Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Spherules and basement analyses from DSDP Hole 5-32

Lower Miocene basaltic glass spherules from DSDP Site 32 pelagic sediments in the eastern Pacific are compositionally diverse, and new analyses and interpretations have been added to those of earlier workers. The spherules are of titanian ferrobasalt which is compositionally similar to highly evolved abyssal basalts and to some oceanic island eruptives, and they were most likely shaped during intense lava fountaining during a number of separate eruptions. These eruptions tapped distinct but related magma batches in terms, for example, of distinctively high TiO2 and FeO* contents. Their age overlaps that of some of the eruptions of the Columbia River Plateau Basalts, but they are compositionally distinct from most of the latter basalts. Although about 15 m.y. old, they show little alteration. The low chlorine and sulfur contents compared to those of abyssal ferrobasalts are consistent with degassing prior to quenching during subaerial eruptions, and rule out production of the spherules by submarine fountaining. Lava fountaining alone is insufficient to account for the distance of about 100 km from even the closest possible seamount source. Instead, large phreatomagmatic eruption columns reaching at least 15 km and including lava fountaining immediately after the initial explosion are required. Alternatively, and deemed less likely, is their deposition by turbidites derived from Pioneer Seamount.

Cd/Ca ratios and element analyses of ODP Hole 115-709C

During three to four d18O cycles (determined on Globigerinoides ruber), more positive d18O (= higher global ice volume) values correlated with higher Globorotalia menardii percentages, total numbers of benthic foraminifers, number of benthic foraminifer species, and the percent of total foraminifers composed of benthic foraminifers. During the same intervals, barite and insoluble residues also generally recorded higher values; however, there was no clear evidence of systematic variation in cadmium/calcium ratios (in benthic foraminifers). Maximum percentages of Globigerinoides sacculifer and Globigerinoides ruber correlate with more negative d18O (= lower global ice volume) values, although they sometimes appear to lead the d18O changes by < =4,000 yr. The increase in percentage of the tropical "divergence" planktonic foraminifer species G. menardii and the reduction of the "nondivergence" tropical species G. ruber and G. sacculifer at times of inferred ice growth is attributed to periodic intensification of divergence associated with the Equatorial Counter Current. Barite and insoluble residue sedi- mentation at the site also generally show a relative increase at those times.

Stable isotope and geochemical analyses of sediment core SO164-17-2 from the southern Florida Straits

Modeling and proxy studies indicate that a reduction of Atlantic Meridional Overturning Circulation (AMOC) strength profoundly impacts temperatures and salinities in the (sub)tropical Atlantic, especially on subsurface levels. While previous studies focused on prominent periods of AMOC reduction during the last deglaciation, we aim to test whether similar reconfigurations of the subtropical hydrography occurred during the moderate climatic alterations punctuating the last interglacial, Marine Isotope Stage (MIS) 5. Here, we present temperature and salinity records from a Florida Straits core by combining d18O and Mg/Ca analyses on surface (Globigerinoides ruber, white) and deep-dwelling (Globorotalia crassaformis) foraminifera, covering MIS 5 in high resolution. The data reveal increasing salinities at intermediate depths during interglacial cooling episodes, decoupled from relatively stable surface conditions. This probably indicates the spatial expansion of saline Subtropical Gyre waters due to enhanced Ekman downwelling and might also point to a changed density structure and altered geostrophic balance in Florida Straits. Notably, these oceanographic alterations are not consistently occurring during periods of AMOC reduction. The data suggest that the expansion of gyre waters into Florida Straits was impeded by the increasing influence of Antarctic Intermediate Water (AAIW) from MIS 5.5 to ~107 kyr BP. Afterwards, increasingly positive benthic d13C values imply a recession of AAIW, allowing the temporary expansion of Gyre waters into Florida Straits. We argue that the inferred transient subtropical salt accumulation and warm pool expansion might have played a pivotal role in reinvigorating meridional overturning and dampen the severity of interglacial cold phases.

Mineralogical, sedimentological and paleontological analyses of ODP Hole 127-797B upper Quarternary sediments

Nearly continuous cores of Quaternary fine-grained sediments with distinct dark-light colored cycles were recovered from Sites 794, 795, and 797 in the basinal parts of the Japan Sea during Leg 127. A comparison of gray value (darkness) profiles supplemented by visual inspection of core photographs between sites indicated that most of the dark and light layers were correlatable between sites, and that two of the dark layers lie close to adjacent marker ash layers. These observations indicate that deposition of dark and light layers resulted from basin-wide synchronous events. In order to understand the origin of these dark-light cycles, petrographical, mineralogical, compositional, and paleontological studies were carried out on closely spaced samples from the upper Quaternary sediments recovered from Site 797. Age model was constructed based on comparison between variation in diatom abundance and the standard oxygen isotope curve of Imbrie et al. (1984), the latter was interpolated between the five age controlled levels established at Site 797. The two curves show similar patterns which enabled us to "tune" the sediment ages to the oxygen isotope stages. We have to use variation in diatom abundance as a substitute for oxygen isotope curve since oxygen isotopic data are not available at the studied sites. Bottom water oxygenation conditions were estimated based on two criteria: (1) the degree of lamina preservation and (2) the ratio of Corg to Stot. The surface water productivity was deduced from the Corg and biogenic silica content. Results suggest that the bottom water oxygenation level and the surface water productivity varied significantly in response to the glacial-interglacial cycles. Glacio-eustatic sea-level changes and subsequent changes in water circulation in the Japan Sea appear to have been responsible for these variations and consequent changes in sediment composition throughout the Quaternary.

Magnetic and mineralogical analyses of Ganzi and Luochuan sections

We present a first combined environmental magnetic and geochemical investigation of a loess-paleosol sequence (<55 ka) from the Chuanxi Plateau on the eastern margin of the Tibetan Plateau. Detailed comparison between the Ganzi section and the Luochuan section from the Chinese Loess Plateau (CLP) allows quantification of the effects of provenance and climate on pedogenic magnetic enhancement in Chinese loess. Rare earth element patterns and clay mineral compositions indicate that the Ganzi loess originates from the interior of the Tibetan Plateau. The different Ganzi and CLP loess provenances add complexity to interpretation of magnetic parameters in terms of the concentration and grain size of eolian magnetic minerals. Enhanced paleosol magnetism via pedogenic formation of ferrimagnetic nanoparticles is observed in both sections, but weaker ferrimagnetic contributions, finer superparamagnetic (SP) particles and stronger chemical weathering are found in the Ganzi loess, which indicates the action of multiple pedogenic processes that are dominated by the combined effects of mean annual precipitation (MAP), potential evapotranspiration (PET), organic matter and aluminium content. Under relatively high MAP and low PET conditions, high soil moisture favours transformation of ferrimagnetic minerals to hematite, which results in a relatively higher concentration of hematite but weaker ferrimagnetism of Ganzi loess. Initial growth of superparamagnetic (SP) particles is also documented in the incipient loess at Ganzi, which directly reflects the dynamic formation of nano-sized pedogenic ferrimagnets. A humid pedogenic environment with more organic matter and higher Al content also helps to form finer SP particles. We therefore propose that soil water balance, rather than solely rainfall, dominates the type, concentration and grain size of secondary ferrimagnetic minerals produced by pedogenesis.

Bulk rock magnetic measurements and thermomagnetic analyses of sediment core GeoB4901-8 from the southeastern flank of the Niger deep-sea fan

Diagenesis has extensively affected the magnetic mineral inventory of organic-rich late Quaternary sediments in the Niger deep-sea fan. Changes in concentration, grain size, and coercivity document modifications of the primary magnetic mineral assemblages at two horizons. The first front, the modern iron redox boundary, is characterized by a drastic decline in magnetic mineral content, coarsening of the grain size spectrum, and reduction in coercivity. Beneath a second front, the transition from the suboxic to the sulfidic anoxic domain, a further but less pronounced decrease in concentration and bulk grain size occurs. Finer grains and higher coercive magnetic constituents substantially increase in the anoxic environment. Low- and high-temperature experiments were performed on bulk sediments and on extracts which have also been examined by X-ray diffraction. Thermomagnetic analyses proved ferrimagnetic titanomagnetites of terrigenous provenance as the principal primary magnetic mineral components. Their broad range of titanium contents reflects the volcanogenic traits of the Niger River drainage areas. Diagenetic alteration is not only a grain size selective process but also critically depends on titanomagnetite composition. Low-titanium compounds are less resistant to diagenetic dissolution. Intermediate titanium content titanomagnetite thus persists as the predominant magnetic mineral fraction in the sulfidic anoxic sediments. At the Fe redox boundary, precipitation of authigenic, possibly bacterial, magnetite is documented. The presence of hydrogen sulfide in the pore water suggests a formation of secondary magnetic iron sulfides in the anoxic domain. Grain size-specific data argue for a gradual development of a superparamagnetic and single-domain iron sulfide phase in this milieu, most likely greigite.