Volatility Measurements of Individual Components in Organic Aerosol Mixtures Using Temperature-Programmed Desorption–Direct Analysis in Real Time–High Resolution Mass Spectrometry

Atmospheric organic aerosols (OA) have profound effects on air quality, visibility, and radiative forcing of climate. Quantitative assessment of gas–particle equilibrium of OA components is critical to understand formation, growth, distribution, and evolution of OA in the atmosphere. This study presents a novel ambient pressure measurement approach developed and tested for untargeted screening of individual components in complex OA mixtures, followed by targeted chemical speciation of identified species and assessment of their physicochemical properties such as saturation vapor pressure and enthalpies of sublimation/evaporation. The method employs temperature-programmed desorption (TPD) experiments coupled to “direct analysis in real time” (DART) ionization source and high resolution mass spectrometry (HRMS) detection. Progression of the mass spectra is acquired in the TPD experiments over a T = 25–350 °C temperature range, and extracted ion chromatograms (EIC) of individual species are used to infer their apparent enthalpies of sublimation/evaporation (ΔH_sub^*) and saturation vapor pressure (p_T^*, Pa, or C_T^*, μg m^–3) as a function of T. We validate application of this method for analysis of selected organic compounds with known ΔH_sub and C_T values, which showed excellent agreement between our results and the existing data. We then extend these experiments to interrogate individual components in complex OA samples generated in the laboratory-controlled ozonolysis of α-pinene, limonene, and β-ocimene monoterpenes. The abundant OA species of interest are distinguished based on their accurate mass measurements, followed by quantitation of their apparent ΔH_sub^* and C_T^* values from the corresponding EIC records. Comparison of C_298K^* values derived from our experiments for the individual OA components with the corresponding estimates based on their elemental composition using a “molecular corridors” (MC) parametrization suggests that the MC calculations tend to overestimate the saturation vapor pressures of OA components. Presented results indicate very promising applicability of the TPD-DART-HRMS method for the untargeted analysis of organic molecules in OA and other environmental mixtures, enabling rapid detection and quantification of organic pollutants in the real-world condensed-phase samples at atmospheric pressure and without sample preparation.