Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

(Table 1) Stable carbon isotope record and total nitrogen concentration in ODP Hole 175-1085B sediments

Variations in the strength of coastal upwelling in the South East Atlantic Ocean and summer monsoonal rains over South Africa are controlled by the regional atmospheric circulation regime. Although information about these parameters exists for the last glacial period, little detailed information exists for older time periods. New information from ODP Site 1085 for Marine Isotope Stages (MIS) 12-10 shows that glacial-interglacial productivity trends linked to upwelling variability followed a pattern similar to the last glacial cycle, with maximums shortly before glacial maxima, and minimums shortly before glacial terminations. During the MIS-11/10 transition, several periodic oscillations in productivity and monsoonal proxies are best explained by southwards shifts in the southern sub-tropical high-pressure cells followed by abrupt northwards shifts. Comparison to coeval sea-surface temperature measurements suggests that these monsoonal cycles were tightly coupled to anti-phased hemispheric climate change, with an intensified summer monsoon during periods of Northern (Southern) Hemisphere cooling (warming). The timing of these events suggests a pacing by insolation over precession periods. A lack of similar regional circulation shifts during the MIS-13/12 transition is likely due to the large equatorwards shift in the tropical convection zone that occurred during this extreme glaciation.

Coastal upwelling and atmospheric CO2 changes

A transfer function relating diatom assemblages in surface sediments and primary production in the photic zone was used to calculate variations in primary production in hole ODP Leg 112, Site 681A over the last 400 kyr. Primary production off central Peru was enhanced during peak glaciations and it decreased during peak interglacials, but low and high production periods also occurred in both glacials and interglacials. The close resemblance of the primary production curve off Peru to the atmospheric CO2 Vostok record suggests a relationship between the Peruvian neritic biological pump and atmospheric pCO2.

Calcareous nannofossil biostratigraphy of ODP Leg 108 sediments

Calcareous nannofossils were examined from the 400 cores recovered at 12 sites during Ocean Drilling Program Leg 108 in the eastern equatorial Atlantic Ocean and along the northwest African margin, representing a transect spanning 24° of latitude. Thirty calcareous nannofossil biohorizons were recognized in the Neogene and Quaternary sequences; only Site 661, located in water depths of 3500 m, contains a fossiliferous record older than the Oligocene. At Site 661, a 200-m-thick sequence of Upper Cretaceous sediments yielded Maestrichtian and uppermost Campanian nannofossils, yet a continuous Cretaceous/Tertiary boundary was not recovered. Widespread sediment slumps and turbidites deposited at many sites interrupted the pelagic sedimentation. A careful study of calcareous nannofossil and foraminifer assemblages correlated to paleomagnetic records suggests that "slumped" units at most sites were added as extra sediments to rapidly deposited pelagic sediments, with minor disturbance of the surrounding layers. Nannofossils are generally common to abundant and moderately preserved at all sites except for those located in two upwelling areas, where placoliths are etched and discoasters overgrown. Typical low-latitudinal zonal markers were used during this study, yet some of them were considered to be of little biostratigraphic value because of their inconsistent stratigraphic ranges and low abundances. This is especially apparent for the intervals representing the Miocene/Pliocene and Oligocene/Miocene boundaries. Characteristic nannofossils of cool-water conditions and low discoaster abundances occur at the coastal African upwelling and along the south equatorial divergence sites, signifying a stronger advection of cold waters toward the equator within the Canary and Benguela eastern boundary currents.