Airborne Extractive Electrospray Mass Spectrometry Measurements of the Chemical Composition of Organic Aerosol

Abstract. We deployed an extractive electrospray ionization time-of-flight mass spectrometer (EESI-MS) for airborne measurements of biomass burning aerosol during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) study onboard the NASA DC-8 research aircraft. Through optimization of the electrospray working solution, active control of the electrospray region pressure, and precise control of electrospray capillary position, we achieved 1 Hz quantitative measurements of aerosol nitrocatechol and levoglucosan concentrations up to pressure altitudes of 7 km. EESI-MS response to levoglucosan and nitrocatechol was calibrated for each flight, with flight-to-flight calibration variability of 60 % (1σ). Laboratory measurements showed no aerosol size dependence in EESI-MS sensitivity below particle geometric diameters of 400 nm, covering 82 % of accumulation mode aerosol mass during FIREX-AQ. We also present a first in-field intercomparison of EESI-MS with a chemical analysis of aerosol online proton-transfer-reaction mass spectrometer (CHARON PTR-MS) and a high-resolution Aerodyne aerosol mass spectrometer (AMS). EESI-MS and CHARON PTR-MS levoglucosan concentrations were well correlated, with a regression slope of 0.94, R² = 0.77. AMS levoglucosan-equivalent concentrations and EESI-MS levoglucosan showed greater difference, with a regression slope of 1.36, R² = 0.96, likely indicating the contribution of other compounds to the AMS levoglucosan-equivalent measurement. Total EESI-MS signal showed correlation (R² = 0.9) with total organic aerosol measured by AMS, and the EESI-MS bulk organic aerosol sensitivity was 60 % of the sensitivity to levoglucosan standards.