Geochemistry of basement carbonates from ODP Site 801 in the western Pacific Ocean

Many studies argue, based partly on Pb isotopic evidence, that recycled, subducted slabs reside in the mantle source of ocean island basalts (OIB) (Hofmann and White, 1982, doi:10.1016/0012-821X(82)90161-3; Weaver, 1991 doi:10.1016/0012-821X(91)90217-6; Lassiter, and Hauri, 1998, doi:10.1016/S0012-821X(98)00240-4). Such models, however, have remained largely untested against actual subduction zone inputs, due to the scarcity of comprehensive measurements of both radioactive parents (Th and U) and radiogenic daughter (Pb) in altered oceanic crust (AOC). Here, we discuss new, comprehensive measurements of U, Th, and Pb concentrations in the oldest AOC, ODP Site 801, and consider the effect of subducting this crust on the long-term Pb isotope evolution of the mantle. The upper 500 m of AOC at Site 801 shows >4-fold enrichment in U over pristine glass during seafloor alteration, but no net change to Pb or Th. Without subduction zone processing, ancient AOC would evolve to low 208Pb/206Pb compositions unobserved in the modern mantle (Hart and Staudigel, 1989 [Isotopic characterization and identification of recycled components, in: Crust/Mantle Recycling at Convergence Zones, Eds. S.R. Hart, L. Gqlen, NATO ASI Series. Series C: Mathematical and Physical Sciences 258, pp. 15-28, D. Reidel Publishing Company, Dordrecht-Boston, 1989]). Subduction, however, drives U-Th-Pb fractionation as AOC dehydrates in the earth's interior. Pacific arcs define mixing trends requiring 8-fold enrichment in Pb over U in AOC-derived fluid. A mass balance across the Mariana subduction zone shows that 44-75% of Pb but <10% of U is lost from AOC to the arc, and a further 10-23% of Pb and 19-40% of U is lost to the back-arc. Pb is lost shallow and U deep from subducted AOC, which may be a consequence of the stability of phases binding these elements during seafloor alteration: U in carbonate and Pb in sulfides. The upper end of these recycling estimates, which reflect maximum arc and back-arc growth rates, remove enough Pb and U from the slab to enable it to evolve rapidly (<<0.5 Ga) to sources suitable to explain the 208Pb/206Pb isotopic array of OIB, although these conditions fail to simultaneously satisfy the 207Pb/206Pb system. Lower growth rates would require additional U loss (29%) at depths beyond the zones of arc and back-arc magmagenesis, which would decrease upper mantle kappa (232Th/238U) over time, consistent with one solution to the "kappa conundrum" (Elliott et al., 1999, doi:10.1016/S0012-821X(99)00077-1). The net effects of alteration (doubling of l [238U/204Pb]) and subduction (doubling of omega [232Th/204Pb]) are sufficient to create the Pb isotopic signatures of oceanic basalts.

Results from ikaite investigations in the Kara Sea

The authigenic carbonate mineral ikaite is specific of low-temperature high latitude environments. The depletion of ikaite carbon in 13C isotopes in most cases implies a causal relation of ikaite generation with methane geochemistry. In this paper we present new data on ikaite minerals in Holocene sediments sampled along the Yenisei channel at the southern (74°N) and northern (77°N) ends. Stable carbon isotopes of the ikaite crystals were studied in conjunction with the hydrochemistry and isotope geochemistry of the sediments. Pore water and natural gas samples were separated from sediments to describe the methane carbon isotope distribution pattern throughout two sedimentary sequences embedding the ikaite crystals of different isotope composition (-24 per mil and -42 per mil). The biogenic nature of the methane is indicated by 51 C values being as low as -104.4 per mil. In the case of the moderately depleted sample (-24 per mil) from the southern location the small-scale ikaite formation fits best into the concept of a 'closed» sediment system, with a limited diagenetic carbon dioxide source being present. In the second case, formation of highly abundant and isotopically depleted ikaite crystals (-42 per mil) were caused by upwards flux of biogenic methane from below. Contribution of two main carbon sources to the ikaite crystals was estimated by using a isotope-mass balance equation. Organic-derived CO2 constitutes the principal source in both samples, amounting to 50 % of the total carbon of the strongly depleted ikaite crystals (-42 per mil) sampled at the northern end and 83 % for the moderately (-24 per mil) depleted crystals from the southern end. Methane-derived CO2 comes to 42 % for the isotopically light ikaite crystals and to 9% for the isotopically heavy crystals. The importance of sediment lithology and diffusive transport for ikaite formation is emphazied.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Ice and snow characteristics in Prydz Bay in 2006

Under the Chinese National Antarctic Research Expedition program in 2006, the annual thermal mass balance of landfast ice in the vicinity of Zhongshan Station, Prydz Bay, east Antarctica, was investigated. Sea ice formed from mid-February onward, and maximum ice thickness occurred in late November. Snow cover remained thin, and blowing snow caused frequent redistribution of the snow. The vertical ice salinity showed a 'question-mark-shaped' profile for most of the ice growth season, which only turned into an 'I-shaped' profile after the onset of ice melt. The oceanic heat flux as estimated from a flux balance at ice-ocean interface using internal ice temperatures decreased from 11.8 (±3.5) W/m**2 in April to an annual minimum of 1.9 (±2.4) W/m**2 in September. It remained low through late November, in mid-December it increased sharply to about 20.0 W/m**2. Simulations applying the modified versions of Stefan's law, taking account the oceanic heat flux and ice-atmosphere coupling, compare well with observed ice growth. There was no obvious seasonal cycle for the thermal conductivity of snow cover, which was also derived from internal ice temperatures. Its annual mean was 0.20 (±0.04) W/m/°C.