High-Resolution Fluorescence Spectra of Airborne Biogenic Secondary Organic Aerosols: Comparisons to Primary Biological Aerosol Particles and Implications for Single-Particle Measurements.

Aqueous extracts of biogenic secondary organic aerosols (BSOAs) have been found to exhibit fluorescence that may interfere with the laser/light-induced fluorescence (LIF) detection of primary biological aerosol particles (PBAPs). In this study, we quantified the interference of BSOAs to PBAPs by directly measuring airborne BSOA particles, rather than aqueous extracts. BSOAs were generated by the reaction of d-limonene (LIM) or α-pinene (PIN) and ozone (O3) with or without ammonia in a chamber under controlled conditions. With an excitation wavelength of 355 nm, BSOAs exhibited peak emissions at 464-475 nm, while fungal spores exhibited peak emissions at 460-483 nm; the fluorescence intensity of BSOAs with diameters of 0.7 μm was in the same order of magnitude as that of fungal spores with diameters of 3 μm. The number fraction of 0.7 μm BSOAs that exhibited fluorescence above the threshold was in the range of 1.9-15.9%, depending on the species of precursors, relative humidity (RH), and ammonia. Similarly, the number fraction of 3 μm fungal spores that exhibited fluorescence above the threshold was 4.9-36.2%, depending on the species of fungal spores. Normalized fluorescence by particle volumes suggests that BSOAs exhibited fluorescence in the same order of magnitude as pollen and 10-100 times higher than that of fungal spores. A comparison with ambient particles suggests that BSOAs caused significant interference to ambient fine particles (15 of 16 ambient fine particle measurements likely detected BSOAs) and the interference was smaller for ambient coarse particles (4 of 16 ambient coarse particle measurements likely detected BSOAs) when using LIF instruments.