Siliceous components of Pliocene-Holocene sediments of the South Atlantic

The Pliocene-Holocene sediments recovered on ODP Leg 114 from Holes 699A, 701C, and 704B are the subject of a detailed investigation to interpret changes in the Oceanographic environment of the South Atlantic in the vicinity of the Polar Front Zone (PFZ). The cores sample sediments at shallow (Hole 704B, 2532 m), intermediate (Hole 699A, 3716 m), and basinal (Hole 701C, 4647 m) depths. Sites 699 and 704 come under the influence of the Antarctic Circumpolar Current (ACC) and Circumpolar Deep Water. It is possible that the upper reaches of Antarctic Bottom Water (AABW) may also affect Hole 699A. Site 701 is influenced by AABW. Closely spaced samples were analyzed for grain-size distribution, sand fraction components, biosiliceous microfossils, organic carbon, and water content. PFZ migrations are traced using changes in bulk sedimentaccumulation rates and the abundance of the diatoms Actiniscus ssp. and Genus et species indet. 1 Fenner (1991), as well as changes in sediment grain size and composition. Diatomaceous sediments of Gilbert age in Hole 699A indicate that the PFZ was positioned over this site, but during the Gauss it migrated north, bringing in less productive Antarctic Surface Water. All cores document a very gradual southerly movement of the PFZ throughout the Matuyama (with some sharp fluctuations of the northen PFZ border over Site 704 between 1.45 and 1.83 m.y.). This regressive shift culminated in the late Matuyama. The latest Matuyama to earliest Brunhes record in Hole 699A has been removed by a hiatus lasting from 1.0 to 0.6 m.y., which was probably caused by intensification of the deep-reaching ACC. The corresponding interval in Hole 704B, the shallowest core, contains evidence of winnowing. Sharp fluctuations of large amplitude and high frequency in the lithology of the sediments from Hole 704B in the eastern South Atlantic, starting at about 0.75 m.y. and characterizing the whole Brunhes Epoch, record the rapid movement of the northern border of the PFZ over the site. These reflect strong glacial/interglacial alternations in climate. To a lesser extent, lithologic fluctuations in Hole 701C reflect the same phenomenon, whereas in Hole 699A the lithology does not vary as dramatically.

Age model and grain size distribution of the fine fraction of ODP Site 114-704

The physical properties of sediments beneath an upwelling area in the southern part of the Atlantic Ocean (ODP Hole 704A) were investigated. Highly significant correlations characterize the relationship of carbonate content to bulk density (R = 0.85), carbonate content to porosity (R = 0.84), and carbonate content to impedance (R = 0.84). No relationship exists between carbonate content and compressional-wave velocity (R = 0.24), indicating that amplitude variations in impedance are primarily controlled by variations in bulk density, which, in turn, are controlled by climatically driven biogenic opal and carbonate deposition. In general, maxima in impedance correspond to maxima in carbonate content (minima in opal content). The impedance record exhibits its most drastic change at about 2.4 Ma, marking dramatic increases in the average content of biogenic opal and the beginning of large-amplitude fluctuations. Between 0.7 and 0.4 Ma carbonate content, bulk density, and grain density decrease while opal content drastically increases. Similar changes have been observed in sediments beneath an upwelling cell off northwest Africa, indicating an oceanwide enhancement in upwelling or in the calcite corrosiveness of bottom water that appears to be isochronous.

Concentrations and accumulation rates of chemical elements and sediment components in sediments of central equatorial Pacific, DSDP data

Accumulation rates of Mg, Al, Si, Mn, Fe, Ni, Cu, Zn, opal, and calcium carbonate have been calculated from their concentrations in samples from equatorial Deep Sea Drilling Project sites. Maps of element accumulation rates and of Q-mode factors derived from raw data indicate that the flux of trace metals to equatorial Pacific sediments has varied markedly through time and space in response to changes in the relative and absolute influence of several depositional influences: biogenic, detrital, authigenic, and hydrothermal sedimentation. Biologically derived material dominates the sediment of the equatorial Pacific. The distributions of Cu and Zn are most influenced by surface-water biological activity, but Ni, Al, Fe, and Mn are also incorporated into biological material. All of these elements have equatorial accumulation maxima similar to those of opal and calcium carbonate at times during the past 50 m.y. Detritus distributed by trade winds and equatorial surface circulation contributes Al, non-biogenic Si, Fe, and Mg to the region. Detrital sediment is most important in areas with a small supply of biogenic debris and low bulk-accumulation rates. Al accumulation generally increases toward the north and east, indicating its continental source and distribution by the northeast trade winds. Maxima in biological productivity during middle Eocene and latest Miocene to early Pliocene time and concomitant well-developed surface circulation contributed toward temporal maxima in the accumulation rates of Cu, Zn, Ni, and Al in sediments of those ages. Authigenic material is also important only where bulk-sediment accumulation rates are low. Ni, Cu, Zn, and sometimes Mn are associated with this sediment. Fe is almost entirely of hydrothermal origin. Mn is primarily hydrothermal, but some is probably scavenged from sea water by amorphous iron hydroxide floes along with other elements concentrated in hydrothermal sediments, Ni, Cu, and Zn. During the past 50 m.y. all of these elements accumulated over the East Pacific Rise at rates nearly an order of magnitude higher than those at non-rise-crest sites. In addition, factor analysis indicates that some of this material is carried substantial distances to the west of the rise crest. Accumulation rates of Fe in basal metalliferous sediments indicate that the hydrothermal activity that supplied amorphous Fe oxides to the East Pacific Rise areas was most intense during middle Eocene and late Miocene to early Pliocene time.

Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Carbonat-free sediment components of ODP Leg 115 holes

From the equatorial Indian Ocean, carbonate-free portions of sediment samples of Paleocene to Miocene calcareous oozes and chalks from Sites 707, 709, and 711 were studied using X-ray diffraction measurements and the scanning electron microscope. Downhole variations in biogenic opal, quartz, barite, and clinoptilolite were investigated. The abundance patterns of these major mineral phases show several similarities and may be used for additional lithologic correlations. Variations in biogenic opal contents reflect biogenic silica productivity. Beside the general pattern, a succession in biogenic silica decrease through time is generally recorded since the Oligocene. This succession started earliest at northernmost Site 711 and latest at southernmost Site 707, including Site 709 within these two. Opal-A variations as well as the barite distribution may be influenced by the paleoposition of the sites in relation to the high-productivity zone, which today lies south of the equator. Authigenic clinoptilolite apparently formed in two different modes. In deeper sediment intervals, clinoptilolite was the last mineral phase formed associated with enhanced silica diagenesis. In late Oligocene to middle Miocene sediments, clinoptilolite was the only authigenic silica phase encountered where otherwise strong opal dissolution was observed. The sponge spicules showed special dissolution features probably related to microbiological activity. Silica concretions mainly composed of opal-CT and authigenic quartz occur in carbonate-rich environments and are formed during later diagenesis when burial depth causes the sediments to reach higher temperatures. Opal-CT concretions in carbonate-free siliceous oozes were found at Site 711 and are probably formed during an early stage of silica diagenesis.

Bulk mineralogy of Cretaceous to Quaternary sediments from the Kerguelen Plateau

Carbonate-free portions of Upper Cretaceous to Holocene sediment samples from the Kerguelen Plateau in the southern Indian Ocean were investigated by X-ray diffraction. Downhole variations in the content of opal-A, opal-CT, quartz, feldspar, barite, and clinoptilolite were studied at Site 737 on the northern Kerguelen Plateau and at Sites 744 and 738 on the southern Kerguelen Plateau. The variation of these components reflects temporal changes in the depositional history of the Kerguelen Plateau as well as major differences in the sedimentary evolution between the northern plateau and the southern plateau. Carbonate is the dominant component in the pelagic sediments on the Kerguelen Plateau. In addition, biogenic opal sedimentation plays an important role throughout most of the sequence. A major increase in opal accumulation is documented at all sites in late Miocene time, which is in accordance with the well-known increase in silica productivity probably caused by a major cooling step. Because of its position near the Polar Frontal Zone, sediments from Site 737 show a more extensive opal deposition than at Sites 744 and 738. An earlier productivity pulse is documented at Site 744 on the southern plateau within the early Oligocene, following the initial phase of intense East Antarctic glaciation. This cooling event resulted in higher amounts of ice-rafted terrigenous quartz and, to a lesser extent, feldspar. With the exception of the Site 744 sediments, opal deposition in Paleogene and older sediments can be reconstructed only from the diagenetic transformation products of opal-CT and probably clinoptilolite. In contrast to the southern sequence, on the northern Kerguelen Plateau higher amounts of clinoptilolite and no opal-CT were found. These major differences in the diagenetic environments may be due to extensive volcanism in the northern area. The volcanic influence at Site 737 is well recorded by the higher feldspar content and higher amounts of volcanic glass shards.

Geochemistry of terrigenous material in deep-sea sediments of the equatorial Pacific

Biological productivity in the modern equatorial Pacific Ocean, a region with high nutrients and low chlorophyll, is currently limited by the micronutrient Fe. In order to test whether Fe was limiting in the past and to identify potential pathways of Fe delivery that could drive Fe fertilization (i.e., dust delivery from eolian inputs vs. Fe supplied by the Equatorial Undercurrent), we chemically isolated the terrigenous material from sediment along a cross-equatorial transect in the central equatorial Pacific at 140°W and at Ocean Drilling Program Site 850 in the eastern equatorial Pacific. We quantified the contribution from each potential Fe-bearing terrigenous source using a suite of chemical- and isotopic discrimination strategies as well as multivariate statistical techniques. We find that the distribution of the terrigenous sources (i.e., Asian loess, South American ash, Papua New Guinea, and ocean island basalt) varies through time, latitude, and climate. Regardless of which method is used to determine accumulation rate, there also is no relationship between flux of any particular Fe source and climate. Moreover, there is no connection between a particular Fe source or pathway (eolian vs. Undercurrent) to total productivity during the Last Glacial Maximum, Pleistocene glacial episodes, and the Miocene "Biogenic Bloom". This would suggest an alternative process, such as an interoceanic reorganization of nutrient inventories, may be responsible for past changes in total export in the open ocean, rather than simply Fe supply from dust and/or Equatorial Undercurrent processes. Additionally, perhaps a change in Fe source or flux is related to a change in a particular component of the total productivity (e.g., the production of organic matter, calcium carbonate, or biogenic opal).

Composition of surface layer bottom sediments from the Chukchi Sea

Abundance of noble metals and bulk chemical composition have been studied in bottom sediments of the Chukchi Sea. Distribution of noble metals and their correlation with major and trace elements in the sediments have been analyzed using multicomponent statistics. It was established that average contents of noble metals in the bottom sediments of the Chukchi Sea significantly exceed those both in shelf terrigenous sediments and stratisphere. Osmium and iridium enrich mixed and pelitic sediments relative to shallow-water sediments and their influx is presumably determined by erosion of coastal and bottom unconsolidated deposits. High Ag, Ru, Au, and Pt contents were identified in clayey sediments enriched in biogenic elements in the some areas of the Southern Chukchi plain (Chukchi Sea) confined to intersection zones of submeridional and sublatitudinal structures of the graben-rift system, which formed in Mesozoic and activated in Late Cenozoic.

Chemical and mineral compositions of bottom sediments from the Sea of Japan

Physical properties (water content, bulk density, magnetic susceptibility, natural remanent magnetization, nature of magnetization, and composition of ferromagnetic fraction), chemical, and (optionally) mineral composition of bottom sediments from the north-west Sea of Japan have been studied. Their stratigraphic subdivision based on composition of diatoms has been carried out. Obtained data have allowed to find out some aspects of influence of paleogeographic conditions and diagenetic processes on change of physical properties of the sediments, as well as on their composition in Holocene and Late Pleistocene.

Composition and distribution of silica in sediments of the Broken Ridge

Within a dipping sequence of middle Cretaceous to Eocene sediments on Broken Ridge, opal-A, opal-CT, and quartz occur as minor constituents in carbonate and ash-rich sediments. Biogenic opal-A is mainly derived from diatoms and radiolarians. Opal-A and almost all siliceous microfossils disappear within a narrow (<20-m-thick) transition zone below which authigenic opal-CT and quartz are present. These latter silica polymorphs occur together within a 750-m-thick interval, but the ratio of quartz/opal-CT increases with increasing age and depth within the pre-rift sediment sequence. The boundary between opal-A- and opal-CT-bearing sediments is also a physical boundary at which density, P-wave velocity, and acoustic impedance change. This physical transition is probably caused by infilling of pore space by opal-CT lepispheres.

Chert petrology and geochemistry at DSDP Leg 62 Holes

Sixty-five chert, porcellanite, and siliceous-chalk samples from Deep Sea Drilling Project Leg 62 were analyzed by petrography, scanning electron microscopy, analysis by energy-dispersive X-rays, X-ray diffraction, X-ray spectroscopy, and semiquantitative emission spectroscopy. Siliceous rocks occur mainly in chalks, but also in pelagic clay and marlstone at Site 464. Overall, chert probably constitutes less than 5% of the sections and occurs in deposits of Eocene to Barremian ages at sub-bottom depths of 10 to 820 meters. Chert nodules and beds are commonly rimmed by quartz porcellanite; opal-CT-rich rocks are minor in Leg 62 sediments 65 to 108 m.y. old and at sub-bottom depths of 65 to 520 meters. Chert ranges from white to black, shades of gray and brown being most common; yellow-brown and red-brown jaspers occur at Site 464. Seventy-eight percent of the studied cherts contain easily recognizable burrow structures. The youngest chert at Site 463 is a quartz cast of a burrow. Burrow silica maturation is always one step ahead of host-rock silicification. Burrows are commonly loci for initial silicification of the host carbonate. Silicification takes place by volume-f or-volume replacement of carbonate sediment, and more-clay-rich sediment at Site 464. Nannofossils are commonly pseudomorphically replaced by quartz near the edges of chert beds and nodules. Other microfossils, mostly radiolarians and foraminifers, whether in chalk or chert, can be either filled with or replaced by calcite, opal-CT, and (or) quartz. Chemical micro-environments ultimately control the removal, transport, and precipitation of calcite and silica. Two cherts from Site 465 contain sulfate minerals replaced by quartz. Site 465 was never subaerially exposed after sedimentation began, and the formation of the sulfate minerals and their subsequent replacement probably occurred in the marine environment. Several other cherts with odd textures are described in this paper, including (1) a chert breccia cemented by colloform opal-CT and chalcedony, (2) a transition zone between white porcellanite containing opal-CT and quartz and a burrowed brown chert, consisting of radial aggregates of opal-CT with hollow centers, and (3) a chert that consists of silica-replaced calcite pseudospherules interspersed with streaks and circular masses of dense quartz. X-ray-diffraction analyses show that when data from all sites are considered there are poorly defined trends indicating that older cherts have better quartz crystallinity than younger ones, and that opal-CT crystallite size increases and opal-CT cf-spacings decrease with depth of occurrence in the sections. In a general way, depth of burial and the presence of calcite promote the ordering in the opal-CT crystal structure which allows its eventual conversion to quartz. Opal-CT in porcellanites converts to quartz after reaching a minimum d-spacing of 4.07 Å. Quartz/opal-CT ratios and quartz crystallinity vary randomly on a fine scale across four chert beds, but quartz crystallinity increases from the edge to the center of a fifth chert bed; this may indicate maturation of the silica. Twenty-four rocks were analyzed for their major- and minor-element compositions. Many elements in cherts are closely related to major mineral components. The carbonate component is distinguished by high values of CaO, MgO, Mn, Ba, Sr, and (for unknown reasons) Zr. Tuffaceous cherts have high values of K and Al, and commonly Zn, Mo, and Cr. Pure cherts are characterized by high SiO2 and B. High B may be a good indicator of formation of chert in an open marine environment, isolated from volcanic and terrigenous materials.

Chemical composition of surficial bottom sediments from the Chukchi Sea and adjacent part of the Arctic Ocean

This paper presents data on chemical composition of bottom sediments from the Chukchi Sea and the adjacent Arctic Ocean. Multivariate statistical techniques were used for analysis of the data set and revealed that grain size fractionation of the original terrigenous component during sedimentation was the major factor of clustering of the samples in study. Secondary factors include accumulation of biogenic siliceous and carbonate material and chemogenic or biochemical accumulation of iron, manganese, and some trace elements. The latter factor was significant in areas of tectonic activity within the graben-rift system of the Chukchi Sea.

Radiolarian Paleogene biostratigraphy in the southern Indian Ocean, ODP Leg 120

During Ocean Drilling Program Leg 120, an almost complete Paleogene sediment section on the Kerguelen Plateau in the southern Indian Ocean was recovered. The biostratigraphy of radiolarians from these sediments at Sites 748 and 749 is studied. A biostratigraphic framework established in low and middle latitudes is not applicable because of the absence of most zonal marker species. Biogenic opal is present only in middle Eocene to Oligocene sediments, and three new zones-Lychnocanoma conica, Axoprunum (?) irregularis, and Eucyrtidium spinosum zones-are proposed. The Paleogene antarctic radiolarian fauna is different from that in low and middle latitudes. Three new species, Axoprunum (?) irregularis, Eucyrtidium cheni, and Eucyrtidium spinosum, are described.

Quartz and opaline silica in ocean sediments

A new method of quantitative analysis of quartz and opal in bottom sediments is developed. It is based on the study of sediment samples in form of suspensions in petrolatum where potassium rhodanate is added as an internal standard.