Mineralogy and incipient diagenesis of Pigmy Basin sediments, DSDP Hole 96-619

Pigmy Basin sediments cored in Hole 619 of Deep Sea Drilling Project Leg 96 are silty clays composed, on the average, of < 1% sand, 37% silt, 48% clay, and 14% carbonate minerals. Except for minor grain dissolution in some silt grains, there is no distinctive variation with depth in either composition or texture of the sand- and silt-sized minerals. This suggests a constant source of sediment supply and little diagenetic alteration of these size fractions. Clay minerals are dominated by smectite or, more precisely, montmorillonite. On the average, the clay-sized fraction consists of 48% smectite and mixed layer minerals, 30% illite, and 23% total kaolinite and chlorite. There appears to be a slight decrease in smectite and concomitant increases in other clay minerals with depth. These changes are further substantiated by the variations of ammonium acetate exchangeable K+, Mg2+, and Na+ in bulk samples. Thus, incipient diagenesis of Pigmy Basin sediments is evidenced in the mineralogical and associated chemical characteristics of the clay fractions.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.

Radiocarbon ages, d13C values and rare earth element content of sediment cores BP00-23/07 and BP00-07/06

Two bottom sediment cores (BP00-23/7 and BP00-7/6) recovered from the Yenisei transect in the southern Kara Sea are described. Data on their grain size composition, clay and heavy mineral assemblages, and distribution of a large group of chemical elements are presented. Radiocarbon dates based on AMS C-14 method suggest the Holocene age of sediments in the cores. Literature data on physical properties and foraminifers have also been analyzed. The facies affiliation of the lithostratigraphic subdivisions has been unraveled. History of the Yenisei River runoff in the Holocene has been reconstructed on the basis of different indicators.

Messinian and pre-Messinian sediments of ODP Holes 107-652A and 107-654A

Sedimentology, mineralogy, and petrology of the pre-Pliocene sediments drilled at ODP Sites 652 and 654 in the Tyrrhenian Sea (Leg 107) have been studied with emphasis on the lower Messinian to pre-Messinian intervals. Messinian at Site 652 is essentially turbiditic and basinal in character; it was deposited during the syn-rift phase in a strongly subsiding half-graben and is correlatable with emerged coeval sequences; in part with the Laga Formation of the foredeep of Apennines, and in part with the filling of grabens dissecting that chain in the Tyrrhenian portion of Tuscany. The sequence found in Site 654 indicates an upper Tortonian to Messinian transgression accompanying crustal stretching in the western Tyrrhenian Sea and is perfectly correlatable with the so-called "Sahelian cycle" and with "postorogenic" cycles recognized in peninsular Italy and in Sicily.

Barium concentrations und stable isotope ratios of late Paleocene deep-sea sediments

Deep-sea sediment Ba* (Ba/Al2O3(sample) * 15% - Ba(aluminosilicate) records show increasing values synchronous with the evolution of the late Paleocene global d13C maximum, reflecting an increase in marine surface primary production and biogenic barite formation at this time. At two oligotrophic locations, Deep Sea Drilling Project (DSDP) Sites 384 and 527 in the North and South Atlantic, respectively, Ba* increases from 160-360 ppm in the early Paleocene to 1100-3000 ppm during the d13C maximum. At equatorial DSDP Site 577, positioned within or near the high-productivity zone, Ba* increases from ~15,500 ppm in the early Paleocene to ~25,400 ppm in conjunction with late Paleocene maximum d13C values. Linear fitted correlation plots of sediment Ba* content versus surface water d13C in all three regions support barite originating in the euphotic zone. The early to late Paleocene relative increase in Ba* illustrates how burial rates of Corg (relative to Al2O3) accelerated by a factor of ~1.8 and ~6.0 in the eutrophic and oligotrophic areas, respectively. A tentative estimate, weighing our result for the entire ocean, suggests that accumulation rates of organic carbon increased by a factor of 2 during the late Paleocene d13C maximum.

Geochemistry, SiO2 minerals and isotopes at DSDP Hole 72-516F

Cherts recovered during DSDP Leg 72 from Rio Grande Rise sediments (Site 516) consist of both cristobalite and quartz, and contain ghosts of foraminifers and (more rare) radiolarians. Porcelanite made of disordered cristobalite is found in most old enclosing sediments. Local dissolution of siliceous microfossils during diagenesis is the most likely source of the silica required for the chert formation. As sediment age increases, the proportion of biogenic silica decreases and authigenic silica increases.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Stable carbon and oxygen isotopes of foraminifera fand carbon content of ODP Leg 107 holes

High-resolution bio- and chemostratigraphy of an earliest Pliocene section from ODP Site 652 indicates that postflood paleoceanographic conditions in the Tyrrhenian Sea can be sub-divided into two discrete intervals. The first is manifested by an acme of Sphaeroidinellopsis spp., increasing carbonate contents, and a progressive decrease upsection in both the d13C and dl8O values of the planktonic foraminifera. The lower part of the acme interval contains unusual surface-to-bottom water isotope gradients suggesting a stratification of two water masses. Normal gradients in the upper part of the acme interval suggest a well-mixed water body. Between the end of the acme interval and the MP11/MP12 boundary, denoted by the first occurrence (F.O.) of Globorotalia margaritae, a migrational first appearance, there was a catastrophic collapse of the gradient marking an onset of the second post-flood interval. The disintegration of habitable conditions is suggested by a sharp decrease in carbonate content and the disappearance of the benthonic assemblage, which is subsequently replaced predominantly by Uvigerinapygmea, indicative of cold, low-oxygenated bottom waters. The introduction of benthonic species denoting well-oxygenated bottom conditions occurs within the lower MP12 zone. Superimposed on these overall trends are shorter term, warm-cold cycles, which are interpreted as orbitally induced, climatic fluctuations. Correlative studies of the less complete earliest Pliocene sections from ODP Holes 653B and 654A confirm these interpretations. A scenario derived from an integration of all the stratigraphic data indicates that normal paleoceanographic conditions were operating in the Tyrrhenian Sea only approximately 250,000 yr after the cessation of Messinian evaporative conditions at the Miocene/Pliocene boundary. The post-flood interval is marked by an initial period of gradual infilling, the Sphaeroidinellopsis spp. acme interval, followed by a disintegration of oceanographic conditions and a second recovery period. A sudden influx of cold, deep Atlantic waters into the Tyrrhenian Sea, resulting from a major tectonic break in the Gibraltar sill, may have caused this catastrophic reversal in the orderly recovery of normal paleoceanographic conditions in the post-flood period.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Lithology and organic geochemistry at DSDP Hole 77-535

Analyses of extractable organic matter from selected core samples obtained at DSDP Site 535 in the eastern Gulf of Mexico show that the asphalt (or tar) and adjacent oil stains in Lower Cretaceous fractured limestones have a common origin and are not derived from the surrounding organic-matter-rich limestones. Organic matter indigenous to those surrounding limestones was shown to be thermally immature and incapable of yielding the hydrocarbon mixture discovered. In contrast, the oil-stained and asphaltic material appears to be a post-migration alteration product of a mature oil that has migrated from source rocks deeper in the section, or from stratigraphically equivalent but compositionally different source-facies down-dip from the drill site. Further, hydrocarbons of the altered petroleum residues were shown to be similar to Sunniland-type oils found in Lower Cretaceous rocks of South Florida. The results suggest that shallowwater, platform-type source-rock facies similar to those that generated Sunniland-type oils, or deeper-water facies having comparable oil-generating material, are present in this deep-water (> 3000 m) environment. These findings have important implications for the petroleum potential in the eastern Gulf of Mexico and for certain types of deep-sea sediments.

Composition of organic matter from water, suspended matter, and bottom sediments of Nha Trang Bay, South China Sea

This research has been carried out in the Nha Trang Bay (Southern Vietnam, South China Sea) at a section from the estuary of the Cai River to the marine part of the bay, as well as in the area of coral reefs. River- and sea waters, suspended matter, and bottom sediments are studies. Data on dissolved organic carbon and total nitrogen in water are obtained. Organic carbon concentration is estimated in suspended matter; organic carbon and molecular and group compositions of n-alkanes are determined in bottom sediments. Molecular and group compositions of n-alkanes in bottom sediments of the landfill made it possible to identify three types of organic matter (OM): marine, mixed, and mainly of terrigenous origin. All these types of OM are closely related to specificity of sedimentation and hydrodynamics of waters in this area.

Isotopic composition and Strontium/Calcium ratios of foraminifera of ODP Holes 113-689B and 113-690C

Oxygen and carbon isotopic ratios were measured from Maestrichtian benthic and planktonic foraminifer species and bulk carbonate samples from ODP Sites 689 and 690, drilled on the Maud Rise during Leg 113. Careful scanning electron microscope observations reveal that test calcite in some intervals was diagenetically altered, although Sr/Ca and isotopic ratios of these tests do not appear to have been modified significantly. Foraminifer d18O values at both sites document a cooling trend during early Maestrichtian time, a rapid drop in water temperatures at the time of the first appearance of Abathomphalus mayaroensis in the high southern latitude regions (about 69.9 Ma), and lower water temperatures during late Maestrichtian time. d13C values record a depletion in 13C in the latest early Maestrichtian time beginning at about 72.2 Ma, just prior to the sharp late Maestrichtian increase in d18O values. These trends are similar to those previously reported for well-preserved benthic foraminifer species from Seymour Island, in the Antarctic Peninsula. Paleotemperature estimates are also comparable to those at Seymour Island and suggest temperate climatic conditions in Antarctica and that bottom waters in the southern South Atlantic region were of Antarctic origin. Benthic and planktonic foraminifer 613C values fluctuate sympathetically and are higher in upper Maestrichtian sediments than in the lower Maestrichtian sequence.

Organic-geochemical and petrographical composition of sediments from ODP Leg 164 sites

Sediments from Holes 994C, 995A, 997A, and 997B have been investigated for "combined" gases (adsorbed gas and that portion of free gas that has not escaped from the pore volume during core recovery and sample collection and storage), solvent-extractable organic compounds, and microscopically identifiable organic matter. The soluble materials mainly consist of polar compounds. The saturated hydrocarbons are dominated by n-alkanes with a pronounced odd-even predominance pattern that is derived from higher plant remains. Unsaturated triterpenoids and 17ß, 21ß-pentacyclic triterpenoids are characteristic for a low maturity stage of the organic matter. The low maturity is confirmed by vitrinite reflectance values of 0.3%. The proportion of terrestrial remains (vitrinite) increases with sub-bottom depth. Within the liptinite fraction, marine algae plays a major role in the sections below 180 mbsf, whereas above this depth sporinites and pollen from conifers are dominant. These facies changes are confirmed by the downhole variations of isoprenoid and triterpenoid ratios in the soluble organic matter. The combined gases contain methane, ethane, and propane, which is a mixture of microbial methane and thermal hydrocarbon gases. The variations in the gas ratios C1/(C2+C3) reflect the depth range of the hydrate stability zone. The carbon isotopic contents of ethane and propane indicate an origin from marine organic matter that is in the maturity stage of the oil window.