Abstract: The reconstruction of past volcanism from glaciological archives is based on the measurement of sulfate concentrations in ice. This method does not allow a proper evaluation of the climatic impact of an eruption owing to the uncertainty in classifying an event between stratospheric or tropospheric. This work develops a new method, using anomalous sulfur isotope composition of volcanic sulfate in order to identify stratospheric eruptions over the last millennium. The advantages and limits of this new method are established with the examination of the 10 largest volcanic signals in ice cores from Dome C and South Pole, Antarctica. Of the 10, seven are identified as stratospheric eruptions. Among them, three have been known to be stratospheric (Tambora, Kuwae, the 1259 Unknown Event) and they exhibit anomalous sulfur isotope compositions. Three unknown events (circa 1277, 1230, 1170 A.D.) and the Serua eruption have been identified as stratospheric eruptions, which suggests for the first time that they could have had significant climatic impact. However, the Kuwae and the 1259 Unknown Event stratospheric eruptions exhibit different anomalous sulfur isotope compositions between South Pole and Dome C samples. Differences in sulfate deposition and preservation patterns between the two sites can help explain these discrepancies. This study shows that the presence of an anomalous sulfur isotope composition of volcanic sulfate in ice core indicates a stratospheric eruption, but the absence of such composition does not necessarily lead to the conclusion of a tropospheric process because of differences in the sulfate deposition on the ice sheet.

Abstract: Simulations of ozone loss rates using a three-dimensional chemical transport model and a box model during recent Antarctic and Arctic winters are compared with experimental loss rates. The study focused on the Antarctic winter 2003, during which the first Antarctic Match campaign was organized, and on Arctic winters 1999/2000, 2002/2003. The maximum ozone loss rates retrieved by the Match technique for the winters and levels studied reached 6 ppbv/sunlit hour and both types of simulations could generally reproduce the observations at 2-sigma error bar level. In some cases, for example, for the Arctic winter 2002/2003 at 475 K level, an excellent agreement within 1-sigma standard deviation level was obtained. An overestimation was also found with the box model simulation at some isentropic levels for the Antarctic winter and the Arctic winter 1999/2000, indicating an overestimation of chlorine activation in the model. Loss rates in the Antarctic show signs of saturation in September, which have to be considered in the comparison. Sensitivity tests were performed with the box model in order to assess the impact of kinetic parameters of the ClO-Cl2O2 catalytic cycle and total bromine content on the ozone loss rate. These tests resulted in a maximum change in ozone loss rates of 1.2 ppbv/sunlit hour, generally in high solar zenith angle conditions. In some cases, a better agreement was achieved with fastest photolysis of Cl2O2 and additional source of total inorganic bromine but at the expense of overestimation of smaller ozone loss rates derived later in the winter.