(Table 1) U and Th isotope analyses of pyrite and anhydrite of ODP Site 158-957

Hydrothermal circulation at oceanic spreading ridges causes sea water to penetrate to depths of 2 to 3 km in the oceanic crust where it is heated to ~400 °C before venting at spectacular 'black smokers'. These hydrothermal systems exert a strong influence on ocean chemistry (Edmond et al., 1979, doi:10.1016/0012-821X(79)90061-X), yet their structure, longevity and magnitude remain largely unresolved (Elderfield and Schultz., 1996, doi:10.1146/annurev.earth.24.1.191). The active Transatlantic Geotraverse (TAG) deposit, at 26° N on the Mid-Atlantic Ridge, is one of the largest, oldest and most intensively studied of the massive sulphide mounds that accumulate beneath black-smoker fields. Here we report ages of sulphides and anhydrites from the recently drilled (Humphris et al., 1995, doi:10.1038/377713a0) TAG substrate structures -determined from 234U-230Th systematics analysed by thermal ionization mass spectrometry. The new precise ages combined with existing data (Lalou et al., 1993, doi:10.1029/92JB01898; 1998, doi:10.2973/odp.proc.sr.158.214.1998) show that the oldest material (11,000 to 37,000 years old) forms a layer across the centre of the deposit with younger material (2,300-7,800 years old) both above and below. This stratigraphy confirms that much of the sulphide and anhydrite are precipitated within the mound by mixing of entrained sea water with hydrothermal fluid (James and Elderfield, 1996, doi:10.1130/0091-7613(1996)024<1147:COOFFA>2.3.CO;2). The age distribution is consistent with episodic activity of the hydrothermal system recurring at intervals of up to 2,000 years.

Geochemistry and mineralogy at DSDP Holes 61-462, 61-462A and 33-315A

Sedimentary rocks of Barremian through early Maestrichtian age recovered on Deep Sea Drilling Project Leg 61 had their principal source in the complex of igneous rocks with which they are interlayered in the Nauru Basin. Relict textures and primary sedimentary structures show these Cretaceous sediments to be of hyaloclastic origin, in part reworked and redeposited by slumps and currents. The dominant composition now is smectite, but locally iron, titanium, and manganese oxides, plagioclase, pyroxene, analcime, clinoptilolite, chalcedonic quartz, cristobalite, amphibole, nontronite, celadonite, and pyrite are also present. The mineral assemblages and the geochemistry reflect the original basaltic composition and its subsequent alteration by one or more processes of submarine weathering, authigenesis, hydrothermal circulation, and contact metamorphism. Hyaloclastitic sandstone, siltstone, and breccia within the sheet flows below 729 meters sub-bottom depth have Barremian fossils, thus establishing the age of the lower, or extrusive, complex of post-ridge-crest volcanism. Similar hyaloclastites between 564 and 729 meters are invaded by hypabyssal sills of the upper igneous complex, and fossil ages of Albian or Cenomanian set an older limit to the age of that second post-ridge-crest episode. Cenomanian to early Campanian sedimentary rocks between 490 and 564 meters have a substantial contribution of clays of submarine-weathered-basalt origin, as well as hydrothermal and pelagic components. The interval of reworked hyaloclastitic siltstone, sandstone, and breccias between 450 and 490 meters is of late Campanian and early Maestrichtian age. These sediments probably formed from glassy basalt that fragmented upon eruption nearby, when sills were being emplaced. In addition to pelagic elements, these Upper Cretaceous volcanogenic sediments include redeposited material of shallow-water origin, apparently derived from the Marshall Islands.

Rb-Sr and K-Ar data for Upper Vendian clayey rocks of the Russian Platform

Geochemical behavior of Rb-Sr and K-Ar systems in Upper Vendian clayey rocks of the Russian Platform is under consideredation. The use of additional data on grain size fractions of sedimentary rocks recovered from boreholes drilled in the Gavrilov Yam area made it possible to confirm the previous conclusion on two stages of epigenetic matter transformation (approximately 600 and 400 Ma ago). Distortions are related to transformation of sediments due to interaction in the water-rock system. Interaction degree was more intense in the upper part of the sedimentary section relative to its lower strata. These conclusions are substantiated by materials from boreholes that characterize different types of Vendian sections and different tectonic zones.

(Table 1) Mineralogy of veins in basalts at DSDP Hole 61-462A

Numerous veins are present in basalts recovered from Hole 462A, Leg 61 of the Deep Sea Drilling Project. Three mineral assemblages are recognized and stratigraphically controlled. These assemblages are (1) a zeolite-bearing, quartz-poor assemblage which occurs from Core 44 to the bottom of the hole and contains smectite, clinoptilolite, calcite, pyrite, ± chabazite, ± analcime, ± quartz, ± apophyllite, ± talc (?); (2) a quartz-rich, pyrite-bearing assemblage, found between Cores 19 and 29, which contains smectite, calcite, quartz, and pyrite; and (3) a quartz-rich, celadonite-bearing assemblage which occurs from Cores 14 through 17 and contains smectite, calcite, quartz, celadonite, and Fe oxide. These data are interpreted to represent two episodes of vein mineral formation with an oxidative overprint on the more recent. The first episode followed the outpourings of basaltic lavas onto the sea floor. Zeolite-bearing veins were formed at elevated temperatures under low PCO2 while the thermal gradient was high and before a cover of calcareous sediments had formed. The second mineralization episode followed injection of basalt and microdiabase sills into a thick layer of sediments, and produced all the vein minerals now occurring between Cores 14 and 29. These veins formed at lower temperature and higher PCO2 than zeolite-bearing veins. The presence of pyrite indicates a nonoxidative environment. After the initial formation of these veins, oxygenated seawater diffused through the sedimentary cover and oxidized the pyrite and smectite, forming celadonite and Fe oxides.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

Chemical and isotopic compositions of ocean authigenic carbonates

Oceanic authigenic carbonates are classified according to origin of the carbonate carbon source using a complex methodology that includes methods of sedimentary petrography, mineralogy, isotope geochemistry, and microbiology. Mg-calcite (protodolomite) and aragonite predominate among the authigenic carbonates. All authigenic carbonates are depleted in 13C and enriched in 18O (in PDB system) that indicates biological fractionation of isotopes during carbonate formation. Obtained results show that authigenic carbonate formation is a biogeochemical (microbial) process, which involves carbon from ancient sedimentary rocks, abiogenic methane, and bicarbonate-ion of hydrothermal fluids into the modern carbon cycle.

Thermal conductivity at DSDP Leg 60 Holes

A total of 1547 thermal conductivity values were determined by both the NP (needle probe method) and the QTM (quick thermal conductivity meter) on 1319 samples recovered during DSDP Leg 60. The NP method is primarily for the measurement of soft sedimentary samples, and the result is free from the effect of porewater evaporation. Measurement by the QTM method is faster and is applicable to all types of samples-namely, sediments (soft, semilithified, and lithified) and basement rocks. Data from the deep holes at Sites 453, 458, and 459 show that the thermal conductivity increases with depth, the rate of increase ranging from (0.18 mcal/cm s °C)/100 m at Site 459 to (0.72 mcal/cm s °C)/100 m at Site 456. A positive correlation between the sedimentary accumulation rate and the rate of thermal conductivity increase with depth indicates that both compaction and lithification are important factors. Drilled pillow basalts show nearly uniform thermal conductivity. At She 454 the thermal conductivity of one basaltic flow unit was higher near the center of the unit and lower toward the margin, reflecting variable vesicularity. Hydrothermally altered basalts at Site 456 showed higher thermal conductivity than fresh basalt because secondary calcite, quartz, and pyrite are generally more thermally conductive than fresh basalt. The average thermal conductivity in the top 50 meters of sediments correlates inversely with water depth because of dissolution of calcite, a mineral with high thermal conductivity, from the sediments as the water depth exceeds the lysocline and the carbonate compensation depth. Differences between the Mariana Trench data and the Mariana Basin and Trough data may reflect different abundances of terrigenous material in the sediment. There are remarkable correlations between thermal conductivity and other physical properties. The relationship between thermal conductivity and compressional wave velocity can be used to infer the ocean crustal thermal conductivity from the seismic velocity structure.