According to evidence from our laboratory, acidic surfaces on atmospheric aerosols lead to potentially multifold increases in secondary organic aerosol (SOA) mass. Experimental observations using a multichannel flow reactor, Teflon (polytetrafluoroethylene) film bag batch reactors, and outdoor Teflon-film smog chambers strongly confirm that inorganic acids, such as sulfuric acid, catalyze particle-phase heterogeneous reactions of atmospheric organic carbonyl species. The net result is a large increase in SOA mass and stabilized organic layers as particles age. If acid-catalyzed heterogeneous reactions of SOA products are included in current models, the predicted SOA formation will be much greater and could have a much larger impact on climate forcing effects than we now predict.

The formation of oligomeric molecules, an important step in secondary organic aerosol production, is reported. Aerosols were produced by the reaction of alpha-pinene and ozone in the presence of acid seed aerosol and characterized by exact mass measurements and tandem mass spectrometry. Oligomeric products between 200 and 900 u were detected with both electrospray ionization and matrix-assisted laser desorption ionization. The exact masses and dissociation products of these ions were consistent with various combinations of the known primary products of this reaction ("monomers") with and/or without the expected acid-catalyzed decomposition products of the monomers. Oligomers as large as tetramers were detected. Both aldol condensations and gem-diol reactions are suggested as possible pathways for oligomer formation. Exact mass measurements also revealed reaction products that cannot be explained by simple oligomerization of monomers and monomer decomposition products, suggesting the existence of complex reaction channels. Chemical reactions leading to oligomer formation provide a reasonable answer to a difficult problem associated with secondary organic aerosol production in the atmosphere. It is unlikely that monomers alone play an important role in the formation and growth of nuclei in the atmosphere as their Kelvin vapor pressures are too high for them to significantly partition into the particle phase. Polymerization provides a mechanism by which partitioning to the particle phase becomes favored.

Secondary organic aerosol (SOA) from the photooxidation of toluene in a hydrocarbon-NOx mixture was generated in a 190 m3 outdoor Teflon chamber. The photooxidation reaction of toluene in the gas phase leads to substituted aromatics (TOL-AR), nonaromatic ring retaining (TOL-R), and ring opening products (TOL-RO). In this work, the following ring opening oxycarboxylic acids were newly identified: glyoxylic acid, methylglyoxylic acid, 4-oxo-2-butenoic acid, oxo-C5-alkenoic acids, dioxopentenoic acids, oxo-C7-alkadienoic acids, dioxo-C6-alkenoic acids, hydroxydioxo-C7-alkenoic acids, and hydroxytrioxo-C6-alkanoic acids. The newly characterized TOL-R and TOL-RO products included methylcyclohexenetriones, hydroxymethylcyclohexentriones, 2-hydroxy-3-penten-1,5-dial, hydroxyoxo-C6-alkenals, hydroxy-C5-triones, hydroxydioxo-C7-alkenals, and hydroxy-C6-tetranones. Products in both the gas and aerosol phases were derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) for carbonyls and pentafluorobenzyl bromide (PFBBr) for carboxylic acid and phenol groups and analyzed using a gas chromatograph/mass spectrometry (GC/MS) in an electron impact mode (EI) and a gas chromatograph/ion trap mass spectrometry (GC/ITMS) in both chemical impact and EI modes. To confirm different isomers, the PFBHA-derivatives of products were rederivatized by silylation using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). The Fourier transform infrared spectroscope (FTIR) was used to obtain additional functional group information for SOA products impacted on a zinc selenide FTIR disk. The major SOA products under the high NOx conditions of the above experiment included methylnitrophenols, methyldinitrophenols, methylbenzoquinones, methylcyclohexenetriones, 4-oxo-2-butenoic acid, oxo-C5-alkenoic acids, hydroxy-C3-diones, hydroxyoxo-C5-alkenals, hydroxyoxo-C6-alkenals, and hydroxydioxo-C7-alkenals. Of the major SOA products, the experimental partitioning coefficients (iKp) of aldehyde products were much higher and deviated more from predicted iKp values. This is an extremely important result, because it shows that aldehyde products can further react through heterogeneous processes, which may be a very significant SOA generation mechanism from the oxidation of aromatics in the atmosphere.

Particle growth by the heterogeneous reaction of aldehydes was evaluated in 0.5 m3 Teflon film bags under darkness in the presence of background seed aerosols. The aldehydes used were as follows: glyoxal, butanal, hexanal, octanal, and decanal. To study acid catalyst effects on aldehyde heterogeneous reactions, one of the Teflon bags was initially filled with seed aerosols composed of ammonium sulfate-aerosol acidified with sulfuric acid. These results were compared to particle growth reactions that contained only ammonium sulfate as a background seed aerosol. The gas-phase aldehydes were then added to the Teflon bags. In selected experiments, 1-decanol was also added to the Teflon bags with aldehydes to clarify particle growth via a heterogeneous hemiacetal/acetal formation in the presence/absence of an acid catalyst. The particle size distribution and growth were measured using a scanning mobility particle sizer (TSI-SMPS), and the results were applied to predicting aerosol growth and size distribution changes by condensation and heterogeneous reactions. Aerosols created from the heterogeneous reactions of aldehydes were collected directly on an ungreased zinc selenide (ZnSe) FTIR disk (25 mm in diameter) by impaction. The ZnSe disks were directly analyzed for product functional groups inthe aerosol phase using a Fourier transform infrared (FTIR) spectrometer with a deuterated triglycine sulfate (DTGS) detector. Aerosol growth by heterogeneous aldehyde reactions proceeds via a hydration, polymerization process, and hemiacetal/acetal formation from the reaction of aldehydes with alcohols. These aldehyde heterogeneous reactions were accelerated in the presence of an acid catalyst, H2SO4, and led to higher aerosol yields than when H2SO4 was not present in the seed aerosol. The FTIR spectra obtained from the growing aerosol, also illustrated aldehyde group transformation in the particle phase as a function of the heterogeneous reaction. It was concluded that aldehydes, which can be produced by atmospheric photochemical reactions, can significantly contribute on secondary aerosol formation through heterogeneous reactions in the presence of an acid catalyst.

The effect of relative humidity (RH) on secondary organic aerosol (SOA) formation from the photooxidation of isoprene under initially high nitric oxide (NO) conditions (i.e., isoprene/NO ~3) was investigated in a dual outdoor smog chamber. Based upon particle volume concentration measurements and the detailed chemical characterization of isoprene SOA using gas chromatography/mass spectrometry (GC/MS) and ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), enhanced SOA formation was observed under lower RH conditions (15–40 %) compared to higher RH conditions (40–90 %). 2-methylglyceric acid (2-MG) and its corresponding oligoesters, which have been previously shown to form from further oxidation of methacryloylperoxynitrate (MPAN), were enhanced in the particle-phase under lower RH conditions. In addition, an abundant unknown SOA tracer likely derived from the further oxidation of MPAN was detected and enhanced under lower RH conditions. In contrast, the 2-methyltetrols, which are known to mainly form from the reactive uptake of isoprene epoxydiols (IEPOX) under low-NO conditions in the presence of acidified aerosol, did not substantially vary under different RH conditions; however, isoprene-derived organosulfates were found to be enhanced under high-RH conditions, indicating the likely importance of the aqueous aerosol phase in their formation. Based upon the detailed chemical characterization results, particle-phase organic esterification is tentatively proposed to explain the observed enhancements of isoprene SOA mass under lower RH conditions. Alternative mechanisms explaining the enhancement of 2-MG and its corresponding oligoesters cannot be completely ruled out. This is one of only a few chamber studies that have examined the effect of RH on isoprene SOA formation. In comparison to our recent results obtained from aromatic SOA formation, the effect of RH on isoprene SOA formation is reversed. The results of this study highlight the importance of elucidating the key reactive intermediates that lead to SOA formation, especially since RH likely affects their ability in forming SOA. Furthermore, ignoring the effects of RH may significantly affect the accuracy of both regional and global SOA models