Relating aerosol mass spectra to composition and nanostructure of soot particles

The composition and carbon nanostructure of soot are important parameters influencing health and climate effects, and the efficacy of soot mitigation technologies. We used laser-vaporization, electron-ionization aerosol mass spectrometry (or SP-AMS) to systematically investigate relationships between aerosol mass spectra, carbon nanostructure (HRTEM), and composition (thermal-optical carbon analysis) for soot with varying physicochemical properties. SP-AMS refractory black carbon concentrations (based on C≤5+ clusters) were correlated to elemental carbon (r = 0.98, p < 10−8) and equivalent black carbon (aethalometer) concentrations. The SP-AMS large carbon (C≥6+, midcarbons and fullerene carbons) fraction was inversely correlated to fringe length (r = −0.97, p = 0.028) and linearly correlated to the fraction of refractory organic carbon that partially pyrolize during heating (r = 0.89, p < 10−4). This refractory organic carbon material was incompletely detected with conventional aerosol mass spectrometry (flash vaporization at 600 °C). This suggests that (SP-AMS) refractory carbon cluster analysis provides insight to chemical bonding and nanostructures in refractory carbon materials, lowcarbons (C≤5+) indicate mature soot and large carbons indicate refractory organic carbon and amorphous nanostructures related to C5-components. These results have implications for assessments of soot particle mixing state and brown carbon absorption in the atmosphere and enable novel, on-line analysis of engineered carbon nanomaterials and soot characteristics relevant for climate and health