Improved UHPLC-MS/MS Methods for Analysis of Isoprene-Derived Organosulfates

Secondary organic aerosol (SOA) is an important yet not fully characterized constituent of atmospheric particulate matter. A number of different techniques and chromatographic methods are currently used for the analysis of SOA, so the comparison of results from different laboratories poses a challenge. So far, tentative structures have been suggested for many organosulfur compounds that have been identified as markers for the formation of SOA, including isoprene-derived organosulfates. Despite the effectiveness and robustness of LC-MS/MS analyses, the structural profiling of positional isomers of recently discovered organosulfates with molecular weights (MI/Vs) of 214 and 212 from isoprene was entirely unsuccessful. Here, we developed a UHPLC combined with high-resolution tandem mass spectrometric method that significantly improves the separation efficiency and sensitivity of these compounds in aerosol matrices. We discovered that selection of the proper solvent for SOA extracts was a key factor in improving the separation parameters. Later, we took advantage of the enhanced sensitivity, combined with a short scan time window, to perform detailed structural mass-spectrometric studies. For the first time, we elucidate a number of isomers of the MW 214 and the MW 212 organosulfates and provide strong evidence for their molecular structures. The structure of trihydroxyketone sulfate MW 214 that we propose has not been previously reported. The methods we designed can be easily applied in other laboratories to foster an easy comparison of related qualitative and quantitative data obtained throughout the world.