JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 104, NO.

D9, PAGES 11,633–11,641, MAY 20, 1999

Atmospheric processing of organic aerosols

G. Barney Ellison
Department of Chemistry and Biochemistry, University of Colorado, Boulder

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.

1. Introduction al., 1991; Odum et al., 1997]. Field measurements documented

Aerosols are ubiquitous in the troposphere and are recog-
nized to play important roles in climate and elsewhere through
their interaction with solar and terrestrial radiation [Andreae,
1995; Andreae and Crutzen, 1997; Dickerson et al., 1997]. Re-
flection of radiation by the Earth’s atmosphere is augmented
by natural and anthropogenic aerosols through their size-
dependent light-scattering effects and by their ability to act as
condensation nuclei and increase the reflectivity of clouds
[Twomey et al., 1984; Charlson et al., 1992; Pandis et al., 1995;
Rivera-Caprio et al., 1996; Schwartz, 1996; Tegen et al., 1997;
Liao and Seinfeld, 1998; Pan et al., 1998]. Chemical composi-
tion plays an important role in determining the optical and
chemical properties of aerosols [Fitzgerald, 1991; O’Dowd and
Smith, 1993; Quinn et al., 1996; Saxena et al., 1996; Jennings et
al., 1997; Novakov et al., 1997]. Organic compounds are pro-
duced anthropogenically as well as by combustion, vegetation,
and oceanic phytoplankton [Hildemann et al., 1991; Pandis et
Copyright 1999 by the American Geophysical Union.
Paper number 1999JD900073.
0148-0227/99/1999JD900073$09.00
11,633
that organic aerosols are widespread in continental and marine
environments. Ambient cloud condensation nuclei contain 10 –
20% organic carbon (by mass), suggesting the need for a model
of the physicochemical structure of organic atmospheric aero-
sols [Li et al., 1998]. Questions about the role of sulfate, sea
salt, and organic compounds in determining the composition of
aerosols in the marine boundary layer have been the focus of
recent field studies, a notable example being the first Aerosol
Characterization Experiment (ACE 1) performed at Cape
Grim, Tasmania [Murphy et al., 1997; Middlebrook et al., 1998;
Murphy et al. 1998a, b]. In the context of ACE 1, the compo-
sition of single aerosol particles was directly measured using
particle analysis by laser mass spectrometry (PALMS) [Murphy
et al., 1997; Middlebrook et al., 1998; Murphy et al. 1998a, b].
The PALMS measurements established (1) that pure sulfate
aerosols are not prevalent in the marine boundary layer and
(2) that a significant fraction of the mass of the sea-salt aero-
sols is organic material (and not CO2 or carbonate) [Middle-
brook et al., 1998; Murphy et al., 1998a]. The best estimate from
these PALMS measurements is that ;10% of the marine aero-
sols is organic matter. Organic compounds in marine boundary
11,634 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS
Figure 1. (a) Lipid bilayer membrane. (b) Phosphatidylcholine.
layer aerosols are expected to significantly affect their direct
and indirect radiative properties and, consequently, to play an
important, if difficult to assess, role in controlling the Earth’s
climate [Saxena et al., 1995]. The recent ACE-1 results provide
the database needed to develop predictive models of radiative
and chemical properties of aerosols in the marine boundary
layer. The central difficulty with these high levels of observed
organic content in atmospheric aerosol is that they are inex-
plicable on the basis of bulk solubility (Henry’s law).
We describe a model that proposes a chemical structure for
marine aerosols, accounts for the organic content, and de-
scribes the chemical evolution or “atmospheric processing” of
the organic material. Our model of an organic aerosol consists
of an aqueous core encapsulated by an inert, hydrophobic
organic monolayer, in much the same manner suggested 15
years earlier [Gill et al., 1983]. However, Gill et al. concluded
that the inertness of this outer monolayer would minimize any
participation in atmospheric chemistry or cloud microphysics.
We point out that this surface organic grease layer will react
with atmospheric hydroxyl radicals. The resulting surface film
is functionalized and rendered hydrophilic. The optical and
chemical properties of organic aerosols as well as their ability
to nucleate will be dramatically enhanced as a result of the
chemistry we describe. Our proposed organic aerosol model
displays a complex set of properties that are consistent with
recent field measurements [Middlebrook et al., 1998; Murphy et
al., 1998a]. Furthermore, this model makes a number of pre-
dictions that may be amenable to test by field observations.
Finally, there is an intriguing suggestion of a novel atmospheric
transport mechanism for organics and other water insoluble
molecules from the ocean into the atmosphere.
2. Formation, Structure, and Composition of
Model Organic Marine Aerosols
Our picture of a marine aerosol is that of a brine core
surrounded by an organic surfactant layer which is called an
inverted micelle [Roberts et al., 1977; Gill et al., 1983; Adamson
et al., 1997]. By “inverted” we mean that the polar, hydrophilic
ends of the long-chain surfactant are inward toward the ionic
brine core and the aliphatic, hydrophobic tails are facing out-
ward to the atmosphere. The world’s oceans are teeming with
life. Approximately 50% of the oxygen in our planet’s atmo-
sphere is produced by marine organisms (mostly phytoplank-
ton). All living organisms are made of carbon and all are
enclosed by plasma membranes. These biological membranes
are exceedingly complex structures composed of a mixture of
lipids, hydrophobic proteins, and carbohydrates. The exact
composition of these membranes varies considerably from or-
ganism to organism; however, the components of these mem-
branes are all hydrophobic. In particular, lipid membranes are
universally described as having a bilayer structure with polar
heads facing the aqueous medium and sets of hydrophobic,
alkyl chains folded inward as in Figure 1a [Roberts and Caserio,
1977; Gill et al., 1983; Alberts et al., 1989; Ables et al., 1992]. The
long hydrophobic tails of the lipid membranes are composed of
fatty acids (shown in Figure 1) and those most commonly
found are palmitic acid [CH3(CH2)14COOH] and stearic acid
[CH3(CH2)16COOH] [Bruice, 1995]. Phosphatidylcholines
(lecithins) such as shown in Figure 1b are the typical constit-
uents of lipid membranes [Ables et al., 1992; Bruice, 1995].
Disintegration of the lipid bilayers in seawater at pH 8 will
produce phospholipids which slowly hydrolyze to fatty acids.
As cells die, they decompose and the hydrophobic cellular
constituents rise toward the ocean’s surface where they accu-
mulate. The phospholipids and fatty acids (such as stearic acid,
CH3(CH2)16COOH, for example) are common products of
lipid membrane disintegration and will be important surfac-
tants. Because seawater has a pH of ;8, most fatty acids will
exist as carboxylates [CH3(CH2)16CO2 2 ] and will be floating on
the surface of the ocean at the air/water interface [Quinn et al.,
1972; Marty et al., 1979]. The seas cover 71% of the Earth and
have large regions of water coated with surfactants. Photosyn-
thesis by marine organisms produces 30 – 60 3 1015 g of or-
ganic carbon yr21 [Duarte and Cebrián, 1996]. Most of the
organic matter in the sea originates from phytoplankton pro-
duction [Biddanda and Benner, 1997]. If one estimates that
20% of the net primary production of carbon is exported from
the ecosystem, this amounts to ;9 3 1015 g C yr21. If 5% of
the organic carbon is lipid and 1/2 of the exported lipids survive
to rise to the surface of the ocean, one conjectures that the
“biological oil slick” is about 1/2 3 5% 3 9 3 1015 g C yr21 or
2 3 1014 g C yr21 [Biddanda and Benner, 1997]. This is 200 Tg
C yr21 which will be “accumulated” or concentrated at the
ocean/atmosphere interface. More than 70% of the fatty acids
in seawater and the surface microlayer are present in esterified
form as triglycerides, stearyl esters, and phospholipids [Marty et
al., 1979]. These estimates roughly corroborate our contention
that a monolayer of hydrophobic organics will cover the sur-
face of the ocean and is available for incorporation on to the
surface of marine aerosols [Seinfeld et al., 1998].
Marine aerosol particles are formed by mechanical ejection
from the ocean’s surface, and as they form, they acquire a
coating of hydrocarbon surfactants [Pockels, 1891; Tseng et al.,
1992; O’Dowd and Smith, 1993; Russel et al., 1994]. There will
be water molecules present in these nascent aerosols, but as
H2O evaporation continues and the inner core shrinks, the
NaCl/H2O sphere will be covered with an organic layer with
polar heads anchored to the “brine,” as sketched in Figure 2.
The binding energy of carboxylates (RCO2 2 ) to H2O clusters is
;20 kcal mol21.
Our model for a marine aerosol is sketched in Figure 3 and
 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS
is a film of hydrophobic hydrocarbons covering a salt particle.
The model we propose emphasizes that all of the hydrophobic
organics will be on the surface of the aerosol and not dissolved
within the droplet. Aerosol size distributions have been mea-
sured during ACE 1 to be in the range of 0.02 and 0.8 mm with
concentrations of 500 cm23 for aerosols of 0.2 mm diameter
[Brechtel et al., 1998]. PALMS can characterize particles of
diameter $0.16 mm, which led us to choose 0.2 mm as the
diameter of the model aerosol described. The solubility of
individual alkanoic and alkenoic acids in water is miserably
small [Streitweiser et al., 1992], and we estimate that each 0.2
mm aerosol particle will contain no more than 25 dissolved
fatty acid molecules within the brine core (in a total of ;108
water molecules). In light of the negligible water solubility
(even lower in brine) of the functionalized long-chain hydro-
carbons, we propose that the only structural picture of organic
aerosols consistent with the large measured organic content is
that the hydrophobic organics must reside at the exterior of the
aerosol. Measurements of the temperature- and concentra-
tion-dependent surface tension of aqueous solutions of organic
compounds have recently been used to determine standard-
free energies of adsorption from the vapor phase [Donaldson et
al., 1998]. The results show that while the partitioning from
bulk to the surface is minor for soluble organics, water-
insoluble species stay on the surface. This result and the hy-
drophobic nature of the surface will affect the growth and
reactivity of droplets in the micrometer size range [Gill et al.,
1983; Shulman et al., 1996].
The PALMS measurement that ;10% of marine aerosol
mass is organic material [Middlebrook et al., 1998] is incompat-
ible with the notion that the organics are dissolved within the
droplet. We suggest that the working model of a nascent ma-
rine aerosol is that pictured in Figure 3; in it the exterior of the
Figure 2. Formulae for some common hydrophobic mole-
cules that reside at the ocean’s surface and on the surface of
sea spray. Typical organic molecules such as the anions of
palmitoleic acid, a phosphatidylcholine, and stearic acid are
shown.
11,635
Figure 3. An inverted micelle model for a marine aerosol;
the numbers are worked out for a representative 0.2 mm particle.
nascent aerosol is composed of “inert,” aliphatic hydrocarbon
chains that are exposed to the oxidizing troposphere.
For illustrative purposes, we choose the overall aerosol di-
ameter to be ;0.2 mm as we explicitly wish to test the prop-
erties of our model against the ACE-1 field observations [Mur-
phy et al., 1997; Middlebrook et al., 1998; Murphy et al. 1998a, b].
The core of the marine aerosol is a salt/water brine that will be
composed of about 1 3 108 molecules in a sphere 2000 Å in
diameter coated with a 25 Å deep film of about 6 3 105
surfactant molecules; recall that 1 Å [ 1028 cm 5 10210 m.
The hydrophobic material (fatty acids and phospholipids) will
be arranged on the surface of the aerosol (Figure 3) with the
polar groups binding to the NaCl/H2O brine.
If the nascent marine aerosol particles are properly de-
scribed by Figure 3, then they will be chemically inert and will
not react with most atmospheric species (acid, base, H2O, O2,
O3, SO2, NO, NO2, etc.). Because the marine aerosol is coated
with hydrophobic molecules, water will not stick to it, and these
nascent marine aerosol particles will not nucleate water drop-
lets. The effect is large and is several orders of magnitude
[Rideal, 1925; Langmuir and Schaefer, 1943; Archer and La Mer,
1955]. Laboratory studies show that formation of organic sur-
factant layers on deliquescent salt particles effectively limit
water uptake by salt aerosols in atmospheric conditions, al-
though in much larger particles than we consider here [An-
drews and Larson, 1993; Wagner et al., 1996]. Measurements of
the loss rate of H2SO4 on to NaCl have shown that aerosols
coated with stearic acid resulted in significantly lower mass
accommodation coefficients, corroborating the predictions
presented here [Jefferson et al., 1997].
3. Chemical Processing of Organic Aerosols
Previous writers who arrived at an inverted micelle model of
organic aerosols pointed out that the organic coating will be
inert and optically inactive and concluded that their effect on
radiative transfer will be negligible [Gill et al., 1983]. We ex-
tend the inverted micelle idea by pointing out that the atmo-
sphere will react with the aerosol particle in Figure 3 and
transform it. Atmospheric hydroxyl radicals (and, to a much
lesser extent, Cl atoms) trigger a cascade of organic free radical
reactions on the aerosol which lead to processing of the inert
and hydrophobic organic coating. The chain reactions initiated
by OH radicals will oxidize the marine aerosol particles so that
they become coated with alcohol, aldehyde, ketone, and car-
boxylic acid functional groups. The thermochemistry of OH
reactions with hydrocarbons is exothermic. Because the bond
energy for water is so high, DH 298 (HO™H) 5 119.30 6 0.05
kcal mol21, hydroxyl radical can abstract H atoms from all
hydrocarbons but alkynes (C§C™H) [Berkowitz et al., 1994]. For
11,636 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS

but because DH 298 (HO2™H) is 87.1 6 0.6 kcal mol21, the

hydroperoxyl radical is a poor H atom abstracting reagent
[Clifford et al. 1998; Seinfeld and Pandis, 1998]. The important
reactions of O3 and NO3 with alkenes will have a major effect
on these organic films to the extent that unsaturated double
bonds (™CH¢CH™) exist; although, as seen above, OH reacts at
a considerable fraction of the collision rate at these double
bonds [Atkinson, 1994; Finlayson-Pitts and Pitts, 1997; de Gouw
Figure 4. Atmospheric processing of a 0.2 mm organic ma- and Lovejoy, 1998]. Commonly 50% of the mammalian phos-
rine aerosol.
pholipids contain an unsaturated ester (as shown in Figure 1b),
but the alkenes are generally buried along the alkyl chain. The
fraction of unsaturated phospholipids in phytoplankton is
example, H atom abstraction from the alkyl tail of a carboxylic likely higher than mammalian cells. This is because the fluidity
acid is exothermic by ;20 kcal mol21. of a plasma membrane is controlled by the ratio of saturated
CH3CH2(CH2)nCOOH 1 OH 3 H2O fatty esters to unsaturated esters [Alberts et al., 1989; Ables et al.
1992]. Mammalian membranes function at 378C, but phyto-
1 CH3CH(CH2)nCOOH (1) plankton live in the colder (188C) ocean; consequently, the
phytoplankton lipid bilayers will probably contain a higher
Similarly, it is exothermic by about 60 kcal mol21 for hydroxyl
fraction of alkenes to maintain the membrane fluidity at ocean
radicals to add to double bonds. For a long flexible molecule
temperatures. Note that while the product of ozonolysis of
such as an alkenoic acid, OH probably does not even need a
alkenes will be aldehydes and ketones, the product of reaction
third body to add.
with NO3 will be organic nitrates, mainly produced at night.
CH3CH¢CH(CH2)nCH2COOH Some oxidation of hydrophobic surfactants will occur right
at the ocean’s surface. Solar radiation between 280 and 320 nm
OH is reported to produce OH in the ocean by photolysis of dis-
u solved organic matter [Mopper and Zhou, 1990]. The concen-
1 OH 3 CH3CH™CH(CH2)nCH2COOH (2) tration of hydroxyl radical in the sea was indirectly measured
The kinetics of [OH 1 alkane] reactions has been studied and found to be r(OH) > 8 3 105 cm23 at the ocean’s surface.
and these processes are fast. As a model for hydroxyl 1 alkyl However, any reaction of hydrophobic surfactants with aque-
CH abstraction, CH3(CH2)n COOH 1 OH 3 carboxyalkyl ous OH radicals will steadily convert these hydrophobic hydro-
radical 1 H2O, consider [Atkinson, 1994; DeMore et al., 1997] carbons to water-soluble organics. So oxidation of hydrophobic
the following: hydrocarbons by aqueous OH simply removes them from the
ocean’s surface, and they are not available for incorporation
Reaction k(298 K)/cm3 s21 into the aerosol.
OH 1 CH3CH3 3 CH3CH2 1 H2O 3 3 10213 The alkyl radicals resulting from OH abstractions/addition
OH 1 CH3CH2CH3 3 CH3CHCH3 1 H2O 1 3 10212 at the surface of the aerosol R react rapidly with oxygen to
OH 1 CH3CH2CH2CH2CH3 3 4 3 10212 produce alklyperoxyl radicals; the high-pressure-limiting rate
CH3CH2CH2CHCH3 1 H2O
OH 1 CH3(CH2)5CH¢CH2 3 7 3 10211 constants will be k(R 1 O2) $ 10212 cm3 s21 [Lightfoot et al.,
CH3(CH2)5CH™CH2OH 1992].

We conjecture that tropospheric hydroxyl radicals will oxidize R 1 O2 3 RO2 (3)

the organic layer of marine aerosol particles with a rate con-
The surface-bound alkyl radicals will all react with atmo-
stant, k(OH 1 aerosol) $ 1 3 10212 cm3 s21.
spheric oxygen at an encounter-controlled rate to produce
The steady state rate of impingement of OH radicals onto an
surface-bound peroxyl radicals, aerosol/RO2. These surface-
aerosol surface can be estimated. The relationship between the
bound peroxyl radicals will rapidly be transformed into a vari-
flux of incident molecules striking a surface and the ambient
ety of oxygenated functional groups. As marine aerosol parti-
pressure is given by F/molecules cm22 s21 5 3.52 3 1022
cles rise from the ocean, the organic material is oxidized by
P(torr)(MT)21/2 [Somorjai, 1981]. For OH radicals (M 5 17
atmospheric reactions to produce alcohols (™OH), alkenes
amu) at 300 K, F 5 4.9 3 10 20 P(torr) cm22 s21, and the
(™C¢C™), aldehydes (™CHO), ketones (™CO™), and carboxylic
steady state concentration of hydroxyl radical in the tropo-
acids (™COOH). Consequently, the surface coating of the ma-
sphere is r(OH) > 106 cm23 or 2.8 3 10211 torr [Seinfeld and
rine particle in Figure 3 is “functionalized” and changed, as
Pandis, 1998]. Consequently, the steady state flux is F(OH, 300
suggested by Figure 4.
K) 5 1.4 3 1010 cm22 s21. An aerosol “sphere” that is 0.2 mm
in diameter has a surface area of p D 2 or 1.3 3 1029 cm2, while
the volume is p D 3 /6 or 4.2 3 10215 cm3. Thus the aerosol
particle consists of a core of 1.3 3 108 molecules covered by 4. Discussion and Conclusions
;6.3 3 105 molecules. In a single second a 0.2 mm aerosol is The model organic aerosol proposed and its atmospheric
struck by ;15 hydroxyl radicals, which implies that in 3.5 3 104 processing (see Figure 4) lead to some definite predictions
s (10 hours), every molecule on the aerosol’s surface will suffer concerning its size distribution, aging process, and radiative
a collision with hydroxyl. The rate constants used in this cal- and chemical properties, all of which can be tested by atmo-
culation are approximate and do not justify a more sophisti- spheric measurement.
cated kinetic analysis suggested by Fuchs and Sutugin [1970]. Primary sea-salt aerosols are produced by the mechanical
There is 100 times more HO2 in the troposphere than OH, disruption of the ocean surface. The intermediate size particles
 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS
(0.08 –1 mm diameter) are especially important in influencing
climate since they are involved in radiative transfer, directly by
their ability to absorb and scatter solar radiation and indirectly
by their role in producing condensation nuclei and making
clouds more reflective [Twomey et al., 1984; Charlson et al.,
1992; Novakov and Penner, 1993; Quinn et al., 1996; Rivera-
Caprio et al., 1996; Schwartz, 1996; Tegen et al., 1997; Liao and
Seinfeld, 1998; Pan et al., 1998]. Individual marine particles of
this intermediate size (diameter $ 0.16 mm) have been studied
in situ only recently via particle analysis by PALMS and have
been shown to contain a significant organic component (5–
50% by mass) [Murphy et al., 1997; Middlebrook et al., 1998;
Murphy et al., 1998a, b].
We can make a crude estimate of “organic mass transfer”
from the surface of the ocean into the troposphere for the
marine aerosol pictured in Figure 3. Fatty acids are the main
hydrophobic components of lipid membranes, and those most
commonly found are palmitic acid [CH3(CH2)14COOH] and
stearic acid [CH3(CH2)16COOH]. Consider the case of an
aerosol coated with stearate. If the aerosol particle is 0.2 mm in
diameter, then it has an area of 1.3 3 1029 cm2 and a volume
of about 4.2 3 10215 cm3. Such a particle contains ;1.3 3 108
molecules of water/salt that make up the brine core. Because
stearate [CH3(CH2)16CO2 2 ] has only a single polar end, it can
bind only a single monolayer to the brine core. The areal size
(“footprint”) of a fatty acid molecule bound on a water surface,
the “Pockels limit,” is ;20 6 2 Å2 [Pockels, 1891; Adamson
and Gast, 1997]. The molecular weight of CH3(CH2)16CO2 2 is
283 amu; consequently, the “load” of stearate carried away
from the ocean by a 0.2 mm aerosol particle into the tropo-
sphere will be (1.3 3 1029/[20 Å2])(283/6.02 3 1023) or about
3 3 10216 g. If we assume that most of the “brine core” is
water, then the entire aerosol has an approximate weight of
about 5 3 10215 g. Consequently, the mass ratio of the (or-
ganic layer)/(entire aerosol) of a 0.2 mm marine aerosol par-
ticle is ;5%. This mass ratio of the (organic layer)/(entire
aerosol) will change with the size of the aerosol particle with
diameter D and will vary as D 21 . Organics will be about 50%
of the weight of small particles (0.01 mm diameter), while
larger ones (1 mm diameter) will have only 1% organic mass.
Our estimated mass ratio of the (organic layer)/(entire aero-
sol) for a 0.2 mm aerosol of 5% is roughly that reported by the
PALMS field measurements [Middlebrook et al., 1998]. Figure
5 is a sketch of the fraction of the aerosol’s mass belonging to
the hydrocarbon film. We have plotted the percent carbon
versus the diameter of the aerosol. The solid experimental
circles are from Gill et al. [1983], and the open circle is the
PALMS measurement [Middlebrook et al., 1998].
The ocean surface is covered with a “biological oil slick,”
and water evaporation will be suppressed by the low vapor
pressure organic film [Rideal, 1925; Gershy, 1983]. Conse-
quently, sea-spray-generated aerosols will shrink in size by
continuously ejecting H2O molecules up to the point where a
complete hydrocarbon surface monolayer encapsulates the
aerosol. At this point, water evaporation ceases, and the aero-
sol no longer shrinks in size. For the marine aerosols charac-
terized by PALMS (diameter . 0.16 mm) the measured 10%
organic mass corresponds to a fatty acid surface monolayer
(Figure 5) [Middlebrook et al., 1998]. One prediction of our
model is that marine aerosols will exhibit a multimode size
distribution. The simplest view would be that there will be
small sulfate aerosol particles, which originate by the clustering
of water about a nucleation point, and intermediate to big
11,637
Figure 5. A graph of the variation of the (carbon film)/(total
aerosol) mass ratio as a function of the diameter of a spherical
aerosol [Middlebrook et al., 1998; Gill et al., 1983].
aerosol particles, which are the survivors of the drops that are
formed by mechanical ejection from the ocean’s surface. These
drops shed water molecules until hydrocarbon encapsulation
intervenes. Our model clearly suggests that the organic species
will preferentially reside on the surface of intermediate size
(0.1–1 mm) and large ($1 mm) aerosols.
Processing of the inert, organic surface layer can only be
initiated by reactions with atmospheric OH (and, to a lesser
extent, Cl atoms). Reaction rates at the interface are thought
to be fast but are not known quantitatively. We estimated
earlier that aerosol processing in the atmosphere will take
several hours/days. Convective clouds can transport insoluble
materials from low altitude to the upper troposphere and lower
stratosphere in a few hours during deep convection in the
tropics [Gidel, 1983; Chatfield and Crutzen, 1984; Pickering et
al., 1992; Danielsen, 1993; Kritz et al., 1993]. Our model pre-
diction, superimposed on the timescale for vertical transport in
the tropics, suggests that at least some of this population of
organic aerosols could be transported up into the stratosphere.
We emphasize here that the timescales are approximate, be-
cause of the paucity of quantitative data for the relevant rate
coefficients. However, a very interesting competition is likely
to exist between the chemical processing time and the tropo-
spheric residence time (estimated to be 5–15 days due to rain
scavenging) [Balkanski et al., 1993] of the organic aerosols.
Our model organic aerosol sketched in Figure 3 provides a
possible vehicle for transport into the atmosphere of water-
soluble species trapped in the “brine core” as well as water-
insoluble substances “dissolved” in the encapsulating organic
film. This “bus” would also deliver smaller organics (such as
acetone, OCS, methyl halides, simple alcohols, small alde-
hydes) into the upper troposphere [Singh et al., 1995; Kotch-
enruther et al., 1999]. In particular, the “bus” might provide a
natural means to transport CH3I into the atmosphere from the
ocean, and the PALMS field measurements commonly find
iodide associated with organic fragments [Murphy et al., 1997;
Middlebrook et al., 1998]. Of course, the oxidative destruction
of the hydrophobic film that encapsulates the brine core by
11,638 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS
OH, O2, NO will shred the large alkyl chains and will produce
small carbon fragments which will be ejected into the tropo-
sphere.
Much of the OH, O2, NO surface chemistry can be antici-
pated by analogy to well-known gas phase homogeneous chem-
istry, but there surely are chemical surprises awaiting us [At-
kinson, 1994]. As a possible example, notice that RO2 radicals
readily oxidize NO to NO2 with an exothermicity of 212 kcal
mol21 (250 kJ mol21); the rate constant for peroxyl radical
oxidation of NO is ;8 3 10212 cm3 s21 [Eberhard and Howard,
1997]. For ozone and sulfur dioxide, peroxide oxidation reac-
tions are even more exothermic.
(R4a) CH3O2(2A0) 1 NO 3 CH3O(2E) 1 NO2
D rxnH 298 5 212 kcal mol21
(R4b) CH3O2(2A0) 1 O3(1A1) 3 CH3O(2E) 1 2O2
D rxnH 298 5 232 kcal mol21
(R4c) CH3O2(2A0) 1 SO2 3 CH3O(2E) 1 SO3
D rxnH 298 5 222 kcal mol21
Yet the gas phase (R4b) and (R4c) do not go at room tem-
perature [Tyndall et al., 1998]. However, the kinetics on an
aerosol surface of (R4b) peroxyl radical oxidation of O3 to
generate alkoxy radicals or (R4c) with SO2 to produce organic
sulfates might be another story. We note that current field
measurements of SO2 oxidation to sulfate could not distinguish
between this route and the other oxidation paths in the bulk
liquid phase.
The temperature drop from the tropical ocean surface to the
tropopause (17 km above) is 1158C. Any hydrocarbons that
boil in the range 2858C , T , 308C will form inverted micelles
on any aerosol en route. The vertical transport will probably
occur mainly in the Intertropical Convergence Zone (ITCZ).
The D 21 dependence of the organic content implied by the
inverted micelle model suggests that the aerosols in the upper
tropical troposphere will contain a high fraction of organic
material (Figure 5). This prediction is testable by observation.
Once in the stratosphere, the aerosol particle will warm, and
some of the lighter organics will evaporate. This is another way
that aerosols could act as a “bus” to transport organics to the
stratosphere via the ITCZ. We expect that the inverted micelle
could “protect” the marine core in Figure 3 and allow it to also
reach the stratosphere. The overwhelming balance of evidence
suggests that there is little marine Cl in the middle and upper
stratosphere. Russell et al. [1996] show that nearly all the Cl
and F in the upper stratosphere comes from CFCs. However,
Rosenlof et al. [1997] find that most of the air crossing the inner
tropical tropopause (100 mbar) goes sideways instead of up-
ward: the flux up through 50 mbar is only about 10% of the
mass that goes up through 100 mbar. So, the lowermost strato-
sphere, where the greatest ozone losses are, could be affected
by a flux of “protected” brine. There are very few measure-
ments in the lower stratosphere that could be used in this
context, nevertheless, one example of high chloride (0.4 ppbv
of HCl vapor) is available [Tuck et al., 1995].
The direct and indirect aerosol effect on radiative transfer
can be predicted as a consequence of this chemical model for
aerosol processing. The processed, “aged” aerosol contains
chromophores which will be significantly more absorbing than
their aliphatic precursors. The saturated hydrocarbon coating
of the nascent aerosol has no accessible electronic states (elec-
tronic states of such compounds can only be reached in the
vacuum ultraviolet) [Ellison, 1974; Robin, 1985]. However, the
processed aerosol organic coating of alcohols, aldehydes, and
ketones have near-ultraviolet states, making these compounds
effective atmospheric chromophores. In the near IR, very weak
vibrational C™H overtones (from the organic coating) and
O™H overtones (from the water core) can be excited. The key
proposed intermediates in processing organic aerosols are sur-
face-bound RO2 radicals which have been shown to have al-
lowed electronic transitions in the near IR (7000 –9000 cm21)
[Clifford et al., 1998]. While the cross sections of the surface-
bound species are not known, they are expected, as befitting
allowed electronic states, to be 104 to 106 times larger than that
of vibrational overtones. Scaling for the number of molecules
in the core versus those on the surface and explicitly using the
differences in cross sections, we expect the aerosol with surface
RO2 to be 2– 4 orders of magnitude more absorbent in the near
IR than comparably sized “uncoated” or “unprocessed” ma-
rine aerosols.
Most importantly, processing of organic aerosols provides
“defect sites” on the aerosol surface where nucleation rates
can be efficient [Thomas et al., 1998]. Consequently, processed
aerosols can form condensation nuclei, scatter light more ef-
fectively, and increase the reflectivity of clouds. The size of
these processed organic aerosols will be a function of the
aerosol age. Nucleation in this case occurs entirely indepen-
dently of the sulfate content of the aerosol. The model result in
Figure 5 can be applied to the recent ACE-1 field observations
that pure sulfate particles larger than 0.13 mm at Cape Grim
were extremely scarce and that few pure sulfate particles were
acting as cloud condensation nuclei in that region [Murphy et
al., 1998a]. The model presented here for processing of organic
aerosols provides an alternative path to aerosol nucleation and
formation of cloud condensation nuclei.
We consider some potential objections to our picture in this
paragraph. To the suggestion that gas phase coagulation of
smaller particles could account for the organic content of the
actinically active aerosol sizes, we respond that if it did, our
model would still constitute a viable description. We do not
accept, however, that surfactant molecules could accrete at the
surface of a particle by collisions from the gas phase; the vapor
pressure of such molecules is far too low. For example, the
boiling point of stearic acid [CH3(CH2)16COOH] is listed as
1838–1848C at 1 torr vapor pressure; the boiling point at atmo-
spheric pressure is listed as 3608C, accompanied by decompo-
sition. Because of the low vapor pressure, nor do we consider
oxidation of surfactants in the gas phase by the chemistry we
describe.
There are some obvious questions and complexities associ-
ated with our model. For example, in the real atmosphere the
surface film is likely to be made up of several to many different
molecular species, raising the question of how ordered
(aligned) the individual molecules are. It has long been known
that a single double bond, particularly for the cis isomer, can
affect surfactant layer thickness [Langmuir, 1917]. The degree
of functionalization as radical processing proceeds could also
have major effects in this respect. It has been asserted that
removal of a single molecule could provide a “hole” through
which water could exchange between the core and the atmo-
sphere, to the extent that 90 –99% of the inhibition by the film
could be lost [Barger and Garrett, 1970]. Indeed, in an ordered
spherical film, the “hairy ball theorem” necessitates the exis-
 ELLISON ET AL.: ATMOSPHERIC PROCESSING OF ORGANIC AEROSOLS
tence of a whorl point in mapping rods on a sphere. However,
real atmospheric films are more likely to resemble a bramble
patch than a wheat field, and such “holes” could be rare. It is
natural to ask if such films would exist on terrestrial as well as
marine aerosol. One mechanism which could volatilize the
waxes and lipids from plants would be biomass burning; there
must be a zone of temperatures around flames which will
correspond to their boiling points. Terrestrial plant lipids have
been detected in atmospheric aerosol samples. We believe that
the radical processing of the exterior surfactant film from a
hydrophobic to a hydrophilic state offers a further means by
which atmospheric chemistry can affect the radiative balance.
It can do so directly via the effect of the aerosol on the radi-
ation field and indirectly via the aerosol’s cloud nucleation
properties. Because each hydrogen atom on, say, stearic acid,
CH3(CH2)16COOH, is potentially transformable to an OH
free radical, the effect could be nonlinear. It will certainly be a
function of latitude, since the greatest concentrations of atmo-
spheric OH occur near the surface in the tropics. The process-
ing will be much slower in the southern oceans, for example,
where aerosol-producing high wind speeds are accompanied by
much lower actinic light levels. As air moves up from the
surface toward the tropical tropopause in the ITCZ, cooling
from 308 to 2858C, new aerosol films will form as the air cools
through the range of boiling points of the airborne organic
molecules. Combining this fact with the D21 size dependence,
we predict that aerosols in the upper tropical troposphere will
contain a high fraction of organic molecules. Finally, we note
that the actual effects in the atmosphere, both radiative and
chemical, will depend on the actual fluxes of the organic mol-
ecules, both from the planetary surfaces and to and from the
aerosols as they move upward in the ITCZ. The data do not
currently exist to quantify these fluxes.
We would like to point out that the model presented is
applicable not only to marine boundary layer aerosols but,
more generally, is appropriate for all atmospheric aerosols
containing a significant organic component (especially those
with a polar core). The application of this model hinges on the
availability of atmospheric measurements. Such measurements
have recently been made and have shown organic compounds
to be significant in aerosols in continental sites. As an example,
the nature of the organic coating is important, as shown by the
hygroscopic behavior of organic aerosols [Saxena et al., 1995].
For nonurban locations (Grand Canyon), organic coatings en-
hance water absorption by inorganics; organics account for
25– 40% of the total water uptake (on average). In urban
locations (Los Angeles) the net effect of organics is to diminish
water absorption of the inorganics by 25–35% [Rogge et al.,
1993]. This suggests that some organic layers are hydrophilic
(Grand Canyon) and others are hydrophobic (Los Angeles).
Organic compounds in the atmosphere are generated by the
biosphere and, to some extent, anthropogenically. Charlson
et al. [1987] have presented a case for dimethyl sulfide
(CH3SCH3), which is generated in the ocean to form sulfate
aerosols, and that organic sulfates establish a feedback in the
climate system. The model proposed here gives a mechanism
for organic aerosols to be processed and to affect aerosol
nucleation independently of their sulfur content. The conse-
quence of atmospheric processing of organic aerosols is to
provide a direct and general connection between the biosphere
and the atmosphere and establishes a mechanism by which the
former can affect atmospheric radiative transfer and the
Earth’s climate.
11,639
Acknowledgments. GBE is supported by a grant from the Chemi-
cal Physics Program, U.S. Department of Energy (DE-FG02-
87ER13695). VV would like to acknowledge a CRCW Faculty Fellow-
ship from the University of Colorado and the National Science
Foundation for continued support. We are indebted to our NOAA
colleagues Dan Murphy and Anne Middlebrook for sharing their data
with us and for many fine pointers about their PALMS technique. We
acknowledge many of our colleagues for extensive discussions:
Meredithe L. Applebury (Harvard Medical School), Roberto Bianco
(University of Colorado), Jamie Donaldson (University of Toronto),
Ray Fall (University of Colorado), Greg Frost (NOAA), Vicki Gras-
sian (University of Iowa), Anne Jefferson (NOAA), Bruce E. Koel
(USC), Carl A. Koval (University of Colorado), Ron Naaman (Weiz-
mann Institute), Suzanne E. Paulson (UCLA), Stuart Penkett (Uni-
versity of East Anglia), Yinon Rudich (Weizmann Institute), Sally A.
Sullivan (Greenlee, Winner, & Sullivan, PC), Pieter Tans (NOAA),
and Mark Young (University of Iowa).
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G. B. Ellison and V. Vaida, Department of Chemistry & Biochem-
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A. F. Tuck, Meteorological Chemistry Program, NOAA Aeronomy
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(Received October 7, 1998; revised January 19, 1999;
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11,642