Mineralogy and geochemistry of altered ash, pelagic clay, and a clay vein in basalt from DSDP Leg 62 Holes

Volcanic ash was recovered from lower Aptian to Albian deposits from DSDP Sites 463, 465, and 466; pelagic clay of the upper Pleistocene to Upper Cretaceous was recovered mainly from Site 464, with minor amounts at Sites 465 and 466. We present X-ray-mineralogy data on pelagic clay and altered volcanic ash recovered from the four Leg 62 sites. In addition, two ash samples from Sites 463 and 465, a pelagic clay from Site 464, and a clay vein from the basaltic basement at Site 464 each were analyzed for major, minor, and trace elements. Our purpose is to describe the mineralogy and chemistry of altered ash and pelagic clays, to determine the sources of their parent material, and to delineate the diagenetic history of these clay-rich deposits. Correlation of chemistry and mineralogy of ash and pelagic clay with volcanic rocks suspected to be their parent material is not always straightforward, because weathering and diagenetic alteration caused depletion or enrichment of many elements.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Ages, lithologie descriptions and mineral analyses from different DSDP holes in the Indian Ocean

The present work is based on mineralogical studies of sand and silt layers from a number of Deep Sea Drilling Project sites in the Indian Ocean belonging to different physiographic provinces of different ages. The minerals can be grouped into two major associations: a hornblende-opaque association with varying amounts of pyroxene, garnet, epidote, zircon, etc. and a biotite-chlorite-muscovite assemblage. The dominance of unstable minerals indicates a first generation, though evidence of reworking is reflected in the zircon and tourmaline grains at some sites. A large variety of minerals at some sites indicates a complex source. The mineral composition is nearly homogeneous at different sites for the entire length of the core, indicating that they have been derived from the same source during the deposition of that interval. However, the provenance changed by tectonic activity, the effect of which has been reflected in the mineralogy of some sites. An attempt was made to describe the mineralogic characteristics and their tectonic interpretations in the Pliocene and Miocene periods in the Ganges and Indus fan sites and also in the Wharton and Mozambique basin sites. Similar attempts could not be made for other ages in other physiographic provinces as the numbers of samples were too few. Within the limited scope, some idea about the mineralogical character of different basins and different physiographic provinces can be obtained from the present study. Mineralogical evidence also suggests very long transport of sediments in the deep sea. Regional variation of mineralogy has resulted due to source, sea-floor configuration, selective removal, reworking by different agencies and the processes operating in the ocean. There is no relation between a particular age and a set mineral assemblage for the Cenozoic sediments of the Indian Ocean.

Oxygen-isotope composition, temperature and depth of formation of chert at DSDP Leg 62 Holes

We measured oxygen-isotope compositions of 16 siliceous rocks from Deep Sea Drilling Project Sites 463, 464, 465, and 466 (Leg 62). Samples are from deposits that range in age from about 40 to 103 m.y. and that occur at sub-bottom depths of 9 to 461 meters. Mean d18O values range from 28.4 to 36.8 per mil and 36.0 ± 0.3 per mil for quartz-rich and opal-CTrich rocks, respectively. d18O values in chert decrease with increasing sub-bottom depth; the slope of the d18O/depth curve is less steep for Site 464 than for the other sites which indicates that chert at Site 464 formed at higher temperatures than chert at Sites 463, 465, and 466. Temperatures of formation of cherts were 7 to 42°C, using the silica-water fractionation factor of Knauth and Epstein (1976), or 19 to 56°C, using the equation of Clayton et al. (1972). Temperatures in the sediment where the cherts now occur are lower than their isotopically determined temperatures of formation, which means that the cherts record an earlier history when temperatures in the sediment section were greater. Estimated sediment temperatures when the cherts formed are comparable to, but generally slightly lower than, those calculated from Knauth and Epstein's equation. The isotopic composition of cherts is more closely related to environment of formation (diagenetic environment) or paleogeothermal gradients, than to paleoclimates (bottom-water temperatures). Opal-CT-rich rocks may better record paleo-bottom-water temperature. In Leg 62 cherts, better crystallinity of quartz corresponds to lower d18O values; this implies progressively higher temperatures of equilibration between quartz and water during maturation of quartz. The interrelationship of d18O and crystallinity is noted also in continental-margin deposits such as the Monterey Formation - but for higher temperatures. The apparent temperature difference between open-ocean and continental-margin deposits can be explained by the dominant control of temperature on silica transformation in the rapidly deposited continental-margin deposits, whereas time, as well as temperature, has a strong influence on the transformations in open-ocean deposits. Comparisons between the chemistry and d18O values of cherts reveal two apparent trends: both boron and SiO2 increase as d18O increases. However, the correspondence between SiO2 and d18O is only apparent, because the two cherts lowest in SiO2 are also the most deeply buried, so the trend actually reflects depth of burial. The correspondence between boron and d18O supports the conclusion that boron is incorporated in the quartz crystal structure during precipitation

Geochemical composition of olivine, spinel and amphibole in ODP Hole 209-1271B

Dunite and gabbroic materials recovered from Hole 1271B, Ocean Drilling Program (ODP) Leg 209, were examined for mineral chemistry to understand melt flow and melt-mantle reactions in the shallowest upper mantle of the Mid-Atlantic Ridge near the 15°20' Fracture Zone. Hole 1271B was drilled to 103.8 meters below seafloor on the inner corner high along the south wall of the 15°20' Fracture Zone. The total length of core collected was 15.9 m (recovery = ~15%). The dominant rock type in Hole 1271B is dunite, followed by brown amphibole gabbro, olivine gabbro, and troctolite, along with minor amounts of harzburgite and olivine gabbronorite. A large proportion of the dunite is associated with gabbroic rocks in Hole 1271B, similar to those observed in the Mohorovicic (Moho) transition zone of the Oman ophiolite, indicating significant magmatic activity in this region near the 15°20' Fracture Zone. Olivine Fo content varies from 89.2 to 91.2 in impregnated dunite and from 85.6 to 88.6 in troctolite, olivine gabbro, and olivine gabbronorite. Spinel Cr# (= 100 x Cr/[Cr + Al] molar ratio) ranges from 38.9 to 62.7 in dunite and from 46.3 to 57.6 in troctolites, olivine gabbro, and olivine gabbronorite. Compositional trends for spinel from dunite through troctolite toward olivine gabbro/gabbronorite are characterized by increases in TiO2, Cr#, and Fe3+#, very similar to those reported from Hess Deep Site 895. Olivine gabbro, olivine gabbronorite, and troctolite in Hole 1271B are considered to have formed as hybrid rocks between dunite and an evolved melt in the walls of a melt channel in the shallowest upper mantle that is tens of meters wide. The melt trapped in the wall rock crystallized plagioclase and clinopyroxene. On the other hand, dunite in the center of the melt channel became more refractory by melt-mantle reactions, increasing spinel Cr# to 62.5.

Mud, sand, heavy and light minerals composition in lower Cretaceous at DSDP Hole 93-603B

During the drilling of Hole 603B on Deep Sea Drilling Project Leg 93, an unexpected series of sand-, silt-, and claystone turbidites was encountered from Cores 603B-45 through -76 (1224-1512 m sub-bottom depth). Complete and truncated Bouma sequences were observed, some indicating deposition by debris flows. Sand emplacement culminated with the deposition of a 30-m-thick, unconsolidated sand unit (Cores 603B-48 through -45). The purpose of this preliminary study is to determine the nature of the heavy mineral suites of this sediment in order to make tentative correlations with onshore equivalents. The heavy mineralogy of Lower Cretaceous North American mid-Atlantic coastal plain sediment has been extensively studied. This sediment is classified as the Potomac Group, which has a varied heavy mineral suite in its lower part (Patuxent Formation), and a limited suite in its upper part (Patapsco Formation). The results of this study reveal a similar trend in the heavy mineral suites of sediment in Hole 603B. Hauterivian through lower Barremian sediment has a heavy mineral suite that is dominated by zircon, apatite, and garnet, with minor amounts of staurolite and kyanite. Beginning in the mid-Barremian, a new source of sediment becomes dominant, one which supplies an epidote-rich heavy mineral suite. The results of the textural analyses show that average grain size of the light mineral fraction increases upsection, whereas sorting decreases. The epidote-rich source may have delivered sediment with a slightly coarser mean grain size. This sediment may represent a more direct continental input at times of maximum turbidite activity (mid-Barremian) and during deposition of the upper, unconsolidated sand unit.