A Comprehensive Nontarget Analysis for the Molecular Reconstruction of Organic Aerosol Composition from Glacier Ice...

Ice cores are climate archives suitable for the reconstruction of past atmospheric composition changes. Ice core analysis provides valuable insight into the chemical nature of aerosols and enables constraining emission inventories of primary emissions and of gas-phase precursors. Changes in the emissions of volatile organic compounds (VOCs) can affect formation rates and mechanisms as well as chemical composition of aerosols during the preindustrial era, key information for understanding aerosol climate effects. Here, we present an analytical method for the reconstruction of organic aerosol composition preserved in glacier ice cores. A solid-phase-extraction method, optimized toward oxidation products of biogenic VOCs, provides an enrichment factor of ∼200 and quantitative recovery for compounds of interest. We applied the preconcentration method on ice core samples from the high-alpine Fiescherhorn glacier (Swiss Alps), and used high-performance liquid chromatography coupled to high-resolution mass spectrometry as a sensitive detection method. We describe a nontarget analysis that screens for organic molecules in the ice core samples. We evaluate the atmospheric origin of the detected compounds in the ice by molecular-resolved comparison with airborne particulate matter samples from the nearby high-alpine research station Jungfraujoch. The presented method is able to shed light upon the history of the evolution of organic aerosol composition in the anthropocene, a research field in paleoclimatology with considerable potential.