Melanie Behrens

Changing boreal methane sources and constant biomass burning during the last termination

Past atmospheric methane concentrations show strong fluctuations in parallel to rapid glacial climate changes in the Northern Hemisphere superimposed on a glacial–interglacial doubling of methane concentrations. The processes driving the observed fluctuations remain uncertain but can be constrained using methane isotopic information from ice cores. Here we present an ice core record of carbon isotopic ratios in methane over the entire last glacial–interglacial transition. Our data show that the carbon in atmospheric methane was isotopically much heavier in cold climate periods. With the help of a box model constrained by the present data and previously published results, we are able to estimate the magnitude of past individual methane emission sources and the atmospheric lifetime of methane. We find that methane emissions due to biomass burning were about 45 Tg methane per year, and that these remained roughly constant throughout the glacial termination. The atmospheric lifetime of methane is reduced during cold climate periods. We also show that boreal wetlands are an important source of methane during warm events, but their methane emissions are essentially shut down during cold climate conditions.

A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high‐precision δD measurements of atmospheric methane extracted from ice cores

Air enclosures in polar ice cores represent the only direct paleoatmospheric archive. Analysis of the entrapped air provides clues to the climate system of the past in decadal to centennial resolution. A wealth of information has been gained from measurements of concentrations of greenhouse gases; however, little is known about their isotopic composition. In particular, stable isotopologues (deltaD and delta(13)C) of methane (CH(4)) record valuable information on its global cycle as the different sources exhibit distinct carbon and hydrogen isotopic composition. However, CH(4) isotope analysis is limited by the large sample size required and the demanding analysis as high precision is required. Here we present a highly automated, high-precision online gas chromatography/pyrolysis/isotope ratio monitoring mass spectrometry (GC/P/irmMS) technique for the analysis of deltaD(CH(4)). It includes gas extraction from ice, preconcentration, gas chromatographic separation and pyrolysis of CH(4) from roughly 500 g of ice with CH(4) concentrations as low as 350 ppbv. Ice samples with approximately 40 mL air and only approximately 1 nmol CH(4) can be measured with a precision of 3.4 per thousand. The precision for 65 mL air samples with recent atmospheric concentration is 1.5 per thousand. The CH(4) concentration can be obtained along with isotope data which is crucial for reporting ice core data on matched time scales and enables us to detect flaws in the measurement procedure. Custom-made script-based processing of MS raw and peak data enhance the systems performance with respect to stability, peak size dependency, hence precision and accuracy and last but not least time requirement.

A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision δ13C measurements of atmospheric methane extracted from ice core samples

Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of delta13CH4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of approximately 200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 +/- 40 years) show a delta13C(VPDB) of -49.54 +/- 0.13 per thousand and Antarctic samples (1530 +/- 25 years) show a delta13C(VPDB) of -48.00 +/- 0.12 per thousand in good agreement with published data.