The potential contribution of organic salts to new particle growth

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Abstract

Field and lab measurements suggest that low-molecular weight (MW) organic acids and bases exist in accumulation and nucleation mode particles, despite their relatively high pure-liquid vapor pressures. The mechanism(s) by which such compounds contribute to the mass growth of existing aerosol particles and newly formed particles has not been thoroughly explored. One mechanism by which low-MW compounds may contribute to new particle growth is through the formation of organic salts. In this paper we use thermodynamic modeling to explore the potential for organic salt formation by atmospherically relevant organic acids and bases for two system types: one in which the relative contribution of ammonia vs. amines in forming organic salts was evaluated, the other in which the decrease in volatility of organic acids and bases due to organic salt formation was assessed. The modeling approach employed relied heavily on group contribution and other estimation methods for necessary physical and chemical parameters. The results of this work suggest that amines may be an important contributor to organic salt formation, and that experimental data are greatly needed to improve our understanding of organic salt formation in atmospherically relevant systems and to accurately predict the potential contribution of such salts to new particle growth. © 2011 Author(s).

Figures

  • Table 1. Chemical and physical property parameters for acids and bases considered.
  • Table 2. Relative amounts of dimethylamine (DMA) and ammonia (NH3) predicted in the particle phase, expressed as fractions of total base predicted in the particle phase, as a function of gas-phase DMA and NH3 levels (gas-phase acetic acid=100 ppt). Total fractions of DMA and NH3 are emboldened. Activity and curvature corrections have been neglected.
  • Table 3. Observed low and high levels of aliphatic amines measured by Grönberg et al. (1992), and their Henry’s Law (KH) and acid dissociation (Ka, as pKa) constants.
  • Fig. 1. Fraction of amines predicted in the particle phase, famines (=namines,p/ntotalbase,p), for system type one (ST 1) particles (dilute aqueous) as a function of gas-phase NH3 and amine levels, and KH and 1pKa (pKa,amine–pKa,AcOH) values.
  • Fig. 2. The predicted equilibrium distribution of dimethylamine, acetic acid, and pinic acid between the gas (DMAg, HAg) and particle (DMAp, DMAH+, HAp, A−) phases for system type two (ST 2) particles (aqueous particles w/XHA,initial=XDMA,initial=0.25), shown as mass fraction in each phase. The relative mass fractions illustrate the sensitivity of predictions to surface tension estimation (ST 2AcOH,σ ), activity coefficient estimation (ST 2AcOH,ζ ), and vapor pressures/acid dissociation constants (ST 2pinic).

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APA

Barsanti, K. C., McMurry, P. H., & Smith, J. N. (2009). The potential contribution of organic salts to new particle growth. Atmospheric Chemistry and Physics, 9(9), 2949–2957. https://doi.org/10.5194/acp-9-2949-2009

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