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Inorganic components of atmospheric aerosols

Citation

Wexler, Anthony S. (1991) Inorganic components of atmospheric aerosols. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-07172007-083859

Abstract

The inorganic components comprise 15% to 50% of the mass of atmospheric aerosols and, these along with the relative humidity, control the aerosol water content. For about the past 10 years the mass of the inorganic components of atmospheric aerosol was predicted assuming thermodynamic equilibrium between the volatile aerosol-phase inorganic species, NH4NO3 and NH4Cl, and their gas-phase counterparts, NH3, HNO3, and HCl. In this thesis I examine this assumption and prove that 1) the time scales for equilibration between the gas and aerosol phases are often too long for equilibrium to hold, and 2) even when equilibrium holds, transport considerations often govern the size distribution of these aerosol components.

Water can comprise a significant portion of atmospheric aerosols under conditions of high relative humidity, whereas under conditions of sufficiently low relative humidity atmospheric aerosols tend to be dry. The deliquescence point is the relative humidity where the aerosol goes from a solid dry phase to an aqueous or mixed solid-aqueous phase. Previous to this thesis little had been known about the temperature and composition dependence of the deliquescence point. In this thesis I first derive an expression for the temperature dependence of the deliquescence point and then prove that in multicomponent solutions the deliquescence point is lower than in the deliquescence point of the individual single component solutions.

These theories of the transport, thermodynamic, and deliquescent properties of atmospheric aerosols are integrated into an aerosol inorganics model, AIM. The equilibrium predictions of AIM compare well to fundamental thermodynamic measurements. Comparison of the prediction of AIM to those of other aerosol equilibrium models show substantial disagreement in the predicted water content at lower relative humidities. The difference is due to the improved treatment of the deliquescence properties of mixed solute aerosols that is contained in AIM.

In the summer and fall of 1987 the California Air Resources Board conducted the Southern California Air Quality Study, SCAQS. During this study the atmospheric aerosols were measured at nine sites in the Los Angeles air basin. The measurements determined the size and composition distributions of the components of the aerosol and the concentrations of their gas phase counterparts during a series of intensive study periods. The comparison of these SCAQS measurements to the predictions of AIM have so much scatter that a departure from equilibrium, that can be attributed to transport limitations, cannot be discerned. When the measured size distributions are compared as another indication of transport-limited departure from equilibrium, we find that different size aerosol particles are not in mutual equilibrium. Although the SCAQS data do not indicate a transport-limited departure from equilibrium, they do support our hypothesis that transport considerations are essential to predicting the size distribution of the volatile inorganic species.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Mechanical Engineering
Thesis Availability:Restricted to Caltech community only
Research Advisor(s):
  • Seinfeld, John H.
Thesis Committee:
  • Seinfeld, John H. (chair)
  • Cass, Glen Rowan
  • Pandis, Spyros N.
Defense Date:5 December 1990
Record Number:CaltechETD:etd-07172007-083859
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-07172007-083859
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:2910
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:02 Aug 2007
Last Modified:26 Dec 2012 02:55

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