(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

Organic d13C values, kerogen atomic C/N ratios and relative weights of some kerogen pyrolysis products of ODP Hole 112-682A (Table 1)

Carbon isotopic composition of predominantly marine kerogen in latest Oligocene mudstones of the Peru Margin ODP 682A Hole shows an about 3.5? increase with decreasing age. Py-GC and elemental (C=N ratio) analysis of the kerogen plus sulphur isotopic study together with earlier knowledge on geological setting and organic geochemistry results in a better understanding of depositionary environment and allows to separation of the influence of concentration of water dissolved carbon dioxide (ce) on kerogen delta13C from that of other factors (bacterial degradation, sea surface temperature, DIC delta13C, productivity, and admixture of land plant OM). Based on this analysis, the major part of the kerogen shift is considered as a result of the latest Oligocene decrease of marine photosynthetic carbon isotopic fractionation in the Peru Margin photic zone, which in turn possibly reflects a simultaneous drop in atmospheric CO2 level. Uncertainties in the evaluation of the factors affecting the marine photosynthetic carbon isotopic fractionation and the extent of ocean-atmosphere disequilibrium do not permit calculation of the decrease of the atmospheric CO2.

Middle Miocene isotope stratigraphy and paleoceanographic evolution of the northwest and southwest Australian margins (Wombat Plateau and Great Australian Bight)

The benthic stable isotope record from ODP Site 761 (Wombat Plateau, NW Australia, 2179.3 m water depth) documents complete recovery of the middle Miocene delta13C excursion corresponding to the climatic optimum and subsequent expansion of the East Antarctic Ice Sheet. The six main delta13C maxima of the "Monterey Excursion" between 16.4 and 13.6 Ma and the characteristic stepped increase in delta18O between 14.5 and 13.9 Ma are clearly identified. The sedimentary record of the shallower ODP Sites 1126 and 1134 [Great Australian Bight (GAB), SWAustralia, 783.8 and 701 m water depth, respectively] is truncated by several unconformities. However, a composite benthic stable isotope curve for these sites provides a first middle Miocene bathyal record for southwest Australia. The delta18O and delta13C curves for Sites 1126 and 1134 indicate a cooler, better-ventilated water mass at ~700 m water depth in the Great Australian Bight since approximately 16 Ma. This cooler and younger water mass probably originated from a close southern source. Cooling of the bottom water at ~16 Ma started much earlier than at other sites of equivalent paleodepths in the central and western parts of the Indian Ocean. At Site 761, the delta18O curve shows an excellent match with the global sea level curve between ~11.5 and 15.1 Ma, and thus closely reflects changes in global ice volume. Prior to 15.1 Ma, the mismatch between the delta18O curve and the sea level curve indicates that delta18O fluctuations are mainly due to changes in bottom water temperature.

Benthic foraminiferal assemblages and epifaunal isotope record of the Agulhas Plateau

Benthic foraminiferal assemblages and the carbon isotope composition of the epifaunal benthic foraminifera Epistominella exigua and Fontbotia wuellerstorfi have been investigated along core MD02-2589 located at the southern Agulhas Plateau (41°26.03'S, 25°15.30'E, 2660 m water depth). This study aims to evaluate changes in the benthic paleoenvironment and its influence on benthic d13C with a notable focus on E. exigua, a species associated with phytodetritus deposits and poorly studied in isotope paleoceanographic reconstructions. The benthic foraminiferal assemblages (>63 µm) show large fluctuations in species composition suggesting significant changes in the pattern of ocean surface productivity conceivably related to migrations of the Subtropical Convergence (STC) and Subantarctic Front (SAF). Low to moderate seasonality and relatively higher food supply to the seafloor are indicated during glacial marine isotope stages (MIS) 6, 4, and 2 and during MIS 3, probably associated with the northward migration of the SAF and confluence with the more stationary STC above the southern flank of the Agulhas Plateau. The lowest organic carbon supply to the seafloor is indicated from late MIS 5b to MIS 4 as a consequence of increased influence of the Agulhas Front (AF) and/or weakening of the influence of the STC over the region. Episodic delivery of fresh organic matter, similar to modern conditions at the core location, is indicated during MIS 5c-MIS 5e and at Termination I. Comparison of this paleoenvironmental information with the paired d13C records of E. exigua and F. wuellerstorfi suggests that organic carbon offsets d13C of E. exigua from ambient bottom water d13CDIC, while its d13C amplitude, on glacial-interglacial timescales, does not seem affected by changes of organic carbon supply to the seafloor. This suggests that this species calcifies preferentially during the short time span of the year when productivity peaks and phytodetritus is delivered to the seafloor. Therefore E. exigua, while offset from d13CDIC, potentially more faithfully records the amplitude of ambient bottom water d13CDIC changes than F. wuellerstorfi, notably in settings such as the Southern Ocean that experienced substantial changes through time in the organic carbon supply to the seafloor.

Appendix A Table SD1. CaCO3, d18O, d13C and Sr isotopes from ODP Site 181-1120

An integrated chemostratigraphic (87Sr/86Sr, d13C and 18O) study of benthic foraminifera is presented for a 210 m-thick, intermediate depth (upper/middle bathyal transition), Miocene nannofossil ooze section of Ocean Drilling Program Site 1120, Campbell Plateau off New Zealand. Our results indicate that new 87Sr/86Sr, d13C and d18O profiles are wholly consistent with their respective Miocene reference curves. These observations facilitate identification of a total of five reliable chemostratigraphic datums, which are based on the fundamental structural changes in the 87Sr/86Sr curve and paired simultaneous d13C and d18O events. The resultant age-depth relationship clearly shows that the Miocene (20-5 Ma) biopelagic sedimentation on the Campbell Plateau was essentially continuous at a moderate to high, linear sedimentation rate (17.5 m/m.y. with an exception of the uppermost 13 m). Our findings do not support the shipboard biostratigraphic age model, which assumes that the critical early-middle Miocene transition was interrupted by a major hiatus (<~3 m.y.). Because of its unique bathymetric setting at a paleowater-depth of ~ 600 m, which is among the shallowest of the coeval isotopically studied deep-sea sections in the South Pacific/Southern Ocean, Site 1120 will serve as a reference section for surveying the evolution of intermediate-water paleoceanography in the Southern Hemisphere across the middle Miocene climatic transition.

Benthic foraminifera of late Quaternary sediments in the northern North Atlantic

Four long sediment cores from locations in the Framstrait, the Norwegian-Greenland Seas and the northern North Atlantic were analysed in a high resolution sampling mode (1 - 2 cm density) for their benthic foraminiferal content. In particular the impact of the intense climatic changes at glacial/interglacial transitions (terminations I and II) on the benthic community have been of special interest. The faunal data were investigated by means of multivariate analysis and represented in their chronological occurence. The most prominent species of benthic foraminifera in the Norwegian-Greenland Seas are Oridorsalis umbonatus, Cibicidoides wuellerstorfi, the group of Cassidulina, Pyrgo rotalaria, Globocassidulina subglobosa and fragmented tubes of arenaceous species. The climatic signal of termination I as well as termination II is recorded in the fossil foraminiferal tests as divided transition from glacial to interglacial. The elder INDAR maximum (individuals accumulation rate = individuals/sq cm * 1.000 y; Norwegian-Greenland Seas: average 3.000 - 6.000 individuals/sq cm * 1.000 y; northern North Atlantic: average 150 individuals/sq cm * 1.000 y) is followed by a period of decreased values. The second, younger maximum reaches comparable values as the elder maximum. The interglacial INDAR are in average 700 individuals/sq cm * 1.000 y in the Norwegian-Greenland Seas and 200 individuals/sq cm * 1.000 y in average in the northern North Atlantic. The occurence of the elder INDAR maximum shows a distinct chronological transgressivity between the northern North Atlantic (12.400 ybp.) and the Framstrait (8.900 ybp.). The time shift from south to north amounts 3.500 yrs., the average expanding velocity 0,78 km per year. Within the Norwegian-Greenland Seas the average expanding velocity amounts 0,48 km per year. This chronological transgressivity is interpreted as impact of the progressive expanding of the North Atlantic and the Norwegian Current during the deglaciation. The dynamic of the faunal development is defined as increasing INDAR per time. The elder INDAR maximum shows in both glacial/interglacial transitions an exponential increase from south to north. Termination II is characterized by a general higher dynamic as termination I. By means of the high resolution sampling density the impact of regional isotopic recognized melt-water events is recognized by an increase of endobenthic and t-ubiquitous species in the Norwegian-Greenland Seas sediments. During termination I the relative minimum between both INDAR maxima occur chronological with an decrease of calculated sea surface temperatures. This is interpreted as indication of the close pelagic - benthic coupling. The climatic signal in the northern North Atlantic recorded in the fossil benthic foraminiferal community shows a lower amplitude as in the Norwegian-Greenland Seas. The occurence of the epibenthic Cibicidoides wuellersforfi allows to evaluate the variability of the bottom water mass. In general at all core locations increasing lateral bottom currents are recognized with the occurence of the second younger INDAR maximum. In comparison with various paleo-climatological data sets fossil benthic foraminifers show a distinct koherence with changes of the atmospheric temperatures, the SSTs and the postglacial sea level increase. The benthic foraminiferal fauna is bound indirectly on and indicative for regional climatic changes, but principal dependent upon global climatic changes.

Mineralogy, geochemistry, isotopic ratios and foraminifer occurrence in ODP Hole 183-1139A

Mixed terrigenous-pelagic sediments from the Oligocene-lower Miocene interval of Hole 1139A accumulated on the flank of an eroded alkalic volcano, Skiff Bank. In this study, I explore relationships among sediment fluxes, especially of organic carbon and the clay mineral by-products of silicate weathering, and lithologic, tectonic, climatic, and biologic forcing factors. Benthic foraminifers indicate that Skiff Bank had subsided to lower bathyal depths (1000-2000 m) by the Oligocene. Two prominent maxima in noncarbonate concentration at 28 and 22 Ma correspond to peaks in the terrigenous flux; also, high noncarbonate concentrations are associated with larger grain sizes (silt) and higher opal concentrations. These and higher-frequency variations of noncarbonate concentration were probably controlled by glacioeustatic/climatic changes, with higher noncarbonate concentrations caused by increased erosion during glacial lowstands. Around 27 Ma, benthic foraminiferal d18O values decreased 0.7 per mil as the noncarbonate concentration decreased after the 28-Ma maximum. A paucity of clay-sized sediment and clay minerals suggests that physical erosion, by waves and/or ice, predominated under weathering-limited conditions. Low organic carbon concentrations (~0.13 wt%) also suggest a harsh environment and/or poor preservation in coarse (>2 µm) sediments that were extensively bioturbated below the oxygen minimum zone.