(Table 1) Deuterium ratios, chloride content and hydrate volume of pore water and hydrate meltwater from ODP Site 164-996

Site 996 is located above the Blake Diapir where numerous indications of vertical fluid migration and the presence of hydrate existed prior to Ocean Drilling Program (ODP) Leg 164. Direct sampling of hydrates and visual observations of hydrate-filled veins that could be traced 30-40 cm along cores suggest a connection between fluid migration and hydrate formation. The composition of pore water squeezed from sediment cores showed large variations due to melting of hydrate during core recovery and influence of saline water from the evaporitic diapir below. Analysis of water released during hydrate decomposition experiments showed that the recovered hydrates contained significant amounts of pore water. Solutions of the transport equations for deuterium (d2H) and chloride (Cl-) were used to determine maximum (d2H) and minimum (Cl-) in situ concentrations of these species. Minimum in situ concentrations of hydrate were estimated by combining these results with Cl- and d2H values measured on hydrate meltwaters and pore waters obtained by squeezing of sediments, by the means of a method based on analysis of distances in the two-dimensional Cl- d2H space. The computed Cl- and d2H distribution indicates that the minimum hydrate amount solutions are representative of the actual hydrate amount. The highest and mean hydrate concentrations estimates from our model are 31% and 10% of the pore space, respectively. These concentrations agree well with visual core observations, supporting the validity of the model assumptions. The minimum in situ Cl- concentrations were used to constrain the rates of upward fluid migration. Simulation of all available data gave a mean flow rate of 0.35 m/k.y. (range: 0.125-0.5 m/k.y.).

delta Deuterium of alkenone and BIT index of sediment core 64PE304-80 samples

Reconstructing past ocean salinity is important for assessing paleoceanographic change and therefore past climatic dynamics. Commonly, sea water salinity reconstruction is based on foraminifera oxygen isotope ratio values combined with sea surface temperature reconstruction. However, the approach relies on multiple proxies, resulting in relatively large uncertainty and, consequently, relatively low accuracy of salinity estimates. An alternative tool for past ocean salinity reconstruction is the hydrogen isotope composition of long chain (C37) alkenones (dDalkenone). Here, we applied dDalkenone to a 39 ka long coastal sediment record from the Eastern South African continental shelf in the Mozambique Channel, close to the Zambezi River mouth. Despite changes in global sea water dD related to glacial - interglacial ice volume effects, no clear changes were observed in the dDalkenone record throughout the entire 39 ka. The BIT index record from the same core showed high BIT values during the glacial and low values during the Holocene. This indicates a more pronounced freshwater influence at the core location during the glacial, resulting in alkenones depleted in deuterium during that time and, thereby, explains the lack of a clear glacial-interglacial alkenone dD shift. Correlation between the BIT index and dDalkenone during the glacial period suggests that increased continental runoff potentially changed the growth conditions of the alkenone producing haptophytes, promoting coastal haptophyte species with generally more enriched dDalkenone values. We therefore suggest that the application of dDalkenone for reconstructing past salinity in coastal settings may be complicated by changes in the alkenone producing haptophyte community.

(Table 1) Gas molecules, isotopic composition and delta Deuterium in DSDP Holes 95-603D and 95-613

Methane is the major hydrocarbon gas measured in Vacutainer samples from Holes 603D and 613 ( C1/sumCn > 0.999). In Hole 613 the concentration of this dry hydrocarbon gas is highest (7.4 x 10 **5 ppm max.) in the upper 60 to 120 m, then decreases erratically to low trace levels by 261 m sub-bottom (lower Pliocene). No gas accumulations were observed in older sediments. Methane from both holes is strongly depleted in both 13C (d13C, - 75 to -85 per mil) and deuterium (D/H, - 175 to -262 per mil), indicating the biogenic origin of the methane. The C and H isotopic compositions support methanogenesis via the CO2-reduction pathway; this is also corroborated by the dissolved-sulfate and alkalinity minima at these depths. The relationship between D/H of the methane and coexisting interstitial water from Site 613 further show the methanogenesis to be primarily by CO2 reduction.

Deuterium isotope ratios of Victoria Lower Glacier Ice Core

The Little Ice Age (LIA) is one of the most prominent climate shifts in the past 5000 yrs. It has been suggested that the LIA might be the most recent of the Dansgaard-Oeschger events, which are better known as abrupt, large scale climate oscillations during the last glacial period. If the case, then according to Broecker (2000a, 2000b) Antarctica should have warmed during the LIA, when the Northern Hemisphere was cold. Here we present new data from the Ross Sea, Antarctica, that indicates surface temperatures were ~2 °C colder during the LIA, with colder sea surface temperatures in the Southern Ocean and/or increased sea-ice extent, stronger katabatic winds, and decreased snow accumulation. Whilst we find there was large spatial and temporal variability, overall Antarctica was cooler and stormier during the LIA. Although temperatures have warmed since the termination of the LIA, atmospheric circulation strength has remained at the same, elevated level. We conclude, that the LIA was either caused by alternative forcings, or that the sea-saw mechanism operates differently during warm periods.

Talos Dome Ice Core Deuterium Data

During the 1996 Programma Nazionale di Ricerche in Antartide-International Trans-Antarctic Scientific Expedition traverse, two firn cores were retrieved from the Talos Dome area (East Antarctica) at elevations of 2316 m (TD, 89 m long) and 2246 m (ST556, 19 m long). Cores were dated by using seasonal variations in non-sea-salt (nss) SO42- concentrations coupled with the recognition of tritium marker level (1965-1966) and nss SO42- spikes due to the most important volcanic events in the past (Pinatubo 1991, Agung 1963, Krakatoa 1883, Tambora 1815, Kuwae 1452, Unknown 1259). The number of annual layers recognized in the TD and ST556 cores was 779 and 97, respectively. The dD record obtained from the TD core has been compared with other East Antarctic isotope ice core records (Dome C EPICA, South Pole, Taylor Dome). These records suggest cooler climate conditions between the middle of 16th and the beginning of 19th centuries, which might be related to the Little Ice Age (LIA) cold period. Because of the high degree of geographical variability, the strongest LIA cooling was not temporally synchronous over East Antarctica, and the analyzed records do not provide a coherent picture for East Antarctica. The accumulation rate record presented for the TD core shows a decrease during part of the LIA followed by an increment of about 11% in accumulation during the 20th century. At the ST556 site, the accumulation rate observed during the 20th century was quite stable.