Barium concentration in sediments of the central Equatorial Pacific

High resolution pore-water dissolved Ba concentration-depth profiles were determined at seven sites across an Equatorial Pacific productivity gradient from 12°S to 9°N, at 140°W. These data are important for understanding the physical, chemical, and biological controls on Ba recycling in the ocean, and for evaluating the paleo-oceanographic significance of Ba content in central Equatorial Pacific sediments. Pore-water Ba concentrations at all sites are higher than in the overlying bottom water, leading to a diffusive flux of Ba into the ocean. A pronounced subsurface concentration maximum exceeding barite solubility characterizes the dissolved Ba pore-water profiles, suggesting that the Ba regenerated in the upper few millimeters of sediment is not controlled by barite solubility. A few centimeters down-core Ba concentrations reach a relatively constant value of approximately barite saturation. The benthic Ba flux shows a clear zonal trend, with a maximum between 2°S and 2°N, most probably due to higher productivity at the equatorial divergence zone, and with lowest values at the southern and northern extremes of the transect. The dissolved Ba flux between 2°S and 2°N is ~30 nmol/cm**2 yr and drops to 6 nmol/cm**2 yr at 12°S. Even the lowest fluxes are significantly higher than those previously reported for the open ocean. In the Equatorial Pacific the calculated Ba recycling efficiency is about 70%. Thus, ~30% of the particulate Ba flux to the deep ocean is preserved in the sediments, compared with less than 1% for organic carbon and ~5% for biogenic silica. Mass balance calculation of the oceanic Ba cycle, using a two-box model, implies benthic Ba fluxes similar to those reported here for a steady-state ocean.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.

Changes in calcareous nannofossil assemblages across the Paleocene/Eocene transition from the paleo-equatorial Pacific Ocean

Quantitative analyses of selected calcareous nannofossils in deep-sea sections recovered from the paleo-equatorial Pacific (ODP Leg 199) provide new information about biostratigraphy, biochronology and the evolutionary history of calcareous nannofossils across the Paleocene/Eocene transition interval. The sediment cores from ODP Leg 199 represent the first continuous Paleocene/Eocene boundary sections ever to be sampled in the central equatorial Pacific Ocean. Calcareous nannofossil assemblages are studied to document the distribution of biostratigraphically useful taxa such as Ericsonia, Discoaster, Fasciculithus, Rhomboaster and Tribrachiatus. Focus is given to the evolution of the Rhomboaster-Tribrachiatus lineage in the lower Eocene interval at Site 1215, and on the stratigraphic relationship of these taxa relative to species in the genus Fasciculithus. Critical intervals of North Atlantic DSDP Site 550 have also been re-examined. The Tribrachiatus digitalis morphotype was described at Site 550 from an interval affected by down-hole contamination, partly originating from within the Tribrachiatus orthostylus range. The T. digitalis morphotype represents an evolutionary transitional form between T. contortus and T. orthostylus, entering the stratigraphic record within the range of the former species and disappearing within the lower part of the range of the latter species. The subzonal subdivision of Zone NP10 hence collapses. Lithological and colour variability reflecting orbital cyclicity occur in the lower Eocene of Site 1215, permitting a relative astronomical age calibration of the Tribrachiatus taxa. The distinct Rhomboaster spp.-Discoaster araneus association also occurs in the paleo-equatorial Pacific Ocean, together with a marked decrease in diversity of Fasciculithus spp. Site 1220 reveals a short peak abundance of Thoracosphaera spp. just above the P/E boundary interval, which probably reflects a stressed surface water environment.

Vertical distribution of phytoplankton pigments in the equatorial Pacific

Abundance distribution and cellular characteristics of picophytoplankton were studied in two distinct regions of the equatorial Pacific: the western warm pool (0°, 167°E), where oligotrophic conditions prevail, and the equatorial upwelling at 150°W characterized by high-nutrient low-chlorophyll (HNLC) conditions. The study was done in September-October 1994 during abnormally warm conditions. Populations of Prochlorococcus, orange fluorescing Synechococcus and picoeukaryotes were enumerated by flow cytometry. Pigment concentrations were studied by spectrofluorometry. In the warm pool, Prochlorococcus were clearly the dominant organisms in terms of cell abundance, estimated carbon biomass and measured pigment concentration. Integrated concentrations of Prochlorococcus, Synechococcus and picoeukaryotes were 1.5x10**13, 1.3x10**11 and 1.5x10**11 cells/m**2, respectively. Integrated estimated carbon biomass of picophytoplankton was 1 g/m**2, and the respective contributions of each group to the biomass were 69, 3 and 28%. In the HNLC waters, Prochlorococcus cells were slightly less numerous than in the warm pool, whereas the other groups were several times more abundant (from 3 to 5 times). Abundance of Prochlorococcus, Synechococcus and picoeukaryotes were 1.2x10**13, 6.2x10**11 and 5.1x10**11 cells/m**2, respectively. The integrated biomass was 1.9 g C/m**2. Prochlorococcus was again the dominant group in terms of abundance and biomass (chlorophyll, carbon); the respective contributions of each group to the carbon biomass were 58, 7 and 35%. In the warm pool the total chlorophyll biomass was 28 mg/m**2, 57% of which was divinyl chlorophyll a. In the HNLC waters, the total chlorophyll biomass was 38 mg/m**2, 44% of which was divinyl chlorophyll a. Estimates of Prochlorococcus, Synechococcus and picoeukaryotes cell size were made in both hydrological conditions.

Age determination of equatorial Pacific sediments

Radiocarbon age differences for pairs of coexisting late glacial age benthic and planktic foraminifera shells handpicked from 10 sediment samples from a core from a depth of 2.8 km in the western equatorial Pacific are not significantly different from that of 1600 years calculated from measurements on prenuclear seawater. This places a lower limit on the depth of the interface for the hypothetical radiocarbon-depleted glacial age seawater reservoir required to explain the 190 per mil drop in the 14C/C for atmospheric CO2, which occurred during the mystery interval (17.5 to 14.5 calendar years ago). These measurements restrict the volume of this reservoir to be no more than 35% that of the ocean. Further, 14C measurements on a single Last Glacial Maximum age sample from a central equatorial Pacific core from a depth of 4.4 km water fail to reveal evidence for the required 5- to 7-kyr age difference between benthic and planktic foraminifera shells if the isolated reservoir occupied only one third of the ocean. Nor does the 13C record for benthic forams from this abyssal core yield any evidence for the excess respiration CO2 expected to be produced during thousands of years of isolation. Nor, as indicated by the presence of benthic foraminifera, was the dissolved oxygen used up in this abyssal water.

Radiolarian faunal turnover across the Oligocene/Miocene boundary in the equatorial Pacific Ocean

The global warming trend of the latest Oligocene was interrupted by several cooling events associated with Antarctic glaciations. These cooling events affected surface water productivity and plankton assemblages. Well-preserved radiolarians were obtained from upper Oligocene to lower Miocene sediments at Ocean Drilling Program (ODP) Leg 199 Sites 1218 and 1219 in the equatorial Pacific, and 110 radiolarian species were identified. Four episodes of significant radiolarian faunal changes were identified: middle late Oligocene (27.5 to 27.3 Ma), latest Oligocene (24.4 Ma), earliest Miocene (23.3 Ma), and middle early Miocene (21.6 Ma). These four episodes approximately coincide with increases and decreases of biogenic silica accumulation rates and increases in delta18O values coded as "Oi" and "Mi" events. These data indicate that Antarctic glaciations were associated with change of siliceous sedimentation patterns and faunal changes in the equatorial Pacific. Radiolarian fauna was divided into three assemblages based on variations in radiolarian productivity, species richness and the composition of dominant species: a late Oligocene assemblage (27.6 to 24.4 Ma), a transitional assemblage (24.4 to 23.3 Ma) and an early Miocene assemblage (23.3 to 21.2 Ma). The late Oligocene assemblage is characterized by relatively high productivity, low species richness and four dominant species of Tholospyris anthophora, Stichocorys subligata, Lophocyrtis nomas and Lithelius spp. The transitional assemblage represents relatively low values of productivity and species richness, and consists of three dominant species of T. anthophora, S. subligata and L. nomas. The characteristics of the early Miocene assemblage are relatively low productivity, but high species richness. The two dominant species present in this assemblage are T. anthophora and Cyrtocapsella tetrapera. The most significant faunal turnover of radiolarians is marked at the boundary between the transitional/early Miocene assemblages.

Age model and color measurements of sediment cores from the eastern equatorial Pacific

High-resolution records of glacial-interglacial variations in biogenic carbonate, opal, and detritus (derived from non-destructive core log measurements of density, P-wave velocity and color; r >= 0.9) from 15 sediment sites in the eastern equatorial (sampling resolution is ~1 kyr) clear response to eccentricity and precession forcing. For the Peru Basin, we generate a high-resolution (21 kyr increment) orbitally-based chronology for the last 1.3 Ma. Spectral analysis indicates that the 100 kyr cycle became dominant at roughly 1.2 Ma, 200-300 kyr earlier than reported for other paleoclimatic records. The response to orbital forcing is weaker since the Mid-Brunhes Dissolution Event (at 400 ka). A west-east reconstruction of biogenic sedimentation in the Peru Basin (four cores; 91-85°W) distinguishes equatorial and coastal upwelling systems in the western and eastern sites, respectively. A north-south reconstruction perpendicular to the equatorial upwelling system (11 cores, 11°N-°3S) shows high carbonate contents (>= 50%) between 6°N and 4°S and highly variable opal contents between 2°N and 4°S. Carbonate cycles B-6, B-8, B-10, B-12, B-14, M-2, and M-6 are well developed with B-10 (430 ka) as the most prominent cycle. Carbonate highs during glacials and glacial-interglacial transitions extended up to 400 km north and south compared to interglacial or interglacial^glacial carbonate lows. Our reconstruction thus favors glacial-interglacial expansion and contraction of the equatorial upwelling system rather than shifting north or south. Elevated accumulation rates are documented near the equator from 6°N to 4°S and from 2°N to 4°S for carbonate and opal, respectively. Accumulation rates are higher during glacials and glacial-interglacial transitions in all cores, whereas increased dissolution is concentrated on Peru Basin sediments close to the carbonate compensation depth and occurred during interglacials or interglacial-glacial transitions.

Finely dispersed fraction of particulate organic matter and primary production in sea water of the Equatorial East Pacific

Qualitative and quantitative evaluation of the finely dispersed fraction of particulate organic matter in sea water is given. It is demonstrated that in the euphotic zone of high productivity waters this fraction constitutes 86%, in waters with low productivity 61%, and in deep waters (>200 m) 53% of the organic carbon in particulate matter. Formation of the finely dispersed fraction and its role in distribution of energy in the detrital food chain of the ecosystem are discussed.

Sea-surface reconstruction of the east-equatorial South Atlantic

In order to reconstruct Late Quatemary variations of surface oceanography in the eastequatorial South Atlantic, time series of sea-surface temperatures (SST) and paleoproductivity were established from cores recovered in the Guinea and Angola Basins, and at the Walvis Ridge. These records, based on sedimentary alkenone and organic carbon concentrations, reveal that during the last 350,000 years surface circulation and productivity changes in the east-equatorial South Atlantic were highiy sensitive to climate forcing at 23- and 100-kyr periodicities. Covarying SST and paleoproductivity changes at the equator and at the Walvis Ridge appear to be driven by variations in zonal trade-wind intensity, which forces intensification or reduction of coastal and equatorial upwelling, as well as enhanced Benguela cold water advection from the South. Phase relationships of precessional variations in the paleoproductivity and SST records from the distinct sites were evaluated with respect to boreal summer insolation over Africa, movements of southem ocean thermal fronts, and changes in global ice volume. The 23-kyr phasing implies a sensitivity of eastem South Atlantic surface water advection and upwelling to West African monsoon intensity and to changes in the position ofthe subtropical high pressure cell over the South Atlantic, both phenomena which modulate zonal strength of southeasterly trades. SST and productivity changes north of 20°S lack significant variance at the 41-kyr periodicity; and at the Walvis Ridge and the equator lead changes in ice volume. This may indicate that obliquity-driven clirnate change, characteristic for northem high latitudes, e.g fluctuations in continental ice masses, did not substantially influence subtropical and tropical surface circulation in the South Atlantic. At the 23-kyr cycle SST and productivity changes in the eastern Angola Basin lag those in the equatorial Atlantic and at the Walvis Ridge by about 3500 years. This lag is explained by variations in cross-equatorial surface water transport and west-east countercurrent retum flow modifying precessional variations of SST and productivity in the eastem Angola Basin relative to those in the mid South Atlantic area under the central field of zonal trade winds. Sea level-related shifts of upwelling cells in phase with global clirnate change may be also recorded in SST and productivity variability along the continental margin off Southwest Africa. They may account for the delay of the paleoceanogreaphic signal from continental margin sites with respect to that from the pelagic sites at the equator and the Walvis Ridge.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

CaCO3 content and bulk densitiy of east equatorial Pacific Ocean sediment cores

Nine piston cores and six triggerweight cores retrieved from the eastern equatorial Pacific Ocean during the Venture 1 expedition were analyzed for dry-bulk density (DBD) and CaCO3 content. Sites are located along a north-south transect at 110°W from 11°N to 3°S and along an east-west transect from 110° to 90°W, at approximately 3°S. The data reveal two DBD-CaCO3 relationships and four patterns of CaCO3 abundance.