Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.

Sulfur concentrations and isotopic composition of serpentinized oceanic peridotites

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200°-400°C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low fO2 and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-delta34S sulfide (1.5? to -23.7?). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures(~20°-200°C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-delta34S sulfide (~15 to ~43?) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high delta34S of total sulfur (mean ~8?). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in delta34S of total sulfur (mean ~ -5?). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 * 10**12 g S/yr from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Chemistry of interstitial waters of samples from DSDP Leg 25

Interstitial water analyses from sediments collected during Leg 25 of the Deep Sea Drilling Project have revealed that in the southwest Indian Ocean, great chemical activity exists in sediments in various depositional environments. Variable sedimentation rates allow us to set some interesting boundary conditions on chemical and transport processes in these interstitial waters, particularly with regard to the distribution of dissolved sulfate. In terrigenous rapidly deposited sediments, large depletions are observed in magnesium and potassium, whereas relatively small decreases in dissolved calcium occur. In slowly deposited detrital sediments, also, large decreases in potassium and magnesium coincide with very large calcium increases. In truly pelagic sediments, a one to one replacement of magnesium by calcium is observed in the interstitial waters, presumably due to reactions in the basal sediment layers. Biogenous deposits have great influence on dissolved silica (sponge spicules and radiolarians) and on dissolved strontium (carbonate recrystallization). Otherwise, dissolved silica reflects the clay mineralogy and shows variations which seem particularly dependent on the presence or absence of kaolinite. Variable dissolved manganese values reflect reducing conditions and/or availability of manganese in the solid phases for mobilization in reducing sediments.

Gas hydrates of the Gulf of Mexico

Gas hydrates were recovered from eight sites on the Louisiana slope of the Gulf of Mexico. The gas hydrate discoveries ranged in water depths from 530 to 2400 m occurring as small to medium sized (0.5-50 mm) nodules, interspersed layers (1-10 mm thick) or as solid masses (> 150 mm thick). The hydrates have gas:fluid ratios as high as 170:1 at STP, C1/(C2 + C3) ratios ranging from 1.9 to > 1000 and d13C ratios from -43 to -71 per mil. Thermogenic gas hydrates are associated with oil-stained cores containing up to 7% extractable oil exhibiting moderate to severe biodegradation. Biogenic gas hydrates are also associated with elevated bitumen levels (10-700 ppm). All gas hydrate associated cores contain high percentages (up to 65%) of authigenic, isotopically light carbonate. The hydrate-containing cores are associated with seismic "wipeout" zones indicative of gassy sediments. Collapsed structures, diapiric crests, or deep faults on the flanks of diapirs appear to be the sites of the shallow hydrates.

Moleculare composition of sediments from ODP Hole 116-717C

We describe the molecular composition of a portion of the solvent-soluble organic material (lipid extract), from three organic rich muds (samples 116-717C-22X-1, 80-86 cm, 116-717C-34X-3, 130-135 cm, and 116-717C-55X-1, 65-70 cm). These samples were taken from Hole 717C, located on the Bengal Fan at a position of 0°55.8'S and 81°23.4'E. Both the palaeoenvironmental and digenetic significance of these lipid distributions have been assessed and found to be consistent with their suspected origins, i.e., turbidites from the upper slope of the western Bay of Bengal and the Ganges-Brahmaputra delta.

Oxidation rate of thiosulfate and elemental sulfur in the Black Sea

Oxidation rate of 35S-thiosulfate under simulated natural conditions and abundance of thiosulfate-oxidizing bacteria in a redox zone of the Black Sea are lower during winter and spring than in summer, especially in halistatic regions. Oxidation of thiosulfate under natural conditions is performed chiefly by lithotropic thionic bacteria, whose activity is limited by low temperatures. Adding thiosulfate and readily available organic matter to water samples from the redox zone and raising temperature of water stimulated activity of heterotrophic thiosulfate-oxidizing bacteria. Oxidation of elemental sulfur tagged with 35S apparently invovled two stages: abiotic oxidation of thiosulfate and subsequent bacterial oxidation of thiosulfate to sulfate.

Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Chemical composition of hydrothermal deposits and vulcanites from the Menez Gwen vent field, Mid-Atlantic Ridge

Surface hydrothermal deposits of the shallow-water Menez Gwen vent field located in the rift zone of the Mid-Atlantic Ridge are mostly composed of nonmetalliferous minerals in contrast to sulfide deposits of deep-water fields. Here sulfide minerals occur only in dispersed form. High-temperature sulfide deposits strongly enriched in copper and zinc occur only immediately below the surface of the bottom. This is related to subsurface boiling and phase separation of initial high-temperature hydrothermal ore-bearing solution that ascends from the interior to the floor surface.

Mineralogy, chemistry and stable isotope composition of hydrothermal altered sheeted dikes of ODP Hole 111-504B

During ODP Leg 111 Hole 504B was extended 212 m deeper into the sheeted dikes of oceanic Layer 2, for a total penetration of 1288 m within basement. Study of the mineralogy, chemistry, and stable isotopic compositions of the rocks recovered on Leg 111 has confirmed and extended the previous model for hydrothermal alteration at the site: axial greenschist hydrothermal metamorphism was followed by seawater recharge and subsequent off-axis alteration. The dikes are depleted in 18O (mean delta18O = +5.1 ? +/- 0.6 ?) relative to fresh mid-ocean ridge basalt. Oxygen isotopic data on whole rocks and isolated secondary minerals indicate temperatures during axial metamorphism of 250°-350°C and water/rock ratios about one. Increasing amounts of actinolite with depth in the dike section, however, suggest that temperatures increased downward in the dikes. Pyrite + pyrrhotite + chalcopyrite + magnetite was the stable sulfide + oxide mineral assemblage during axial alteration, but these minerals partly re-equilibrated later at temperatures less than 200°C. The dikes sampled on Leg 111 contain an average of 500 ppm sulfur, slightly lower than igneous values. The delta34S values of sulfide average 0?, which indicates the presence of basaltic sulfide and incorporation of little or no seawater-derived sulfide into the rocks. These data are consistent with models for the presence of rock-dominated sulfur in deep hydrothermal fluids. The presence of anhydrite at 1176 m within basement indicates that unaltered seawater can penetrate to significant depths in the crust during recharge.