Composition of ferromanganese crusts from the Atlantic, Pacific and Indian Oceans

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples. The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10-50) are related to their layer-to-layer variations within a given ore field. The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.

Geochemistry of Eocene sediments from ODP Site 171-1052 on the Black Nose, Atlantic Ocean

We use an X-ray fluorescence (XRF) Core Scanner to obtain records of elemental concentrations in sediment cores from Ocean Drilling Program (ODP) Leg 171B, Site 1052 (Blake Nose, Atlantic margin of northern Florida).This record spans the Middle to Late Eocene, as indicated by bio- and magnetostratigraphy, and displays cyclicity that can be attributed to the orbital forcing of a combination of climate, ocean circulation, or productivity. We use the XRF counts of iron and calcium as a proxy of the relative contribution from calcium carbonate and terrestrial material to construct a new composite depth record. This new composite depth record provides the basis to extend the astronomically calibrated geological time scale into the Middle Eocene and results in revised estimates for the age and duration of magnetochrons C16 through C18. In addition, we find an apparent change in the dominance of orbitally driven changes in obliquity and climatic precession at around 36.7 Ma on our new time scale. Long term amplitude modulation patterns of eccentricity and obliquity in the data do not seem to match the current astronomical model any more, suggesting the possibility of new constraints on astronomical calculations.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

Geochemistry of basalts of the Indian Ocean

Indian Ocean crust formed at Sites 765 and 766 is geochemically comparable to that presently forming in the Red Sea. In both cases, we interpret the crust as reflecting high degrees of mantle melting that are associated with an enhanced thermal gradient below recently rifted continental lithosphere. Asthenospheric melts formed in this environment are rich in CaO and FeO, poor in Na2O and Al2O3, and characterized by depleted rare earth element (REE) profiles ([La/Sm]n approximately 0.5-0.6). Both the Red Sea basalts and the basalts at Sites 765 and 766 are distinct from those erupted at the present Mid-Indian Ocean Ridge. The isotope characteristics of the Site 765 basalts define a geochemical signature similar to that of the present-day Mid-Indian Ocean Ridge basalts (MIORB). The Indian Ocean mantle domain is distinct from that of the Atlantic and Pacific oceans, and this distinction has persisted since Jurassic time, when the Site 765 oceanic crust was formed.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Chemical composition of Black Sea bottom sediments

Concentrations of major-, trace- and rare earth elements in recent and Old Black Sea bottom sediments are reported in the paper. Data presented suggest that accumulation of black shale deposits was not constrained to a certain time span but proceeds in certain modern basins and generates sediments with metal contents close to those in their ancients analogues in hydrogen sulfide contaminated environments. If REE are involved in the process, their composition can vary depending on such factors as variations in redox conditions and occurrence of phosphate and barite nodules, which can induce development of either positive or negative Eu anomalies.

(Table 1) Heat flow measurements in the Black Sea

New data show that the thermal field is definitely related to the geologic structure at depth and to other geophysical fields. Low heat-flow values along reliably established subsurface faults suggest absence of a heated zone of the earth's crust and upper mantle in these regions.

(Table) Specific activities of 137Cs, 90Sr and 239,240Pu in surface waters obtained during cruises BP06-BP09, Indian Ocean

One of the main sources of anthropogenic radionuclides in the ocean is the global fallout resulting from the nuclear tests that had been conducted by the United States, the former Soviet Union, and other countries between 1945 and 1990 mainly in the Northern Hemisphere. The most extensive fallout was observed in the middle latitudes of the Northern Hemisphere in 1963 immediately after the nuclear tests of 1961-1962 conducted by the United States and the Soviet Union. In 2006-2009, under the auspices of an agreement between the Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences and the National Center of Antarctic and Marine Research of the Ministry of Earth Sciences of India, cooperative geological and geochemical investigations were organized in several regions of the Indian Ocean. During these expeditions, the spatial distribution of anthropogenic radionuclides was investigated in the water of the Indian Ocean. The main results of these investigations are reported in this paper.

Trace element contents in different types of recent bottom sediments from the Indian Ocean

Trace element contents in different types of recent botoom sediments of the Indian Ocean are given. Sediment samples were obtained during cruises of the P.P. Shirshov Institute of Oceanology, Moscow.