Bacteriohopanepolyol biomarkers of sediments from the Congo fan

The transport and deposition of terrestrially derived organic matter (TOM) into the ocean is an important but poorly constrained aspect of the modern global carbon cycle. A preliminary study of Late Quaternary sediments from the Congo deep sea fan (ODP leg 175, site 1075, 2 km water depth) and four surface samples from associated cores has confirmed the presence of proposed soil-specific bacteriohopanepolyol biomarkers (BHPs) including adenosylhopane, in samples to a depth of 89 m. Concentrations of soil marker BHPs are high in the upper sediment section (to 49 m) and the closest related surface sample (4913), supporting the case for these molecular markers as novel proxies for soil organic carbon (SOC) supply via riverine transport and subsequent burial. Distinct peaks for the markers at about 21, 34 and 60 m below surface level tentatively imply that the rate of TOM discharge from tropical Africa significantly increased at these times, possibly associated with periods of reduced soil stability in the Congo catchment.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Pollen record of sediment core GeoB1008-3 from the Congo fan

Palynological investigation of the marine core, GeoB1008-3, from near the mouth of the Congo river (6°35.6'S/10°19.1'E), provides information about the changes in vegetation and climate in West Equatorial Africa during the last 190 ka. The pollen diagram is divided into zones 1-6 which are considered to correspond in time with the marine isotope stages 1-6. Oscillations in temperature and moisture are indicated during the cold stage 6. During stage 5, two cooler periods (5d and 5b) can be shown with an expansion of Podocarpus forests to lower elevations on the expense of lowland rain forest. Extended mangrove swamps existed along the coast in times of high sea level (stages 5 and 1).

Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

Palynological record and radiocarbon dates for sediment core T89-16, Congo River mouth

We present a high-resolution reconstruction of tropical palaeoenvironmental changes for the last deglacial transition (18 to 9 cal. kyr BP) based on integrated oceanic and terrestrial proxies from a Congo fan core. Pollen, grass cuticle, Pediastrum and dinoflagellate cyst fluxes, sedimentation rates and planktonic foraminiferal d18O ratios, uK37 sea-surface temperature and alkane/alkenone ratio data highlight a series of abrupt changes in Congo River palaeodischarge. A major discharge pulse is registered at around 13.0 cal. kyr BP which we attribute to latitudinal migration of the Intertropical Convergence Zone (ITCZ) during deglaciation. The data indicate abrupt and short-lived changes in the equatorial precipitation regime within a system of monsoonal dynamics forced by precessional cycles. The phases of enhanced Congo discharge stimulated river-induced upwelling and enhanced productivity in the adjacent ocean.

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.

Pollen analysis of sediment cores from the mouth of the river Congo to Walvis Bay and Lüderitz

The distribution of pollen in marine sediments is used to record vegetation changes over the past 30,000 years on the adjacent continent. A transect of marine pollen sequences from the mouth of the river Congo (~5°S) to Walvis Bay and Lüderitz (~25°S) shows vegetation changes in Congo, Angola and Namibia from the last glacial period into the Holocene. The comparison of pollen records from different latitudes provides information about the latitudinal shift of open forest and savannahs (Poaceae pollen), the extension of lowland forest (rain forest pollen) and Afromontane forest (Podocarpus pollen), and the position of the desert fringe (pollen of Caryophyllaceae, Chenopodiaceae and Amaranthaceae). High Cyperaceae pollen percentages in sediments from the last glacial period off the mouth of the river Congo suggest the presence of open swamps rather than savannah vegetation in the Congo Basin. Pollen from Restionaceae in combination with Stoebe-type pollen (probably from Elytropappus) indicates a possible northwards extension of winter rain vegetation during the last glacial period. The record of Rhizophora (mangrove) pollen is linked to erosion of the continental shelf and sea-level rise. Pollen influx is highest off river mouths (10-2000 grains year**-1 cm**-2), close to the coast (300-6000 grains year**-1 cm**-2), but is an order of magnitude lower at sites situated far from the continent (<10 grains year**-1 cm**-2).

Methylation index of Branched Tetraethers (MBT) and Cyclization ratio of Branched Tetraethers (CBT), annual mean air temperature and soil pH of sediment core GeoB6518-1 in the Congo River basin

We analyzed the distribution of branched tetraether membrane lipids derived from soil bacteria in a marine sediment record that was recovered close to the Congo River outflow, and the results enabled us to reconstruct large-scale continental temperature changes in tropical Africa that span the past 25,000 years. Tropical African temperatures gradually increased from ~21° to 25°C over the last deglaciation, which is a larger warming than estimated for the tropical Atlantic Ocean. A direct comparison with sea-surface temperature estimates from the same core revealed that the land-sea temperature difference was, through the thermal pressure gradient, an important control on central African precipitation patterns.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.