Applications of online high resolution time of flight chemical ionization mass spectrometry (HRToF-CIMS): opportunities and challenges for aircraft measurements, atmosphere-ecosystem exchange, and organic aerosol composition

Abstract:

Over the past five years, field deployable high resolution time of flight chemical ionization mass spectrometers (HRToF-CIMS) have been developed and deployed for a range of problems relevant to atmospheric chemistry. The inherent duty cycle, dynamic range, mass accuracy, and resolving power of these instruments provide transformative capabilities for deriving new insights into atmospheric composition. We present examples of these capabilities from the deployments of the University of Washington HRToF-CIMS aboard research aircraft, an eddy flux tower in a boreal forest, and to measure organic aerosol composition upon temperature-programmed thermal desorption in field and chamber experiments. Specific examples include measurements of reactive halogens with all relevant isotopes simultaneously resolved from potential interferences, the opportunity for discovery, after the fact, of previously unmeasured or unexpected compounds with acquisition of the full mass spectrum, and providing a broad survey of the 100s of organic compounds that desorb from complex isoprene and monoterpene derived secondary organic aerosol matrices. While there are unique opportunities, there are also significant technical challenges to realizing the full analytical potential these instruments can provide. Many of these challenges are common to any analytical technique, but perhaps seemingly more demanding for HRToF-CIMS, such as the presumed need to calibrate 100s of molecular ion signals routinely detected in each spectrum. We detail some of the more pressing challenges and our approach towards addressing them.