Detection of Organic Compounds in Ice Cores for Application to Palaeoclimate Reconstruction - Methodological Development

Records of inorganic gases and particles trapped in ice core layers have provided some of the most important insights to our understanding of climate of the last 800,000 years. Organic compounds within the ice, however, are an un-tapped reservoir of information. In particular, two groups of compounds emitted from the terrestrial biosphere, fatty acids and terpene secondary oxidation aerosols (SOAs), display characteristics required for ice core paleoclimate reconstruction; emission rates depend on atmospheric states (e.g. temperature), compounds survive long-distance transport in the atmosphere to high altitudes and latitudes (Grannas et al., 2004; Fu et al., 2013 among others), and are shown to survive in ice layers up to 450 yrs old for fatty acids in Greenland (Kawamura et al., 1996) and 350 yrs for SOAs in Alaska (Pokhrel et al., 2015). Here, we aim to develop a single method for quantification of all compounds of interest over longer timescales and further locations using liquid chromatography (LC) ultrahigh resolution mass spectrometry (LTQ Orbitrap). Initial quantification of compound contamination from sources such as drilling fluids and storage bags, diffusing through outer ice core surfaces, suggests compound contamination is limited to the outer few mm's of ice over periods of a few months. Detection limits were in the order of 1-5 ppb for the compounds of interest, leading to the trial of pre-concentration methods using stir bar sorbtive extraction (SBSE) to facilitate detection of ppt concentration levels, as expected for these types of compounds based on previous analysis of snow samples (Pokhrel et al., 2015). Detection of these compounds seems highly viable, with promise for long-term records being achieved in the near future. Fu et al.(2013) Biogeosciences, 10(2), 653-667; Grannas et al.(2004) Global Biogeochem. Cycles, 18, GB1006; Kawamura et al.(1996) Geophys. Res. Lett., 23(19), 2665-2668; Pokhrel et al.(2015) Atmos. Environ., 130, 105-112.