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Molecular and isotopic compositions of hydrocarbons at Site 533, Deep Sea Drilling Project Leg 76

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (δ13C = -68‰; CJ/CJ = 5000) was the dominant gas (>90%); (2) little fractionation in the C,/ C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experi ments; (3) the percent of C3 , i-C4 , and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) Cj/Q ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also con tained trace amounts of saturated, acyclic, cyclic, and aromatic C5 -C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (δ13C of -68% for methane and a q/ Q ratio of -6000). Regular trends in the δ 13C of methane ( 95 60%) and C{ /C2 ratios (-25000 — 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Initial Reports of the D.S.D.P.

Concentrations and carbon isotopic compositions of CH4 and CO2 in gas from sediments of the Blake Outer Ridge, Deep Sea Drilling Project Leg 76

The principal gaseous carbon-containing components identified in the first 400 m of sediment at Deep Sea Drilling Project Site 533, Leg 76, are methane (CH4 ) and carbon dioxide (CO2 ). Below a sub-bottom depth of about 25 m, sedi ment cores commonly contained pockets caused by the expansion of gas upon core recovery. The carbon isotopic com position (δ13C %0 relative to PDB standard) of CH4 and CO2 in these gas pockets has been measured, resulting in the following observations: (1) δ 1 3CC H 4 values increase with depth from approximately -94% in the uppermost sediment to about -66% in the deepest sediment, reflecting a systematic but nonlinear depletion of 12C with depth. (2) δ 1 3Cc θ 2 values also increase with depth of sediment from about - 25% to about - 4%, snowing a depletion of 12C that closely parallels the trend of the isotopic composition of CH4 . The magnitude and parallel distribution of δ 13C values for both CH4 and CO2 are consistent with the concept that the formation of the CH4 resulted from the microbiological reduction of CO2 from organic substances. These results imply that CH4 and CO2 incorporated in gas hydrates at this site are biogenic.

Initial Reports of the D.S.D.P.

Neogene silicoflagellates from Deep Sea Drilling Project Site 543, western tropical Atlantic Ocean

The upper lower Miocene silicoflagellate assemblage in Core 19 from DSDP Hole 543 in the western Atlantic Ocean contains the greatest concentration (41%) of deflandroid Dictyochapulchella yet observed. The deflandroid morphology in Dictyocha persisted through the Eocene and Oligocene at middle and high latitude, but virtually disappeared in the late Oligocene, only to reappear as a short-lived variant of D. pulchella near the end of the early Miocene or the beginning of the middle Miocene at several low-latitude sites. Correlations with coeval tropical silicoflagellate and diatom assemblages from the tropical eastern Pacific and eastern Atlantic suggest that this deflandroid morphotype may be stratigraphically useful. A new diatom, Craspedodiscus barronii Bukry, found in Core 543-19, is described.

Initial Reports of the D.S.D.P.

Cenozoic silicoflagellates from Rockall Plateau, Deep Sea Drilling Project Leg 81

Eocene to Pliocene silicoflagellates from the Rockall Plateau are sparse to moderately abundant and include assem blages at the upper and lower boundaries of the Miocene Series. Relative paleotemperature values for silicoflagellates from the upper Miocene and lower Pliocene at DSDP Hole 552A based on quantitative data are cooler than are those from equatorial Pacific Sites 503 and 504, but show a matching warm peak at the Miocene/Pliocene boundary and a major cooling in the lower Pliocene. Five new taxa of silicoflagellates are defined from Rockall Plateau assemblages: Corbisema panda Bukry, n. sp., Dictyochapulchella var. inflata Bukry, n. van, Distephanus xenus Bukry, n. sp., Mesocena apiculata evexa Bukry, n. subsp., and Naviculopsis pacifica pansa Bukry, n. subsp.

Initial Reports of the D.S.D.P.

Mid-Atlantic Ridge coccolith and silicoflagellate biostratigraphy, Deep Sea Drilling Project Sites 558 and 563.

Low-latitude coccolith zonation can be used for biostratigraphy at Mid-Atlantic Ridge sites DSDP 558 (lat. 38°N) and DSDP 563 (lat. 34°N). The low-latitude zonal sequence from lower Oligocene to Holocene is interrupted by coolwater assemblages in upper middle Miocene and by hiatuses that removed the lower Pliocene and part of the upper Pliocene. A gap in the range of zonal guide fossil Discoaster druggii in the lower Miocene, also identified in other ocean basins, occurs at both DSDP 558 and 563. Coccoliths are abundant and moderately overgrown at both sites. Pentaliths occur in the Oligocene at DSDP 563 but are missing at DSDP 558, probably the result of diagenesis. New taxa of coccoliths identified include Cyclolithellai neoaprica Bukry, n. sp., and Sphenolithus calyculus Bukry, n. sp. Silicoflagellates are limited to the upper Quaternary at DSDP 558 with warm-water assemblages of the Dictyocha aculeata Zone and possibly the upper Mesocena quadrangula Zone, as indicated by the presence of Dictyocha lingii. A new silicoflagellate species, Distephanus floridus Bukry, n. sp., is described.

Initial Reports of the D.S.D.P.

Tropical Pacific silicoflagellate zonation and paleotemperature trends of the late Cenozoic

Quantitative study of late Cenozoic silicoflagellates at tropical Pacific DSDP Sites 572 and 575 shows that the greatest amplitude of fluctuation in relative paleotemperature values occurred in the late Miocene. The coolest minimum paleotemperature values (near 75 = 30) also occurred in the late Miocene. The warmest intervals (Ts = 80 to 100) occurred in the middle Miocene and late Pliocene to Quaternary. In detail, the silicoflagellate relative paleotemperature curve correlates fairly well with the eustatic sea-level curve and deep-sea hiatus sequence. The only upper Cenozoic low-latitude biostratigraphic units not identified are the Distephanus speculum haliomma Subzone and Naviculopsis quadrata Zone, owing to the absence of the nominative species, which probably had nontropical ecologic preference. Several Naviculopsis occurrence events within the Naviculopsis ponticula Zone correlate between DSDP Hole 575A and DSDP Hole 495 off Guatemala. Many local and regional biostratigraphic events are recognized. New taxa identified from DSDP Leg 85 include Dictyocha nola Bukry, n. sp., Distephanus stradneri var. grandis Bukry, n. var., Mesocena elliptica var. rhomboidea Bukry, n. van, and Naviculopsis obtusarca var. acicula Bukry, n. var.

Initial Reports of the D.S.D.P.

Isotopic composition of interstitial fluids in sediment of the Nankai Trough, Deep Sea Drilling Project Leg 87

The isotopic compositions of dissolved CO2 and CH4 in sediments of the Nankai Trough indicate that CH4 is formed during early diagenesis by microbial reduction of CO2 . At the shallowest sampled depths, the CO2 dissolved in the pore water is unusually enriched in 12C (δ13C = - 35.2‰), indicating contribution of CO2 from oxidation of CH4 . The most intense microbiological activity appears to be confined to the uppermost 50 m of sediment, based on relative lack of change in the isotopic compositions below this depth. Gas hydrate probably is not present at these localities (Sites 582, 583) because of CH4 concentrations that are insufficient to saturate the pore water with respect to gas hy drate stability

Initial Reports of the D.S.D.P.

Miocene silicoflagellates from Chatham Rise, Deep Sea Drilling Project Site 594

Miocene silicoflagellates, dominated by Mesocena, are identified and correlated from Site 594 to other Deep Sea Drilling Project sites. Relative paleotemperature values from silicoflagellates at Site 594 are very low, supporting the evidence of the associated cold-water, low-diversity Coccolith assemblages. The greatest abundances of Mesocena diodon nodosa yet recorded occur at Site 594, which is near the present Subtropical Convergence. Similarities in the ecostratigraphic records between Chatham Rise (Site 594) and the Falkland Plateau (Site 329) in the late Miocene indicate widespread events within the circum-Antarctic water mass.

Initial Reports of the D.S.D.P.

Late Neogene and Quaternary coarse-fraction and carbonate stratigraphies for Site 586 on Ontong-Java Plateau and Site 591 on Lord Howe Rise

Carbonate oozes recovered by hydraulic piston coring at DSDP Site 586 on Ontong-Java Plateau and Site 591 on Lord Howe Rise have carbonate contents that are consistently higher than 90% with only minor variations. Consequently, paleoceanographic signals were not recorded in detail in the carbonate contents. However, mass accumulation rates of carbonate increased in the late Miocene to mid-Pliocene, reflecting an increase in productivity, then abruptly decreased from mid-Pliocene to the present. Variations in relative abundances of coarse material (foraminifers) and fine material (mostly calcareous nannofossils) do reflect histories of current winnowing and biogenic productivity at the two sites. The late Miocene from 10.5 to 6.5 m.y. ago was a time of relatively constant, quiet, pelagic sedimentation with typical southwest Pacific sedimentation rates of 20-25 m/m.y. The average coarse-fraction abundances are always higher at Site 586 than at Site 591, which reflects winnowing at Site 586. These conditions were interrupted between 6.5 to 4.0 m.y. ago when increased upwelling at the Subtropical Divergence and the Equatorial Divergence produced greater productivity of calcareous planktonic organisms. The increased productivity is suggested by large increases in both fineand coarse-fraction material and constant ratios of foraminifers to nannofossils. The maximum of productivity was about 4.0 m.y. ago. This period of increased upwelling is coincident with the inferred development of the West Antarctic ice sheet. The high productivity was followed by an abrupt increase in winnowing about 2.5 m.y. ago at Site 591, but not until about 2.0 m.y. ago at Site 586. By 2.0 m.y. ago in the late Pliocene, quiet, pelagic sedimentation conditions prevailed, similar to those of the late Miocene. The last 0.7 m.y. has been a period of relatively intense winnowing on Lord Howe Rise but not on Ontong-Java Plateau. The coarse-fraction data have both long- and short-period fluctuations. Long-period fluctuations at Site 591 average about 850 × 103 yr./cycle and those at Site 586 average 430 × 103 yr./cycle. The highest amplitudes are found in the Pliocene and Quaternary sections. The short-period fluctuations range from 100 to 48 × 103 yr./cycle at Site 586 and from 250 to 33 × 103 yr./cycle at Site 591. The effects of local fluctuations of productivity and winnowing have modified the primary orbital forcing signals at these two sites to yield complex paleoceanographic records

Initial Reports of the D.S.D.P.

Inorganic and organic geochemistry of Eocene to Cretaceous strata recovered from the lower continental rise, North American Basin, Site 603, Deep Sea Drilling Project Leg 93

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 δ 13 C. 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.

Initial Reports of the D.S.D.P.

North Atlantic Quaternary silicoflagellates, Deep Sea Drilling Project Leg 94

Quaternary silicoflagellates from Deep Sea Drilling Project (DSDP) Mid-Atlantic Leg 94 are generally sparse and dissolution-thinned. Mesocena quadrangula, a low-latitude biostratigraphic guide species, occurs at all four sites studied (606, 607, 609, and 611), allowing identification of low-latitude zones—Dictyocha aculeata Zone, Mesocena quadrangula Zone, and Dictyocha stapedia stapedia Zone. A lack of cool-water Distephanus speculum speculum reflects warm relative paleotemperature values (Ts 74 to 98) for Leg 94. Comparison with assemblages at coastal DSDP Hole 397, off Africa, shows that Hole 397 has more abundant D. speculum speculum, suggesting that upwelling nutrient supply may significantly affect the total numbers of this species. The siliceous record of Leg 94 is sporadic, with several levels of nonpreservation that make paleotemperature trends difficult to establish by silicoflagellates. The northern range of M. quadrangula is extended to 52°50'N at Hole 611C. Opal phytoliths occur at southern Holes 606 and 607. These grasslands-produced nannofossils, representing eolian sedimentation from northwestern Africa, were likely distributed most widely during arid glacial intervals.

Initial Reports of the D.S.D.P.

Eocene siliceous and calcareous phytoplankton, Deep Sea Drilling Project Leg 95

Eocene siliceous and calcareous phytoplankton, with emphasis on silicoflagellates, were studied in 62 samples from DSDP Sites 612 and 613 on the continental slope and rise off New Jersey. The mid-latitude assemblages correlate well with assemblages from California, Peru, and offshore of southern Brazil, but are distinctly different from high-latitude cold-water assemblages of the Falkland Plateau off southern Argentina. Coccoliths and silicoflagellates provide evidence for the presence of a fairly complete middle and upper Eocene sequence, represented by a composite of Sites 612 and 613. A major unconformity occurs at the middle Eocene to upper Eocene contact at Site 612. The genus Bachmannocena Locker is emended and proposed as a replacement for genus Mesocena Ehrenberg for ring silicoflagellates. Six new silicoflagellates and one new diatom are described: Bachmannocena apiculata monolineata Bukry, n. subsp., Corbisema amicula Bukry, n. sp., C. bimucronata elegans Bukry, n. subsp., C. hastata incohata Bukry, n. subsp., C. jerseyensis Bukry, n. sp., Dictyocha acuta Bukry, n. sp., and Coscinodiscus eomonoculus Bukry, n. sp. Also, one new replacement name, B. paulschulzn Bukry, nom. nov., and 24 new combinations are proposed for genus Bachmannocena.

Initial Reports of the D.S.D.P.