(Table 3) Li concentrations and isotopic compositions in foraminiferal shells, carbonate sediments, and associated pore waters from ODP Sites 131-806 and 138-851

An improved procedure for lithium isotope analysis using Li3PO4 as the ion source has been investigated for application to geological samples. The 7Li/6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li+ ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li2BO2+ method while maintaining a comparable precision of better than 1? (1 sigma). Replicate analyses of the NBS L-SVEC Li2CO3 standard yielded a mean value of 12.1047+/-0.0043 (n=21), which is close to the reported absolute value of 12.02+/-0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li3PO4 and Li2BO2+ techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.

(Table 2) Age interval and accumulation rates of organic and inorganic carbon from ODP Sites 175-1082, 175-1084, 175-1085 and 175-1087

The Ocean Drilling Program Leg 175 recovered a unique series of stratigraphically continuous sedimentary sections along the SW African margin, an area which is presently affected by active coastal upwelling. The accumulation rates of organic and inorganic carbon are a major component of this record. Four Leg 175 sites (1082, 1084, 1085, 1087) are chosen as part of a latitudinal transect from the present northern to southern boundaries of the Benguela Current upwelling system, to decipher the Pliocene-Pleistocene history of biogenic production and its relationship with global and local changes in oceanic circulation and climate. The pattern of CaCO3 and Corg mass accumulation rates (MARs) over 0.25-Myr intervals indicates that the evolution of carbon burial is highly variable between the northern and the southern Benguela regions, as well as between sites that have similar hydrological conditions. This, as well as the presence over most locations of high-amplitude, rapid changes of carbon burial, reflect the partitioning of biogenic production and patterns of sedimentation into local compartments over the Benguela margin. The combined mapping of CaCO3 and Corg MARs at the study locations suggests four distinct evolutionary periods, which are essentially linked with major steps in global climate change: the early Pliocene, the mid-Pliocene warm event, a late Pliocene intensification of northern hemisphere glaciation and the Pleistocene. The early Pliocene spatially heterogeneous patterns of carbon burial are thought to reflect the occurrence of mass-gravitational movements over the Benguela slope which resulted in disruption of the recorded biogenic production. This was followed (3.5-3 Ma) by an episode of peak carbonate accumulation over the whole margin and, subsequently, by the onset of Benguela provincialism into a northern and a southern sedimentary regime near 2 Ma. This mid and late Pliocene evolution is interpreted as a direct response to changes in the ventilation of bottom and intermediate waters, as well as to dynamics of the subtropical gyral circulation and associated wind stress.