anoxic sulfide oxidation or to non-local transport mechanisms of pore waters. The subject of this study is to investigate whether this feature could be better explained by non-steady state conditions in the pore-water system. To this end, data are presented from two gravity cores recovered from the Zaire deep-sea fan. The sediments at this location can be subdivided into two sections. The upper layer, about 10 m thick, consists of stratified pelagic deposits representing a period of continuous sedimentation over the last 190 kyr. It is underlain by a turbidite sequence measuring several meters in thickness, which contains large crystals of authigenic calcium carbonate (ikaite: CaCO3·6H2O). Ikaite delta13C values are indicative of a methane carbon contribution to the CO2 pool. Radiocarbon ages of these minerals, as well as of the adjacent bulk sediments, provide strong evidence that the pelagic sediments have overthrust the lower section as a coherent block. Therefore, the emplacement of a relatively undisturbed sediment package is postulated. Pore-water profiles show the depth of the sulfate-methane transition zone within the turbiditic sediments. By the adaptation of a simple transport-reaction model, it is shown that the change in the geochemical environmental conditions, resulting from this slide emplacement, and the development towards a new steady state are fully sufficient to explain all features related to the pore-water profiles, particularly, [SO4]2- and dissolved inorganic carbon (DIC). The model shows that the downslope transport took place about 300 yr ago.