Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

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.

Calcareous dinoflagellate cysts analysis of sediment cores from the Equatorial South Atlantic Ocean

An overview is presented of the current state of knowledge on paleo-ecological aspects of calcareous dinoflagellate resting cysts. Apart from literature-based information, a discussion of new results is also provided from Equatorial Atlantic surface plankton samples, surface sediment samples and Late Quaternary sediments from two gravity cores. With the aid of redundancy analysis statistics, variations in the calcareous cyst content of both cores are correlated to variations in total organic carbon (TOC). On a global scale, the calcareous cyst distribution in bottom sediments varies with latitude and inshore-offshore gradients. In the Equatorial Atlantic Ocean, enhanced calcareous cyst production can be observed in regions and time intervals with stratified, oligotrophic conditions in the upper water masses.

Sea surface temperatures derived from alkenones from Late Quaternary sediments of the East Equatorial South Atlantic

Angola Basin and Walvis Ridge records of past sea surface temperatures (SST) derived from the alkenone Uk 37 index are used to reconstruct the surface circulation in the east equatorial South Atlantic for the last 200,000 years. Comparison of SST estimates from surface sediments between 5° and 20°S with modern SST data suggests that the alkenone temperatures represent annual mean values of the surface mixed layer. Alkenone-derived temperatures for the warm climatic maxima of the Holocene and the penultimate interglacial are 1 to 4°C higher than latest Holocene values. All records show glacial to interglacial differences of about 3.5°C in annual mean SST, which is about 1.5°C greater than the difference estimated by CLIMAP (1981) for the eastern Angola Basin. At the Walvis Ridge, significant SST variance is observed at all of the Earth's orbital periodicities. SST records from the Angola Basin vary predominantly at 23- and 100-kyr periodicities. For the precessional cycle, SST changes at the Walvis Ridge correspond to variations of boreal summer insolation over Africa and lead ice volume changes, suggesting that the east equatorial South Atlantic is sensitive to African monsoon intensity via trade-wind zonality. Angola Basin SST records lag those from the Walvis Ridge and the equatorial Atlantic by about 3 kyr. The comparison of Angola Basin and Walvis Ridge SST records implies that the Angola-Benguela Front (ABF) (currently at about 14-16°S) has remained fairly stationary between 12° and 20°S (the limits of our cores) during the last two glacial-interglacial cycles. The temperature contrast associated with the ABF exhibits a periodic 23-kyr variability which is coherent with changes in boreal summer insolation over Africa. These observations suggest that surface waters north of the present ABF have not directly responded to monsoon-modulated changes in the trade-wind vector, that the central field of zonally directed trades in the southern hemisphere was not shifted or extended northward by several degrees of latitude during glacials, and that a cyclonic gyre circulation has existed in the east equatorial South Atlantic over the last 200,000 years. This scenario contradicts former assumptions of glacial intensification of the Benguela Current into the eastern Angola Basin and increased coastal upwelling off Angola.

Stable oxygen and carbon isotope ratios of Pliocene benthic foraminifera in the Atlantic Ocean

Large changes in benthic foraminiferal delta180 and delta13C occurred during the Pliocene (between 3.0 and 2.0 Ma) at Hole 665A. Oxygen isotopic compositions increased to maximum values at 2.4 Ma, correlating with an 18O enrichment observed at Hole 552A and other locations (Shackleton et al., 1984). As at Hole 606 (Keigwin, 1986), however, maximum delta180 values at 2.4 Ma were not as great as at Hole 552A, and enrichments in delta180 also occurred before 2.4 Ma. We believe that the section representing sediments from 2.5 to 2.7 or 2.8 Ma is missing at Hole 552A because of incomplete core recovery. Consequently, the older delta180 increases are not found at Hole 552A. Benthic foraminiferal delta13C values are much lower at Hole 665A than at Hole 552A, approaching the low values observed in the Pliocene Pacific Ocean. This geographic distribution of delta13C suggests that, like late Quaternary glaciations, the equatorial Atlantic Ocean was dominated during the Pliocene by deep water that originated in the Southern Ocean and had chemical characteristics very similar to the Pacific Ocean. Reduced O2 values were probably associated with low delta13C values and contributed to increased preservation of organic carbon during enriched 180 intervals of the Pliocene equatorial Atlantic.

Late Pliocene stratigraphic distribution of Globoconella taxa in the North Atlantic

Quantitative records of Globorotalia puncticulata and Globorotalia inflata, the last two members of the Globorotalia (Globoconella) lineage, obtained from North Atlantic sediments collected at DSDP Site 552, ODP Site 659 and ODP Site 665, are used to examine fluctuations in the biogeographic distribution of these species in the Late Pliocene between 3 and 2 Ma. Abundance data indicate that prior to the expansion of Northern Hemisphere glaciation at about 2.5 Ma, Gr. puncticulata was an important component of the planktonic foraminiferal fauna and had a geographic distribution ranging from 2°N to at least 56°N in the North Atlantic. A previously undescribed 6 chambered variant of Gr. puncticulata is found at both Sites 659 and 665. The stratigraphic distribution of this morphotype is restricted, first occurring at 2.9 Ma and then disappearing when glacial intensity increased at 2.75 Ma (isotope stage 110). Similar declines in Gr. puncticulata abundances occurred during glacial isotope stages 102, 100, and 98 immediately prior to the extinction of Gr. puncticulata during glacial isotope stage 96. It appears that this extinction event was latitudinally diachronous within the North Atlantic, occurring earliest in the north at Site 552 (2.453 Ma), then at Site 659 (2.443 Ma) and later still in the Site 665 equatorial record (2.438 Ma). At Site 665 the first record of Gr. inflata occurs during glacial isotope stage 94 (2.416 Ma), shortly after the extinction of Gr. puncticulata. In the mid latitude North Atlantic there was a 340,000 year period following the disappearance of Gr. puncticulata when the Globoconella lineage was absent (the Gr. inflata gap). The Gr. inflata population found in the equatorial Atlantic must therefore have been introduced from the South Atlantic, probably by the South Equatorial Current. Faunal records from Sites 552 and 659 show that it was not until glacial isotope stage 78 (2.10 Ma) that Gr. inflata became widely established in the North Atlantic. Prior to this large-scale migration event, there were two limited colonisation events during glacial isotope stages 86 and 82 when Gr. inflata populations reached as far as Site 659 in the eastern North Atlantic. These incursions are believed to be reflect the entrainment of Gr. inflata within South Atlantic Central Water and the northward subsurface transport of individuals to the coastal upwelling zone off northwest Africa. It seems likely that the same mechanism was responsible for the re-establishment of the Globoconella lineage in the North Atlantic at 2.10 Ma, but in this instance additional factors, such as enhanced glacial circulation patterns and ecological changes within planktonic foraminiferal faunas, resulted in the successful expansion of Gr. inflata across the North Atlantic and the Mediterranean.

Radium concentration in water samples from the Northeast Atlantic

We present field measurements of air-sea gas exchange by the radon deficit method that were carried out during JASIN 1978 (NE Atlantic) and FGGE 1979 (Equatorial Atlantic). Both experiments comprised repeated deficit measurements at fixed position over periods of days or longer, using a previously descibed precise and fast-acquiaition, automatic radon measuring system. The deficit time series exhibit variations that only partly reflect the expected changes in gas transfer. By evaluating averages over each time series we deduce the following gas transfer velocities (average wind velocity and water temperature in parentheses): JASIN phase 1: 1.6 ± 0.8 m/d (at ~6 m/s, 13°C) JASIN phase 2: 4.3 ± 1.2 m/d (at ~8 m/s, 13°C) FGGE: 1.2 ± 0.4 m/d (at ~5 m/s, 28°C) 0.9 ± 0.4 m/d (at ~7 m/s, 28°C) 1.5 ± 0.4 m/d (at ~7 m/s, 28°C) The large difference betwen the JASIN phase 2 and FGGE values despite quite similare average wind velocity becomes even larger when the values are, however, fully compatible with the range of gas transfer velocities observed in laboratory experiments and the conclusion is suggested that their difference is caused by the highly different wind variability in JASIN and FGGE. We conclude that in gas exchange parameterization it is not sufficinent to consider wind velocity only. A comparison of our observations with laboratory results outlines the range of variations of air-sea gas transfer velocities with wind velocity and sea state. We also reformulate the radon deficit method, in the light of our observed deficit variations, to account explicitely for non-stationary and horizontal inhomogeneity in previous radon work introduces considerable uncertainty in deduced gas transfere velocity. We furthermore discuss the observational rewuirements that have to be met for an adequate exploitation of the radon deficit method, of which an observation area of minimum horizontal inhomogeneity and monitoring of the remaining inhomogeneities are thought to be the most stringent ones.

Late Cretaceous benthic foraminiferal assemblages from Demerara Rise, western tropical Atlantic

This paper is based on Santonian-Campanian sediments of Ocean Drilling Program Sites 1257 (2951 mbsl) and 1259 (2353 mbsl) from Demerara Rise (Leg 207, western tropical Atlantic, off Surinam). According to its position, Demerara Rise should have been influenced by the early opening of the Equatorial Atlantic Gateway and the establishment of a bottom-water connection between the central and South Atlantic Oceans during the Late Cretaceous. The investigated benthic foraminiferal faunas demonstrate strong fluctuations in bottom-water oxygenation and organic-matter flux to the sea-floor. The Santonian-earliest Campanian interval is characterised by laminated black shales without benthic foraminifera in the lowermost part, followed by an increasing number of benthic foraminifera. These are indicative of anoxic to dysoxic bottom waters, high organic-matter fluxes and a position within the oxygen minimum zone. At the shallower Site 1259, benthic foraminifera occurred earlier (Santonian) than at the deeper Site 1257 (Early Campanian). This suggests that the shallower site was characterised by fluctuations in the oxygen minimum zone and that a re-oxygenation of the sea-floor started considerably earlier at shallower water-depths. We speculate that this re-oxygenation was related to the ongoing opening of the Equatorial Atlantic Gateway. A condensed glauconitic chalk interval of Early Campanian age (Nannofossil Zone CC18 of Sissingh) overlies the laminated shales at both sites. This interval contains benthic foraminiferal faunas reflecting increasing bottom-water oxygenation and reduced organic-matter flux. This glauconitic chalk is strongly condensed and contains most of the Lower and mid-Campanian. Benthic foraminiferal species indicative of well-oxygenated and more oligotrophic environments characterise the overlying mid- to Upper Campanian nannofossil chalk. During deposition of the nannofossil chalk, a permanent deep-water connection between the central and South Atlantic Oceans is proposed, leading to ventilated and well-oxygenated bottom waters. If this speculation is true, the establishment of a permanent deep-water connection between the central and South Atlantic Oceans terminated Oceanic Anoxic Event 3 "black shale" formation in the central and South Atlantic marginal basins during the Early Campanian (Nannofossil Zone CC18) and led to well-oxygenated bottom waters in the entire Atlantic Ocean during the Late Campanian (at least from Nannofossil Zone CC22 onwards).