Novel Method to Quantify Trace Amounts of Isoprene and Monoterpene Secondary Organic Aerosol-Markers in Antarctic Ice

Biogenic volatile organic compounds (BVOCs) contribute to the formation of secondary organic aerosol (SOA) through atmospheric oxidation. Previously detected SOA-markers in northern hemisphere ice cores from Alaska, Greenland, Russia, and Switzerland indicate the transportation of isoprene and monoterpene oxidation products from their forestry sources to these glacial regions. Antarctica is geographically further removed from the BVOC's source, indicating significantly lower SOA-marker concentrations are likely in southern hemisphere ice cores. The aim of this study was to develop a sensitive mass-spectrometric method to detect and quantify low-abundance SOA-markers of isoprene and monoterpenes in ice core samples. Employment of a triple quadrupole HPLC-MS method enabled limit of detections in the range of 0.4-10 ppt for nine terrestrial SOA-markers and a marker of biomass burning, levoglucosan. Quantification was conducted in the multiple reaction monitoring mode with two specific transitions monitored for each target compound. Application of the developed method onto a section of a Jurassic ice core from Antarctica revealed the presence of seven of the target compounds: 2-methylerythritol, 2-methylglyceric acid, <i>cis</i>-pinonic acid, 3-methyl-1,2,3-butanetricarboxylic acid, pinolic acid, <i>cis</i>-norpinonic acid, and pinic acid. Repeatability ranged between 2.2% and 6.2%. This is the first time that such SOA-markers have been discovered and quantified in Antarctic ice.