Real time in situ chemical characterization of sub-micron organic aerosols using Direct Analysis in Real Time mass spectrometry (DART-MS): the effect of aerosol size and volatility

Direct Analysis in Real Time (DART) mass spectrometry is an atmospheric pressure ionization technique suitable for in situ chemical analysis of organic aerosols. Here, mass spectra are obtained by introducing a stream of nanometer-sized aerosols into the ionization region, which is an open space between the ion source and the atmospheric inlet of mass spectrometer. Model single component aerosols are used to show how the aerosol size and volatility influence the measured ion signals at different DART gas temperatures. The results show that for equivalent aerosol mass concentrations, the ion signal scales with particle surface area, with smaller diameter oleic acid aerosols yielding higher ion signals relative to larger diameter aerosols. For the aerosols of the same size, but different vapor pressures, the ion signal is larger for more volatile succinic acid aerosols than less volatile adipic and suberic acid particles. From the measured changes in aerosol size, produced by the DART source, the radial probing depth for these model aerosols range from 1 to 10 nm, the magnitude of which depends upon the physiochemical properties of the aerosols and DART gas temperature. An aerosol evaporation model reveals that the ion signal is correlated with changes in aerosol size and depends upon the total quantity of evaporated aerosol mass, consistent with a mechanism in which gas-phase molecules are first desorbed from the aerosol surface prior to ionization. The results of this work serve as a basis for future investigations of the mass spectra, ionization pathways, and probing depth of the aerosols using DART.