Revised geomagnetic polarity timescale for the late Oligocene to early Miocene of ODP Site 177-1090

At Ocean Drilling Program (ODP) Site 1090 (subantarctic South Atlantic), benthic foraminiferal stable isotope data (from Cibicidoides and Oridorsalis) span the late Oligocene through early Miocene (~24-16 Ma) at a temporal resolution of ~5 ky. Over the same interval, a magnetic polarity stratigraphy can be unequivocally correlated to the geomagnetic polarity time scale (GPTS), thereby providing direct correlation of the isotope record to the GPTS. In an initial age model, we use the newly derived age of the Oligocene/Miocene (O/M) boundary of 23.0 Ma of Shackleton et al. (2000, doi:10.1130/0091-7613(2000)28<447:ACAFTO>2.0.CO;2), revised to the new astronomical calculation (La2003) of Laskar et al (2004, doi:10.1016/j.icarus.2004.04.005) to recalculate the spline ages of Cande and Kent (1995, doi:10.1029/94JB03098). We then tune the Site 1090 dekta18O record to obliquity using La2003. In this manner, we are able to refine the ages of polarity chrons C7n through C5Cn.1n. The new age model is consistent, within one obliquity cycle, with previously tuned ages for polarity chrons C7n through C6Bn from Shackleton et al. (2000) when rescaled to La2003. The results from Site 1090 provide independent evidence for the revised age of the Oligocene/Miocene boundary of 23.0 Ma. For early Miocene polarity chrons C6AAr through C5Cn, our obliquity-scale age model is the first to allow a direct calibration to the GPTS. The new ages are generally within one obliquity cycle of those obtained by rescaling the Cande and Kent (1995) interpolation using the new age of the O/M boundary (23.0 Ma) and the same middle Miocene control point (14.8 Ma) used by Cande and Kent (1995).

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.

Density, d18O and accumulation rates from snow pits on the Filchner-Ronne Ice Shelf

Accumulation rates in the eastern part of Ronne Ice Shelf were determined by isotopic stratigraphy (18O). The samples were taken from snow-pits dug during the Filchner I and II operations in 1984 and 1986. In general, the accumulation rate decreases towards the south; the greatest decrease, from 21.3 to 13.3 g/cm**2/a, was observed between Filchner Station and measuring point 341, sited 270 km up-stream of the ice edge. The d18O values of the near-surface layers vary between -25 and -29 per mil. The 18O content in the more southerly part is progressively depleted in the direction of Möllereisstrom, paralleling a decrease in the accumulation rate. Near the ice edge the 18O content decreases to the west. A 100 m ice core drilled in 1984 at point 340, 22 km from the ice edge, probably goes back to A.D. 1460; it has been dated by isotopic stratigraphy. The accumulation rate up-stream of the drilling site was deduced from the sequence of annual layers, using a simple ice-flow model. The accumulation shows strong variations over the last 200 years, which may be caused in part by local variations in the accumulation on Ronne Ice shelf.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Results of analyses of fluid inclusions from ODP Site 735B, Leg 118 and 176

Microthermometric and isotopic analyses of fluid inclusions in primitive olivine gabbros, oxide gabbros, and evolved granitic material recovered from Ocean Drilling Program Hole 735B at the Southwest Indian Ridge provide new insights into the evolution of C-O-H-NaCl fluids in the plutonic foundation of the oceanic crust. The variably altered and deformed plutonic rocks span a crustal section of over 1500 m and record a remarkably complex magma-hydrothermal history. Magmatic fluids within this suite followed two chemically distinct paths during cooling through the subsolidus regime: the first path included formation of CO2+CH4+H2O+C fluids with up to 43 mole% CH4; the second path produced hypersaline brines that contain up to 50% NaCl equivalent salinities. Subsequent to devolatilization, respeciation of magmatic CO2, attendant graphite precipitation, and cooling from 800°C to 500°C promoted formation of CH4-enriched fluids. These fluids are characterized by average d13C(CH4) values of -27.1+/-4.3 per mil (N=45) with associated d13C(CO2) compositions ranging from -24.9 per mil to -1.9 per mil (N=39), and average dD values of exsolved vapor of -41+/-12 per mil (N=23). In pods, veins, and lenses of highly fractionated residual material, hypersaline brines formed during condensation and by direct exsolution in the absence of a conjugate vapor phase. Entrapped CO2+CH4+H2O-rich fluids within many oxide-bearing rocks and felsic zones are significantly depleted in 13C (with d13C(CO2) values down to about -25 per mil) and contain CO2 concentrations higher than those predicted by equilibrium devolatilization models. We hypothesize that lower effective pressures in high-temperature shear zones promoted infiltration of highly fractionated melts and compositionally evolved volatiles into focused zones of deformation, significantly weakening the rock strength. In felsic-rich zones, volatile build-up may have driven hydraulic fracturing of gabbroic wall rocks resulting in the formation of magmatic breccias. Comparison of isotopic compositions of fluids in plutonic rocks from 735B, the MARK area of the Mid-Atlantic Ridge, and the Mid-Cayman Rise indicate (1) that the carbon isotope composition of the lower oceanic crust may be far more heterogeneous than previously believed and (2) that carbon-bearing species in the oceanic crust and their distribution at depth are highly variable.