Antarctica has allowed the extension of the ice record of atmospheric composition and climate to the past four glacial-interglacial cycles. The succession of changes through each climate cycle and termination was similar, and atmospheric and climate properties oscillated between stable bounds. Interglacial periods differed in temporal evolution and duration. Atmospheric concentrations of carbon dioxide and methane correlate well with Antarctic air-temperature throughout the record. Present-day atmospheric burdens of these two important greenhouse gases seem to have been unprecedented during the past 420,000 years.

International audienceA high-resolution deuterium profile is now available along the entire European Project for Ice Coring in Antarctica Dome C ice core, extending this climate record back to marine isotope stage 20.2, 800,000 years ago. Experiments performed with an atmospheric general circulation model including water isotopes support its temperature interpretation. We assessed the general correspondence between Dansgaard-Oeschger events and their smoothed Antarctic counterparts for this Dome C record, which reveals the presence of such features with similar amplitudes during previous glacial periods. We suggest that the interplay between obliquity and precession accounts for the variable intensity of interglacial periods in ice core records

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A record of atmospheric carbon dioxide (CO2) concentration during the transition from the Last Glacial Maximum to the Holocene, obtained from the Dome Concordia, Antarctica, ice core, reveals that an increase of 76 parts per million by volume occurred over a period of 6000 years in four clearly distinguishable intervals. The close correlation between CO2 concentration and Antarctic temperature indicates that the Southern Ocean played an important role in causing the CO2 increase. However, the similarity of changes in CO2 concentration and variations of atmospheric methane concentration suggests that processes in the tropics and in the Northern Hemisphere, where the main sources for methane are located, also had substantial effects on atmospheric CO2 concentrations.

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extended-H[ckel approach to electronic coupling calculation is certainly dependent on its parameterization.The existence of multiple tunneling regimes also provides insight into several recent (and otherwise puzzling) experimental and theoretical observations in biological ET reaction kinetics. Winkler, Gray, and co-workers found that ET across protein-protein interfaces in protein crystals mediated by three water molecules is nearly as rapid as unimolecular ET is over the same distance (7). Canters and co-workers showed that water dimers between covalently cross-linked azurin complexes could substantially enhance the intermolecular ET kinetics (15). Similarly, Klinman and coworkers investigated the copper-to-copper ET over about 7 ) in the hydroxylating domain of peptidylglycine a-amidylating monooxygenase and found an unusually large electronic coupling mediated, apparently, by water rather than by the protein or substrate (17). Using Pathways-level analysis, Onuchic and co-workers found that water molecules mediate the dominant ET coupling routes between cytochrome c 2 and the photosynthetic reaction center (18). Cave and co-workers showed that water molecules between model D and A pairs substantially enhance intermolecular ET rates as well (19). All of these recent observations support our conclusion that a small number of structured water molecules interposed between the donor and the acceptor cofactors can substantially enhance ET rates.The influence of aqueous tunneling pathways on interprotein ET kinetics has remained a key open issue in biological ET for some time. Single-exponential decay models fail to describe water-mediated ET reactions properly. The existence of multiple tunneling mediating regimes identified above is evinced by a body of recent experimental and theoretical observations. Most importantly, the structured water coupling regime may provide an important mechanism to facilitate ET reactions in the critical near-contact distance range relevant to biological ET kinetics. We hypothesize that water may be a particularly strong tunneling mediator when it occupies a sterically constrained space between redox cofactors with strong organizing forces that favor constructively interfering coupling pathways. It will be particularly interesting to use both theory and experiment to explore how the watermediated coupling between proteins varies with protein-protein shape complementarity, surface charge and polarity, and dynamical fluctuations of the proteins and of the organized water at the interface. Chem. 88, 1321Chem. 88, (1984 . 106, 6647 (1997). 23. M. D. Newton, J. Electroanal. Chem. 438, 3 (1997). 24. S. Larsson, J. Phys.

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