Sable isotope record and sediment composition of Cretaceous samples of Deremara Rise

We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84-100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal d18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d13C values of phytane, combined with foraminiferal d13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal d18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane d13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.

Composition of Cape Leeuwin Manganese nodule deposit off Western Australia

In 1970 a large deposit of ferromanganese nodules was discovered on the floor of the Indian Ocean southwest of Cape Leeuwin by the research vessel USNS Eltanin. This discovery, which was based largely on bottom photographs from about 20 stations, was discussed by Frakes (1975) and Kennett and Watkins (1975, 1976). The photographs suggest that the deposit spreads, nearly continuously, over 900 000km^2, and cores showed that the nodules are essentially confined to the sediment surface. Kennett and Watkins (op. cit.) pointed to the abundance of ripple and scour marks and current-formed lineations on the present surface, and of extensive disconformities in the cores, as evidence of strong present and past bottom currents in the region. They suggested that the current action had resulted in very low sedimentation rates, which had allowed the nodule field, named by them (1976) the 'Southeast Indian Ocean Manganese Pavement', to develop. In early 1976 the authors used the research vessel HMAS Diamantina for a 10-day cruise in the region to sample the nodules in order to study their chemistry and mineralogy. During the cruise 9 stations were occupied, 8 of them successfully (Figure 1), and about 2000 nodules were recovered from the sea bed. The apparatus used was a light box dredge on the ships hydrowire, which had a breaking strain of about one tonne. Although an attempt was made to reoccupy Eltanin photographic stations, it should be noted that positioning was by celestial navigation, so errors of up to 10 km are possible.

Processed CO2/O2 Float data from 4 deployments near Cape Verde Island (11/2010 - 06/2011)

In recent years, profiling floats, which form the basis of the successful international Argo observatory, are also being considered as platforms for marine biogeochemical research. This study showcases the utility of floats as a novel tool for combined gas measurements of CO2 partial pressure (pCO2) and O2. These float prototypes were equipped with a small-sized and submersible pCO2 sensor and an optode O2 sensor for highresolution measurements in the surface ocean layer. Four consecutive deployments were carried out during November 2010 and June 2011 near the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic. The profiling float performed upcasts every 31 h while measuring pCO2, O2, salinity, temperature, and hydrostatic pressure in the upper 200 m of the water column. To maintain accuracy, regular pCO2 sensor zeroings at depth and surface, as well as optode measurements in air, were performed for each profile. Through the application of data processing procedures (e.g., time-lag correction), accuracies of floatborne pCO2 measurements were greatly improved (10-15 µatm for the water column and 5 µatm for surface measurements). O2 measurements yielded an accuracy of 2 µmol/kg. First results of this pilot study show the possibility of using profiling floats as a platform for detailed and unattended observations of the marine carbon and oxygen cycle dynamics.

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.

Sedimentology of ODP sites in the Cape Basin, southeast Atlantic Ocean

Middle/late Miocene to early Pliocene sedimentary sequences along the continental margin of southwest Africa have changes that correspond to the carbonate crash (12-9 Ma) and biogenic bloom events (~7-4 Ma) described in the equatorial Pacific by Farrell et al. (1995, doi:10.2973/odp.proc.sr.138.143.1995). To explore the origins of these changes, we analyzed the carbon and coarse fraction contents of sediments from ODP Sites 1085, 1086, and 1087 at a time resolution of 5 to 30 kyr. Several major drops in CaCO3 concentration between 12 and 9 Ma are caused by dilution from major increases in clastic input from the Oranje River during global sea level regressions. Abundant pyrite crystals and good preservation of fish debris reflect low oxygenation of bottom/pore waters. Regional productivity was enhanced during the time equivalent to the carbonate crash period. Higher benthic/planktic foraminiferal ratios indicate that CaCO3 dissolution at Site 1085 peaked between 9 to 7 Ma, which was after the global carbonate crash. This period of enhanced dissolution suggests that Site 1085 was located within a low-oxygen water mass that dissolved CaCO3 more easily than North Atlantic Deep Water, which began to bathe this site at 7 Ma. At 7 to 6 Ma, the onset of the biogenic bloom, increases and variations in total organic carbon and benthic foraminiferal accumulation rates show that paleoproductivity increased significantly above values observed during the carbonate crash period and fluctuated widely. We attribute the late Miocene paleoproductivity increase off southwest Africa to ocean-wide increases in nutrient supply and delivery.