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.

Lithology, stage, organic carbon, d13C, hydrocarbons and fatty acids at DSDP Hole 93-603B

Organic-matter-rich Upper Cretaceous claystones from DSDP Hole 603B, lower continental rise, had organic carbon values ranging from 1.7 to 13.7%, C/N ratios from 32 to 72, and d13C values from -23.5 to -27.1 per mil. Lipid class maxima for the unbound alkanes (C29 and C31), unbound fatty acids (C28 and C30), and bound fatty acids (C24, C26 , and C28) and the strong odd-carbon and even-carbon preferences, respectively, suggested that the organic matter in these sediments was partially the result of input from continental plant waxes. Transport of the organic-matter-rich sediments to the deep sea from the near-shore environment probably resulted from turbiditic flow under oxygen-stressed conditions.

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.

Epoch, organic carbon and compounds at DSDP Holes 93-605 and 95-613

Twenty-four sediment samples from DSDP Holes 605 (Leg 93) and 613 (Leg 95) on the New Jersey continental rise were analyzed by pyrolysis-gas chromatography. Twelve of these samples were also analyzed by pyrolysis-gas chromatography/mass spectrometry. The degree of preservation of sediment organic matter, as determined by these techniques, helped to distinguish slumped sediments from sediments that have not moved from their original place of deposition. Total levels of pyrolyzable organic material, as determined from pyrolysis-gas chromatography, were low in sediments that were not slumped, indicating that the organic material is highly degraded. Nitrogen- and oxygen-containing compounds were the primary compounds detected by gas chromatography/mass spectrometry (GCMS) analysis of the pyrolyzate of non-slumped sediments. Smaller amounts of aromatic compounds and branched alkanes were also present in some of these samples. In contrast, slumped sediments showed larger amounts of pyrolyzable organic matter, as determined from pyrolysis-gas chromatography, and better preservation of alkyl chains in the sediment organic matter, as suggested by the presence of n-alkanes in GCMS analysis of the pyrolyzate. Better preservation of the organic matter in slumped sediments can be attributed to more moderate bioturbation by bottom-dwelling organisms at the original deposition site.

Physical properties of sediments at DSDP Sites 93-603, 93-604, and 93-605

On Leg 93, physical properties measurements were made of vertical and horizontal sonic velocity, acoustic impedance, vane shear strength, and penetrometer strength, using procedures discussed in Boyce (1973, 1976, 1984). Gravimetric procedures were used to determine wet-bulk density, grain density, porosity, and water content, using either the chunk method or the cylinder method. Calcium carbonate content of Leg 93 sediments was determined by the carbonate.

Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.

C1-C8 hydrocarbons at DSDP Site 93-603

Small amounts of C1-C8 hydrocarbons were detected in continental rise sediments from DSDP Site 603. Organiccarbon- lean sections contained only C1-C3 compounds believed to have migrated from organic-carbon-rich sections. Heavier (C4-C8) hydrocarbons were found only in organic-carbon-rich sections. Restricted and sporadic distribution of C4-C6 compounds in 0-1100 m sub-bottom sediments suggest low-temperature (<20°C) biological/chemical generation processes. Increased C4-C8 concentrations and complexity, including unusually high levels of xylene, were detected in two deeper Cretaceous sections (603-34-2, 134 cm and 603-81-3, 120 cm). This behavior, which was not observed in 17 other samples from sub-bottom depths greater than 1100 m, is similar to that observed in immature surface sediments from the geothermally active Guaymas Basin (Gulf of California) area.

(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.