title: A new method for high-resolution methane measurements on polar ice cores using continuous flow analysis.
abstract: 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.
authors.affiliation: Climate and Environmental Physics, Physics Institute, University of Bern, Switzerland. schuepbach@climate.unibe.ch
authors.forename: Simon
authors.initials: S
authors.lastname: Schüpbach
authors.forename: Urs
authors.initials: U
authors.lastname: Federer
authors.forename: Patrik R
authors.initials: PR
authors.lastname: Kaufmann
authors.forename: Manuel A
authors.initials: MA
authors.lastname: Hutterli
authors.forename: Daphné
authors.initials: D
authors.lastname: Buiron
authors.forename: Thomas
authors.initials: T
authors.lastname: Blunier
authors.forename: Hubertus
authors.initials: H
authors.lastname: Fischer
authors.forename: Thomas F
authors.initials: TF
authors.lastname: Stocker
mesh_terms: D000864:Antarctic Regions; D001272:Atmosphere / Q000737:chemistry; D002138:Calibration; D002845:Chromatography / Q000295:instrumentation / Q000379:methods; D002980:Climate; D004784:Environmental Monitoring / Q000379:methods*; D031521:Fractionation, Field Flow / Q000295:instrumentation / Q000379:methods; D006801:Humans; D007053:Ice / Q000032:analysis*; D008697:Methane / Q000032:analysis*; D015203:Reproducibility of Results
chemical_list: D007053:Ice; D008697:Methane