Geochemistry at DSDP Leg 62 Holes

A total of 191 samples was collected for inorganic geochemical analyses from DSDP Holes 463, 464, 465, 465A, and 466. These samples were collected with two main goals. First, at least one sample was collected from each core, whenever possible, to document the general geochemical variability within lithologic units. Unfortunately, several lithologic units were inadequately sampled because of poor recovery, mostly due to the presence of chert. The least-sampled units are Units III in Hole 464 and Units IB and II in Hole 466. The second goal was to look for geochemical differences between contrasting lithologies within main lithologic units, particularly between cyclic interbeds of red and green limestone in Lithologic Unit II, Hole 463, and between olive, laminated limestone and gray, massive limestone in Lithologic Unit II, Hole 465A.

Composition of ocean suspended matter

Compositions of different types of ocean suspended matter are under consideration.

Chemical composition of bottom sediments from the northern part of the Deryugin Trough, Sea of Okhotsk

Distribution trace element contents in the upper (up to 5 m) Holocene-Upper Pleistocene sediment layer along the northern and southern sublatitudinal profiles in the northern part of the Deryugin Trough is discussed. Mathematical processing of chemical analysis data has been made. On the basis of the cluster analysis 16 elements have been combined into 5 geochemical groups. Two of them (1 - Ag-Mo group and 2 - Mn-Ba-Ni-Sr group) were considered in detail. Analysis of Ag and Mo distributions in the sediments and findings of molybdenite permitted to conclude that enrichment of the sediments by these elements resulted from edaphic washing of magmatic rocks containing Ag-Mo mineralization and probably located on the northwestern slope of the Deryugin trough. The second geochemical group is most likely connected with hydrothermal barite mineralization found in the northeastern part of the Deryugin trough. Considering Mn distribution in bottom sediment cores supply of Mn was pulsating. This allows concluding that during Holocene - Late Pleistocene three cycles of hydrothermal activity occurred in the Deryugin Trough, and the most intensive one was in Holocene.

Chemical composition of ferromanganese manifestations from the Sea of Okhotsk

New data on microstructures and mineral and chemical compositions of ferromanganese crusts sampled from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. Lithic mineral assemblage includes apatite, quartz, epidote, and montmorillonite. According to chemical analysis most of the crusts contain significant part of volcanogenic and hydrothermal material. It is evident from elevated values of Mn/Fe and (Mn+Fe)/Ti ratios, low concentrations of some trace elements, and positive Eu anomaly.

Granulometry, biogenic silica content, magnetic susceptibility and bulk densities of ODP Site 188-1165

The Prydz Bay area is a key region for studying and understanding the history of the eastern Antarctic Continental Ice Sheet (O'Brien, Cooper, Richter, et al., 2001, doi:10.2973/odp.proc.ir.188.2001). Ocean Drilling Program (ODP) Site 1165 is situated in a water depth of 3357 m on the continental rise offshore from Prydz Bay and lies in front of the outlet for the Lambert Glacier-Amery Ice Shelf system that today drains 22% of East Antarctica. The site was drilled into mixed pelagic and hemipelagic sediments from the southwestern side of the Wild Drift. The drift is an elongate sediment body formed by the interaction of sediment supplied from continental shelf and slope with westward-flowing bottom currents. The sedimentary sequence is characterized by alternations between a generally gray to dark gray facies and a green to greenish gray facies. The greenish facies are structureless diatom-bearing clays with common bioturbation and larger amounts (>15%-20%) of biogenic silica, dispersed clasts, and lonestones than the dark gray facies, which are mostly less bioturbated clay with some silt laminations (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.188.103.2001). High-quality advanced piston corer and extended core barrel cores containing nearly complete sections of middle Miocene to early Pliocene age allow a detailed characterization of sedimentary cycles and can provide indications for ice advances of the Lambert Glacier system into Prydz Bay, for the extent of sea ice, and for changes in oceanic circulation. The purpose of this work is to provide a data set of coarse-fraction mass percentage (>63, >125, and >250 µm) and biogenic silica content measured on sediments of late Miocene to early Pliocene age drilled at Site 1165. Additionally, high-resolution records of magnetic susceptibility (MS) and gamma ray attenuation (GRA) bulk density are presented. These shipboard data sets were edited postcruise. Furthermore, I provide a high-resolution dry bulk density record that is derived from GRA bulk density and can be used for the calculation of mass accumulation rates. These sedimentological and physical parameters will be used in future work to understand the depositional pattern of alternating biogenic and terrigenous sediments that was observed at Site 1165 (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.188.103.2001).

Composition of sediments and cores from DSDP Legs 54 and 61-63

The monograph gives results of studies of sediments and rocks collected from D/S Glomar Challenger in the Pacific Ocean. These studies have been based on the lithological facial analysis applied for the first time for identificating genesis of ocean sediments. These results include new ideas on formation of the Earth's sedimentary cover and can be used for constructing regional and global schemes of ocean paleogeography, reconstructing some structures, correlating sedimentation on continents and in oceans, estimating perspectives of oil- and gas-bearing deposits and ore formation. The monograph also gives the first petrographic classification of organic matter in black shales.

Geochemistry of sediments from the mid-oceanic Kolbeinsey Ridge

In order to assess recent submarine volcanic contributions to the sediments from the active Kolbeinsey Ridge, surface samples were analyzed chemically. The contribution of major and trace elements studied differ within the study area. A statistical analysis of the geochemical variables using factor analysis and cluster method allows to distinguish possible sample groups. Cluster method identifies three distinct sediment groups located in different areas of sedimentation. Group 1 is characterized by highest contents of Fe2O3, V, Co, Ni, Cu and Zn demonstrating the input of volcaniclastic material. Group 2 comprises high values of CaCO3, CaO and Sr representing biogenic carbonate. Group 3 is characterized by the elements K, Rb, Cs, La and Pb indicating the terrigenous component. The absolute percentage of the volcanic, biogenic and terrigenous components in the bulk sediments was calculated by using a normative sediment method. The highest volcanic component (> 60% on a carbonate free basis) is found on the ridge crest. The biogenic component is highest (10-30%) in the eastern part of the Spar Fracture Zone influenced by the East Iceland Current. Samples from the western and southeastern region of the study area contain more than 90% of terrigenous component which appears to be mainly controlled by input of ice-rafted debris.

Mineralogy and geochemistry at DSDP Hole 62-465A

Core recovered from Hess Rise contains concentrations of pyrite, marcasite, and barite in the lowermost meter of limestone (Unit II) and in the brecciated upper part of the underlying volcanic basement (Unit HI). Petrographic and chemical data indicate that the sulfide-barite assemblage in the limestone is mainly a product of low-temperature diagenetic processes. The iron-sulfide phases are biogenic and their concentrations mark the diffusion of sea water sulfate through sedimentary horizons containing abundant organic matter and mafic, glassy volcanogenic detritus. There is some evidence, however, that elevated temperatures augmented or intensified the synsedimentary diagenetic process.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Mineralogical and isotopic compositions of ODP Hole 107-650A

Red-brown dolomitic claystones overlay the Marsili Basin basaltic basement at ODP Site 650. Sequential leaching experiments reveal that most of the elements considered to have a hydrothermal or hydrogenous origin in a marine environment, such as Fe, Cu, Zn, Pb, Co, Ni, are present mainly in the aluminosilicate fraction of the dolomitic claystones. Their vertical distribution, content and partitioning chemistry of trace elements, and REE patterns suggest enhanced terrigenous input during dolomite formation, but no significant hydrothermal influence from the underlying basaltic basement. Positive correlations in the C and O isotopes in the dolomites reflect complex conditions during the dolomitization. The stable isotopes can be controlled in part by temperature variations during the dolomitization. Majority of the samples, however, form a trend that is steeper than expected for only temperature control on the C and O isotopes. The latter indicates possible isotopic heterogeneity in the proto-carbonate that can be related to arid climatic conditions during the formation of the basal dolomitic claystones. In addition, the dolostones stable isotopic characteristics can be influenced by diagenetic release of heavier delta18O from clay dehydration and/or alteration of siliciclastic material. Strontium and Pb isotopic data reveal that the non-carbonate fraction, the "dye" of the dolomitic claystones, is controlled by Saharan dust (75%-80%) and by material with isotopic characteristics similar to the Aeolian Arc volcanoes (20%-25%). The non-carbonate fraction of the calcareous ooze overlying the dolomitic claystones has a Sr and Pb isotopic composition identical to that of the dolomitic claystones, indicating that no change in the input sources to the sedimentary basin occurred during and after the dolomitization event. Combination of climato-tectonic factors most probably resulted in suitable conditions for dolomitization in the Marsili and the nearby Vavilov Basins. The basal dolomitic claystone sequence was formed at the initiation of the opening of the Marsili Basin (~2 Ma), which coincided with the consecutive glacial stage. The glaciation caused arid climate and enhanced evaporation that possibly contributed to the stable isotope variations in the proto-carbonate. The conductive cooling of the young lithosphere produced high heat flow in the region, causing low-temperature passive convection of pore waters in the basal calcareous sediment. We suggest that this pumping process was the major dolomitization mechanism since it is capable of driving large volumes of seawater (the source of Mg2+) through the sediment. The red-brown hue of the dolomitic claystones is terrigenous contribution of the glacially induced high eolian influx and was not hydrothermally derived from the underlying basaltic basement. The detailed geochemical investigation of the basal dolomitic sequence indicates that the dolomitization was most probably related to complex tectono-climatic conditions set by the initial opening stages of the Marsili Basin and glaciation.