Atmospheric EnvironmentVol. 26A,No. 13, pp. 2269-2282, 1992. 0004-6981/92 $5.00+0.

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Printed in Great Britain. © 1992Pergamon Press Ltd

SECONDARY ORGANIC AEROSOL

FORMATION A N D TRANSPORT

SPYROS N. PANDIS,* ROBERT A. HARLEY,t GLEN R. CASSt and JOHN H. SEINFELD*

*Department of Chemical Engineering and ~'Dcpartment of Environmental Engineering Science,
California Institute of Technology, Pasadena, CA 91125, U.S.A.

(First received 28 October 1991 and in final form 2 March 1992)

AImtmet--A Lagrangian trajectory model simulating the formation, transport and deposition of secondary
organic aerosol is developed and applied to the Los Angeles area, for the air pollution episode of 27-28
August 1987. The predicted secondary organic aerosol on 28 August 1987 represents 15-22% of the
measured particulate organic carbon at inland locations in the base case simulations, and 5-8% of that at
coastal locations. A maximum secondary organic aerosol concentration of 6.8/~gm- 3 is predicted for
Claremont, CA, during this episode. On a daily average basis at Claremont about 46% of this secondary
organic aerosol is predicted to be a result of the oxidation of non-toluene aromatics (xylenes,alkylbenzenes,
etc.), 19% from toluene, 16% from biogenic hydrocarbons (a-pinene, fl-pinene, etc.), 15% from alkanes and
4% from alkenes. The major uncertainties in predicting secondary organic aerosol concentrations are the
reactive organic gas emissions, the aerosol yields and the partitioning of the condensable gases between the
two phases. Doubling the reactive organic gas (ROG) emissions results in an increase of the secondary
organic aerosol predicted at Claremont by a factor of 2.3. Predicted secondary organic aerosol levelsare less
sensitive to changes in secondary organic aerosol deposition and NOx emissions than to ROG emissions.

Key word index: Secondary organic aerosol, reactive organic gases, gas-to-particle conversion, SCAQS,
photochemical modeling.

INTUODUCTiON An alternative approach is the theoretical estima-

Atmospheric particulate carbon consists of both ele-
mental (EC) and organic carbon (OC). EC has a
chemical structure similar to impure graphite and is
emitted directly by sources. Organic carbon can either
be emitted directly by sources (primary OC) or can be
the result of the condensation of low vapor pressure
products of the gas-phase reactions of hydrocarbons
onto the existing aerosol (secondary OC). Organic
carbon aerosol accounted for roughly 65% of the fine
particulate carbonaceous aerosol on an annual aver-
age basis for 1982 in the Los Angeles area (Gray et al.,
1986). In the Los Angeles area, fine (dp < 2 #m) partic-
ulate carbon accounts for 40% of the fine particulate
mass concentration on an annual average basis (Gray
et al., 1986), and 33% of the fine aerosol mass during
summer midday periods (Larson and Cass, 1989).
The contributions of the primary and the secondary
components of aerosol OC have been difficult to
quantify. The lack of a direct chemical analysis
method for the identification of either of these OC
components has led researchers to the employment of
several indirect methods. These methods include the
use of tracer compounds for either the primary or
the secondary OC (Larson et al., 1989; Turpin
and Huntzicker, 1991; Turpin et al., 1991) and the use
of models describing the emission and dispersion
of primary OC (Gray, 1986; Larson et al., 1989;
Hildemann, 1990).
tion of the secondary organic aerosol (SOA) concen-
tration based on first principles: emissions of the
precursors, atmospheric dispersion, photochemical
reaction, production and dispersion of the SOA. Such
an approach has the advantage of identifying and
connecting the gas-phase precursors to the SOA, so
that the effects of a hydrocarbon control strategy can
be directly evaluated. Pilinis and Seinfeld (1988) fol-
lowed such an approach by accounting for the aerosol
products of a few hydrocarbons, namely diolefins,
cyclic olefins, toluene and xylenes.
In this study a comprehensive model able to simu-
late the production, dispersion and deposition of SOA
is developed. The model predictions are compared
against measurements of aerosol OC in the South
Coast Air Basin of California in an effort to estimate
the contribution of SOA to the aerosol OC in that
region and to identify the main precursors.
FORMATIONOF SECONDARYORGANICAEROSOL
Secondary organic aerosols are formed in the atmo-
sphere by the condensation of low vapor pressure
products of the oxidation of organic gases. A hypo-
thetical reaction mechanism for a generic hydro-
carbon HCA is presented in Fig. 1. As the hydrocarbon
is oxidized by species such as the hydroxyl radical

2269
 2270 S.N. PANDIS et al.

co (tot)
bB/fF

o. CC\ Aerosol

HC / O: ~ olD YAG
"rim
NO$ ~ eE ~ , ~ ...

Fig. 1. Schematic of a general mechanism for atmospheric oxidation of a

generic hydrocarbon. Also shown schematicallyis the equilibrium distribu-
tion of some of the reaction products between the gas and aerosol phases.

(OH), ozone and the nitrate radical (NO3), the pro- condensed to
ducts of these reactions accumulate in the gas phase.
H C A + OH--*aIB + a2C + . . . + y^G,
Each species is characterized by a temperature-de-
pendent saturation concentration that represents the where G is a condensable gas that forms secondary
maximum capacity of the air for this species. If the organic aerosol and YAis the corresponding stoichio-
concentration of the species is less than this saturation metric coefficient relative to one molecule of HCx. The
concentration, the species will remain in the gas phase. calculation of an aerosol yield from experimental data
If its concentration exceeds this saturation concentra- is now discussed.
tion the species condenses on available aerosol surface
such that at equilibrium its gas-phase concentration
equals the saturation concentration (Fig. 1). If the AEROSOLYIELDS
concentration of a product, say G, in the gas phase is
reduced to less than the saturation concentration, So, Let us assume that in a closed system, the hydro-
as a result of dilution, deposition or chemical reaction, carbon HCA is oxidized by OH. Assuming that YA
the aerosol phase G will evaporate in an effort to remains constant with time during the experiment,
maintain thermodynamic equilibrium (Fig. 1). then the total concentration of G, CG(tot), is equal to
The above secondary organic aerosol production the sum of the concentrations of G in the gas, Co(g)
picture neglects certain gas-to-particle conversion and in the aerosol phase, CG(aer):
phenomena. A gas-phase species can be adsorbed on
available aerosol particles even if its concentration is Co(tot) = Co(g) + Co(aer) = yAACHcA, (1)
less than its saturation concentration (Pankow, 1987). where AC.cA is the change in the concentration of the
Such an adsorption process has been found to be hydrocarbon that has reacted. The concentration of
significant for polycyclic aromatic hydrocarbons the secondary organic aerosol Co(aer) can be calcu-
(Ligocki and Pankow, 1989) but the extent of this lated by:
process for the major secondary organic aerosol
CG(aer) = max (0, Co(tot)- So), (2)
species is unknown. If the secondary organic species
interact (e.g. forming solutions) with species that where So is the saturation concentration of the
already exist in the aerosol phase, these species can be condensable gas.
partially removed from the gas phase even if their The direct measurement of the stoichiometric coeffi-
concentrations do not exceed the corresponding cient YA is difficult in typical smog chamber ex-
saturation concentration values. These processes have periments because one can easily measure the aerosol-
been neglected in the current model, but further phase concentration Co(aer) but often not the gas-
analysis of their importance is required. phase concentration Co(gas). The quantity that is
While measured or estimated final aerosol yields readily available is the aerosol yield for hydrocarbon
from the oxidation of various hydrocarbons have been HCA, YA:
studied, the exact chemical pathways leading to the
Co(aer)
formation of the condensable organic species, includ-
YA =ACnc------
~- (3)
ing the stoichiometry and rate constants (Fig. 1), often
are not known. Therefore, at this time the description The aerosol yield, Y^, iscalculated afterall,or at least
of the chemical processes leading to the production of most, of the hydrocarbon HCA has reacted. Com-
the condensable organic species must follow the style bining formulas (I),(2) and (3) one gets:
of the condensed mechanisms currently in use in
urban and regional air pollution models. For example, So
the reaction scheme depicted in Fig. 1 would be YA=y^-AC.c------ ~. (4)
 Secondary organic aerosol 2271

The saturation concentration of secondary organic
aerosol species is usually less than 1 ppb (Grosjean
and Seinfeld, 1989) and in most smog chamber ex-
periments the aerosol yield is calculated after more
than 500 ppb of hydrocarbon have reacted. Consider-
ing the uncertainty of the experimental measurements
of the aerosol concentrations one can safely assume
that
YA~ YA
and use directly the experimentally calculated aerosol
yields, YA, instead of the condensable gas stoichio-
metric coefficients required by the model.
The aerosol yields used in this study are presented
in Table 1. Values are based on smog chamber ex-
periments where available and also on estimates by
Grosjean and Seinfeld (1989) that were made using
structure-reactivity relationships. Model predictions
of secondary organic aerosol will respond linearly to
changes in aerosol yield, provided that saturation
concentrations for the condensable species have
already been exceeded.
THE SECONDARYORGANICAEROSOLMODEL
The secondary organic aerosol model simulates
atmospheric chemistry, equilibrium partitioning of the
(5) condensable gases between the gas and aerosol phases,
turbulent vertical diffusion, horizontal advective
transport and ground-level pollutant deposition. It is
based on the numerical solution of the Lagrangian
trajectory form of the atmospheric diffusion equation
presented by Russell et al. (1983) and McRae et al.
(1982). Except for the changes mentioned below the
methods employed here are as described by Russell et
al. (1983). The trajectory model was configured with
five vertical cells; the height of each individual com-
putational cell was 120 m.

Table 1. Measured and estimated aerosol yields (Y~)

Aerosol
Model yield
Species species* (~g m - 3 ppm - 1) Comments Reference

Alkanes
Propane AAR 1 0 estimated Grosjean and Seinfeld (1989)
n-Butane AAR 1 0 estimated Grosjean and Seinfeld (1989)
Isobutane AAR 1 0 estimated Grosjean and Seinfeld (1989)
n-Pentane AAR2 0 estimated Grosjean and Seinfeld (1989)
Cyclopentane AAR2 0 estimated Grosjean and Seinfeid (1989)
Pentane isomers AAR2 0 estimated Grosjean and Seinfeld (1989)
n-Hexane AAR2 0 estimated Grosjean and Seinfeld (1989)
Methylcyclopentane AAR3 17 estimated Grosjean and Seinfeld (1989)
Cyciohexane AAR3 17 estimated Grosjean and Seinfeld (1989)
Hexane isomers AAR2 0 estimated Grosjean and Seinfeld (1989)
n-Heptane AAR3 7 estimated Grosjean and Seinfeld (1989)
Methylcyclohexane AAR3 120 estimated Grosjean and Seinfeld (1989)
C7-Cycloparaffins AAR3 120 estimated Grosjean and Seinfeld (1989)
Heptane isomers AAR3 0 estimated Grosjean and Seinfeid (1989)
n-Octane AAR3 98 estimated Grosjean and Seinfeld (1989)
Ethyicyclohexane AAR4 275 estimated Grosjean and Seinfeld (1989)
C8-Cycloparaflins AAR4 275 estimated Grosjean and Seinfeld (1989)
Octane isomers AAR3 98 estimated Grosjean and Seinfeid (1989)
n-Nonane AAR3 236 estimated Grosjean and Seinfeld (1989)
C9-Cycioparaflins AAR4 466 estimated Grosjean and Seinfeld (1989)
Nonane isomers AAR3 236 estimated Grosjean and Seinfeld (1989)
n-Decane AAR4 348 estimated Grosjean and Seinfeld (1989)
C10-Cycloparaffins AAR4 687 estimated Grosjean and Seinfeld (1989)
Decane isomers AAR4 348 estimated Grosjean and Seinfeld (1989)
n-Undecane AAR4 479 estimated Grosjean and Seinfeld (1989)
C1 l-Cycloparaflins AAR4 945 estimated Grosjean and Seinfeld (1989)
Undecane isomers AAR4 479 estimated Grosjean and Seinfeld (1989)
n-Dodecane AAR4 626 estimated Grosjean and Seinfeld (1989)
C12-Cycloparattins AAR4 1100 estimated Grosjean and Seinfeld (1989)
Dodecane isomers AAR4 626 estimated Grosjean and Seinfeld (1989)
n-Tridecane AAR4 865 estimated Grosjean and Seinfeid (1989)
C 13-Cycloparattins AAR4 1265 estimated Grosjean and Seinfeld (1989)
Tridecane isomers AAR4 865 estimated Grosjean and Seinfeld (1989)
n-Tetradecane AAR4 972 estimated Grosjean and Seinfeld (1989)
C 14-Cycloparaffins AAR4 1443 estimated Grosjean and Seinfeld (1989)
Tetradecane isomers AAR4 972 estimated Grosjean and Seinfeld (1989)
n-Pentadecane AAR4 1300 estimated Grosjean and Seinfeld (1989)
C15-Cycioparaffins AAR4 1717 estimated Grosjean and Seinfeld (1989)
Pentadecane isomers AAR4 1300 estimated Grosjean and Seinfeld (1989)
2272 S.N. PANDISet al.

Table 1. (Contd.)

Aerosol
Model yield
Species species* ~g m- 3 ppm- 1) Comments Reference
Alkenes
Ethene ETHE 0 estimated Grosjean and Seinfeld(1989)
Propene OLE1 0 estimated Grosjean and Seinfeld(1989)
1-Butene OLE1 0 estimated Grosjean and Seinfeld(1989)
1-Butene isomers OLE2 0 estimated Grosjean and Seinfeld(1989)
2-Butene OLE2 0 estimated Grosjean and Seinfeld(1989)
2-Butene isomers OLE2 0 estimated Grosjean and Seinfeld(1989)
1,3-Butadiene OLE3 0 estimated Grosjean and Seinfeid(1989)
1-Pentene OLE1 0 estimated Grosjean and Seinfeld(1989)
l-Pentene isomers OLE1 0 estimated Grosjean and Seinfeld(1989)
2-Pentene isomers OLE3 0 estimated Grosjean and Seinfeld(1989)
Cyclopentene OLE3 132 measured Izumi and Fukuyama (1989)
1-Hexene OLEI 0 estimated Grosjean and Seinfeld(1989)
1-Hexene isomers OLE1 0 estimated Grosjean and Seinfeid(1989)
2-Hexene isomers OLE3 0 estimated Grosjean and Seinfeld(1989)
Cyclohexene OLE3 278 measured Izumi and Fukuyama (1989)
1-Heptene isomers C7OL 78 measured Grosjean (1984)
2-Heptene isomers C7OL 78 estimated Grosjean and Seinfeld(1989)
1-Octene isomers C8OL 227 measured Wang et al. (1992)
2-Octene isomers C8OL 227 estimated
1-Nonene isomers C9OL 304 estimated Grosjean and Seinfeld(1989)
2-Nonene isomers C9OL 304 estimated Grosjean and Seinfeld(1989)
Decene isomers OLE3 470 estimated Grosjean and Seinfeld(1989)
Undecene isomers OLE3 743 estimated Grosjean and Seinfeld(1989)
Dodecene isomers OLE3 878 estimated Grosjean and Seinfeld(1989)
Tridecene isomers OLE3 1024 estimated Grosjean and Seinfeld(1989)
Tetradecene isomers OLE3 1180 estimated Grosjean and Seinfeld(1989)
Pentadecene isomers OLE3 1350 estimated Grosjean and Seinfeld(1989)
Bioalkenes
Isoprene ISOP 0 measured Pandis et al. (1991)
• -Pinene APIN 762 measured Shaw et al. (1991)
p-Pinene BPIN 720 measured Pandis et al. (1991)
Monoterpenes APIN 762 estimated

Aromatics
Benzene C6H6 0 measured Izumi and Fukuyama (1990)
Toluene TOLU 424 measured Izumi and Fukuyama (1990)
Ethylbenzene AAR5 440 measured Izumi and Fukuyama (1990)
Isopropylbenzene AAR5 334 measured Izumi and Fukuyama (1990)
n-Propylbenzene AAR5 138 measured Izumi and Fukuyarna (1990)
Isobutylbenzene AAR5 334 estimated Grosjean and Seinfeld(1989)
m-Xylene AAR6 419 measured Izumi and Fukuyama (1990)
o-Xylene AAR6 428 measured Izumi and Fukuyama (1990)
p-Xylene AAR6 180 measured Izumi and Fukuyama (1990)
1,3,5-Trimethylbenzene AAR7 5?7 measured Izumi and Fukuyama (1990)
1,2,3-Trimethylbenzene AAR6 496 measured Izumi and Fukuyama (1990)
1,2,4-Trimethylbenzene AAR6 251 measured Izumi and Fukuyama (1990)
Naphthalene AAR6 400 estimated
2,3-Dimethylnaphthalene AAR7 600 estimated
Methylnaphthalenes AAR7 500 estimated
Tetralin AAR7 400 estimated

Other
Methyl ethyl ketone MEK 0 estimated Grosjean and Seinfeld(1989)
Alkyl phenols CRES 221 estimated Grosjean and Seinfeld(1989)
Glyoxal GLY 0 estimated Grosjean and Seinfeld(1989)
Methyl glyoxal MGLY 0 estimated Grosjean and Seinfeld(1989)
Higher aldehydes RCHO 0 estimated Grosjean and Seinfeld(1989)
Acetone ACET 0 estimated Grosjean and Seinfeld(1989)
Higher PAN analogues PPN 0 estimated Grosjean and Seinfeld(1989)
Aromatic aldehydes BALD 5 estimated Grosjean and Seinfeld(1989)
Peroxy benzoyl nitrate PBZN 5 estimated Grosje,an and 8¢infeld(1989)
Phenols PHEN 192 estimated Grosjean and Seinfeld(1989)
Nitrophenols NPHE 285 estimated Grosjean and Seinfeld(1989)
* Each individual organic chemical species is assigned to a lumped model species.
 Secondary organic aerosol 2273

The photochemical trajectory model cited above
was modified to track the condensable oxidation
products of reactive organic gases. The detailed
SAPRC gas-phase chemical reaction mechanism
(Carter, 1990) has been incorporated into the model
and extended to include production of condensable
organic gases (Table 1) using the photochemical mech-
anism preparation and emissions processing software
of Carter (1988). The mechanism uses four classes of
lumped alkanes (AAR1 to AAR4 in order of increasing
reactivity), three classes of lumped aromatics (AAR5
to AAR7 in order of increasing reactivity), and three
classes of lumped olefins (OLE1 to OLE3 in order of
increasing reactivity). Some species that Carter (1990)
originally included in lumped classes are now carried
as individual species. They include the alcohols (new
lumped species), ~t-pinene, fl-pinene, isoprene, toluene,
acetylene, heptene, octene and nonene. A condensable
product species and a corresponding aerosol yield
coefficient was added to each reaction involving an
organic gas precursor, as shown in Table 2. The final
mechanism contains a total of 195 reactions and 100
chemical species. In the eases where no information is
available on the chemical nature of the reaction
products, they are represented by generic lumped
species. For example, the unknown condensable
products of the higher alkanes (lumped species AAR4
in the mechanism) are represented by the generic
species AEA4. The concentrations of these species are
computed by the model and when they exceed the
saturation threshold, the excess is transferred to the
aerosol phase. If the gas-phase concentration of these
condensable products becomes less than the satura-
tion level, the corresponding organic species is as-
sumed to evaporate, in an effort to maintain the
equilibrium between the two phases. A summary
listing of the lumped and explicit organic species, their
basin-wide emission rates in the Los Angeles area, and

Table 2. Summary of emissions and aerosol yields for model species

Basin-wide Aerosol
Gas-phase Chemical emissions* Aerosol yield
species description (kmol d - 1) species ~g m- 3/ppm)

AAR1 lumped alkane 4392 AEA1 0

AAR2 lumped alkanet 3395 AEA2 3.8
AAR3 lumped alkane 1965 AEA3 80
AAR4 lumped alkane 727 AEA4 335
AAR5 lumped aromatic 213 AEA5 426
AAR6 lumped aromatic 876 AEA6 398
AAR7 lumped aromatic 252 AEA7 562
OLE1 lumped alkene:~ 1223 AEO1 9.2
OLE2 lumped alkene:~§ 104 AEO2 0
OLE3 lumped alkene~: 508 AEO3 19
ROH1 lumped alcohol 1673
ETHE ethene 3295 -- --
APIN ~t-pinene:l: II 229 AEAP 762
BPIN fl-pinene:~ 38 AEBP 720
C7OL heptene, 36 AEC7 78
C8OL octene, 34 AEC8 227
C9OL nonene:l: 9 AEC9 304
C6H6 benzene 332 --
C2H2 acetylene 1531 -- --
ISOP isoprene 579 -- --
TOLU toluene 1633 AETL 424
HCHO formaldehyde 634 -- --
CCHO acetaldehyde 208 -- --
RCHO lumped aldehyde 44 -- --
ACET acetone 357 -- --
MEK lumped ketone 338 -- --
BALD benzaldehyde 8 AEBA 5
PBZN peroxybenzoyl
nitrate 0 AEPB 5
PHEN phenol 0 AEPH 192
CRES cresol 0 AECR 221
NPHE nitrophenol 0 AENP 285

* Includes portions of South Central and Southeast Desert Air Basins of

addition to the South Coast Air Basin.
t Aerosol yield results from oxidation of esters assigned to this lumped species.
Value for yield is highly uncertain.
~:Same aerosol yield used for reactions with O, OH, NO3 and 0 3.
§Isobutene is the only assigned species; it has zero aerosol yield.
I[Includes other terpenes such as limonene and carene.

AE(A) 26:13-B
2274 S .N . PANDIS et al,
their aerosol yields is presented in Table 2. In this
study whenever a unit conversion is required, and no
other data are available, we assume a density of the
secondary organic aerosol equal to 1.2 g cm- 3 and an
organic aerosol carbon mass content equal to 0.7
(Pandis et al., 1991).
Knowledge of the saturation vapor concentrations
of the organic condensable species is incomplete.
These vapor pressures are expected to vary signific-
antly with temperature. The few available relevant
measurements of species identified as constituents of
SOA include the temperature-dependent saturation
vapor concentrations of monocarboxylic and dicar-
boxylic acids (Tao and McMurry, 1989) and of the//-
pinene condensable products at 31°C (Pandis et al.,
1991). The saturation vapor concentrations of
condensable products from the oxidation of aromatic
hydrocarbons (in particular toluene, m-xylene and
1,3,5-trimethylbenzene) were estimated to lie in the
range 3-30 ppt (Seinfeld et al., 1987). McMurry and
Grosjean (1985) estimated saturation vapor concen-
trations for condensable products from the oxidation
of 1-heptene (0.14-1.28 ppb), o-cresol (0.06-1.6 ppb)
and nitrocresol (1.7-2.2 ppb). Ideally, individual satu-
ration vapor concentrations would be specified for
each condensable species. In this study, a saturation
vapor concentration of 2 ppt has been adopted for
each condensable product species and for all temper-
atures. This value is at the low end of the range of
estimates cited above, and is sufficiently small that
virtually all of the condensable product mass will end
up in the aerosol phase. Therefore, the base case
simulation represents an upper limit estimate on the
formation of SOA from the condensable products.
The sensitivity of the model to the choice of saturation
concentration will be discussed later.
The secondary organic aerosol size distribution is
not calculated by the current model. Dry deposition of
particles is parameterized following McRae et al.
(1982) and assigning a deposition affinity of 0.1, indic-
ating that the dry deposition flux of organic aerosol is
one-tenth of the mass transport-limited value of gas-
eous pollutants. This choice results in deposition
velocities consistent with those for particles of the size
range (less than 2 #m) in which most of the organic
carbon is found. The sensitivity of the model to this
choice of dry deposition velocity also will be
examined.
MODEL APPLICATION TO THE LOS ANGELES AREA
In the summer and fall of 1987, a comprehensive air
pollution data set was collected in the Los Angeles
area, during the Southern California Air Quality
Study (SCAQS; Hering and Blumenthal, 1989;
Lawson, 1990). Our analysis will focus on one of the
summertime intensive monitoring periods, beginning
on Thursday 27 August 1987. An in situ carbon
analyser measured particulate OC and EC with a 2-h
time resolution for this period at Claremont (Turpin
and Huntzicker, 1991). The above authors used the
correlation between the diurnal profiles of OC and EC
and estimated the diurnal variation of secondary
organic aerosol during this period at Claremont.
Therefore, our analysis will focus initially on measure-
ments and model predictions at the Claremont
sampling site.
The meteorological input data needed for these
calculations were assembled and processed as de-
scribed by Harley et al. (1992). In brief, the objective
analysis techniques of Goodin et al. (1979) were ap-
plied to produce gridded hourly temperature, humid-
ity, mixing depth, surface wind, total solar and ultra-
violet radiation scaling fields. The mixing depths were
determined from potential temperature analysis of
SCAQS upper air soundings; other input data were
assembled directly from ground-based measurements.
Day-specific emission inventories for the South
Coast Air Basin on 27 and 28 August 1987 were
received from the California Air Resources Board
(Wagner and Allen, 1990). The emission inventory was
processed to compute total hourly pollutant emissions
in each cell of a regular 5 x 5 km grid system. A
biogenic emissions inventory matching the isoprene
emissions estimates of Winer et al. (1983) has been
included. The organic gas emissions were broken
down into over 400 individual chemical species using
speciation profiles supplied by Wagner and Allen
(1990). Then the individual species were combined into
the lumped species required by the chemical mech-
anism using the emissions processing software of
Carter (1988). Direct primary emissions of particulate
OC were not tracked in the present model application.
Air parcel trajectory paths were computed by
specifying the trajectory endpoint and time of arrival,
and then integrating backward in time using the
gridded hourly wind fields. The wind fields were
prepared using the method of Goodlin et al. (1979) and
the available SCAQS wind data (Crees, 1990). The air
parcels were tracked over a period of up to 2 days,
which meant that all of the air parcels arriving at
inland receptors originated over the ocean. One of the
24 hourly surface air parcel trajectories arriving at
Claremont is depicted in Fig. 2. The open circles along
the trajectory path indicate the air parcel location at
each hour. Initial species concentrations were es-
timated using air quality measurements made at San
Nicolas Island (Chan and Durkee, 1989; Main et al.,
1990). The initial secondary organic aerosol concen-
trations in all the air parcels are assumed to be zero, as
the air parcels start over the ocean far from the coast.
The model sensitivity to this assumption will be
assessed. Once the trajectory paths were computed,
the meteorological conditions and pollutant emission
rates along the path of each air parcel were extracted
from the corresponding gridded hourly meteorologi-
cal and emission fields.
The predicted ground-level secondary organic
aerosol concentrations along three air parcel trajec-
 Secondary organic aerosol 2275

tories art shown in Fig. 3. In all thrt¢ air parcels there pollutant emissions, it collects hydrocarbons that are
is a period of rapid production of secondary organic rapidly photo-oxidized; in a period of 6 h its predicted
aerosol during a period of strong photochemical secondary organic aerosol content has increased by a
activity and high concentrations of the organic aerosol factor of three. The parcel spends the rtmaining hours
precursors. The air parcel arriving at Clartmont moving slowly near Claremont and accumulating
at 0600 PST on 28 August crossed the southern hydrocarbons, but the slow production of SOA is
California coast at 1300 PST on 27 August. Its balanced by the deposition losses and the SOA con-
predicted secondary organic aerosol content at the tent of the air parcel remains almost constant until its
coastline is only 0.5 #gm -a because of the relatively arrival at Claremont. The air parcel arriving at Clare-
low hydrocarbon concentration in the parcel at that mont at 1400 PST on 28 August does not reach the
time. As the parcel passes over regions with high coast until 1600 PST on 27 August with a predicted

' ' ' ' ' • ' ' • t' ' ' ' ' , i, , , , , 1 , , , , w , , ,

3820

380O
;-" Burbank i
3780
g , ~ .... ~ • Azusa i
= e-.,,= ~ ...,"" Central LA • .~jl'Claremont
.. ........
3760 ~,~.,.,#,.i ~ I-~w~horne
wthorne ~ . . . . . .~ • Rubidoux
.- .
w .I "~. t'"

3740 ~Anahoim ",.! ,

3720 PACIFIC OCEAN ~ i,~'

w.,. P "k..~.,
3700
. s a n. i ~.s l_s ~ n d . . . , , , , , , , , . . . . , , , .-. .
~6
. . . . . .

200 240 280 320 360 400 440 480

UTM Easting (kin)

I
I • SCAQS intensive monitoring site . . . . . . County boundary I
o Trajectory of air parcel ardving at 1400 PST
I
Fig. 2. Trajectory of the air parcel arriving at Claremont, CA, on 28 August 1987 at 1400 PST.

6
--- ooa~o 600 PST
? ooooo 1400 PST
t= 5' m-,-,,m 2 2 0 0 PST

0 2-

0 4 8 12 16 20 24 28 32 36 40 44
Time (PST)
Fig. 3. Variation of the predicted secondary organic aerosol concentration along the
trajectories ofth© air parcels arriving at ~ o n t , CA, on 28 August 1987at 0600, 1400
and 2200 PST.
2276 S.N. PANDISet al.

SOA concentration of 0.6/~g m-3. Even though the
gas-phase concentrations of the hydrocarbons in-
crease considerably during the following 16 h, the lack
of photochemical activity at night leads to a small
predicted increase in the SOA content of the parcel to
0.8/~gm -3 by 0600 PST on 28 August. As the sun
rises, there is a burst of photochemical activity and the
SOA increases rapidly to 4.9 #gin -3 before the air
parcel finally arrives at Claremont. The air parcel
arriving at 2200 PST on 28 August at Claremont
spends 27 August over the ocean and does not reach
the shore until 1100 PST on 28 August. From this
point it moves rapidly collecting emissions and the
SOA concentration increases to a maximum of
3.7/~gm -3. The air parcel fails to attain a higher SOA
concentration due to the limited time that it spends
over the hydrocarbon sources as it moves rapidly
across the basin. During the last 2 h of its trip to
Claremont, its SOA concentration is predicted to
decrease due to depositional losses.
The predicted SOA concentrations of the 24 air
parcels upon arrival at Claremont on 28 August 1987
are shown in Fig. 4. Note that SOA mass concentra-
tion has been converted to SOA carbon concentration
by assuming a carbon content of 0.7. Also shown are
the secondary organic aerosol carbon estimates of
Turpin and Huntzicker (1991). The agreement be-
tween the two predictions is reasonable, except during
the period between 1400 and 1800 h PST where the
estimates of Turpin and Huntzicker (1991) are larger
than the values predicted by the SOA model by almost
a factor of two. Note that there are significant un-
certainties in the determination of the secondary
fraction of ambient OC, as indicated in Fig. 4. Reasons
for the differences between model predictions and
observations will be suggested later.
Comparing the model predictions o f secondary
organic aerosol carbon for 28 August with the fine OC
measured by Turpin and Huntzicker (1991), one calcu-
lates that secondary organic aerosol varies from hour
to hour between 10 and 40% of the total particulate
organic aerosol. Up until 0700 PST, the secondary
organic carbon represents about 10% of the measured
OC. Then this contribution increases to around 40%
at 2000 PST and remains at this level until the end of
the day. On average, for 28 August at Claremont, the
predicted secondary organic carbon represents 18%
of the total measured organic carbon; the remaining
82% of the organic carbon can be attributed to direct
emissions.
The model predicts that for Claremont on 28
August, on a daily average basis, 46% of the secondary
organic aerosol originates from the photo-oxidation
of aromatics other than toluene, 19% from toluene,
16% from biogenic hydrocarbons, 15% from alkanes
and 4% from the photo-oxidation of olefins. The
predicted diurnal variations of the above percentage
contributions are depicted in Fig. 5 and are relatively
small. The model predictions are in general agreement
with the estimates of Grosjean and Seinfeld (1989) for
the Los Angeles area: they estimated 58% for aro-
matics, 21% for alkanes, 11% for olefins and 10% for
biogenics.
The contributions of the main individual precursors
to the predicted secondary organic aerosol at
Claremont at 1600 PST are presented in Table 3.
Toluene, the nonmethane hydrocarbon with the. high-
est emission rate in the Los Angeles area (165 t d- 1 for

Claremont, 28 August 1987

18
C o o = o o Predicted ( b a s e case) .
r.j
14 = " = = = Turpln and Huntzlcker (.1991)
t~ o o o o o Predicted (no deposFtion) .
..... Predicted (ROG emission x 2)

L 10-

~ 8-
"~ . A
A A
~ 8- A A
A O A A A
O
[] O
A A O

°°t
A
-

I A r~
O O
o 2- O 0 0 0
[] 121 [] D []

0
0 12 1~ ' 2'0 ' 24
Time (PST)

Fig. 4. Secondaryorganicaerosol carbon concentrationat Claremont,CA, on 28 August

1987: base case model predictions; estimates of Turpin and Huntzicker(1991);sensitivity
test neglecting secondary organic aerosol deposition; and sensitivity test using incteused
ROG emissions to twice the base case values.
 Secondary organic aerosol 2277

Table 3. Predicted per cent contribution to Isomer allocation for this entry would decrease the
base case secondary organic aerosol (SOA) uncertainty of the present model because the different
concentrations due to individual aerosol pre- isomers have different aerosol yields. In this study we
cursors at Claremont, CA, at 1600 PST (peak
SOA) have assumed, following Carter (1988), that this mix-
ture has the aerosol yield of m-xylene. ~-Pinene is used
Contribution as a surrogate species for all the monoterpenes (e.g.
Species (%) limonene, carene, etc.) with the exception of//-pinene
Toluene 27.6 which is represented as an individual species. The next
Xylene isomers 9.8 most significant contributor to SOA formation on the
• -Pinene 7.6 list, "pentadecane" (SAROAD 43260, emission rate
Pentadecane 6.9 16 t d - 1), is a surrogate species created by the emission
Cresols 6.4
inventory's originators to represent a range of hydro-
Decane isomers 4.3
o-Xylene 4.2 carbons with 10-20 carbon atoms that are emitted in
Nitrophenols 3.6 diesel engine exhaust. Its possible importance as a
Trimethylbenzenes 2.9 secondary organic aerosol precursor suggests a need
1,3,5-Tdmethylbenzene 2.2 to elucidate both the emission rates of the individual
Nonane isomers 2.2
Octane isomers 2.1 high molecular weight hydrocarbons and the corres-
Ethylbenzene 2.0 ponding aerosol yields. The aerosol yield used in this
1,2,4-Trimethylbenzene 1.4 study for "pentadecane" (Table 1) is estimated based
Undecane isomers 1.3 on the work of Grosjean and Seinfeld (1989). The
m-Ethyltoluene 1.3 "decane isomers" that are the sixth most important
/~-Pinene 1.3
C10-Aromatics 1.2 secondary aerosol precursor according to the present
CS-Cycloparatfans 1.0 results also lack detailed chemical speciation--instead
C9-Cycloparaffins 0.9 many different isomers of decane have been grouped
m-Xylene 0.9 together. Alkylbenzenes are predicted to act as the
1,2,3-Trimethylbenzene 0.7
C10-Cycloparafl~ns 0.5 precursors for more than 10% of the SOA, with the
m-Diethylbenzene 0.4 trimethylbenzenes being the most important group.
Undecene isomers 0.4 Some of the precursors that have been extensively
o-Ethyltoluene 0.4 studied in the past, like cyclopentene and cyclohexene,
Methylcyclohexane 0.4
o-Dietbylbenzene 0.4 are found to be minor contributors to the SOA. This is
p-Xylene 0.3 mainly a result of their small estimated emission rates,
C7-Cycloparaflins 0.3 0.9 t d - 1 for cyclohexene and 0.8 t d - 1 for cyclopen-
Octene isomers 0.3 tene. Grosjean and Seinfeld (1989) have argued using
Undecane 0.3 ambient concentration measurements that another
Ethyltoluene isomers 0.3
Nonage 0.3 2 t d - 1 of cycloalkenes are emitted, but even after this
Butylbenzene 0.3 correction the contribution of cycloalkenes to the
Cyclohexene 0.2 SOA would remain around 1%. Another 30 species,
Decene isomers 0.2 not included in Table 3, together contribute the re-
Nonene isomers 0.2
Cyclohexane 0.2
maining 3% of the SOA for the air parcel arriving at
Claremont at 1600 PST.
Others 2.8 The model has been applied to seven other SCAQS
intensive monitoring sites (Anaheim, Azusa, Burbank,
central Los Angeles, Hawthorne, Long Beach City
College (LBCC) and Rubidoux) in order to form a
28 August 1987), is predicted to contribute 28% of the more complete picture of the formation and transport
secondary organic aerosol at Claremont at 1600 PST. of secondary organic aerosol in the Los Angeles area.
The emissions inventory indicates that about half of Aerosol samples were collected at all of the SCAQS
the toluene emitted comes from the exhaust and hot intensive monitoring sites (Chan and Durkee, 1989)
soak evaporative emissions of gasoline-powered ve- using specially designed sampling equipment (Fitz et
hicles; most of the remaining toluene emissions are al., 1989). A set of aerosol samples was collected on
attributed to surface coating activities. The com- quartz fiber filters over 4-h sampling intervals, using a
parison of the importance of the various precursors is size-selective inlet to collect only particles smaller than
made more difficult by the fact that several entries in 10 #m in diameter (PM 10). The samples were analysed
the emission inventory represent groups of individual using the technique described by Fung (1990) to
species. The xylenes present an example of the need for determine total particulate OC concentrations, but
further specification within the emission inventory. secondary OC determinations like those of Turpin
While xylene emissions from some sources are broken and Huntzicker (1991) are not available for this set of
down into o-, m- and p-xylene, in other cases the samples.
speciation profiles state only that unspecified isomers The data of Turpin and Huntzicker (1991) show
of xylene are emitted (SAROAD 45102, 40td-~). that under conditions of high photochemical activity,
2278 S. ]q. PANDI$et al.

0.6
ooooo Alkanes
°0~ aaaoa Aromatics
0 LUUIA~ Oleflns
~ 0.5 u n n n n Blogonics
ee Toluene

"L~ 0 . 4

"2 0.3
0

ca
L.

~o.2
0

~0.1
ej

0.0
1 5 9 13 17 21
Time (PST)

Fig. 5. Predicted diurnal variation of the fractional contribution of precursors (alkanes,

aromatics, olefins,biogenics and toluene) to the secondary organic aerosol concentration at
Claremont, CA, on 28 August 1987.

Table 4. Sensitivityanalysis of secondary organic aerosol predictions in the South Coast Air
Basin

Arrival
time SOA Per cent of
Case Location (PST) (~gm -3) measured OC

Base case Claremont 24-h average 3.3 18

Zero aerosol deposition Claremont 24-h average 4.5 25
ROG emissions x 2 Claremont 24-h average 7.6 42
NOx emissions x 0.5 Claremont 24-h average 4.2 23
NO~ emissions x 2 Claremont 24-h average 2.1 12
Saturation cone. 10 ppt Claremont 24-h average 2.8 15
Saturation cone. 100 ppt Claremont 24-h average 0.5 3
Plus initial SOA Claremont 24-h average 4.6 25
Base case Anaheim 1330 1.4 7
Plus initial SOA Anaheim 1330 3.2 16
Base case Azusa 1430 5.9 15
Plus initial SOA Azusa 1430 7.4 18
Base case Burbank 1230 6.7 22
Plus initial SOA Burbank 1230 8.2 27
Base case central LA 1530 1.2 7
Plus initial SOA central LA 1530 2.8 15
Base case Hawthorne 1130 0.7 5
Plus initial SOA Hawthorne 1130 2.7 19
Base case Long Beach 1230 1.4 8
Plus initial SOA Long Beach 1230 3.3 18
Base case Rubidoux 1530 5.7 16
Plus initial SOA Rubidoux 1530 7.3 21

the peak secondary OC and peak total OC concentra-
tions often occur at the same time. Therefore, the
model was used to simulate the SOA production in an
air parcel arriving at each receptor site at a time when
the observed OC concentration was high. The
predicted SOA concentrations listed in Table 4 are
instantaneous values that apply at the air parcel
arrival time specified for each receptor site, except for
Claremont where model results have been averaged
over a set of 24 individual air parcel trajectories. The
results in Table 4 indicate that there are differences in
SOA concentrations between coastal locations and
sites further inland. The model predicts that for loc-
ations near the coast (Hawthorne) the secondary
organic aerosol concentrations will be low, around
0.7/~gm -3. As the air parcels move further inland
(Anaheim, central LA, Long Beach) they collect or-
ganic gases but there is not much t/me for these gases
to react; the average predicted secondary organic
aerosol level is 1.3/~g m - 3. The model predicts that for
 Secondary organic aerosol 2279

28 August 1987 the highest secondary organic aerosol
concentrations existed at the inland locations of
Azusa, Burbank, Claremont and Rubidoux, with an
average value of 6.3 pg m-3.
The peak predicted secondary organic aerosol con-
centration for the inland locations is on average a
factor of 9.0 higher than the predicted SOA for a
coastal site (Hawthorne). The measured aerosol OC
for the inland locations was a factor of two higher than
close to the coast. Therefore, the peak percentage
contribution of the secondary organic aerosol to the
aerosol OC levels for the inland locations is predicted
to be a factor of 4.5 higher than for the coastal
locations. The effect of the initial conditions on these
predictions will be discussed subsequently.
The relative contributions of the various precursors
to the organic aerosol levels at the other inland
locations are quite similar to those already presented
for Claremont.
MODEL SENSITIVITYANALYSIS
Aerosol deposition
The sensitivity of the model to the choice of de-
position velocity for the particles was examined by
setting the SOA deposition velocity equal to zero and
recalculating the SOA for the 24 Claremont trajector-
ies. These results represent an upper limit of the
secondary organic aerosol as related to the dry depos-
ition process and are shown in Fig. 4. Neglecting
aerosol deposition leads to a 50% increase of the
predicted SOA in the evening and a 20% increase
during the daytime. The average increase of the pre-
dicted SOA over all 24 trajectories is 36% when the
depositional losses are neglected. The SOA represents
25% of the OC on a daily average basis as compared
to 18% in the case where dry deposition is included.
Organic gas emissions
The mobile source ROG emission inventory on
which this study is based is likely to be under-
estimated, but the extent of that underestimation is
not clear at present (Pierson et al., 1990). The biogenic
ROG emission inventory is also uncertain. If all ROG
emissions into the model are increased by a factor of
two, then the average daily secondary organic aerosol
concentration increases from 3.3 to 7.6 #g m-a, that is
by a factor of 2.3 (Fig. 4). This larger than unity
sensitivity can be understood by examining the predic-
tions of the model for ozone (Fig. 6). The ROG
emissions increase results in increased predicted ozone
and OH radical concentrations. This increase in oxi-
dant concentrations leads to increased consumption
rates for the organic aerosol precursors in addition to
the higher precursor concentration and consequent
higher organic aerosol production. When the ROG
emissions are doubled, the SOA represents 30% of the
OC during the morning hours of the episode at
Claremont and this percentage increases to 70% at the
end of the day. On a daily average basis for this
sensitivity run the secondary organic aerosol repres-
ents 42% of the measured organic carbon.
NOx emissions
The emissions of the oxides of nitrogen directly
affect the concentrations of oxidants like O a and OH
and therefore influence indirectly the concentration of
secondary organic aerosol. Halving the emission rates
of NOx resulted in an increase of the maximum

4°° i = = = : = Predicted (base case)

=•me= Measured
350 t o~3-D~ Predicted (ROG emissions x 2)

300 -J

Z 250 - ~". " "'B" -"~

',,.
•¢ 200- ?." _.
o / t~.
o 150-

100 -

"
•

,: / Y
...t~. : . y
•
"~
A ,..,
~,,,
:.
#...~'"'~a

• y" • °m

o 4 a 1'2 18 io 24
Time (PST)

Fig. 6. Ozone concentration at Claremont, CA, on 28 August 1987: base case model
predictions; observed values; and sensitivity test using increased ROG emissions to twice the
base ease values.
2280 S.N. PANDISet al.
predicted O3 concentration at Claremont from 140 to
190 ppb and the maximum hydroxyl radical concen-
tration from 0.16 to 0.24 ppt. These increased oxidant
levels result in further conversion of the aerosol pre-
cursors to secondary organic aerosol and in a 27%
increase of the average secondary organic aerosol
concentration.
In another sensitivity test, the NO~ emissions
throughout the basin were doubled. This increase
resulted in a dramatic decrease of the 03 levels at
Claremont, with the maximum predicted value being
reduced from 140 to 28 ppb. These reduced levels of
oxidants resulted in a decrease of the secondary
organic aerosol levels at Claremont by an average of
36% throughout the day. While the model predicts
decreased SOA formation with increased NOx emis-
sions, this decrease may be offset by increased second-
ary aerosol nitrate formation.
Saturation concentrations
The saturation concentration value of 2 ppt that has
been arbitrarily chosen for the base case is such that
practically all the condensable gases produced during
the oxidation of the reactive organic gases are trans-
ferred to the aerosol phase as secondary organic
aerosol. The choice of such a low value also allows us
to obtain an upper limit estimate of the secondary
organic aerosol concentration.
If a saturation vapor concentration of 10 ppt is used
for each condensable species, the predicted daily aver-
age secondary organic aerosol concentration at
Claremont is reduced from 3.3 to 2.8 #gm -3 (i.e. by
15%), while the maximum predicted value is reduced
by 9%. Use of a saturation vapor concentration of 100
ppt for each condensable species results in a reduction
of the predicted SOA average value by 85% and of the
maximum value by 64%.
Initial conditions
In the previous simulations we have assumed that
initially there is zero secondary organic aerosol in the
air parcel even if reactive organic gases are present.
Measurements at San Nicolas Island, 130 km west-
southwest of Long Beach, on 27 August 1987 indi-
cated aerosol organic carbon concentrations that
range from 1.1 to 2.4 #gCm -3 with a daily average of
1.5 #gC m - 3, or equivalently 2.1/~g m - 3 assuming 0.7
grams of carbon per gram aerosol. San Nicolas Island
is located near the starting point of the air parcels that
reach Claremont on 28 August. The nature of this
measured organic carbon (primary versus secondary
and its sources) is not known. In order to test the
sensitivity of the model predictions to the zero initial
conditions used, we have assumed that all of this
aerosol carbon was secondary, assigned it to a dummy
aerosol species in the model and repeated the 24
trajectory runs.
A significant part of this initial SOA is predicted to
be deposited to the Earth's surface during transport of
the air parcel to Claremont, resulting in a final average
SOA concentration increase of 1.3/~gm -3. If the
increased initial conditions are included, the second-
ary organic carbon represents 25% of the measured
organic carbon on a daily basis at Claremont.
The sensitivity of the model results to the initial
conditions for the other locations is shown in Table 4.
The first row for each location contains the model
predictions with zero initial SOA and the second row
shows model predictions using the observed OC at
San Nicolas as the initial SOA concentration. As
expected, the predictions for the coastal sites are more
sensitive to the initial conditions, the most dramatic
being the increase of the Hawthorne SOA concentra-
tion to 3.9 times the value obtained assuming zero
initial SOA. The concentrations at mid-basin sites
such as central Los Angeles increase to 2.3 times the
values obtained in the zero initial condition case, while
for the far inland locations the increase is around 25%.
DISCUSSION
Successful prediction of the secondary organic
aerosol concentration requires knowledge of (a) the
gas-phase chemistry leading to the production of
condensable gases and the associated aerosol yield, (b)
the emission rates of the reactive organic gas pre-
cursors, and (c) the processes affecting the distribution
of the condensable gases between the gas and aerosol
phases. In the present paper, a mathematical model
has been presented that represents these processes at
the level allowed by currently available data and that
focuses attention on those parts of the problem that
are most sensitive to current uncertainties.
For the Los Angeles area the main SOA precursor is
predicted to be toluene. Even though aerosol produc-
tion during toluene photo-oxidation has been studied
extensively (Gery et al., 1985, Leone et al., 1985;
Warren, 1986; Stern 1988; Izumi and Fukuyama,
1990), several questions remain. The aerosol yields
that have been reported vary by more than an order of
magnitude. For example, Stern (1988) measured yields
varying from 12 to 490/an 3 crn- 3 ppm- 1 depending on
the ROG/NOx ratio. Izumi and Fukuyama (1990)
have proposed that NOx influences the aerosol yield in
a complicated manner and have suggested further
study of this effect, Further understanding of the
pathways leading to the production of condensable
gases during the oxidation of toluene is required. The
above comments also apply to aromatics such as the
xylenes (responsible for about 15% of the SOA), to the
various trimethylbenzenes (responsible for about 7%
of the SOA), and to the monoterpenes (responsible for
9% of the SOA). A class of precursors for which
practically no information exists are the higher
alkanes which are predicted to contribute more than
15% of the SOA.
Significant uncertainties continue to exist in the
emission rates of the above secondary organic aerosol
precursors and predictions of SOA levels are very
 Secondary organic aerosol
sensitive to these emissions. As more accurate estim-
ates of the emission rates are sought, attention should
be paid to replacement of generic compound classes
(e.g. isomers of xylene) and surrogate compounds (e.g.
pentadecane as a stand-in for many high molecular
weight hydrocarbons) with the actual species emitted.
The consequences of our incomplete physical un-
derstanding of the partitioning of the condensable
gases between the gas and aerosol phases have been
explored quantitatively during the present study. If
saturation concentrations lie in the range of a few
parts per trillion as assumed in this study, then the
predictions of SOA levels are relatively insensitive to
the exact value. If, on the other hand, these saturation
values are around 0.1 ppb, then the model predictions
are extremely sensitive to them.
All the above uncertainties make it difficult to assess
the SOA contribution to total OC levels. Further-
more, since the direct emissions of OC are not in-
eluded in the model, it has not been determined
whether the model predicts total organic carbon levels
accurately. Our base case simulation suggested that
on a daily average, 18% of the organic aerosol at
Claremont existed as SOA for 28 August 1987.
Elimination of aerosol deposition from the base case
changes this value to 25%, a doubling of ROG
emissions changes the SOA fraction to 42%, increase
in the initial conditions to 25%, and increase in the
saturation concentration to 15%.
Gray et al. (1986) estimated 1982 annual average
secondary organic aerosol carbon at inland sites like
Azusa and Rubidoux to be between 27 and 38% of the
fine organic aerosol based on changes in elemental
carbon to total aerosol carbon ratios. Larson et al.
(1989) calculated 1984 summer midday average sec-
ondary organic aerosol concentrations of 1.6/~g m - 3
for the coastal site of Lennox and 5.1 #gm -3 for
Pasadena; values that agree with the findings of this
study. Hildemann (1990) found ambient concentra-
tions of polar organic aerosol in excess of direct
emissions of such compounds, and thereby estimated
1982 annual average secondary organic aerosol levels
in the range 9-26% of all fine organic aerosol. The
modeling study of Pilinis and Seinfeld (1988) also
suggested that the secondary organic aerosol repres-
ents less than half of the total organic carbon for the
episode beginning on 30 August 1982. In spite of the
uncertainties present, the results of the current study
are in good agreement with other recent efforts to
quantify the secondary contribution to the organic
aerosol in southern California.
CONCLUSIONS
A Lagrangian trajectory model has been developed
to simulate the formation, transport and deposition of
secondary organic aerosol. The model describes
directly the formation of condensable vapors from the
oxidation of specified reactive organic precursors and
2281
assumes that thermodynamic equilibrium governs the
distribution of each condensable vapor between the
gas and aerosol phase. The model has been applied to
the Los Angeles area, for a summertime SCAQS
episode (27-28 August 1987).
The model predicts that for Claremont, CA, during
28 August 1987, the secondary organic aerosol rep-
resented 18% of the observed aerosol organic carbon
on average. The maximum predicted secondary or-
ganic aerosol concentration was 6.8/~g m-3. Approx-
imately 46% of the SOA was predicted to result from
the oxidation of aromatics (alkylbenzenes excluding
benzdne and toluene; e.g. xylene, trimethylbenzene,
ethyltoluene), 19% from toluene, 16% from biogenic
hydrocarbons (~-pinene, ~-pinene, etc.), 15% from
alkanes and 4% from olefins. The concentrations of
secondary organic aerosol on 28 August 1987 are
predicted to increase with increasing distance from the
coast and reach their maximum values at inland sites
like Burbank, Claremont, Azusa and Rubidoux.
The major model uncertainties concern the reactive
organic gas emissions, the aerosol yields and the
partitioning of the condensable gases between the two
phases. The predicted SOA depends linearly on the
aerosol yields. The model is less sensitive to changes in
secondary organic aerosol deposition and NOx emis-
sions. The predictions for the coastal sites are sensitive
to the initial SOA value present over the ocean while
the results at locations far inland are relatively in-
sensitive to the choice of initial conditions. Accounting
for uncertainties in the initial conditions, the model
suggests that the secondary organic aerosol for 28
August 1987 represented 15-27% of the measured OC
at the inland locations, and 5-19% of the measured
OC at coastal locations. It is likely that the official
emission inventory for organic gases in the Los
Angeles area is understated (Pierson et al., 1990).
Doubling all of the organic gas emissions results in an
average increase of the SOA for Claremont by a factor
of 2.3, and also brings the ozone predictions of the
model into closer agreement with observed ozone
levels on that day.
Acknowledoement--This work was supported by the Electric
Power Research Institute, agreement RP3189-3.
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