Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of α-pinene.
ABSTRACT Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species.
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ABSTRACT: Organic compounds are known to comprise a significant fraction of the atmospheric aerosol population and have been found to contribute to the concentration of cloud condensation nuclei (CCN). Much of this organic material is secondary in nature; secondary organic aerosol (SOA) is formed when volatile organic compounds are oxidized to form less volatile products, which then condense into the aerosol phase. Many organic compounds found in the atmosphere, of both anthropogenic and biogenic origin, have been found to produce SOA. Such reactions typically result in complex mixtures of products, only a fraction of which have been identified. Thus while there have been several studies exploring the potential for organic particles to act as CCN (including some of the compounds identified in SOA products), there have been almost no direct investigation of the potential CCN activity of SOA. This paper presents the results of a series of experiments measuring directly the CCN activity of SOA produced by the ozonolysis of several common biogenic compounds. Six compounds were studied: five monoterpenes (α -pinene, β -pinene, Δ 3-carene, limonene, terpinolene) and one terpinoid alcohol (terpinen-4-ol). The chosen monoterpenes represent an estimated 87% of global monoterpene emissions, while the terpenoid alcohols make up approximately 25% of the other biogenic compounds capable of forming SOA. In each experiment, SOA was generated under controlled conditions at the Caltech indoor facility. Over several hours, CCN concentrations were measured at supersaturations ranging from 0.27% to 0.80%. These data are compared to simultaneous particle concentration and size distribution observations to determine the relationship between particle diameter and CCN activity. The analysis indicates considerable variation in CCN activity among the experiments; possible causes for such variability are explored.Journal of Geophysical Research 12/2004; · 3.17 Impact Factor
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ABSTRACT: A model that predicts secondary organic aerosol (SOA) formation based on the thermodynamic equilibrium partitioning of secondary organic oxidation products has been developed for implementation into atmospheric models. Hydrophobic secondary products are assumed to partition to an absorbing organic aerosol consisting of primary organic aerosol (POA) and other secondary hydrophobic organics according to an equilibrium partitioning coefficient calculated iteratively for each secondary compound present. The hydrophobic module is evaluated by studying the partitioning of octadecanoic acid to surrogate POA species. As expected, the amount of octadecanoic acid predicted to be present in the aerosol phase increases as the total amount of absorbing material increases or as the total amount of acid present increases. Hydrophilic secondary compounds partition to an aqueous phase via Henry's law; the fraction of each compound's mass that partitions is determined by its Henry's law constant and its acid dissociation constant(s). The available liquid water content (LWC) of the aerosol is determined iteratively between an inorganic aerosol module and the hydrophilic module, which is evaluated by studying the partitioning of glyoxalic and malic acids. While glyoxalic acid tends to remain in the gas phase, malic acid partitions strongly to the aqueous phase, with ions being the dominant form in the aqueous phase. As expected, an increase in relative humidity increases the amount of water associated with the organics (DeltaLWC), and a lower aerosol pH favors molecular solutes over ionized forms. Increasing pH results in higher effective Henry's law constants for the acids, yielding higher organic aerosol concentrations. Results also indicate that increasing DeltaLWC induces additional partitioning of inorganics to the aqueous phase.Journal of Geophysical Research 01/2002; 107. · 3.17 Impact Factor
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ABSTRACT: Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of α-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semi-empirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought.Geophysical Research Letters 06/2007; 34(20). · 3.98 Impact Factor