Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

A neurophysiological fingerprint of the empty-chair dialogue

The empty chair dialogue is a validated technique used in Gestalt and emotion focused therapy to help clients overcome unresolved interpersonal grievances. It aims at influencing emotional processing in a way that emotional states characterized by advanced meaning making, thus by the integration of cognition and affect, are facilitated. Even though a variety of studies demonstrated the effectiveness of this technique as well as the usefulness of improvements in emotional processing, it remains unclear how these changes are characterized on a neuronal level. The present study aimed at tracing changes induced by the empty-chair dialogue with electrophysiological methods. Subjects reporting long-standing interpersonal grievances were recruited. After informed consent, an experienced therapist guided subjects to work on their individual interpersonal theme using the empty chair dialogue. During this one-session intervention, multichannel EEG was recorded and the session was video-taped. Afterwards, a validated observational rating instrument was used to identify time periods representing emotional states characterized by either high or low meaning making and the preprocessed, artifact-free EEG-data was labeled accordingly. Thus the comparison of neurophysiological activity during two distinct types of emotional processing becomes possible. EEG-data will be analyzed with modern methods of frequency analysis. Furthermore global field synchronization will be compared between the two types of emotional processing.