Composition of carbonaceous sediments from the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region, Russia)

Lithological, geochemical, stratigraphic, and paleoecological features of carbonaceous sediments in the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region) are considered. The shale-bearing sequence studied is characterized by greater sedimentological completeness as compared with its stratotype sections in the Middle Volga region (Gorodishche, Kashpir). Stratigraphic position and stratigraphy of the shale-bearing sequence, as well as distribution of biota in different sedimentation settings are specified. It is shown that Volgian sediments show distinct cyclic structure. The lower and upper elements of cyclites consist of high-carbonaceous shales and clayey-calcareous sediments, respectively, separated by transitional varieties. Bioturbation structures in different rocks are discussed. Microcomponent composition and pyrolytic parameters of organic matter, as well as distribution of chemical elements in lithologically variable sediments are analyzed. Possible reasons responsible for appearance of cyclicity and accumulation of organic-rich sediments are discussed.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.

Composition of sediments, rocks, and ores from the Northern and Equatorial Indian Ocean

The monograph has been written on the base of data obtained from samples and materials collected during the 19-th cruise of RV ''Akademik Vernadsky'' to the Northern and Equatorial Indian Ocean. Geological features of the region (stratigraphy, tectonic structure, lithology, distribution of ore-forming components in bottom sediments, petrography of igneous rocks, etc.) are under consideration. Regularities of trace element concentration in Fe-Mn nodules, nodule distribution in bottom sediments, and engineering-geological properties of sediments within the nodule fields have been studied. Much attention is paid to ocean crust rocks. The wide range of ore mineralization (magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals) has been ascertained.

Revised composite depth scale, Fe content and orbital tuning of Middle Eocene Climate Optimum samples from ODP Site 207-1260

A high-resolution stratigraphy is essential toward deciphering climate variability in detail and understanding causality arguments of events in earth history. Because the highly dynamic middle to late Eocene provides a suitable testing ground for carbon cycle models for a waning warm world, an accurate time scale is needed to decode climate-driving mechanisms. Here we present new results from ODP Site 1260 (Leg 207) which covers a unique expanded middle Eocene section (magnetochrons C18r to C20r, late Lutetian to early Bartonian) of the tropical western Atlantic including the chron C19r transient hyperthermal event and the Middle Eocene Climate Optimum (MECO). To establish a detailed cyclostratigraphy we acquired a distinctive iron intensity records by XRF scanning Site 1260 cores. We revise the shipboard composite section, establish a cyclostratigraphy and use the exceptional eccentricity modulated precession cycles for orbital tuning. The new astrochronology revises the age of magnetic polarity chrons C19n to C20n, validates the position of very long eccentricity minima at 40.2 and 43.0 Ma in the orbital solutions, and extends the Astronomically Tuned Geological Time Scale back to 44 Ma. For the first time the new data provide clear evidence for an orbital pacing of the chron C19r event and a likely involvement of the very long eccentricity cycle contributing to the evolution of the MECO.

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.

Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

Geochemical analysis of minerals from sediment core CRP-2 in the Ross Sea, Antarctica

Distribution patterns, petrography, whole-rock and mineral chemistry, and shape and fabric data are described for the most representative basement lithologies occurring as clasts (granule to bolder grain-size class) from the 625 m deep CRP-2/2A drillcore. A major change in the distribution pattern of the clast types occurs at c. 310 mbsf., with granitoid-dominated clasts above and mainly dolerite clasts below; moreover, compositional and modal data suggest a further division into seven main detrital assemblages or petrofacies. In spite of this variability, most granitoid pebbles consist of either pink or grey biotite±hornblende monzogranites. Other less common and ubiquitous lithologies include biotite syenogranite, biotite-hornblende granodiorite, tonalite, monzogranitic porphyries (very common below 310 mbsf), microgranite, and subordinately, monzogabbro, Ca-silicate rocks, biotite-clinozoisite schist and biotite orthogneiss (restricted to the pre-Pliocene strata). The ubiquitous occurrence of biotite±hornblende monzogranite pebbles in both the Quaternary-Pliocene and Miocene-Oligocene sections, apparently reflects the dominance of these lithologies in the onshore basement, and particularly in the Cambro-Ordovician Granite Harbour Igneous Complex which forms the most extensive outcrop in southern Victoria Land. The petrographical features of the other CRP-2/2A pebble lithologies are consistent with a supply dominantly from areas of the Transantarctic Mountains facing the CRP-2/2A site, and they thus provide further evidence of a local provenance for the supply of basement clasts to the CRP-2/2A sedimentary strata.

Concentration and composition of aerosols over the North Atlantic in August 1995

Data on composition of aerosols are considered. Investigations include electron microscopy, grain size, mineralogical and chemical analyses. Samples of aerosols were collected Cruise 37 of R/V Akademik Mstislav Keldysh along a transatlantic section along 40°-50°N. Variability of concentrations and composition of aerosols with distance from continents is shown: concentrations of aerosols decrease by factor of ten and more. Significant portion of mineral components in aerosols collected over the continent is replaced by organic matter due to mechanical differentiation during transportation. Such anthropogenic components as soot, ash, and combustion spheres were detected in all samples. North African dust was found in one sample in the western part of the section.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Geochemistry and provenance of basaltic clasts within volcaniclastic debris flows at DSDP Site 89-585

Pebble-sized basaltic and glassy clasts were extracted from seamount-derived volcaniclastic debris flows and analyzed for various trace elements, including the rare earths, to determine their genetic relationships and provenance. All the clasts were originally derived from relatively shallow submarine lava flows prior to sedimentary reworking, and have undergone minor low-grade alteration. They are classified into three petrographic groups (A, B, and C) characterized by different phenocryst assemblages and variable abundances and ratios of incompatible elements. Group A (clast from Hole 585) is a hyaloclastite fragment which is olivine-normative and distinct from the other clasts, with incompatibleelement ratios characteristic of transitional or alkali basalts. Groups B and C (clasts from Hole 585A) are quartz-normative, variably plagioclase-clinopyroxene-olivine phyric tholeiites, all with essentially similar ratios of highly incompatible elements and patterns of enrichment in light rare earth elements (chrondrite-normalized). Variation within Groups B and C was governed by low-pressure fractionation of the observed phenocryst phases, whereas the most primitive compositions of each group may be related by variable partial melting of a common source. The clasts have intraplate chemical characteristics, although relative to oceanic hot-spot-related volcanics (e.g., Hawaiian tholeiites) they are marginally depleted in most incompatible elements. The source region was enriched in all incompatible elements, compared with a depleted mid-ocean-ridge basalt source.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Geochemistry of volcanic rocks of ODP Holes 126-792E and 126-793B

The Izu-Bonin forearc basement volcanic rocks recovered from Holes 792E and 793B show the same phenocrystic assemblage (i.e., plagioclase, two pyroxenes, and Fe-Ti oxides ±olivine), but they differ in the crystallization sequence and their phenocryst chemistry. All the igneous rocks have suffered low-grade hydrothermal alteration caused by interaction with seawater. As a result, only clinopyroxenes, plagioclases, and oxides have preserved their primary igneous compositions. The Neogene olivine-clinopyroxene diabasic intrusion (Unit II) recovered from Hole 793B differs from the basement basaltic andesites because it lacks Cr-spinels and contains abundant titanomagnetites (Usp38.5-46.4) and uncommon FeO-rich (FeO = 29%) spinels. It displays petrological and geochemical similarities to the Izu Arc volcanoes and, thus, can be considered as related to Izu-Bonin Arc magmatic activity. The titanomagnetites (Usp28.5-33) in the calc-alkaline andesitic fragments of the Oligocene volcaniclastic breccia in Hole 793B (Unit VI) represent an early crystallization phase. The Plagioclase phenocrysts enclosed in these rocks show oscillatory zoning and are less Ca-rich (An78.6-67.8) than the plagioclase phenocrysts of the diabase sill and the basement basaltic andesites. Their clinopyroxenes are Fe-rich augites (Fs ? 19.4; FeO = 12%) and thus, differ significantly from the clinopyroxenes of the Hole 793B arc-tholeiitic igneous rocks. The 30-32 Ma porphyritic, two-pyroxene andesites recovered from Hole 792E are very similar to the andesitic clasts of the Neogene breccia recovered in Hole 793B (Unit VI). Both rocks have the same crystallization sequence, and similar chemistry of the Fe-Ti oxides, clinopyroxenes, and plagioclases: that is, Ti-rich (Usp25.5-30.4) magnetites, Fe-rich augites, and intensely oscillatory zoned plagioclases with bytownitic cores (An86-63) and labradorite rims (An73-68). They display a calc-alkaline differentiation trend (Taylor et al., this volume). So, the basement highly porphyritic andesites recovered at Hole 792E, and the Hole 793B andesitic clasts of Unit VI show the same petrological and geochemical characteristics, which are that of calc-alkaline suites. These Oligocene volcanic rocks represent likely the remnants of the Izu-Bonin normal arc magmatic activity, before the forearc rifting and extension. The crystallization sequence in the basaltic andesites recovered from Hole 793B is olivine-orthopyroxene-clinopyroxene-plagioclase-Fe-Ti oxides, indicating a tholeiitic differentiation trend for these volcanic rocks. Type i is an olivine-and Cr-spinel bearing basaltic andesite whereas Type ii is a porphyritic pyroxene-rich basaltic andesite. The porphyritic plagioclase-rich basaltic andesite (Type iii) is similar, in most respects, to Type ii lavas but contains plagioclase phenocrysts. The last, and least common lava is an aphyric to sparsely phyric andesite (Type iv). Cr-spinels, included either in the olivine pseudomorphs of Type i lavas or in the groundmass of Type ii lavas, are Cr-rich and Mg-rich. In contrast, Cr-spinels included in clinopyroxenes and orthopyroxenes (Types i and ii lavas) show lower Cr* and Mg* ratios and higher aluminium contents. Orthopyroxenes from all rock types are Mg-rich enstatites. Clinopyroxenes display endiopsidic to augitic compositions and are TiO2 and Al2O3 depleted. All the crystals exhibit strong zoning patterns, usually normal, although, reverse zoning patterns are not uncommon. The plagioclases show compositions within the range of An90-64. The Fe-Ti oxides of the groundmass are TiO2-poor (Usp16-17). The Hole 793B basaltic andesites show, like the Site 458 bronzites from the Mariana forearc, intermediate features between arc tholeiites and boninites: (1) Cr-spinel in olivine, (2) presence of Mg-rich bronzite, Ca-Mg-rich clinopyroxenes, and Ca-plagioclase phenocrysts, and (3) transitional trace element depletion and epsioln-Nd ratios between arc tholeiites and boninites. Thus, the forearc magmatism of the Izu-Bonin and Mariana arcs, linked to rifting and extension, is represented by a depleted tholeiitic suite that displays boninitic affinities.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.