A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols

Zaveri, Rahul A; Easter, Richard C; Wexler, Anthony S

doi:10.1029/2004JD004681

Title: A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols

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Abstract

Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient parameterization of activity coefficients of various electrolytes in multicomponent aqueous solutions. This paper describes the development and application of a new mixing rule for calculating activity coefficients of electrolytes typically found in atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+ SO42-, HSO4-, NO3-, and Cl- ions. The new mixing rule, called MTEM (Multicomponent Taylor Expansion Model), estimates the mean activity coefficient of an electrolyte in a multicomponent solution based on its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson method. For self-consistency, most of the MTEM and Zdanovskii-Stokes-Robinson parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols, and is contrasted against the mixing rule of Kusik and Meissner and the newer approach of Metzger et al. [2002]. Predictions of MTEM are found to be generally within a factor of 0.8 to 1.25 of the comprehensive Pitzer-Simonson-Clegg model, and are shown to be significantly more accuratemore »« less

Authors:: Zaveri, Rahul A; Easter, Richard C; Wexler, Anthony S

Publication Date:: Fri Jan 21 00:00:00 EST 2005

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 15020536

Report Number(s):: PNNL-SA-40638
KP1202010; TRN: US200521%%183

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Journal of Geophysical Research. D. (Atmospheres), 110(D2):D02201

Additional Journal Information:: Journal Volume: 110; Journal Issue: D2

Country of Publication:: United States

Language:: English

Subject:: 54 ENVIRONMENTAL SCIENCES; ACID SULFATES; AEROSOLS; AQUEOUS SOLUTIONS; DISSOCIATION; ELECTROLYTES; HUMIDITY; ITERATIVE METHODS; MIXTURES; REACTION KINETICS; THERMODYNAMIC ACTIVITY; WATER; thermodynamic properties, mixed-electrolytes, activity coefficients, inorganic aerosols

Citation Formats


                    Zaveri, Rahul A, Easter, Richard C, and Wexler, Anthony S. A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols.  United States: N. p., 2005. 
        Web.  doi:10.1029/2004JD004681.

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                    Zaveri, Rahul A, Easter, Richard C, & Wexler, Anthony S. A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols.  United States.  https://doi.org/10.1029/2004JD004681

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                    Zaveri, Rahul A, Easter, Richard C, and Wexler, Anthony S. 2005.  
        "A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols".  United States.  https://doi.org/10.1029/2004JD004681.

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@article{osti_15020536,

  title        = {A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols},

  author       = {Zaveri, Rahul A and Easter, Richard C and Wexler, Anthony S},

  abstractNote = {Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient parameterization of activity coefficients of various electrolytes in multicomponent aqueous solutions. This paper describes the development and application of a new mixing rule for calculating activity coefficients of electrolytes typically found in atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+ SO42-, HSO4-, NO3-, and Cl- ions. The new mixing rule, called MTEM (Multicomponent Taylor Expansion Model), estimates the mean activity coefficient of an electrolyte in a multicomponent solution based on its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson method. For self-consistency, most of the MTEM and Zdanovskii-Stokes-Robinson parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols, and is contrasted against the mixing rule of Kusik and Meissner and the newer approach of Metzger et al. [2002]. Predictions of MTEM are found to be generally within a factor of 0.8 to 1.25 of the comprehensive Pitzer-Simonson-Clegg model, and are shown to be significantly more accurate than predictions of the other two methods. MTEM also yields a non-iterative solution of the bisulfate ion dissociation in sulfate-rich systems – a major computational advantage over other iterative methods. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.},

  doi          = {10.1029/2004JD004681},

  url          = {https://www.osti.gov/biblio/15020536},
  journal      = {Journal of Geophysical Research. D. (Atmospheres), 110(D2):D02201},
number       = D2,

  volume       = 110,

  place        = {United States},

  year         = {Fri Jan 21 00:00:00 EST 2005},

  month        = {Fri Jan 21 00:00:00 EST 2005}

}

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