The effects of structure, NOx conditions, relative humidity, and aerosol acidity on the chemical composition of secondary organic aerosol (SOA) are reported for the photooxidation of three C12 alkanes: n-dodecane, cyclododecane, and hexylcyclohexane. Acidity was modified through seed particle composition: NaCl, (NH4)2SO4, and (NH4)2SO4 + H2SO4. Off-line analysis of SOA was carried out by solvent extraction and gas chromatography-mass spectrometry (GC/MS) and direct analysis in real-time mass spectrometry.
View Article and Find Full Text PDFOrganic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs).
View Article and Find Full Text PDFThe physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation.
View Article and Find Full Text PDFThe extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions.
View Article and Find Full Text PDFLaboratory chambers used to study atmospheric chemistry and aerosol formation are subject to wall loss of vapors and particles that must be accounted for in calculating aerosol yields. While particle wall loss in chambers is relatively well-understood and routinely accounted for, that of vapor is less so. Here we address experimental measurement and modeling of vapor losses in environmental chambers.
View Article and Find Full Text PDFIsoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = beta-IEPOX + delta-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NO(x) conditions, respectively. Isoprene low-NO(x) SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.
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