Biomarkers, stable carbon isotope record and pollen distribution of the soutwest African continental margin

This is part 2 of a study examining southwest African continental margin sediments from nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) representing two glacial (MIS 2 and 6a) and two interglacial stages (MIS 1 and 5e). Contents, distribution patterns, and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) as indicators of land plant vegetation of different biosynthetic types were correlated with concentrations and distributions of pollen taxa in sediments of the same time horizons. Selected single pollen type data reveal details of vegetation changes, but the overall picture is best illustrated by summing pollen known to predominantly derive from C4 plants or C4 plus CAM plants. The C4 plant signals in the biomarkers are recorded in the delta13C data and in the abundances of C31 and C33 n-alkanes, and the C32 n-alkanol. Calculated clusters of wind trajectories for austral summer and winter situations for the Holocene and the Last Glacial Maximum afford information on the source areas for the lipids and pollen and their transport pathways to the ocean. This multidisciplinary approach provides clear evidence of latitudinal differences in leaf wax lipid and pollen composition, with the Holocene sedimentary data paralleling the current major phytogeographic zonations. The northern sites (Congo Fan area and northern Angola Basin) get most of their terrestrial material from the Congo Basin and the Angolan highlands dominated by C3 plants. Airborne particulates derived from the western and central South African hinterland dominated by deserts, semideserts, and savannah regions are rich in organic matter from C4 plants. As can be expected from the present and glacial positions of the phytogeographic zones, the carbon isotopic signatures of n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. In the northern part of the transect the relative importance of C4 plant indicators is higher during the glacials than in the interglacials, indicating a northward extension of arid zones favoring grass vegetation. In the south, where grass-rich vegetation merges into semidesert and desert, the difference in C4 plant indicators is small.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Organic geochemistry of two sediment cores from the Kara Sea

Within the Russian-German research project on "Siberian River Run-off (SIRRO)" devoted to the freshwater discharge and its influence on biological, geochemical, and geological processes in the Kara Sea, sedimentological and organic-geochemical investigations were carried-out on two well-dated sediment cores from the Yenisei Estuary area. The main goal of this study was to quantify the terrigenous organic carbon accumulation based on biomarker and bulk accumulation rate data, and its relationship to Yenisei river discharge and climate change through Holocene times. The biomarker data at both cores clearly indicate the predominance of terrigenous organic matter, reaching 70 to 100% and 50 to 80% of the total organic carbon within and directly north of the estuary, respectively. During the last about 9 Cal. kyrs. BP represented in the studied sediment section, siliciclastic sediment and (terrigenous) organic carbon input was strongly influenced by postglacial sea-level rise and climate-related changes in river discharge. The mid-Holocene Climatic Optimum is documented by maximum river discharge between 8.2 and 7.3 Cal. kyrs. BP. During the last 2000 years river discharge probably became reduced, and accumulation of both terrigenous and marine organic carbon increased due to increased coagulation of fine-grained material.

Dissolved and particulate organic carbon in the Sea of Okhotsk

Data on distribution of dissolved and particulate organic matter obtained during Cruises 21 and 24 of R/V Akademik A. Nesmeyanov in June-August 1992 and 1993 are presented. In general a remarkable heterogeneity in distributions of both dissolved and particulate organic carbon is revealed. Concentrations of dissolved organic carbon vary from 98 to 700 µmol/l and those of particulate organic carbon vary from 3 to 50 µmol/l. Maximum concentrations are commonly observed in the shelf region while minimum concentrations - in the central basin. Run-off of the Amur River raises dissolved matter concentration in the Sakhalin Bay, while oil exploitation at the Sakhalin shelf maximizes particulate organic carbon concentration and minimizes dissolved one. Concentrations of dissolved and particulate organic carbon in the surface microlayer were estimated for the first time and are shown to be 1.5-2.0 times higher than in surface waters.

Iron and manganese in bottom sediments and interstitial waters sampled in the White Sea on August 21-30, 2003

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and speciations depending on sedimentation environment, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in total Fe content (2-8%) are accompanied by changes in concentration of its reactive forms (acid extraction) and concentration of dissolved Fe in interstitial waters (1-14 µM). Variations in Mn content in bottom sediments (0.03-3.7%) and interstitial waters (up to 500 µM) correspond to high diagenetic mobility of this element. Changes in oxidation degree of chemical elements result in redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of bottom sediments with considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface layer bottom sediments (where manganese oxyhydroxide dominates among oxidants) to deeper layers (where sulfate of interstitial water serves as the main oxidant). Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5-0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from bottom sediments (Mn 0.05%).

Organic facies and hydrocarbon potential at DSDP Leg 64 Holes

The sediments from the Gulf of California are potentially good sources for oil and gas. They are rich in organic carbon (av. = 1.9%). Sediments from the margins of the Gulf are rich in oil-prone marine-amorphous organic matter. Sediments from Guaymas Basin contain the same material plus abundant subordinate amounts of gas-prone terrestrially derived organic matter. The enrichment of all of these sediments in marine-amorphous components reflects deposition in a highly productive and oxygen-poor water mass. The sediments are thermally immature, except for those altered by hydrothermal activity or by the intrusion of sills. These sediments are extensively cooked and may have lost their potential for hydrocarbon generation.

Contents of organic compounds in sediments from DSDP Legs 1 and 4

Fifteen sediment samples were studied from five drill sites recovered by the Glomar Challenger on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids. Carbon isotope (dC13) data [values <(-26)?, relative to PDB], long-chain n-alkyl hydrocarbons (>>C27) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized. The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Composition and fluxes of sinking particulate material and bottom sediments in the northeast Black Sea in 1998-1999

For the first time deep-sea mooring stations with sediment traps were deployed in the northeast Black Sea. One sediment trap for long-term studies was located at Station 1 (44°15'N, 37°43'E, deployment depth 1800 m, depth 1900 m). The trap collected sinking sedimentary material from January to May 1998. Material collectors were changed every 15 days. Other stations with sediment traps for short-term studies (September-October 1999) were located on the shelf: Station 2 (44°16'N, 38°37'E, deployment depth 45 m, depth 50 m) and on the bottom of the canyon: Station 3 (44°16'N, 38°22'E, deployment depth 1145 m, depth 1150 m), Station 4 (44°11'N, 38°21'E, deployment depths 200, 1550, 1650 m, depth 1670 m). Collected material indicates that vertical particle fluxes are controlled by seasonal changes of in situ production and by dynamics of terrigenous matter input. Higher vertical particle flux of carbonate and biogenic silica was in spring due to bloom of plankton organisms. Maximum of coccolith bloom is in April-May. Bloom of diatoms begins in March. In winter and autumn lithogenic material dominates in total flux. Its amount strongly depends on storms and river run-off. Suspended particle material differs from surface shelf sediments by finer particles (mainly clay fraction) and high content of clay minerals and biogenic silica. This material may form lateral fluxes with higher concentration of particles transported along the bottom of deep-sea canyons from the shelf to the deep basin within the nepheloid layer. In winter such transportation of sedimentary material is more intensive due to active vertical circulation of water masses.

Lipids in ocean particulate matter and bottom sediments

Lipid contents both in particulate matter and bottom sediments decreases with passage from the shelf toward the open ocean. Lipid concentration in particulate matter collected by a separator (Ls) decreases by a factor of 7 (from 7.05 to 0.95 % of dry matter), while in particulate matter collected on filters (Lf) it decreases by a factor of 13 (from 78 to 6 µg/l) in the vicinity of the Limpopo River and by a factor of 6 (from 74 to 13 µg/l) in the vicinity of the Zambezi River. Concentration of Lf also decreased with depth. In the upper sediment layers lipid concentration was 0.0028-0.039% of dry matter; all mud samples were richer in lipids, than sand samples. During sedimentogenesis there is an increase in proportion of lipids relative to other classes of organic matter, proportion of low-polarity compounds increases among the lipids, and proportion of hydrocarbons rises among these compounds. Sediments inherit composition of particulate matter to the greatest degree in the vicinity of river mouths.

Organic geochemical character of selected cores at DSDP Hole 75-530A

The Albian/Cenomanian strata in Hole 530A are organically richer than are the post-Cenomanian strata. Organic matter is thermally immature and appears to be of dominantly marine origin with either variable levels of oxidation or variable amounts of terrestrial input. Geochemical data alone cannot establish whether the black shales present in Hole 530A represent deposition within a stagnant basin or within an expanded oxygen-minimum layer