(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.

Benthic foraminiferal fauna in the Ionian Sea

To reconstruct paleoceanographic changes in the eastern Mediterranean during the last 330,000 years, we studied benthic foraminifera in a piston core from the Ionian Sea. The fauna exhibits large fluctuations in foraminiferal number, diversity, and species composition. Interglacials are characterized by low foraminiferal number and diversity indicating oligotrophic conditions. Directly below or above interglacial sapropels, increased numbers of low-oxygen-tolerant species indicate a strong reduction of deep water circulation. Glacials are characterized by increased foraminiferal number and diversity and faunas that are dominated by shallow infaunal species indicating mesotrophic conditions. Around glacial sapropel S6 very high foraminiferal numbers and the dominance of shallow and deep infaunal species suggest enhanced organic matter fluxes. These faunal results provide information about changes in the African and North Atlantic climate systems (monsoon and westerlies) controlling the humidity and wind stress in the Mediterranean region.

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.

Absolute abundances of benthic foraminifers and stable isotopes from the Alvin dives 3709-3712

The presence of gas hydrates on the Blake Ridge diapir, northeastern Atlantic Ocean, offers an opportunity to study the impact of methane seepage on the ecology and geochemistry of benthic foraminifera in the late Holocene. Three push cores, covering a time span of ~ 1000 yrs, were retrieved from three distinct microhabitats at the top of the diapir at a water depth of ~ 2150 m: (i) sediments away from seepage (control core), (ii) sediments overlain by clusters of methanotrophic and thiotrophic bivalves, and (iii) chemoautotrophic microbial mats. The foraminiferal assemblages at the two seep sites are marked by a reduction in benthic foraminiferal species diversity, coupled with a near-absence of agglutinated species. However, an opportunistic population rise in CH4- or H2S-tolerant calcareous species (e.g., Globocassidulina subglobosa and Cassidulina laevigata) that utilize the abundant trophic resources at the seeps has led to an increase in the overall assemblage density there. The delta18O and delta13C values of three species of benthic foraminifera - Gyroidinoides laevigatus, Globocassidulina subglobosa, and Uvigerina peregrina - and the planktonic species Globorotalia menardii were acquired from all three cores. The benthic species from methane seeps yield delta13C values of 0.1 to - 4.2 (per mil VPDB), that are distinctly more 13C-depleted relative to the delta13C of 0.4 to - 1.0 (per mil VPDB) at the control (off seep) site. The species from a mussel-bed site exhibit more negative delta13C values than those from microbial mats, possibly reflecting different food sources and higher rate of anaerobic oxidation of methane. The positive delta13C values in the paired planktonic species suggest that authigenic carbonate precipitation did not overprint the observed 13C depletions. Hence the probable cause of negative delta13C of benthic foraminifera is primary calcification from Dissolved Inorganic Carbon (DIC) containing mixed carbon fractions from (a) highly 13C-depleted, microbially-oxidized methane and (b) a seawater source.

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.