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Methane (CH4) is the second most important anthropogenic greenhouse gas in the atmosphere. Rapid variations of the CH4 concentration, as frequently registered, for example, during the last ice age, have been used as reliable time markers for the definition of a common time scale of polar ice cores. In addition, these variations indicate changes in the sources of methane primarily associated with the presence of wetlands. In order to determine the exact time evolution of such fast concentration changes, CH4 measurements of the highest resolution in the ice core archive are required. Here, we present a new, semicontinuous and field-deployable CH4 detection method, which was incorporated in a continuous flow analysis (CFA) system. In CFA, samples cut along the axis of an ice core are melted at a melt speed of typically 3.5 cm/min. The air from bubbles in the ice core is extracted continuously from the meltwater and forwarded to a gas chromatograph (GC) for high-resolution CH4 measurements. The GC performs a measurement every 3.5 min, hence, a depth resolution of 15 cm is achieved atthe chosen melt rate. An even higher resolution is not necessary due to the low pass filtering of air in ice cores caused by the slow bubble enclosure process and the diffusion of air in firn. Reproducibility of the new method is 3%, thus, for a typical CH4 concentration of 500 ppb during an ice age, this corresponds to an absolute precision of 15 ppb, comparable to traditional analyses on discrete samples. Results of CFA-CH4 measurements on the ice core from Talos Dome (Antarctica) illustrate the much higher temporal resolution of our method compared with established melt-refreeze CH4 measurements and demonstrate the feasibility of the new method.

Ice cores are a widely used archive to reconstruct past changes of the climate system. This is done by measuring the concentration of substances in the ice and in the air of bubbles enclosed in ice. Some species pertaining to the carbon cycle (e.g., CO2, CH4) are routinely measured. However, information about the organic fraction of the impurities in polar ice is still very limited. Therefore, we developed a new method to determine the content of total organic carbon (TOC) in ice cores using a continuous flow analysis (CFA) system. The method is based on photochemical oxidation of TOC and the electrolytic quantification of the CO2 produced during oxidation. The TOC instrument features a limit of detection of 2 ppbC and a response time of 60 s at a sample flow rate of 0.7 mL/min and a linear measurement range of 2-4000 ppbC. First measurements on the ice core from Talos Dome, Antarctica, reveal TOC concentrations varying between 80 and 360 ppbC in the 20 m section presented.