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.

Sulfur speciation and isotopic composition in waters and sediments from river and seawater mixing zones

Studies of sulfur behavior in the water column and in sediments in river and seawater mixing zone were conducted in three areas of the Black and Azov Seas. These investigations showed constancy of sulfate concentrations versus chlorinity. Sulfur isotope composition in sulfates of surface, bottom, and pore waters depended on sulfate contents and salinity. The dependence was complicated by partial sulfate depletion in pore water due to bacterial sulfate reduction and also by alteration of isotope composition. Surface sediments in mixing zones are characterized by intensive sulfate reduction, great variability of content and isotopic composition of reduced sulfur, and a low mean isotopic fractionation factor of sulfur.

Chemical and mineral compositions of sedimentary deposits and magmatic rocks from DSDP Legs 41, 45, 48, and 49

This collective monography by a group of lithologists from the Geological Institute of the USSR Academy of Sciences summarizes materials of the Deep-Sea Drilling Project from the Atlantic Ocean. It gives results of processing materials on the sequences drilled during DSDP Legs 41, 45, 48 and 49. These studies were based on lithological-facial analysis combined with detailed mineralogical-petrographic description. Its chapters give a number of ideas on formation of the Earth sedimentary cover, which can be used for compilation of regional and global schemes of ocean paleogeography, reconstruction of history of some structures in the World Ocean, correlation between sedimentary processes on continents and in oceans, estimation of perspectives for oil and gas fields and ore formation.

Biochemical, geochemical and sedimentological study of ODP Leg 112 samples

Organic-rich diatomaceous muds from Ocean Drilling Program Leg 112 (offshore Peru) are the subject of a comprehensive organic diagenetic study covering the burial interval, <1 to >100 m. The organic matter has been classified in terms of its elemental, biochemical, and geochemical compositions. About 60% of the organic carbon in sediments from <1 m can be attributed to hydrolyzable, biochemical constituents, while at 22 m this figure decreased to 20%. Pyrolysis-gas chromatography and gas chromatography-mass spectrometry chromatograms of these same sediments contain mainly hydrocarbons and nitrogenous compounds, with low amounts of other heteroatomic compounds, even though the total organic matter is rich in oxygen (about 35 atoms per 100 carbon atoms) and sulfur (1 to 5 atoms per 100 C atoms). Overall, the organic matter in these sediments, even at these shallow depths and young ages, has many of the geochemical features of far more deeply buried sediments, providing further strong evidence for the claim that "kerogen-formation" is a very early diagenetic process.

Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

Proto-kerogens in Holocene sediments of ODP Hole 165-1002C

Proto-kerogens were isolated, by extraction and HF/HC1 treatment, from core samples of Holocene sediments of the Cariaco Trench, with interpolated ages of 900, 2850 and 6000 years, and examined via a combination of microscopic, spectroscopic and pyrolytic methods. It appears that these proto-kerogens were chiefly formed from phytoplanktonic components via the degradation-recondensation pathway. The natural sulfurisation pathway only afforded a minor contribution, in spite of the conditions prevailing in the water column and sediments that correspond to those generally considered as especially favourable for the formation of sulfurised organic matter. Proto-kerogen formation via sulfurisation, i.e. the endpoint of the continuum leading to insoluble high molecular weight structures cross-linked by sulfur and resistant to acid hydrolysis, is therefore a rather slow process under these conditions. However, the contribution of sulfurised moieties to the total proto-kerogen substantially increased with depth due to continuous sulfurisation in the time/depth interval, whereas formation through degradation-recondensation is almost complete for the 900 years old sample onwards. Proto-kerogen formation via carbohydrate sulfurisation is faster than lipid sulfurisation and only sulfurised carbohydrates were detected in the shallowest sample. In contrast, sulfurised lipids occur in the other two proto-kerogens. Moreover, their contribution relative to sulfurised carbohydrates increases with depth, probably due to the higher resistance of lipids to mineralisation compared to carbohydrates.

Organic matter composition and sulfate reduction intensity in Oman Margin sediments

Petrographical and geochemical studies of Neogene marine sediments from the Oman Sea (Leg 117, Sites 720, 724, 726 and 730), show a close relationship between the nature and amount of the organic matter, and the degree of degradation of organic matter by sulfate reduction, i.e. pyritization. Petrographically, three major pyritization types were observed: (1) Finely dispersed pyrite framboids in sediments from Oman Margin and Indus Fan, enriched in autochthonous marine organic matter. (2) Infilling of pores by massive pyrite crystals in Oman Margin sediments with a low TOC and a high microfossil content. (3) Pyrite mineralization of lignaceous fragments in organic-depleted sediments from the Indus Fan leading to more massive pyrite. Geochemically, we can define a sulfate reduction index (SRI) as the percentage of initial organic carbon versus that of residual organic carbon. Finely laminated Pliocene-Pleistocene sediments from the Oman Margin exclusively contain organic matter deriving from organic phytoplankton, for which the quantity (TOC) positively correlates with the geochemical quality (Hydrogen Index). We think that the occurrence of this residual organic matter is linked mainly to a high primary paleo-productivity. The intensity of sulfate reduction is constant for sediments with TOC up to 2% and becomes more important when organic input decreases. This degradation process can destroy up to 50% of the initial organic matter, but is not sufficient to explain some of the encountered very low TOC values. It can be seen that sharp increases of certain plankton species (with mineral skeletons) are responsible for a pronounced degradation of organic matter, due to increased sulfate reduction. In that case, the organic matter may be strongly degraded (high SRI), although deposited in an oxygen-depleted environment. Conversely, Miocene-Pliocene sediments contain an autochthonous organic matter that is typical of both low productivity and oxic processes; their very low sulfate reduction index indicates that very little metabolizable organic matter was initially present.

Organic geochemistry of ODP Leg 107 sediments

The Rock-Eval pyrolysis of rock samples and the elemental analysis of kerogens show clear differences between Messinian black shales and Pliocene-Pleistocene sapropels recovered during ODP Leg 107. The Messinian black shales are characterized by a large variety of compositions which probably reflects a great diversity of depositional and diagenetic paleoenvironments. In contrast, the Pliocene-Pleistocene sapropels, occurring as discrete layers in nannofossil oozes barren of organic carbon, constitute a rather homogeneous group in terms of organic content. A considerable contribution of terrestrial organic matter in the sapropels could mean that an identical phenomenon of terrestrial input has been periodically reproduced in the basin. The maturity and the nature of the organic matter are discussed with respect to anomalous values recorded for Tmax parameter.

Geochemistry data from the Toupugol volcanogenic complex

A large fragment of a paleovolcano of Silurian to Early Devonian age was discovered in the Voikar volcanic belt suggesting an ensimatic island are as its geodynamic environment. Formationally, the rocks under study are comparable to Pleistocene island arc volcanites and their paleo-analogues. The volcanites of the Toupugol complex underwent strong hydrothermal-metasomatic alteration: propylites, acid metasomatic rocks and quartz-carbonate veins, which must have resulted from hydrothermal-metasomatic alteration of andesitoids. Both volcanites and apovolcanic hydrothermal rocks in Toupugol were found to host noble metal mineralisation. It is found in close association with sulphides, particularly pyrite. Free gold was discovered in all investigated volcanites and hydrothermal rocks and is characterised by low mercury content and an unusual set of microimpurities (Pt, Pd, Cu, Fe, S) suggesting its links to the mantle substrate.