Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

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.

Contents of major and noble chemical elements in phosphorites and bottom sediments

Ag and Au are typically concentrated in phosphorites; they genetically related to organic matter of bottom sediments that extract these elements from seawater or interstitial water. Consequently, the phosphorites inherit Ag and Au from host sediments that are not always enriched in them. In contrast to other organic-rich sediments, analyzed sample of recent diatom ooze from the Namibian shelf is not enriched in Ag and Au, although some sediments from this region are enriched in Au. In addition to authigenic Au, allochthonous Au associated with quartz grains and micrograins can also be present in shelf phosphorites. This was observed in oceanic phosphorites of various types. Anomalous Au and Fe contents recorded in one seamount phosphorite sample can be related to extraction of Au and nonferrous metals by ferromanganese hydroxides from seawater. This process can serve as one of major mechanisms of Au supply to ferromanganese crusts on seamounts. Phosphorites and sediments are enriched in Ru simultaneously with U. Author's data show that U content varies from 17 (seamount phosphorite) to 887 ppm (Pleistocene phosphorite nodule from the Namibian shelf). This is probably caused by different types of behavior of light and heavy PGEs in the marine environment.

Element concentrations, and Sr and Os isotope ratios of DSDP Leg 92 metalliferous carbonates

The Os concentration and isotopic composition of metalliferous carbonates deposited on the East Pacific Rise over the past 28 Ma are reported with complimentary Sr isotope data. Variations in the Os isotopic composition of these samples are interpreted as a record of past changes in the Os isotopic composition of seawater. These results are consistent with isotopic analyses of leachable Os in pelagic clays which have also been interpreted as a record of the 187Os/186Os ratio of seawater through time (Pegram et al., 1992, doi:10.1016/0012-821X(92)90132-F). The metalliferous carbonate record clearly shows that seawater Os and Sr isotope systems are partially decoupled from one another over the past 28 Ma. Accelerated weathering of ancient organic-rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the 187Os//186Os ratio of seawater over the past 15 Ma. This rapid increase suggests that the seawater Os record can potentially be used as a stratigraphic tool in some Neogene marine deposits.

Dissolved chemical elements in river waters of the Wrangel Island

Pioneer information about chemical composition of river waters in the Wrangel Island has been obtained. It is shown that water composition reflects the lithogeochemical specifics of primary rocks and ore mineralization. In contrast to many areas of the Russian Far North river waters of the island are characterized by elevated background value of total mineralization (i.e., total dissolved solids, TDS) (0.3-2 g/l) and specific chemical type (SO4-Ca-Mg). This is related to abundance of Late Carboniferous gypsiferous and dolomitic sequences in the mountainous area of the island. It has also been established that salt composition of some streams is appreciably governed by supergene alterations of sulfide mineralization associated with quartz-carbonate vein systems. They make up natural centers of surface water contamination. Waters in such streams are characterized by low pH values (2.4-5.5), high TDS (up to 6-23 g/l) and SO4-Mg composition. These waters are also marked by anomalously high concentrations of heavy and non-ferrous metals, as well as REE, U, and Th.

(Table 1) Platinoids in Fe-Mn crusts and nodules from the Pacific Ocean

Platinoid element contents were determined in 16 samples of Fe-Mn crusts and nodules collected during dredging deep-sea mound slopes of the Pacific Ocean from the equator to 27°N. The method of neutron activation analysis with pre-concentration of the platinoids was used for these determinations. There is no relationship between platinoid contents in deep-sea (>3000 m) Fe-Mn nodules with depth of sampling, as well as with age of nodule layers. It is concludet that ultramafic rocks are the primary source of platinoids in Fe-Mn nodules.

Re-OS and Pb isotope ratios of sediments from Saanich Inlet, Western Canada

Re-Os and Pb-Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/188Os ratio and Os concentration respectively increase from ~0.8 to ~0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with Corg (R2=0.6) throughout the entire section, whereas Os follows Re and Corg trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ~50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.