A new CF-IRMS system for quantifying stable isotopes of carbon monoxide from ice cores and small air samples

Abstract

We present a new analysis technique for stable isotope ratios (δ¹³C and δ¹⁸O) of atmospheric carbon monoxide (CO) from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS); it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO₂, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ) for δ¹³C and 0.6‰ (±1δ) for δ¹⁸O can be obtained for 100 mL (STP) air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO). Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.