Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.

Iberian Margin 420 kyr geochemical and color variations record

Here we report 420 kyr long records of sediment geochemical and color variations from the southwestern Iberian Margin. We synchronized the Iberian Margin sediment record to Antarctic ice cores and speleothem records on millennial time scales and investigated the phase responses relative to orbital forcing of multiple proxy records available from these cores. Iberian Margin sediments contain strong precession power. Sediment "redness" (a* and 570-560 nm) and the ratio of long-chain alcohols to n-alkanes (C26OH/(C26OH + C29)) are highly coherent and in-phase with precession. Redder layers and more oxidizing conditions (low alcohol ratio) occur near precession minima (summer insolation maxima). We suggest these proxies respond rapidly to low-latitude insolation forcing by wind-driven processes (e.g., dust transport, upwelling, precipitation). Most Iberian Margin sediment parameters lag obliquity maxima by 7-8 ka, indicating a consistent linear response to insolation forcing at obliquity frequencies driven mainly by high-latitude processes. Although the lengths of the time series are short (420 ka) for detecting 100 kyr eccentricity cycles, the phase relationships support those obtained by Shackleton []. Antarctic temperature and the Iberian Margin alcohol ratios (C26OH/(C26OH + C29)) lead eccentricity maxima by 6 kyr, with lower ratios (increased oxygenation) occurring at eccentricity maxima. CO2, CH4, and Iberian SST are nearly in phase with eccentricity, and minimum ice volume (as inferred from Pacific d18Oseawater) lags eccentricity maxima by 10 kyr. The phase relationships derived in this study continue to support a potential role of the Earth's carbon cycle in contributing to the 100 kyr cycle.