Organic matter composition of Cretaceous sediments of the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Marine and terrigenous lipids in ODP Leg 175 holes

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 175 in the eastern South Atlantic reflect a variety of oceanographic and climatological environments. Most of the identified lipids can be ascribed to marine sources, notably haptophytes, eustigmatophytes, dinoflagellates, archaea, and diatoms. Elevated concentrations of cholesterol suggest zooplankton herbivory, characteristic for sites influenced by upwelling. At these sites, sulfurized highly branched isoprenoids from diatoms are also present in high amounts. Sterols, sterol ethers, hopanoids, and midchain hydroxy fatty acids could also be detected. Terrigenous lipids are n-alkanes, fatty acids, n-alcohols, and triterpenoid compounds like taraxerol and -amyrine. n-Alkanes, fatty acids, and n-alcohols are derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Triterpenoid compounds are most probably derived from mangroves and transported solely by rivers. Lipid compositions below the Congo low-salinity plume are strongly influenced by terrigenous material from the Congo River. Elevated organic carbon contents and predominantly marine lipid distributions at the Angola margin may indicate a highly productive plankton population, probably sustained by the Angola Dome. Sedimentary lipids in the Walvis Basin contain an upwelling signal, likely transported by the Benguela Current. Sedimentary lipids off Lüderitz Bay and in the southern Cape Basin are dominated by plankton lipids in high to intermediate amounts, reflecting persistent and seasonal upwelling, respectively.

Pliocene-Plistocene deposition of carbonate and organic carbon in ODP Hole 159-959C

During Ocean Drilling Program (ODP) Leg 159, four sites (Sites 959-962) were drilled along a depth transect on the Côte d'Ivoire/Ghana Transform Margin. In this study, the Pliocene-Pleistocene history of carbonate and organic carbon accumulation at Hole 959C is reconstructed for the eastern equatorial Atlantic off the Ivory Coast/Ghana based on bulk carbonate, sand fraction, organic carbon, and other organic geochemical records (d13Corg, marine organic matter percentages derived from organic petrology, hydrogen index, C/N). Pliocene-Pleistocene sedimentation off the Ivory Coast/Ghana was strongly affected by low mean sedimentation rates, which are attributed to persistently enhanced bottom-water velocities related to the steep topography of the transform margin. Sand fraction and bulk carbonate records reveal typical glacial/interglacial cycles, preserved, however, with low time resolution. Intermediate carbonate accumulation rates observed throughout the Pliocene-Pleistocene suggest intense winnowing and sediment redistribution superimposed by terrigenous dilution. 'Atlantic-type' sand and carbonate cycles, consistent with records from pelagic areas of the eastern equatorial Atlantic, are encountered at Hole 959C prior to about 0.9 Ma. Total organic carbon (TOC) records are frequently inversely correlated to carbonate contents, indicating mainly productivity-driven carbonate dissolution related to changes in paleoproductivity. During Stages 22-24, 20, 16, 12, 8, and 4, sand and carbonate records reveal a 'Pacific-type' pattern, showing elevated contents during glacials commonly in conjunction with enhanced TOC records. Formation of 'Pacific-type' patterns off the Ivory Coast/Ghana is attributed to drastically increased bottom-water intensities along the transform margin in accordance with results reported from the Walvis Ridge area. Short-term glacial/interglacial changes in paleoproductivity off the Ivory Coast/Ghana are to some extend recognizable during glacials prior to 1.7 Ma and interglacial Stages 21, 19, 13, 9, and 1. Enhanced coastal upwelling during interglacials is attributed to local paleoclimatic and oceanographic conditions off the Ivory Coast/Ghana. Quantitative estimates of marine organic carbon based on organic petrologic and d13Corg records reveal an offset in concentration ranging from 15% to 60%. Highest variabilities of both records are recorded since ~0.9 Ma. Discrepancies between the isotopic and microscopic records are attributed to an admixture of C4 plant debris approaching the eastern equatorial Atlantic via atmospheric dust. Terrestrial organic material likely originated from the grass-savannah-covered Sahel zone in central Africa. Estimated C4 plant concentrations and accumulation rates range from 10% to 37% and from almost zero to 0.006 g/cm**2/k.y., respectively. The strongest eolian supply to the northern Gulf of Guinea is indicated between 1.9 and 1.68 Ma and during glacial isotopic Stages 22-24, 20, 14, and 12. The presence of grass-type plant debris is further supported by organic petrologic studies, which reveal well-preserved cell tissues of vascular plants or tube-shaped, elongated terrestrial macerals showing different levels of oxidation.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

Climate proxies in sediment core MD95-2010

High-amplitude, rapid climate fluctuations are common features of glacial times. The prominent changes in air temperature recorded in the Greenland ice cores (Dansgaard et al., 1993, doi:10.1038/339532a0; Grootes et al., 1993 doi:10.1038/366552a0) are coherent with shifts in the magnitude of the northward heat flux carried by the North Atlantic surface ocean (Bond et al., 1993, doi:10.1038/365143a0; Bond and Lotti, 1995, doi:10.1126/science.267.5200.1005); changes in the ocean's thermohaline circulation are a key component in many explanations of this climate flickering (Broecker, 1997, doi:10.1126/science.278.5343.1582). Here we use stable-isotope and other sedimentological data to reveal specific oceanic reorganizations during these rapid climate-change events. Deep water was generated more or less continuously in the Nordic Seas during the latter part of the last glacial period (60 to 10 thousand years ago), but by two different mechanisms. The deep-water formation occurred by convection in the open ocean during warmer periods (interstadials). But during colder phases (stadials), a freshening of the surface ocean reduced or stopped open-ocean convection, and deep-water formation was instead driven by brine-release during sea-ice freezing. These shifting magnitudes and modes nested within the overall continuity of deep-water formation were probably important for the structuring and rapidity of the prevailing climate changes.

Late Quateranry dinoflagellate cysts of ODP Site 202-1233

The late Quaternary organic-walled dinoflagellate cyst record of Site 1233 (41°S, offshore Chile) was studied with a ?200 year resolution spanning the last 25,000 years. The study provides the first continuous record of sub-recent and recent dinoflagellate cysts in the Southeast (SE) Pacific. Major changes in the composition of the cyst association, cyst concentration and morphology of Operculodinium centrocarpum reflect changes in sea surface temperature (SST), sea surface salinity (SSS), palaeoproductivity and upwelling intensity. These changes can be associated with latitudinal shifts of the circumpolar frontal systems. The high cyst concentration, high Brigantedinium spp. abundances, low species diversity and the occurrence of certain cold water species are supportive for a 7-10° equatorward shift of the Antarctic Circumpolar Current (ACC) during the coldest phase of the Last Glacial Maximum (LGM) between 25 and 21.1 cal ka BP. Deglacial warming initiated at ~18.6 cal ka BP. Termination I (18.6-11.1 cal ka BP) is interrupted by an unstable period of extreme seasonality, rather than a cooling event, between 14.4 and 13.2 cal ka BP, synchronous with the Antarctic Cold Reversal (ACR). The Holocene Maximum is observed between 11.6 and 9.8 cal ka BP and is typified by the most southward position of the northern margin of the ACC. A cooling phase occurred during the early Holocene (until ~7 cal ka BP) and during the last ~0.8 ka. Our data indicates that the SE Pacific (41°S) climate has been influenced over the whole record by changes in the Southern Hemisphere (SH) high-latitudes, while during the mid to late Holocene, also a tropical forcing mechanism was involved, including the El Niño Southern Oscillation and the variable Hadley cell intensity. Furthermore, this study showed a relationship between the variable morphology of the spines/processes of O. centrocarpum and the combined variation of sea surface salinity and temperature (SSS/SST-ratio).

Magnetic properties of ODP Site 175-1075

We present sediment magnetic and chemical analysis of cyclic ocean sediments of the upwelling region of the Lower Congo Basin (equatorial Atlantic). We investigated two >100-k.y. intervals from Ocean Drilling Program Site 1075 to analyze the hysteresis properties, sources of magnetic susceptibility, anhysteretic remanent magnetizations, thermomagnetic behavior, and element concentrations of Fe, Ca, Ti, Mn, and K using an X-ray fluorescence (XRF) core scanner. The upper interval was sampled between 14 and 32 meters composite depth (mcd; 0.09-0.21 Ma) and the lower between 141 and 163 mcd (1.31-1.54 Ma) at a resolution of 20 cm, which represents a temporal resolution of 2.0 and 1.3 k.y., respectively. XRF core-scanner data were acquired at 5-cm intervals. The measurements show that ferri(o)magnetic minerals have no significant influence on the cyclicity of the magnetic susceptibility, which is dominated by paramagnetic and diamagnetic minerals and reflects changes of sediment input from the Congo River. The Fe, Ti, K, and Mn concentrations covary with the magnetic susceptibility where high concentrations of these elements correlate with intervals of high susceptibility and low concentrations with intervals of low susceptibility. The Ca counts correlate well with the calcium carbonate concentration but do not show the same cyclicity as the other elements or the susceptibility. With the exception of the Ca concentration, which is significantly higher in the upper interval, and the magnetic grain size, which indicates that less fine grained magnetite is present in the lower interval, no significant differences in the properties of the upper and the lower intervals were detected.

Organic geochemical character and hydrocarbon source potential of selected black shales at DSDP Hole 93-603B

LECO analysis, pyrolysis assay, and bitumen and elemental analysis were used to characterize the organic matter of 23 black shale samples from Deep Sea Drilling Project Leg 93, Hole 603B, located in the western North Atlantic. The organic matter is dominantly gas-prone and/or refractory. Two cores within the Turonian and Cenomanian, however, contained significant quantities of well-preserved, hydrogen-enriched, organic matter. This material is thermally immature and represents a potential oil-prone source rock. These sediments do not appear to have been deposited within a stagnant, euxinic ocean as would be consistent with an "oceanic anoxic event." Their organic geochemical and sedimentary character is more consistent with deposition by turbidity currents originating on the continental shelf and slope.