Molecular properties of gases of ODP Leg 204 sites

The recognition of finely disseminated gas hydrate in deep marine sediments heavily depends on various indirect techniques because this mineral quickly decomposes upon recovery from in situ pressure and temperature conditions. Here, we discuss molecular properties of closely spaced gas voids (formed as a result of core recovery) and gas hydrates from an area of relatively low gas flux at the flanks of the southern Hydrate Ridge offshore Oregon (ODP Sites 1244, 1245 and 1247). Within the gas hydrate occurrence zone (GHOZ), the concentration of ethane (C2) and propane (C3) in adjacent gas voids shows large variability. Sampled gas hydrates are enriched in C2 relative to void gases but do not contain C3. We suggest that the observed variations in the composition of void gases is a result of molecular fractionation during crystallization of structure I gas hydrate that contains C2 but excludes C3 from its crystal lattice. This hypothesis is used to identify discrete intervals of finely disseminated gas hydrate in cored sediments. Variations in gas composition help better constrain gas hydrate distribution near the top of the GHOZ along with variations in pore water chemistry and core temperature. Sediments near the base of the gas hydrate stability zone are relatively enriched in C2+ hydrocarbon gases. Complex and poorly understood geological and geochemical processes in these deeper sediments make the identification of gas hydrate based on molecular properties of void gases more ambiguous. The proposed technique appears to be a useful tool to better understand the distribution of gas hydrate in marine sediments and ultimately the role of gas hydrate in the global carbon cycle.

Mineralogy of sediment core GeoB3313-1

Geochemical and clay mineral parameters of a high accumulation marine sediment core from the Chilean continental slope (41°S) provide a 7700 yr record of rainfall variability in southern Chile related to the position of the Southern Westerlies. We especially use the iron content, measured with a time-resolution of ca. 10 yr on average, of 14C-accelerator mass spectrometry dated marine sediments as a proxy for the relative input of iron-poor Coastal Range and iron-rich Andean source rocks. Variations in this input are most likely induced by rainfall changes in the continental hinterland of the core position. Based on these interpretations, we find a pronounced rainfall variability on multi-centennial to millennial time-scales, superimposed on generally more arid conditions during the middle Holocene (7700 to 4000 cal yr B.P.) compared to the late Holocene (4000 to present). This variability and thus changes in the position of the Southern Westerlies are first compared to regional terrestrial paleoclimate data-sets from central and southern Chile. In order to derive possible wider implications and forcing mechanisms of the Holocene latitudinal shifts of the Southern Westerlies, we then compare our data to ice-core records from both tropical South America and coastal Antarctica. These records show similar bands of variability centered at ca. 900 and 1500 yr. Comparisons of band pass filters suggest a close connection of shifts of the Southern Westerlies to changes within the tropical climate system. The correlation to climate conditions in coastal Antarctica shows a more complicated picture with a phase shift at the beginning of the late Holocene coinciding with the onset of the modern state of El Niño-Southern Oscillation system. The presented data provide further evidence that the well known millennial-scale climate variability during the last glacial continued throughout the Holocene.