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.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

(Table 1) Calcite, siderite, and stable isotopes d13C and d18O at DSDP Hole 93-603B

Diagenesis of the fine-grained, feldspathic sandstones in the Lower Cretaceous submarine fan complex cored in DSDP Hole 603B can be considered to have occurred in three stages: (1) replacement of matrix and framework grains by pyrite, siderite, phillipsite (?), and particularly by ferroan calcite; (2) dissolution of ferroan calcite and feldspars to produce secondary macroporosity; and (3) development of sparse feldspar and quartz overgrowths, and authigenic modification of remnant matrix. Only ferroan calcite is a volumetrically important diagenetic mineral phase (up to 50 vol.%). Matrix in thin sandstone turbidite deposits has been extensively replaced by ferroan calcite. Carbon stable isotope data suggest that organic diagenesis had only a minor influence on calcite precipitation. Oxygen stable isotope data indicate that the minimum average calcite precipitation temperature was 40° C. Preliminary calculations show that steadystate diffusion of Ca+ + from the dissolution of nannoplankton skeletal material in the interbedded pelagic marls to the associated sandstones is a feasible transport mechanism. A thick sandstone unit from 1234-1263 m sub-bottom is extensively replaced by calcite near the upper and lower contacts. Farther into the sand body away from the contacts, the sandstone has good secondary porosity resulting from the dissolution of ferroan calcite that partially replaced matrix and framework grains. The central portion of the thick sand appears to be a channel with high-energy clean sand. We believe that the channel provided a conduit for focused flow of diagenetic compactional fluids responsible for dissolution. Focused flow may be the result of the earlier lithification of the pelagic limestones and thin-bedded sandstones which, then formed vertical permeability barriers. Calcite dissolution has occurred and may still be occurring at temperatures less than 65°C.