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Adrian F. Tuck
NOAA Aeronomy Laboratory, Boulder, Colorado
Veronica Vaida
Department of Chemistry and Biochemistry, University of Colorado, Boulder
Abstract. We suggest a chemical model for the composition, structure, and atmospheric
processing of organic aerosols. This model is stimulated by recent field measurements
showing that organic compounds are a significant component of atmospheric aerosols. The
proposed model organic aerosol is an “inverted micelle” consisting of an aqueous core
that is encapsulated in an inert, hydrophobic organic monolayer. The organic materials
that coat the aerosol particles are surfactants of biological origin. We propose a chemical
mechanism by which the organic surface layer will be processed by reactions with
atmospheric radicals. The net result of an organic aerosol being exposed to an oxidizing
atmosphere is the transformation of an inert hydrophobic film to a reactive, optically
active hydrophilic layer. Consequently, processed organic aerosols can grow by water
accretion and form cloud condensation nuclei, influencing atmospheric radiative transfer.
Radiative transfer may be affected directly by the chromophores left on the surface of the
aerosol after chemical transformation. The chemical model yields certain predictions
which are testable by observations. Among them is a curve of the percent organic material
as a function of particle diameter which predicts that a high fraction of the mass of the
upper tropospheric aerosol will be organic. Atmospheric processing of organic aerosols
will lead to the release of small organic fragments into the troposphere which will play a
subsequent role in homogeneous chemistry. Organic aerosols are likely to act as a
transport vehicle of organics and other water insoluble compounds into the atmosphere.
We speculate that biomass burning will produce a similar coating of surfactants derived
from land sources. Finally, it is pointed out that the radical-induced transformation of the
surface layer of aerosol particles from hydrophobic to hydrophilic offers an additional
means by which the biosphere, through atmospheric chemistry, can affect the radiative
balance.
OH, O2, NO will shred the large alkyl chains and will produce of the nascent aerosol has no accessible electronic states (elec-
small carbon fragments which will be ejected into the tropo- tronic states of such compounds can only be reached in the
sphere. vacuum ultraviolet) [Ellison, 1974; Robin, 1985]. However, the
Much of the OH, O2, NO surface chemistry can be antici- processed aerosol organic coating of alcohols, aldehydes, and
pated by analogy to well-known gas phase homogeneous chem- ketones have near-ultraviolet states, making these compounds
istry, but there surely are chemical surprises awaiting us [At- effective atmospheric chromophores. In the near IR, very weak
kinson, 1994]. As a possible example, notice that RO2 radicals vibrational C™H overtones (from the organic coating) and
readily oxidize NO to NO2 with an exothermicity of 212 kcal O™H overtones (from the water core) can be excited. The key
mol21 (250 kJ mol21); the rate constant for peroxyl radical proposed intermediates in processing organic aerosols are sur-
oxidation of NO is ;8 3 10212 cm3 s21 [Eberhard and Howard, face-bound RO2 radicals which have been shown to have al-
1997]. For ozone and sulfur dioxide, peroxide oxidation reac- lowed electronic transitions in the near IR (7000 –9000 cm21)
tions are even more exothermic. [Clifford et al., 1998]. While the cross sections of the surface-
bound species are not known, they are expected, as befitting
(R4a) CH3O2(2A0) 1 NO 3 CH3O(2E) 1 NO2 allowed electronic states, to be 104 to 106 times larger than that
D rxnH 298 5 212 kcal mol21 of vibrational overtones. Scaling for the number of molecules
in the core versus those on the surface and explicitly using the
(R4b) CH3O2(2A0) 1 O3(1A1) 3 CH3O(2E) 1 2O2 differences in cross sections, we expect the aerosol with surface
RO2 to be 2– 4 orders of magnitude more absorbent in the near
D rxnH 298 5 232 kcal mol21 IR than comparably sized “uncoated” or “unprocessed” ma-
rine aerosols.
(R4c) CH3O2(2A0) 1 SO2 3 CH3O(2E) 1 SO3
Most importantly, processing of organic aerosols provides
D rxnH 298 5 222 kcal mol21 “defect sites” on the aerosol surface where nucleation rates
can be efficient [Thomas et al., 1998]. Consequently, processed
Yet the gas phase (R4b) and (R4c) do not go at room tem- aerosols can form condensation nuclei, scatter light more ef-
perature [Tyndall et al., 1998]. However, the kinetics on an fectively, and increase the reflectivity of clouds. The size of
aerosol surface of (R4b) peroxyl radical oxidation of O3 to these processed organic aerosols will be a function of the
generate alkoxy radicals or (R4c) with SO2 to produce organic aerosol age. Nucleation in this case occurs entirely indepen-
sulfates might be another story. We note that current field dently of the sulfate content of the aerosol. The model result in
measurements of SO2 oxidation to sulfate could not distinguish Figure 5 can be applied to the recent ACE-1 field observations
between this route and the other oxidation paths in the bulk that pure sulfate particles larger than 0.13 mm at Cape Grim
liquid phase. were extremely scarce and that few pure sulfate particles were
The temperature drop from the tropical ocean surface to the acting as cloud condensation nuclei in that region [Murphy et
tropopause (17 km above) is 1158C. Any hydrocarbons that al., 1998a]. The model presented here for processing of organic
boil in the range 2858C , T , 308C will form inverted micelles aerosols provides an alternative path to aerosol nucleation and
on any aerosol en route. The vertical transport will probably formation of cloud condensation nuclei.
occur mainly in the Intertropical Convergence Zone (ITCZ). We consider some potential objections to our picture in this
The D 21 dependence of the organic content implied by the paragraph. To the suggestion that gas phase coagulation of
inverted micelle model suggests that the aerosols in the upper smaller particles could account for the organic content of the
tropical troposphere will contain a high fraction of organic actinically active aerosol sizes, we respond that if it did, our
material (Figure 5). This prediction is testable by observation. model would still constitute a viable description. We do not
Once in the stratosphere, the aerosol particle will warm, and accept, however, that surfactant molecules could accrete at the
some of the lighter organics will evaporate. This is another way surface of a particle by collisions from the gas phase; the vapor
that aerosols could act as a “bus” to transport organics to the pressure of such molecules is far too low. For example, the
stratosphere via the ITCZ. We expect that the inverted micelle boiling point of stearic acid [CH3(CH2)16COOH] is listed as
could “protect” the marine core in Figure 3 and allow it to also 1838–1848C at 1 torr vapor pressure; the boiling point at atmo-
reach the stratosphere. The overwhelming balance of evidence spheric pressure is listed as 3608C, accompanied by decompo-
suggests that there is little marine Cl in the middle and upper sition. Because of the low vapor pressure, nor do we consider
stratosphere. Russell et al. [1996] show that nearly all the Cl oxidation of surfactants in the gas phase by the chemistry we
and F in the upper stratosphere comes from CFCs. However, describe.
Rosenlof et al. [1997] find that most of the air crossing the inner There are some obvious questions and complexities associ-
tropical tropopause (100 mbar) goes sideways instead of up- ated with our model. For example, in the real atmosphere the
ward: the flux up through 50 mbar is only about 10% of the surface film is likely to be made up of several to many different
mass that goes up through 100 mbar. So, the lowermost strato- molecular species, raising the question of how ordered
sphere, where the greatest ozone losses are, could be affected (aligned) the individual molecules are. It has long been known
by a flux of “protected” brine. There are very few measure- that a single double bond, particularly for the cis isomer, can
ments in the lower stratosphere that could be used in this affect surfactant layer thickness [Langmuir, 1917]. The degree
context, nevertheless, one example of high chloride (0.4 ppbv of functionalization as radical processing proceeds could also
of HCl vapor) is available [Tuck et al., 1995]. have major effects in this respect. It has been asserted that
The direct and indirect aerosol effect on radiative transfer removal of a single molecule could provide a “hole” through
can be predicted as a consequence of this chemical model for which water could exchange between the core and the atmo-
aerosol processing. The processed, “aged” aerosol contains sphere, to the extent that 90 –99% of the inhibition by the film
chromophores which will be significantly more absorbing than could be lost [Barger and Garrett, 1970]. Indeed, in an ordered
their aliphatic precursors. The saturated hydrocarbon coating spherical film, the “hairy ball theorem” necessitates the exis-
ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS 11,639
tence of a whorl point in mapping rods on a sphere. However, Acknowledgments. GBE is supported by a grant from the Chemi-
real atmospheric films are more likely to resemble a bramble cal Physics Program, U.S. Department of Energy (DE-FG02-
87ER13695). VV would like to acknowledge a CRCW Faculty Fellow-
patch than a wheat field, and such “holes” could be rare. It is ship from the University of Colorado and the National Science
natural to ask if such films would exist on terrestrial as well as Foundation for continued support. We are indebted to our NOAA
marine aerosol. One mechanism which could volatilize the colleagues Dan Murphy and Anne Middlebrook for sharing their data
waxes and lipids from plants would be biomass burning; there with us and for many fine pointers about their PALMS technique. We
must be a zone of temperatures around flames which will acknowledge many of our colleagues for extensive discussions:
Meredithe L. Applebury (Harvard Medical School), Roberto Bianco
correspond to their boiling points. Terrestrial plant lipids have (University of Colorado), Jamie Donaldson (University of Toronto),
been detected in atmospheric aerosol samples. We believe that Ray Fall (University of Colorado), Greg Frost (NOAA), Vicki Gras-
the radical processing of the exterior surfactant film from a sian (University of Iowa), Anne Jefferson (NOAA), Bruce E. Koel
hydrophobic to a hydrophilic state offers a further means by (USC), Carl A. Koval (University of Colorado), Ron Naaman (Weiz-
mann Institute), Suzanne E. Paulson (UCLA), Stuart Penkett (Uni-
which atmospheric chemistry can affect the radiative balance. versity of East Anglia), Yinon Rudich (Weizmann Institute), Sally A.
It can do so directly via the effect of the aerosol on the radi- Sullivan (Greenlee, Winner, & Sullivan, PC), Pieter Tans (NOAA),
ation field and indirectly via the aerosol’s cloud nucleation and Mark Young (University of Iowa).
properties. Because each hydrogen atom on, say, stearic acid,
CH3(CH2)16COOH, is potentially transformable to an OH References
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