ACS AWARD FOR CREATIVE ADVANCES IN ENVIRONMENTAL SCIENCE &

TECHNOLOGY: HONORING JAMES F. PANKOW

(Sponsored by Air Products and Chemicals, Inc.)
Gas/Particle Partitioning: The State of the Science
Organized by
J.F. Pankow and R.A. Hathaway
(Page 425 in Preprints of Extended Abstracts, Vol. 39 No. 1)
Symposia Papers Presented Before the Division of Environmental Chemistry
American Chemical Society
Anaheim, CA
March 21-25, 1999
THE THEORY OF GAS/PARTICLE PARTITIONING IN THE ATMOSPHERE - THE
HISTORY AND FUTURE NEEDS
James F. Pankow
Department of Environmental Science and Engineering
Oregon Graduate Institute, Portland, OR 97291
The first theoretical framework for understanding gas/particle (G/P) partitioning in the
atmosphere was proposed by Junge (1977). That framework considers atmospheric
particles to be solid in nature, with the consequent importance of the amount of surface
area available for the adsorption of gaseous compounds therefore recognized. Junge
(1977), however, assumed that the only source of variability in the magnitude of the
compound-dependent G/P partitioning constant Kp was compound-to-compound
differences in the pure compound liquid vapor pressure p oL. Thus, Junge (1977) did not
consider the potential importance of variability in either: 1) the chemical properties of
adsorbing surfaces; or 2) adsorbate polarity and/or conformation. The current view for
adsorption to surfaces is that both of these factors are very important in determining Kp
values. And, for a plot of log Kp vs. log p oL for any given surface, it is also now
recognized that compound-to-compound differences in non-pure-liquid-like interactions
can cause slope values that are different than -1.0.
While adsorption to solid surfaces in the atmosphere can be important under some
circumstances, in urban air the likelihood that adsorption dominates G/P partitioning for
organic compounds now seems low: it is very probable that absorption uptake by liquid
(or at least amorphous, and probably mostly organic) atmospheric particulate material
(APM) is more important in most urban circumstances. For absorptive uptake, in place
of the particle surface area, we have the mean molecular weight of the absorptive
phase as a Kp -governing parameter. It has been established by Pankow (1994) that

the importance of non-pure-liquid-like interactions in absorptive uptake is embodied in

the activity coefficient of the compound of interest in the absorbing phase.
Current research on G/P partitioning theory involves the study of how: 1) values for
absorption can be predicted based on the properties of the compound and the
absorptive phase; 2) n-octanol might serve as a surrogate phase for absorptive APM
thus allowing liberation from the need for knowledge of values for the
compounds/phases of interest; 3) the identities of the compounds making up absorptive
APM can be predicted for secondary organic aerosol; and 4) aerosol pH can affect the
partitioning of acid/base active organic compounds such as nicotine.
References
Junge C.E. (1977) Basic considerations about trace constituents in the atmosphere as
related to the fate of global pollutants. In Fate of Pollutants in Air and Water
Environments (edited by Suffett I.H.), Part I, pp.7-26. Wiley, New York.
Pankow J.F. (1994) An absorption model of gas/particle partitioning in the atmosphere.
Atmos. Environ., 28, 185-188.

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