REVIEWS OF GEOPHYSICS AND SPACE PHYSICS, VOL. 19, NO.

4, PAGES 505-539, NOVEMBER 1981

ChemistryWithin AqueousAtmosphericAerosolsand Raindrops

T. E. GRAEDEL

Bell Laboratories,Murray Hill, New Jersey07974

C. J. WESCHLER

Bell Laboratories,Holmdel, New Jersey07733

Hundreds of chemical compoundshave been identified as constituentsof atmosphericaerosolsand

raindrops, and there is substantialevidencefor chemical transformationsoccurring among them. Since
troposphericaerosolshave a water contentof 30--50wt % at typical relativehumidities,aerosolsand rain-
dropsmay be regarded(at leastto a firstapproximation)
as aqueoussolutions.
In this review,atmo-
sphericmeasurementsand solution chemistrydata are combined to examine reactionsand physical pa-
rametersof potential importancein aerosoland raindrop systems;much of the information is potentially
applicableas well to lake and oceansurfacewaters.Among the conclusionsare the following: (1) Solar
radiation penetratesaqueous aerosolsand raindrops, photodissociatingseveral molecules and ions.
H202, formedin the gasphaseand dissolved
in the aerosol,photodissociates
to produceOH', whichis
thusa commonconstituentof aqueousatmosphericsystemsand appearsto play a role in many chemical
processes.
(2) The decomposition of atmospheric ozonedissolvedin aqueousaerosolsor raindropsis a
secondprolificsourceof HOx ß radicals.(3) An analysis
of thetransitionmetalchemistry
appropriateto
thesesystemsindicatesthat copper,manganese,and vanadiumare potentiallythe mostimportant ho-
mogeneouscatalystsand that the concentrationsof transitionmetals in aerosolsare significant.(4) The
oxidationsof alkanesto alcohols,of alcoholsto aldehydes,and of aldehydesto carboxylicacids result
from chemicalchainsinitiated by hydroxyl radicalsor perhapsby organicphotochemistry.(5) Rate pa-
rametersare availablefor many of the reactionsof interest,particularly for the inorganicprocesses.
Tab-
ulationsof relevantrateparameters,
absorption
coefficients,
equilibriumconstants,
andaqueoussolubi-
lities are presented.(6) The troposphericaerosolcan be viewed schematicallyas an aqueoussolution
surrounding
aninsoluble
coreandcovered
by anorganic
surface
filmof varyingintegrity,
thickness,
and
composition.

CONTENTS A. INTRODUCTION

Introduction ......................................................................................... 505 There is little doubt that a rich chemistry occurswithin the
Physicalpropertiesof aerosolsand raindrops................................... 506 liquid phase of atmospheric aerosol particles. Among the
The aqueousaerosol........................................................................ 506 well-documented chemical transitions are the conversion of
Size distributions.............................................................................
506
Lifetimes ............................................................................................ 506 SO,_to sulfate [e.g., Beilke and Gravenhorst,1978], the con-
Solar radiation ................................................................................. 507 versionof NO,_to nitrate[e.g.,Grosjean
et al., 1976],and the
Acidity ..............................................................................................
507 oxidation of hydrocarbons[e.g., Committeeon Medical and
Inorganicaerosoland raindrop chemistry......................................... 508 BiologicEffectsof EnvironmentalPollutants,1977].Often these
Introduction ..................................................................................... 508
chemical processesresult in productsless deskable than the
Oxygen-hydrogenchemistry........................................................... 508
Inorganiccarbonchemistry............................................................ 510 precursorsfrom which they originate. For example, the for-
Nitrogen chemistry..........................................................................511 mation of the strong inorganic acids HNO3 and HaSOn is a
Sulfur chemistry...............................................................................
513 key step in the 'acid rain' process[Likens, 1976].
Halogenchemistry........................................................................... 515 Although many of the processesand products of the gas
Transition metal chemistry............................................................. 516
Organicaerosoland raindrop chemistry............................................ 520
phasechemistryof the earth'satmosphereare now reasonably
Introduction ..................................................................................... 520 well understood, the same cannot be said of the chemical
Alkanes ............................................................................................. 520 processesinvolving atmosphericaerosols.In part, this is be-
Alkenes ............................................................................................. 520 causemany aspectsof aerosolchemistryare much more diffi-
Terpenes......................................................................................;.... 521
Aromatics ......................................................................................... 521
cult to treat analytically than is the casefor atmosphericgas
Alcohols ............................................................................................ 522 phaseprocesses. Aerosolphysicsmustbe considered, sincethe
Carbonyls.........................................................................................
522 condensation,coagulation,and depositionof particlesresult
Carboxylic acids...............................................................................523 in a continually changing environment within which the
Organicbases...................................................................................523 chemicalprocesses occur.Transport propertiesenter both into
Other organiccompounds............................................................... 523 the advection and diffusion of aerosols and into the diffusion
Organicradicals...............................................................................
523
Summary ..........................................................................................
524 of gasesbetweenthe atmosphere
andthe aerosol.Many of the
Thermodynamic andkineticpro.cesses 524 physical processeshave received extensive study, however,
..............................................
Transportbetweengaseousand liquid phases..............................524 and their inclusionin suchan assessment can be accomplished
Scavengingof aerosolsby raindrops.............................................. 525 with reasonableeffort. The chemicalprocesses have received
Aqueoussolubilities........................................................................ 525
Ionization constants ......................................................................... 526 somewhatlessattention, and it is their aspectsthat we exam-
Photochemical data ........................................................................ : 527 ine in detail in this work.
Reaction rate parameter data..........................................................529 A unifying conceptfor the understandingof aerosolchem-
Discussion ............................................................................................ 530
istry is the presenceof an aqueouslayer aroundsolid aerosol
Copyright¸ 1981by the American GeophysicalUnion. particles, at least at low altitudes in regions of moderate or
Paper number 1R1068. 505
0034-6853/81/001 R- 1068506.00
506 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

high humidity. This property,discussed below in more detail, I ! 111111 I I I I I IIII1 I

permitsthe chemistryto be treatedwith the methodsand data

of aqueoussolutions.In addition,it allowsthe assessment
aerosolchemistryto apply to chemistrywithin raindrops,a
of 801 P
R- RICHMOND
SF-SAN FRANCISCO AIRPORT
F- FRESNO
HL- HUNTER-LIGGETT
H F- HARBOR FREEWAY
systemalso of substantialinterest.For simplicity,the term P- POMONA
6O G- GOLDSTONE
'aerosolchemistry'will be used throughoutthis review to in- HF
-- CLEAN CONTINENTAL
clude chemical processeswithin both aqueousaerosolsand BACKGROUND
raindrops. The distinctionsbetween the two systemsare not
central to much of the discussion;most are related to differ-
encesin size, concentration,composition,and lifetime. F

B. PHYSICAL PROPERTIES OF AEROSOLS

AND RAINDROPS <1 3o

1. TheAqueousAerosol
It was discoveredmany years ago that at least a moderate 2O

proportion of atmosphericparticlesare hygroscopic[Tworney,

1953, 1954]. Extensiveexperimentsthen showedthat the size
distributionsof atmospheric particlesare a functionof relative
humidity [e.g., M•szdros, 1971; Winkler, 1973]. More recent
direct examinationsof individual particlesby electronmicros- o
.o• 0.1 1 .o lo 50
copy [Husar et al., 1976]and of an assemblageof particlesby
microwave spectroscopy[Ho et al., 1974] have demonstrated Dp (,u.m}
unambiguouslythat typical atmosphericaerosolsconsistof Fig. 1. In situ atmosphericaerosolsize distributionsfrom mea-
liquid shellssurroundingan electron-opaquenucleus.These surementsat varioussitesin California. The continentalbackground
shells are a natural result of the chemical propertiesof the data are from Fort Collins, Colorado. (Figure is from Whitby [1980].
Reprinted by permissionof the New York Academy of Sciences.
aerosols,sinceboth the common inorganic saltsfound in nat-
ural aerosolsand the combustionfly ash found in urban aero-
solsare hygroscopic[Hiinel and Zankl, 1979;Rothenbergand
Cheng, 1980]. The aerosolwater content at humidities above imated by an exponential distribution of the form [Marshall
40% is estimatedto be at least30% of the total particle weigh•: and Palmer, 1948]
[Whitby et al., 1972; Friedlander, 1973;Ho et al., 1974], with
N(D) -- Noe-x(R)ø (1)
the remainder of the mass including both water-soluble and
water-insolublematerial [Winkler,.1973].The situationis sig- where N(D) is the number of drops per millimeter diameter
nificantly different in dry air: microwave spectroscopicobser- interval per cubic meter of air, X is a parameter which de-
vations in the desert air of Goldstone, California, showed es- pendson the rainfall rate R, and No is a proportionalityfactor.
sentiallyno detectablewater on the surfacesof aerosols[Ho et The exponential expressionmay not be accurate for small
al., 1974]. raindrop sizes,at leastfor sometypesof precipitation[Mark-
owitz, 1976].Both No and X vary with differenttypesof rain as
2. Size Distributions
well as at different times within a singlerain event [e.g., Wald-
There is considerable evidence that atmospheric aerosol vogel 1974]. These features are demonstrated by the in-
size distributions consistbasically of three separate modes: tegrated and average drop spectradata of Simpson[1967]
nucleimode(d < 0.1 •m), accumulationmode(0.1 •m < d < shown in Figure 2 and the time-resolved data of Atlas and
2.0 •m), and coarsemode (d > 2 •m). Much of the evidence Plank [1953] shown in Figure 3.
for this viewpoint comesfrom the work of Whitby and his col- It is of interest to contrast the surface areas and volumes of
leagues [see Whitby, 1978, 1980], but the general pattern is atmosphericaerosolsand raindrops.Aerosol volume densities
confirmed by other workers as well [e.g., Heintzenberg,1975]. rangefromabout(7-90) x 10-•2 cm3aerosolvolumeper cubic
Figure 1 showstypical distributionsthat demonstratethe div- centimeterof air [Whitby, 1980],which for typical size distri-
ersity that is presentin the atmosphere. butionsimpliessurfacearea densitiesof about (0.2-2) x 10-6
The three modes of the aerosol have different sources. The cm2 aerosolsurfaceper cubic centimeterof air. In contrast,
nuclei mode is primarily a result of particlesnucleatedfrom raindropvolumedensitiesare of the order of (1-10) x 10-6
combustion gases,and concentrationsare highest near com- cm3 rain volumeper cubiccentimeterof air. Because of their
bustion sources[e.g., Willeke et al., 1974; Whitby et al., 1975]. much larger volume to surface ratios, however, the corre-
Nuclei producedfrom decayingleaf litter are also within this spondingsurfacearea densitiesare of the order of (1-10) x
sizerange [Schnelland Vali, 1973].The accumulationmode is 10-6 cm2 rain surfaceper cubic centimeterof air. Thus the
largely produced by coagulation involving the nuclei mode raindrop surfacearea will dominate only for high-intensity
[e.g., Gartrell and Friedlander,1975]and by condensation.The rainfalls.
coarsemodeis principallythe resultof mechanicalgeneration
3. Lifetimes
of particlesby suchprocesses as wind erosion[e.g., Gillette et
al., 1972, 1978; Schfitz and Jaenicke, 1974; Patterson and Gil- The mechanismsof aerosolparticleremovalvary markedly
lette, 1977]. Transition of particlesbetweenthe accumulation with particle size; lifetimes are hence quite size-dependent.
mode and the coarsemode is uncommon[Whitby, 1980]. The smallestparticles,thoselessthan 0.1 gm in diameter,are
The sizedistributionsof raindropscan generallybe approx- removedrapidly by coagulationprocesses. The largestparti-
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 507

•oo

80• t023
80
4O
2O

60

40
_ / .
20
1'1//[ i:Li-
THUNDER
SHOWERS - sEA-CON, NUOUS
4O

z 80

0
/• •.•'/ k-
z
60
0 1 2 3 4 5 6 7 8 9
RAINDROP DIAMETER (mm)
..1111111111111111111111L._
Fig. 2a
½:t
•- 60
- 40
lOO
• 20

>' 80-
z
80 1030.8
/ TEMPERATE 60
40
o 60- TROPICAL
----
0 0.4 0.8 t.2 1.6 2.0 2.4
> 40-
mm

Fig. 3. Evolution of raindrop s•e spectra dur•g passageof a

• 20-
D shower,shown by •stograms of percentliquid water content by drop
size.The samplingt•e (EST, November 16, 1951,Wate•own, Mas-
o 3 4 5 6 7 8 sachusetts)is given• the upperfight comerof eachdisplay.The con-
RAINDROP DIAMETER (ram) tinuous cuffes are co•espond•g Marshall-Pa•er distributionsfor
ra• •tensity equal to that obseffed (Figure is from 4tlas and Plank
Fig. 2b [1953]. Reprinted by pe•ission of the •edc• MeteorologicalSo-
ciety.)
Fig. 2. (a) Cumulativefrequencyof occurrenceof raindropsfor
three types of rainfalls. (b) Cumulative frequencyof occurrenceof
raindropsof temperateand tropical regions[after Simpson,1967].
and scatteringof the radiation within both pure water and
natural waters of various origins are sufficientlysmall [Smith
and Tyler, 1976;Zepp and Cline, 1977]that they may be dis-
cles,thosegreater than 10/an in diameter, are removed rap- regardedfor aqueousparticlesof dimensionssmaller than a
idly by rainout and sedimentation.Particlesin the range 0.1- few microns. (Detailed attenuation tables are presentedby
10/•m in diameter have longer residencetimes, since diffu- Smith and Tyler [1976].)
sionaldepositionand sedimentationare not efficientprocesses It is therefore clear that the radiation spectrumwithin the
for particlesof this size [e.g., Hidy, 1973]. aqueousaerosolis essentiallyidenticalwith that in clear air,
Mean lifetimes as a function of diameter for aerosolparti- with flux densitiesreduced by aerosol surface scatteringto
cles have been estimatedby Jaenicke [1980] and are repro- perhaps85%of clear air values.Consequently,a vigorousand
duced here as Table 1. By estimating appropriate meteor- complex photochemicalsystemis to be expectedwithin the
ological dispersionfactors, average horizontal and vertical aerosolparticles.
travel distancesare also derived. Data to be presentedwill
show that the rates of chemical processesare such that they 5. Acidity
proceedto completionduring the lifetime of aerosols,except Acidity is not a useful conceptin the bulk solid phase.The
possiblyfor the very largestand very smallestparticlesand for acidity of aerosols,which are customarily analyzed in the
the very slowestchemical reactions. solidphase,has thereforenot been determinedas such.In the
The lifetimes of raindropsare, of course,relatively shorter, atmosphere,however, the amount of water vapor uptake on
typicalfall speedsbeing-120 cm s-• for a raindropof diame- the aerosolparticlesand the acidity of the resultingsolution
ter 0.3 mm and -800 ½ms-• for oneof diameter3 mm [Dingle will be influenced by the electrolyte propertiesof the solid
and Lee, 1972]. The fall time through a mixed boundary layer phase constituents[Hiinel and Zankl, 1979; Winkler, 1980].
of 2 km is thus -5-30 min. The acidity of the aerosolcan thus be inferred from its chem-
ical makeup and from the amount of water vapor incorpo-
4. Solar Radiation
rated under the temperatureand relative humidity conditions
Within the solution phase of the aqueous aerosol, signifi- that obtain. An additional factor affecting the acidity is that
cant fluxes of solar radiation are expectedto be present. Re- once a significantwater coatingis presenton the particles,the
flection at the droplet surfacewill not reducethe internal flux aqueouslayer will begin to absorbatmosphericCO2 to pro-
levels to lessthan 80-90% of clear air values [Galbally, 1972; duce a weak carbonicacid solution.At equilibrium, and with
Zafiriou, 1977]exceptthat for aqueousaerosolparticleswhose no other ions present,this solutionwill havepH - 5.6 [Reuss,
dimensionsare of the sameorder as the wavelengthof the in- 1977].
cident radiation, the absorptionfunction is complicated and In remoteland areas,primary aerosols(i.e., thoseproduced
wavelength-dependent[cf. Born and Wolf, 1964]. Absorption by injectioninto the air rather than by nucleationor accretion
508 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 1. AverageLifetimesand Travel Distancesof Atmospheric C. INORGANIC AEROSOL AND RAINDROP CHEMISTRY
Aerosol Particles
1. Introduction
Travel Distances, km

Radius,/an •-,days Horizontal Vertical Studiesof chemicalreactionsoccurringin aqueousaerosols

0.001 0.01 8 20
or raindropshavebeenentirelyconfinedto thoseof inorganic
0.01 I 800 2,000 species.The earliestwork of this kind wasthat of Jungeand
0.1 10 8,000 20,000 Ryan [1958], who investigatedthe productionof sulfate from
I 10 8,000 20,000 SO: in an atmospherealso containingNH3. The calculations
10 I 800 2,000 were extendedby Scottand Hobbs [1967.'with the addition of
100 0.01 8 20
carbon dioxide equilibrium equations.This chemicalap-
Table adaptedfrom Jaenicke[1980]. proach has been utilized in several related studiesover the
years[e.g.,Miller and dePena,1971;ddamowicz,1979];recent
additions include limited treatments of the effects of NO,
NO:, and NaC1 [Orel and $einfeld, 1977;Petersonand $ein-
feld, 1979], O3 and H20: [Larson and Harrison, 1977; Mid-
of gas phasemolecules)consistchiefly of clay minerals pro-
dletonet al., 1978;Petersonand $einfeld, 1980],and metal
ducedby wind-driven fragmentationand erosion[Schnelland
catalysis[Overtonet al., 1979].
Vali, 1973; Gillette and Walker, 1977]. Soil particles range
In the sections
below,the inorganicaerosolchemistryof ni-
from slightly alkaline to moderately acidic (•9.0 >_pH >_
trogen,sulfur,carbon,the halogens,oxygen,and hydrogenis
•4.5); mostare neutral or weakly acid [Bush-Brown and Bush-
reviewed, since it can be demonstrated that ions and radicals
Brown, 1965],althoughbasicpH's are encounteredin arid re-
derived from theseelementsare commonlypresentin atmo-
gions[Penkettet al., 1979c].Urban primary aerosolsappear to
sphericsystems.Catalyticprocesses
involvingmetalsare defi-
be largely soot emissions[Rosenet al., 1980], some of which
nitely of significance;
they are discussed
in the final part of
are acidic. During their atmospheric lifetimes the particle
thissection(sectionC7). Gigu•re[1979]hasrecentlyreempha-
acidity is altered by the incorporationof gasphasemolecules.
sizedthat the proton in aqueoussolutionis properlywritten
Except for the weakly basic ammonia molecule,thesemole-
H30 +, a notation which will be utilized herein. In addition,
culesare either neutral (e.g., the nonoxygenatedorganics)or
chemicalreactionsare assumedto take placein aqueoussolu-
acidic (e.g., the inorganic and organic acidsand their deriva-
tion unlessotherwiseindicated.In this review, gas phase
tives). Sulfates have been detected chemically on individual
moleculesare alwaysindicatedby the subscriptg; aqueous
particles[Heard and Wiffen, 1969;Bigg et al., 1974a],as have
phasemoleculesare alwayswritten without subscripts.
nitrates [Bigg et al., 1974a;Parungoand Pueschel,1980]. Cun-
ninghamand Johnson[1976] have usedinfrared spectralanal-
ysis of particulatesto show that the characteristicsignalsof 2. Oxygen-Hydrogen
Chemistry
sulfate and ammonium ions on urban aerosols fluctuate a. Oxygen-hydrogencompoundsin atmosphericaero-
within time intervals of a few hours or less,with that of sulfate sols. Water is the most commonof the oxygen-hydrogen
being consistentlygreater than or equal to that of ammo- compounds in aerosols
and makesup, of course,nearlyall the
nium. Similar results have been obtained by Brossetet al. massof raindrops.The liquid water in aerosolform shows
[1975],Brosset[1978], Charlsonet al. [1978],and Cobournet al. diurnal variations associated with both the diurnal aerosol
[1978],usingdifferentexperimentalapproaches. concentration patternsand the relativehumidity;a typical
Aerosolsgeneratedby the bursting of bubbles at sea are pattern is reproducedin Figure 4.
substantiallydifferent from those generated on land. Since Oxygenmoleculesand ozone[Kilpatricket al., 1956]are
these aerosolsinitially have compositionssimilar to seawater both moderatelysolublein water (Table 6). Hydrogenper-
[e.g., Blanchardand Woodcock,1980], they are mostly water oxide is very solublein water and has ben detectedin rain-
but include about 3.5 wt % sea salt, which is •85% sodium drops[Bufaliniet al., 1979;Kok, 1980].O-H chemistryin
chloride. Seawateris slightly alkaline (pH • 7.8-8.3 [Parker, aerosolsand raindropsthusconsistsof the aqueoussolution
1980]), as are the newly generatedparticles. chemistryof O:, H:O:, 03, and their derivatives.
The acidity of raindropsis set initially by the equilibrium b. Water. Water molecules in bulk water establish an
with atmosphericCO: and is modified by the incorporation equilibriumrelationshipwith their ions:
into the drops of aerosolparticles and gases[Granat, 1972].
2H:O •- H30 + + OH- (2)
Rain is unquestionablyacidic in certain regions,with pH val-
ues of •4 being common and aciditiesof <2 being occasion- In aqueoussolutionone thus has the potential for reactions
ally observedin bulk rainwater [Likens, 1976; Marsh, 1978; betweenionsand moleculesas a naturalconsequence of the
Graves, 1980]. Values of pH for individual raindrops have dissociation
equilibriumof water (and of othersolutioncom-
been determinedby Esmanand Fergus[1976];they find values ponents).
ranging from 2 to 7, with evidencefor a bimodal distribution c. Molecularoxygen. The presenceof molecularoxygen
with modesat pH • 2.5-3 and pH • 4.5. in aqueousaerosolsis importantto this reviewbecauseof sub-
In summary,the data indicatethat a rangeof aciditiesis stantial evidencethat addition of O: to certain free radicalsof
foundin aerosolsand raindrops;a pH rangeof •-5 _+3 (a interestis a commonoccurrence(as will be pointedout sub-
range of 6 ordersof magnitudein hydrogenion concentra- sequently).Winterand Briscoe[1951]haveusedisotopestud-
tion!)seemsappropriate
for analysisof mostof the controlling ies to demonstratethat the oxygenatomsinvolvedin certain
processesandrates.Somewhat higherpH valuesseemappro- aqueousoxidation reactionsare thoseof dissolvedO: mole-
priatefor themarineaerosol, andsomewhat lowervaluesmay cules.The dissolved
O: thusformsa reservoirof potentialoxi-
be appropriate for the urban industrial aerosol. dizingpower,analogous to the oxidizingpowerof gaseous O:,
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 509

which leads to the gas phase formation of a number of oxi- I

dized speciesin the atmosphere.

d. Ozone. Ozone dissolvesreadily in water, and there is
experimentalevidencethat it can decomposeto form more re-
200
-f ] • TOTAL
MASS
active intermediates [Hoign• and Bader, 1975]. The exact • / X cONcENTRATION
mechanismof the decompositionhas not been firmly estab- / \
fished(see,for example,the discussion by Penkettet al. [1980]
and Dasgupta[1980]), but it is known to be catalyzedby OH-
ions and to result in formation of hydroxyl radicals [Weiss,
1935; Forchheimerand Taube, 1954; Kilpatrick et al., 1956; /
lvanovet al., 1972;Hoign• and Bader, 1975;Peleg,1976].A re-
action chain consistent with the data, but in which all details
have not been confirmed, is

03 + OH---• 02-' + HO2'

= 50h / % LIQUID
WATER
(3)
03 + HO2 '---• OH' + 202 (4) L '•-: 7773 68 58 • 50
03 + OH '---• HO2' + 02
040006000800 lO00 1200 1400 1600 1800 2000 2200 2400
OH' + HO2 ß-+ 02 + H20 (6) TIME(PST)
Fig. 4. Diurnal variation in liquid water concentrationin atmo-
HO2' + HO2'---•H202+ 02 (7) spheric
aerosols
at Pasadena,
California,
September
15,1972.Note
the dependenceof the fractional water contenton relative humidity,
Thegreatpotential
significance
ofthese
chemical
processes
is' indicated
atthebottom
ofthefigure.
(Figure
isfromHoetal.[1974].
that theyprovidea sourceof HOx radicalsin solutionand the Reprinted
by permission
of theAmerican
Meteorological
Society.)
means for cycling between OH. and HO2
Ozone photolysisin solutionis lessdramatic than in the gas
phase,sincethe oxygenatom formed by
Becauseof the dependenceof many of the O-H reactions
o, ---, o: + o('P) (8) on OH- and H30 +, one can anticipatethat the rates and equi-
320<X<675nm
librium positionsof these equationswill be stronglypH-de-
is contained within the solvent cage and reacts to reform pendent.Full chemicalcalculationsare thusrequiredfor each
ozone [Taube, 1957]. Photolysisin the far ultraviolet to form specificsystemof interest.For example, one should not as-
O(ID), however,resultsin reactionwith a cagemoleculeto sumethat the samereactionswill dominate in raindropsofpH
form H202 [Taube, 1957]: 5.6 and raindropsofpH 3.4.
hv
e. Hydrogen peroxide. Hydrogen peroxide is a widely
03 • O2(IA)'•' O(ID) (9) used oxidizing agent in aqueoussolution, wherein it estab-
X<320nm
lishesthe equilibrium[Adamset al., 1966;Beharand Czapski,
19681
O(ID) + H20-• H202 (10)
H•O
Althoughin principlethe O(•D) atom can react with other H202 • H3O+ + HO2- (16)
solvatedspecies(such as CO2 [Weissbergeret al., 1967]), in --H20

practice,its chemistryis restrictedprimarily to reactions(9) A more important processin aqueousaerosolsis likely to be

and (10).
that of photolysis[Phibbsand Gigudre,1951;Livingstonand
The presenceof OH. and HO:- as a result of the inter- Zeldes, 1966]:
action of ozone with water immediately allows a number of
hv
additional reactions, all determined or suggestedin solution
H202 • OH'+OH' (17)
chemistry experiments,to take place in aerosolsand rain- X<380nm

drops. These include an equilibrium dissociation [Bielski,

1977] which servesas a direct sourceof hydroxyl radicals,although
H•O
the OH. yield is reducedby recombinationwithin the solvent
HO2' • HaO++O2 -' (11) cage. Other solutionreactionsinvolving H202 and its deriva-
--H20 tives are [Adamset aL, 1966; Weinsteinand Bielski, 1979]:
and a number of ion-molecule, radical-molecule, radical-radi- H202 + OH ß----•H02' + H20 (18)
cal, and equilibriumprocesses [McLachlanet al., 1959;Adams
et al., 1966; Dogliotti and Hayon, 1967; Behar and Czapski, H202 + H02 ß---• OH ß+ H20 + 02 (19)
1968; $ehestedet al., 1968; Buxton, 1969; Zehavi and Rabani, H202 + O- ''-'• H02' + OH- (20)
1971; Weinsteinand Bielski, 1979]:
H202 -I- 02-'---) OH'-I- OH- -I- 02 (21)
OH. + OH ß---• H202 (12)
The HO2- ion resultingfrom H202 deprotonationis itself
OH- + H02 ' '-'• 02- + H20 (13) photosensitive,
givingriseto [Treinin,1970]
02-' + HO2 ' -"• HO2- + 02 (14) ha,

HO2- 3,•360nm
• OH' + 0-' (22)
O2-' + OH '---• OH- + 02 (15)
510 GRAEDELAND WESCHLER:AEROSOLAND RAINDROP CHEMISTRY

H20
the O-. rapidly combining with water:
H2CO3 • H3O+ + HCO3- (28)
O-' + H:O--• OH. + OH- --H20
(23)
H20
Additional reactionsinvolving HO:- are HCO3- • H3O+ + CO32- (29)
--H20
OH' + HO•---• HO:,_.+ OH- (24)
The equilibrium quotient of (28) is conventionallygiven as
O-' + HO•---• OH- + O•-. (25) 4.16 x 10-7. However, this value assumesthat all of the dis-
Hydrogenperoxidethus servesas a prolific radical sourcein solved,nondissociatedCO2 is presentas H,.CO3. This is not
aqueoussolutionand participatesin a number of radical and correct,sinceH2CO3is alsoin equilibriumwith hydrated CO,.;
anion reactions. for the equilibrium H2CO3 • CO2 + H20 the quotient is ap-
f Molecular hydrogen. H2 is a ubiquitous atmospheric proximately 600 [Cottonand Wilkinson,1980].Hencemostof
constituentwhoseconcentrationmay reach severalparts per the dissolved,nondissociatedCO2 is actually present as hy-
million in urban areas [Scrantonet al., 1979].It is slightly sol- drated CO2, and the correct dissociationconstantfor H2CO3,
uble in water and will serveas a hydroxyl radical scavengerin usingits true concentration, is about2 x 10-4 (seeTable 7).
solutionthrough the reaction [Thomas,1965] As was mentioned above, the atmosphericCO2 concentration,
in conjunctionwith the equilibrium relationshipsjust dis-
H2 + OH .--• H. + H20 (26) cussed,establishes a pH of about 5.6 in otherwisepure water.
followed by [Dainton and Hardwick, 1957] In principle,the reactionof-carbonateand bicarbonateions
with hydroxyl radicals will yield the carbonateradical ion
H' + 02 '-• HO2' (27) (CO3- ß) by
g. Summary of oxygen-hydrogenchemistry. In terms of HCO3- + OH'--• CO3- ß+ H20 (30)
atmosphericaerosolchemistry,water, molecular oxygen,and
hydrogen peroxide are the most important of the oxygen-hy- CO32- -¾OH '--• CO3-' + OH- (31)
drogencompounds.
Water servesas a .solvent,
as an acid, and
Although the carbonateradical ion can react with many com-
as a base. O,. is among the primary oxidizing agentswith a
mon aqueous species[•/Feeksand Rabani, 1966; Behar et al.,
typicalaqueousphaseconcentrationof--3 x l0 -4 M. Hydro-
1970;Lilie et al., 1978;Rossand Neta, 1979],preliminary com-
gen peroxide, with an aqueousphase concentrationof--3 x
putational modeling studies by us indicate that the
l0 -6 M (seesectionE3) has perhapsan evengreaterrole in
CO•-. concentrationsare so low in atmosphericaerosolsand
aerosol chemistry, since it servesas both an oxidant and a
raindrops that its reactions will be quite unimportant. We
source of hydroxyl radicals. Ozone dissolvedin water is a
therefore will not discussthe chemistryof CO3-' in this pa-
sourceof HOx' radicals;this sourceis potentially significant
per.
in situationswhere H202 concentrationsare low. Although H 2
c. Carbon monoxide. The principal reaction of carbon
can scavengehydroxyl radicals,its concentrationin the aque-
monoxidein solutionis expectedto be that with the hydroxyl
ousphaseof the aerosolwill be too low to be of any chemical
radical [Daintonand Hardwick, 1957;Laming et al., 1969]:
importance.
CO + OH .--• CO2 + H. (32)
3. Inorganic Carbon Chemistry
a. Inorganic carbon compounds in atmospheric aero- followed by
sols. Most of the carbonaceous material in aerosols is in the
H. + 02 --• HO2' (33)
form of graphitic soot [Rosenet al., 1980, 1981].This material
is produced in the combustionof virtually all fossilfuels and d. Graphitic soot. Considerable evidence now exists to
is nonvolatile,insolublein organicsolvents,and stronglylight demonstratethat graphitic soot particles can function effec-
absorbing.The decreasein atmospherictransparencythat oc- tively as oxidation catalysts,at least for the SO,. to SO42-
curs at high aerosolconcentrationsappearsto be due largely transformation[Novakovet al., 1974]. Cofer et al. [1980] have
to the graphitic soot component. shown that a wetted particle surface is needed for efficient
Several inorganic carbonateshave been found in aerosols catalysis.Brodzinskyet al. [1980] find that the catalyticoxida-
[Graedel, 1978]. Although small amounts of Na2CO3 and tion of SO2 on carbon particlesin mildly acidic aqueoussus-
(NH4)2CO3 may contribute carbonate artions to solution pensionsis first order with respectto the concentrationof car-
chemistry,most of the carbonateresultingfrom direct injec- bon particles and that the first step in the reaction is the
tion is calcium carbonate in windblown dust. The main source adsorption of oxygen onto the active carbon sites. The SO2
of carbonatein aqueousaerosolsis dissolvedcarbon dioxide, oxidation on sootis enhancedby the presenceof NO2, at least
a stable gas present in the atmosphereat concentrationsof at low NO2 concentrations[Britton and Clarke, 1980; Corer et
about 330 ppm [Woodwell, 1978]. al., 1980]. Comparisonof the carbon-catalyzedreaction with
Carbon dioxide and carbon monoxide are both ubiquitous other atmosphericallyimportant SO,_oxidation reactionsin-
in the atmosphere.Carbon dioxide, with a greater aqueous dicatesthat the former can be a significantcontributor to the
solubility (Table 6) and a greater atmospheric abundance formation of aerosol sulfate.
[Woodwell, 1978], has a much greater concentration in the e. Summaryof inorganiccarbonchemistry. The initialpH
aqueousphaseof atmosphericaerosols. of the aqueousphaseof the aerosolis determinedby the CO2-
b. Carbon dioxide. Carbon dioxide dissolvesreadily in HCO3--CO32- system.The chemicalreactionsof theseionsdo
water to form hydrated CO2 and carbonicacid. The latter is in not appear to be significant.Carbon monoxide is capable of
equilibrium with both the bicarbonate(HCO3-) and the car- scavenginghydroxyl radicals, but its aqueousconcentrations
bonate(CO32-)ion: are too low to render its reactionsimportant. Graphitic soot
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 511

particlesappear to be effectiveoxidationcatalystsin aqueous I I I I I I I

atmosphericaerosolsystems.
-0.6

4. Nitrogen Chemistry
•oo %
a. Inorganic nitrogen compoundsin atmospheric aero- 0.4+
sols. The nitrate ion is a commonconstituentof atmospheric
aerosolsin both urban [Gordonand Bryan, 1973] and remote 80%

[Huebert and Lazrus, 1978] areas.Although it may be present

as sodiumnitrate [Schuetzle,1972]or potassiumnitrate [Schul-
60•/, -o
ten and $churath, 1975a], the most common associatedcation
is ammonium [Gordonand Bryan, 1973; Grosjeanet al., 1976].
Other nitrogen compoundspresentin aerosolsinclude nitric 40*/,

oxide (NO) and nitrogen dioxide (NO2), both of which are

moderately soluble in water. Inorganic nitrogen compounds 2O%
generallycompose10-30 wt % of urban aerosols[Gordonand - SOg-
NO•
Bryan, 1973;Grosjeanet al., 1976]and of the order of 10 wt % ORGANICS
of remote aerosols[Huebert and Lazrus, 1980]. , i I I i I I
It is often possibleto infer information about physical or 6:30 :30 16:30
T•ME (PDT}
chemical sourcesof speciesof interest by •xamining tllt•11
diurnal concentrationpatternsin the atmosphere.In the case Fig. 5. Diurnal concentration
patternsof nitrate,sulfate,and am-
monium ions,total aerosolorganics(as weight percentof the total dry
of aerosolnitrate the coarsemode nitrate generally showsa
aerosol),and ozonein Pasadena,California, on July 25, 1973. (Figure
diurnal maximum in early or middle morning [Hidy et al., is from Grosjeanand Friedlander[1975]. Reprinted by permissionof
1975; Orel and $einfeld, 1977;Kleinman et al., 1979], while the the Air Pollution Control Association.)
accumulation mode nitrate has middle to late afternoon max-
ima [Grosjeanet al., 1976;Orel and Seinfeld,1977].This sug-
geststwo primary sources:a wind erosion sourceof coarse This seemsunlikely, however, since gas phase measurements
mode nitrate-containing soil particles [Hermance et al., 1971] of the rate constantof (36) by Lesclauxand Demissy[1977] in-
and a chemical sourceof accumulationmode nitrate [Orel and dicatethe formation of NH202 ß to be a very slowprocess.Al-
$einfeld, 1977]. In the caseof aerosolammonium (most com- ternatively, a chemical chain proceeding through NH2OH
mon on the smaller particles), fewer data are available, but may be involved:
they appearto showa diurnal pattern similar to that for accu-
NH2' + OH.--> NH2OH (38)
mulation mode nitrate. This suggeststhat its sourceis related
to photochemicalprocesses, either in the generationof am- and Hoign• and Bader [1978] suggestthat direct reaction be-
monia or in its depositionon the aerosol.An example of the tween NH3 and 03 can initiate the process.In any case, the
diurnal patterns for aerosol ammonium and nitrate ions is protonationof NH3 appearsmore important than its reactions
shown in Figure 5. for the systemsof interesthere.
b. Ammonia and ammonium ion. Ammonia is the most c. Nitric oxide. Nitric oxide has an aqueous solubility
important alkaline compoundcommonly found in the atmo- comparableto that of 02; dilute solutionscan be prepared by
sphereand playsa key role in limiting the pH of the aqueous careful laboratory techniques[$eddonand Sutton, 1963]. It is
aerosol.It is extremely solublein water, and the resulting so- alsoknown to be generatedin solutionby photolysisof NO2-,
lutions are best describedas NH3(aqueous)with the equilib- NO3, and HNO2 (see sectionsC4e and C4f), and its sub-
rium written as sequentreactionsare of interest.
Two reactionsconverting NO into nitrous acid have been
NH3' H20 •---NHn+ + OH- (34) identified:
The equilibrium constantfor this reaction at 25ø is 1.81 x
NO + OH.--> HNO2 (39)
10-5 (i.e., NH•(aqueous)is a weak base).
As was mentioned above, ammonium salts are very com- NO + NO2 _•o HNO2 + HNO2 (40)
mon in atmosphericaerosols(e.g., (NHn)2SOn,(NHn)HSOn,
Their importance(both absoluteand relative) is uncertain.
NHnNO•, NHnC1, etc.). In solutionthese saltsare highly ion-
d. Nitrogen dioxide. The determinationof the solubility
ized and slightlyacid by hydrolysis(Ka -- 5.5 x 10-•ø).Con-
of NO2 in water has a long and confusinghistory. England
sequently,a 1 N NHn+ solutioncontains2.3 x 10-5 N H•O+
and Corcoran[1974] have reviewedin detail the experimental
(pH = 4.6) [Latimer and Hildebrand, 1951].
evidence for the systemand have concluded that NO2 is not
The possibilityof reactionsof free ammonia should also be
considered, since it has been shown that ammonia can be oxi-
absorbedto any significantdegree.Recently,however,a series
of careful experimentsand analysesof previous laboratory
dized to nitrite in aqueoussolutionif air is present[Rigget al.,
work [Lee and Schwartz, 1981] appears to have verified that
1952].The mechanismis known to involve both hydroxyl rad-
the process
icals and molecular oxygen, and it is suggestedto be
2NO2 + 3H20--> 2H30 + + NO2- + NO3- (41)
NH3 + OH---> NH2' + H20 (35)
doesoccurin solutionbut is very slow. It thus may not pro-
NH2. + O2--->NH202 ß (36)
vide a significantalternative sourceof odd nitrogen to com-
NH202' + OH.--> HNO2 + H20 (37) pete with the incorporationof moleculesoxidized in the gas
512 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

phase by reactionssuch as HNO2 can also react with any aminespresent[Novakovet aL,
1972] to form N-nitroso amines [Pitts, 1979]:
2NO2(g)
+ H20(g)-->HNO2(g)+ HNO3(g) (42)
R2NH + HONO--> R2N--NO + H20 (54)
HNO3(g)• HNO3 (43)
The nitrite ion also participatesin a variety of chemical
HNO2(g)•---HNO2 (44)
processesin aqueoussolution.Of perhapsgreatestinterest is
In addition to theseprocesses, NO2 is formed and removed photodissociation[Treinin and Hayon, 1970; Zafiriou and
by other aqueous chemical mechanisms. Its most common McFarland, 1980],
fate is the formation of oxy acidsby reactionssuchas hv

NO2 + OH.--> HNO3 (45) NO2- •<41-->

Ohm
NO + O- (55)

Evidencehasalsobeenprovidedfor the presence of an equi- which has been shown to produce NO in surfaceseawater
librium with peroxynitricacid [Suttonet al., 1978]' [Zafiriou and McFarland, 1981].
NO2 q- HO2'•--- HO2NO2 (46) A secondprocessof importancefor the nitrite ion in solu-
tion is singleelectrontransfer[SchwartzandAllen, 1955;Dan-
which is the analogof a gasphaseatmosphericprocess. ielsand Wigg, 1967;Daniels,1968;Buxton, 1969]:
In the gasphase,NO2 absorptionat wavelengths
lower than
400 nm resultsin cleavage: NO2- q- OH'--> NO2 q- OH- (56)
hv
H20
NO2(g)--> NO(g)+ O(3p){g) (47) NO2- q-O- --> NO2q-2 OH- (57)

Studiesof the photolysisof NO2 in water (at least someof In addition,nitriteion in solutionundergoes
two-equivalent
which was aerated)have not establishedthat cleavageoccurs, oxidationby ozone[Espenson
and Taube,1965]:
however [Ottolenghi and Rabani, 1968; Grdtzel et al., 1969;
Treinin and Hayon, 1970].It is possiblethat the data can be re- NO2- + 03--> NO3- q-02 (58)
solvedby recallingthe resultsof ozonephotolysisin solution. The primaryfate of bothnitrousacidandsolutionnitriteis
For that molecule, cleavage to produce O('D) provided thusthe formationof the commonatmospheric oxidesof ni-
enough energy for the oxygen atom to react with the solvent trogen, whose anticipatedsolution reactionshave been dis-
cage rather than to be contained within it. In the case of cussed above.
O(3p), that reactiondid not occur.Sincethe thresholdfor f. Nitric acid, nitrate ion, and nitrogentrioxideradi-
O('D) formationin NO2 photolysisis -244 nm [Okabe,1978], cal. Nitric acidis formedin the atmosphereby the reaction
it is possiblethat the absorptionof radiation by NO2 in aque-
oussolutionwill resultin no net reaction.Other workers[e.g., NO2(g)
+ HO. (g)-• HNO3(g) (59)
Treinin,1970]who haveproducedO(3p) in oxygen-containing The vaporpressure of HNO3is onlymoderate; it readflydis-
solution,however,have observedozoneformation by solves
in water,whereinit behaves
asa strongacid;thatis,the
O(3p)q-02 • 03 (48) equilibriumof (60) liesfar to the fight:
H20
The yield for this processis presumably dependent on the
HNO3 • H30+ + NO3- (60)
presenceof 02 within the solventcage,that is, the concentra- --H20
tion of 02 in solution. More data are needed to resolve this
uncertainty. NO3- weakly absorbssolarradiation between325 and 350 nm
e. Nitrous acid and nitrite ion. Nitrous acid is formed in [Meyersteinand Treinin,1961;Zafiriouand True, 1979b].Evi-
the gas phase by the reaction dencehas beenpresentedfor two fragmentationpaths[Dan-
iels et al., 1968]:
NO(g)
+ HO.(g)--•HNO2(g) (49) hv

and possiblyalso by NO3- --> NO2-+ O (61)

2•<350nm

NO(g)+ NO2(g)+ H20(g)-->2 HNO2(g) (50)

hv

although the latter reaction is suspectedof being hetero- NO3- 2•<350nm

--> NO2 + O- (62)
geneous[Chan et al., 1976] and is, in any case,much lessim-
portant
thantheformer.
Nitrous
acidreadily
dissolves
inwa- Althoughas yet somewhat
uncertain
[Zafiriou
andTrue,
terandparticipates
inthechemical
equilibrium
process 1979b], it appears
fromtheworkofBayliss
andBucat
[1975]
-20 thatthefirstreactionchannelis of primaryimportance
(but
HNO2 •--- H30+ + NO2- (51) seealsoDaniels
etal. [1968],
Baratetal. [1969],
andShuali,
et
--H20 al. [1969]).
Evidencehasbeenpresented
[Treinin
andHayon,
1970;
Ret- Thenitrogentrioxide
radical
isproduced
in thegasphase
tich,1978]
thattheundissociated
compound
canundergo
the bythereaction
following
solution
reactions: hv
NO2(g)
+ O3(g)-->
NO3(g)
+ O2(g) (63)
HNO2 --> NO + OH. (52) andhasbeendetected
at lowconcentrations
in theurbanat-
2•<390nm mosphere
byPlattetal.[1980].
It maybeincorporated
into
HNO2+ OH .-->NO2+ H20 (53) aerosol
andraindropsolutions,
whereit will undergo
slowhy-
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP
drolysis[Martin et al., 1963, 1964]:
NO3 + 2H•_O--• NO3- + H3O+ + OH' (64)
NO3 is susceptibleto photolysisin solutionat visible wave-
lengths [Hayon and Saito, 1965]:
NO3-•NO2+ O (65)
NO3-%NO+ O,_ (66)
The branchingratio for thesetwo channelsin aqueoussolu-
tion is not known, but the data of Hayon and Saito [1965] sug-
gestthat a significantfractionof the total processproceedsby
each channel. In the gasphase,Magnotta and Johnston[1980]
have reported values of the product of the absorptioncross
sectionand the quantum yield over the wavelength interval
470-700 nm.
g. Summary of nitrogen chemistry. Ammonia (and the
ammonium ion) and nitric acid (and the nitrate ion) are the
mostimportant inorganicnitrogencompoundsin atmospheric
aerosols.Ammonia is the principal speciesthat reacts with
strongacidsin the atmosphere,as evidencedby the large con-
centrationsof ammonium salts found in aerosols.Although
nitric acid can serveas an oxidizingagent,its chief action is to
reducethe pH of the aqueousaerosol.
The most common fate for the N Ox compounds(NO and
NO2) is conversionto either nitric acid or nitrous acid. Since
nitrousacid (or nitrite ion) will eventuallybe convertedto ni-
trate ion, the net effect is for the majority of the NOx mole-
culesin atmosphericaerosolsto be oxidized to nitrate.
5. Sulfur chemistry
a. Inorganic sulfur compounds in atmospheric aero-
sols. Sulfur compoundsare important constituentsof atmo-
sphericaerosols.The most obviousare the sulfates,including
sulfuric acid, acid ammonium sulfates, and ammonium sul-
fate. However, the simple inorganic sulfur gasesOCS, SO2,
H2S, and CS2 are all appreciablysolublein water (Table 6)
and can therefore be expectedto participate in the chemistry
of aqueousatmosphericaerosols.
Sulfates are major componentsof both urban and marine
aerosols,composing15-30 wt % of the former and 30-60 wt %
of the latter [Whitby, 1978].Concentrationsrangefrom about
0.2to 15/•gSO42-
m-3 [Flyger
etal.,1976;Friedlander,
1977].As
Figure 5 demonstrates,the amount of sulfate in the aerosolin-
creasesduring the day, in approximatecoincidencewith the
intensityof photochemicalactivity. (Similar resultshave been
presentedby Wolff et al. [1979].)Isotopicstudiesby Cunning-
ham and Holt [1976] suggestthat at leastsomeambient sulfate
ions contain two oxygen atoms originating from sulfur diox-
ide, one oxygen atom from air and one oxygen atom from
condensed phase atmospheric water. As will be seen, this
analysisis consistentwith interactive gas phase and liquid
phasechemicalprocesses.
The most common of the atmospheric inorganic sulfur
gasesappear to be (in order of decreasingconcentration)
OCS, SO2, H2S, and CS2 [Sze and Ko, 1979a, b; Turco et al.,
1980]. Sulfur-containing radicals are also present [Graedel,
1977; Davis et al., 1979].
b. Hydrogensulfide. Hydrogensulfideis approximately3
times as soluble in water as is carbon dioxide. In water it func-
tionsasa weakacidwith dissociation
constants
Ka, = 1.3 x
10-7 and Ka2= 7.1 x 10-•5 [I,Vidmerand Schwartzenbach,
1964].Hence, in the absenceof other complexingagents,an
CHEMISTRY 513
aqueoussolutionofœH 6.9 containsalmostequal amountsof
H2S and HS-; at a pH of 5.9 the amount of H2S is 10 times
greaterthan that of HS-. Theseequilibriaare important,since
the autoxidationof H2S dependson pH in a manner implying
that HS- is the principal reactive speciesin solution [Abel,
1956; Hoffmann, 1977].
Hydrogen sulfide is known to be oxidized in aerated solu-
tions, and this processhas been the object of a number of ki-
netic and mechanisticstudies [Ostlund and Alexander, 1963;
A vrahamiand Golding,1968; Cline and Richards,1969; Demir-
jian, 1971; Chen and Morris, 1972; Alrngren and Hagstrom,
1974;Moussavi,1974; O'Brien and Birkner, 1977;Hoffmann
and Lim, 1979]. Unfortunately, the reported rate constants
and the derived mechanismsare not in agreement. To some
extent this is likely the result of varying reaction conditions
(pH range, ionic strength,[sulfidespecies]/[O2],etc.). How-
ever, the more extreme discrepanciessuggestthat the autoxi-
dation is easily catalyzedby trace contaminants,a thesissup-
ported by numerous reports that the oxidation of reduced
suffur speciesis affected by small quantities of selectedor-
ganic molecules and transition metals [Cline and Richards,
1969; Chen and Morris, 1972; Demirfian, 1971; Avrahami and
Golding, 1968]. Indeed, Hoffmann and Lim [1979] have dem-
onstratedthat a seriesof water-solublemetal-phthalocyanine
complexes(the metal being Co (II), Ni (II), or Ca (II)) are ef-
fective homogeneouscatalystsfor the oxidation of hydrogen
sulfide in aqueoussystems.Addition of the cobalt speciesat
partsper billion levelscan increasethe rate of autoxidationby
a factorof 104.The copperand nickel speciesare lesseffective
catalysts.
For autoxidation in aqueous solution, the formation of
HSO2- is probably the rate-determiningstep. In the absence
of catalyststhis step appearsto be
HS- + O2 '-> HSO2- (67)
For the cobalt-phthalocyanine-catalyzed reaction, Hoffmann
and Lim [1979] proposerapid formation of an adduct contain-
ing HS-, 02, and the cobalt complex followed by the rate-de-
termining step
Hs-Co-phthalocyanine-O23-
+ A-
--> Co-phthalocyanine
3- + HSO2- + HA (68)
where A- is a Bronsted base. The major reaction products,
SO42- and 82032-, suggestpossiblefates for the HSO2-
formed in this step:
HSO2- q- 02 •> HSO4- (69)
HSO2- + HSO2- --> HS203- q- OH- (70)
(Reaction (70) will have a very low net rate due to the low
concentrationsof HSO2- anticipated in the atmosphericaero-
sol.)
The radical HS ßmay also play a role in the oxidation of
hydrogensulfide.In solutionit can be producedby
H•S + OH.--> HS. + H20 (71)
H2S + C1.--> HS. + HC1 (72)
The possiblesolutionreactionsin which HS .may participate
are uncertain. Thiemensand Schwartz[1978] detected SO2 fol-
lowingthe generationof HS. in simulatedair and proposed
HS ß(g)+ O2{g)'->HSO2ß(•) (73)
HSO2(•)'+ O2(•)•> SO2(•)+ HO2ß(g) (74)
514 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

as the mechanism. However, the importance of this mecha- dation of SO2 to SO3 [Urone et al., 1968],a number of transi-
nismmay be minimal, as the first reactionis known to be very tion metal ions catalyzethe oxidationof SO32-to SO42-in
slow in the gas phase [Schofield,1973]. aqueoussolution[DriscollandBerger,1971].However,higher
There are a number of oxidation processesinvolving sul- molecularalcoholsand phenolshave the oppositeeffect--they
fidesthat are difficult to evaluatein termsof aqueousaerosol inhibitthe aqueousoxidationof SO32-[Bienstock
et al., 1958;
chemistry.For example,ferric ion in aqueoussolutionis re- Alvea and Backstrom, 1929;Flint, 1948].
ported to oxidize sulfideion [Cottonand Wilkinson,1980]. The sulfite(SO32-)anioncan alsoreactwith HO,• radicals
One might envisionthat ferric sulfide,if presentin the aque- [Schrnidkunz,1963; I-Iayon et al., 1972] to produce sulfate
ous aerosol,would evolveto iron (II) sulfideand free sulfur. (SO42-) and persulfite(SO3-) ions: _
Whether such chemistry actually occurs at typical atmo-
SO32-q- go2'--> SO42-q- OH- (85)
sphericconcentrations remainsto be determined.
As is discussed below,H2Sis'likelyto be generatedin the 8032--q- OH' • SO3- + OH- (86)
aqueousshellof atmospheric aerosolsthroughbothOCS and
CS2hydrolysis. The formeris of moreimportancethan the lat- An alternativemechanism proposed
for the latterreactionby
ter becausethe atmosphericconcentrationof OCS is generally Schmidkunz [ 1963] is
greaterthan that of CS2and becauseOCS hydrolyzesat a fas- 8032--q- OH' • 8042- q- H' (87)
ter rate.
c. Sulfurdioxide. Sulfur dioxideis very solublein water. This appearslesslikely than (86), however.It wasproposedin
The resultingsolutionsare acidic and have been erroneously order to regenerateHO2', but as can be seen,a number of re-
referred to as solutionsof sulfurous acid, H2803. However, if actionsto accomplishthat generationare commonlypresent
presentat all, H2803 is presentonly in extremelysmall in atmosphericaqueoussystems.Reaction(85) seemslikely to
amounts [Cotton and Wilkinson, 1980]. The equilibria in- be very importantin aqueousaerosols,sinceit providesan ef-
volving SO2in aqueoussolutionare bestrepresentedas ficient path for the conversionof SO2 to SO42-and at the
sametime regeneratesthe reactivehydroxyl radical from the
SO2 -[-xH20 • SO2 ßxH20 (SO2(aq)) (75) less reactive HO2'.
SO2 ßxg20 • H2803 K << 1 (76) Hydrogen peroxide reactsdirectly with sulfite ion to form
sulfuric acid. The processis suggestedto be
SO2' xH20---> HSO3{aq)- + H30+ + (x - 2)H20 (77)
HSO3- q- H202 • A- + H20 (88)
and the first acid dissociationconstantis properly defined as
[Cottonand Wilkinson,1980] A- + H3O+ --• g2so 4 q- H20 (89)
where A- is an intermediatespeciesof undeterminedstructure
K•= [totaldissolved
[HSO3-][H30+] = 1.3
SO2]- [HSO3-]- [SO32-]
x 10
-2 [Hoffmannand Edwards, 1975;Martin and Damschen,1981].
SO2 is oxidized by ozone in aqueous solution [Penkett,
(78) 1972;Larson et al., 1978; Penkett et al., 19798], but the direct
reactionis slow [Ericksonet al., 1977] and may involve inter-
From the above considerations,SO2 is obviously much less
soluble in acidic solutions than it is in neutral or basic solu-
mediates [Forchheirnerand Taube, 1954;Espensonand Taube,
1965].In any case,in the slightlyacid atmosphericaerosol,bi-
tions. Although sulfurousacid itself apparentlydoesnot ex-
sulfite ion is the predominant form of sulfur (IV) present.It
ist,saltscontaining HSO3-(bisulfites) andSO32-(sulfites) are
and sulfite react with ozone by [Ericksonet al., 1977]
well known.
The reactionsinvolving SO2 and 02 in aqueoussolution gso3- q- 03 --• gso4- q- 02 (90)
have been well studied[Beilke et al., 1975;Scott and Hobbs,
1967; Miller and dePena, 1972; McKay, 1971; Hegg and SO32- q- 0 3 --->SO42- q- 0 2 (91)
Hobbs, 1979; MOller, 1980]. At 25øC the oxidation appears Ozone is thus capable of oxidizing sulfiteto sulfateeither di-
bestdescribedby the mechanism[Beilkeet al., 1975] rectly by thesereactionsor indirectly through the HO,•. radi-
SO2 + xH20 • SO2' xH20 (79) cals generatedupon dissolution.
The SO3- radical is well known to solution chemists,who
SO2' xH20 • HSO3- + H30 + + (x - 2)H20 (80) regardits probablefate as [Hayon et al., 1972]
SO2 ßxH20 q- OH- • HSO3- q- xH20 (81) SO3- + 02--• SOs- (92)
aso3--%o
•.•o SO3
2-q-a30+ (82) The reactions of SOs- in solution have not been delineated,
but the most probable is [Hayon et al., 1972]
SO32- q- «0 2 --->SO42- (83)
The oxidationof SO32-to SO42-is firstorderin SO32-,and di- SO5- + g30 + • HSOs' + g20 (93)
rect oxidationof HSO3- appearsnegligible.The rate of reac-
The routesoutlinedaboveare capableof producingthe sul-
tion is given by [Beilke et al., 1975]
fate anion SO42-so commonlyobservedin aerosolsand rain-
dISO42-]/dt---
1.58x 10•[H]-2'•6ps02 drops.It is evidentthat the SO2--• SO42-processis in-
extricablytied to the chemistryof HOx' radicalsand ozone
molesSO42-1-• s-• atm-• (84)
moleculesin aqueousatmosphericsystems.Synergisticeffects
The rate of oxidation is zero order with respectto molecular are also operable; for example, Martin et al. [1981] have
oxygenover a wide rangeof concentrations. shown that NO2- promotesthe oxidation of SO2 in aqueous
Justas a number of metal oxidescatalyzethe gasphaseoxi- solution.
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 515

d. Carbon disulfide. Carbon disulfideis slightly lesssol- f. Sulfur-containingradicalsgeneratedby atmosphericgas

uble in water than is carbondioxide,and at ambienttemper- phasereactions. The principal gas phasereaction of atmo-
aturesthere is no evidenceof a significantreactionbetween sphericsulfurdioxideis [Calvertet al., 1978]
CS: and water. However, between ambient and 200øC, carbon
disulfide
does
react
withwater
to yieldcarbonyl
sulfide SO:{s)
+ OH'{s)--•
HSO3'(s) (99)
[Bailaret al., 1973]: followedby [Benson,
1978]
CS: + H:O--} OCS + H:S (94) HSO3'{s)+ O2{s)
--• HSOs'{s) (100)
At still higher temperatures,and in the presenceof an appro- This radical may hydrolyzeand nucleateto form a new aero-
priate catalyst,carbon disulfideand water react to yield hy- sol particle [Davis et al., 1979],it may be incorporateddirectly
drogensulfid•e andCO2[Bailaret al., 1973]: into preexistingaerosolsor raindropsor it may be reducedby
catalyst
reaction with NO:
CS: + 2H:O --• 2H2S + CO:(200ø-500øC) (95)
HSOs' + NO -• HSOn' + NO: (101)
Virtually nothing is known of the reactionsof CS:, in aque- The HSO4' radical is then available for nucleation or incor-
oussolution.Somepossibilitiesare suggested, however,by re- poration.In any case,the solutionreactionsof oxysuffurradi-
actionsstudiedin the gasphase,where the principal oxidation cals are of interest,and rese•irchin this area is clearly war-
mechanism may be [Wood and Heicklen, 1971, 1973/1974; ranted.
Wine et al., 1981]
g. Summaryof sulfurchemistry. Surfateis the dominant
suffur-containingspeciesin atmosphericaerosols.The high
CS2(s) -• CS2*(s)
•>280nm
(96) aqueoussolubilityof the submicronfraction of atmospheric
aerosols(often greater than 50% by weight) reflectsthe high
(97) sulfate content [Walker and Weschler,1980]. It also follows
thatthereducedpH of the submicron
fractionis dueprimarily
to surfuric acid and acid ammonium sulfate.
The fate of CS is uncertain.In any case,it is stablein solution
Suffur dioxide has the highestaqueousphaseconcentration
only ff coordinatedto transitionmetals[De Boer et al., 1966]
and will thus not be available for reaction with other trace
of the suffur-containinggases(seeTable 8). It is the most im-
portant reducing agent in atmosphericaerosols,and its own
species. eventual fate is oxidation to surfate.
Olszynaand Heicklen[1970]have studiedthe gasphasere-
The aqueousphaseconcentrationsof hydrogensulfide,car-
action betweenozone and carbondisulfideat relatively high
bonyl sulfide,and carbondisulfideare severalordersof mag-
CS: concentrations(>1300 ppm). The principal reaction
nitude less than that of suffur dioxide (Table 8). Carbonyl
products,in order of decreasingyield, were SO:, OCS, CO,
sulfide hydrolyzes to yield H:S, carbon disulfide can yield
and CO:. The importanceof this reaction at typical tropo-
OCS, H:S, or SO:, and hydrogensulfideis oxidized to surfate.
sphericconcentrationsin aqueoussolution is difficult to as-
sess.
Hence surfateis the eventual product of reducedsuffur gases
dissolvedin the aqueousphaseof the aerosol.
In summary, in aqueousatmosphericaerosols,CS: may
serveas a precursorfor OCS, H:S, CS, and SO2,but the ap- 6. Halogen Chemistry
propriatereactionsand mechanismsare not known as of this
a. Inorganic halogenated compounds in atmospheric
writing.
aerosols. The most commonof the halogenatedcompounds
e. Carbonyl sulfide. Carbonyl sulfide is on average the
in aqueousatmosphericsystemsare the chlorides,including
most abundantsulfur-containinggas in the atmosphere.It is
hydrochloricacid, ammonium chloride, and sodium chloride.
slightly less soluble in water than is carbon dioxide and, in
The last is derived principally from sea spray, while the am-
aqueoussolution,is hydrolyzedto carbondioxideand hydro-
monium chloride appearsto result from neutralization reac-
gen sulfide [Thompsonet al., 1935;Philipp and Dautzenberg,
tions. Chloride may compose0.1-1 wt % of the land aerosol
1965]:
[Friedlander,1973;Rahnet al., 1979]and 1-10%of the marine
OCS + H20--} CO2 + H:S (98) aerosol[Bergand Winchester, 1978],or asmuchas 10/•gm-3.
b. Hydrochloricacid and chlorideion. Hydrochloric acid
The kineticsof this reactionhave beenstudiedboth by Buch-
may be generatedin the combustionof chlorine-containing
bOck[1897] from 15ø to 40øC and by Thompsonet al. [1935]
species,or it may evolvefrom acidifiedseasalt aerosol.Ocean
from 15o to 47øC. Both studiesfound that the reactionclosely
water, the primary sourceof the sodiumchloride,is normally
followed a unimolecular rate law, and the results of the two
basic(pH 7.8-8.3 [Parker, 1980]).As the acidityof the seasalt
studiesare in excellent agreement.At 25ø the first-order rate
aerosolincreases,the formation of hydrogen chloride is in-
constantfor the hydrolysisreactionis 2.1 x 10-5 s-•; this cor-
creasinglyfavored:
respondsto a haft-life of 9.2 hours.The rate of hydrolysisis --H20
slowedonly slightly in acidic solution.The reaction is •28% H•O* + CI- • HCI•s• (102)
slowerin 1 N hydrochloricacid and •6% slowerin 1 N acetic H20

acid[Thompson et aL, 1935].Hydrolysis is definitelyfasterin This equilibriumhasfrequentlybeeninvokedas a sourceof

basicsolution,andThompson et al. reportthatthereactionis the gasphasechlorinein the atmosphere [Hitchcocket al.,
catalyzedby a numberof substances, 'of whichthe hydroxyl 1980](however,seeBergand Winchester [1978]for counter-
ionisperhaps themosteffective.' Oncehydrolysis of OCShas arguments). It isapparent
thattheefficiency of thissource
will
occurred,the resultingH:S will be subjectto the sameoxida- be a functionof the pH of the aqueousaerosoland of the
tion processesthat are discussed in sectionC5b. competingsolutionreactionsof the chlorideion.
516 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 2. Abundanceof Transition Metals in AtmosphericAerosols

Concentration
Range,/•g/m
3
Element Urban" Nonurban" Global b Enrichment Classification

Fe 1.1-2.1 0.19-0.51 0.5-2.0 intermediate

Cu 0.15-0.26 0.16-0.36 0.01-0.80 enriched
Zn 0.10-0.80 enriched
Ti 0.03-0.05 0.009-0.028 0.01-0.08 nonenriched
Mn 0.04-0.08 0.004-0.018 0.01-0.12 intermediate
V 0.016-0.052 0.004-0.008 0.01-0.10 intermediate
Ni 0.014-0.017 0.002-0.011 0.008-0.05 enriched
Cr 0.006-0.009 0.002-0.004 0.005-0.02 intermediate
Cd 0.001-0.004 0.0001-0.0005 0.001-0.010 enriched
Co 0.001 0.002 0.0003-0.003 intermediate
Sc 0.0001 nonenriched
Hg 0.0003-0.002 enriched
Ag 0.001-0.003 enriched
Arithmetic means, 1970-1976, from EnvironmentalProtection•lgency [1979].
Rahn [1976].

In dilute aqueoussolution,hydrogenchlorideand the com- number of radical processes in solution,and aciditicationof

mon chloride saltsare essentiallycompletelydissociated.The chloride-containing aerosols can generate HC1. However,
aqueouschemistryof thesespeciesis, in effect,the aqueous chloride'sgreatestinfluenceis likely to be as an electrolyte,
chemistry of the respectiveions. The solution reactions of that is, as a contributor to the overall ionic strength of the
chloride ion generally convert it into the chlorine atom. For aqueousphaseof the aerosol.
example, the reaction sequencewith the hydroxyl radical is
[Jaysonet al., 1973] 7. TransitionMetal Chemistry
C1- + OH.•- C1OH- (103) a. Transitionmetals in atmosphericaerosols. In terms of
C1OH--• C1. + OH- (104) the chemistry that can occur within aqueous atmospheric
aerosols,transition metals are most interesting as possible
C1OH- + H3O+ •- C1- + 2H20 (105) catalystsfor redox processes. Suchcatalysishasbeen hypothe-
sizedfor many years [e.g.,Jungeand Ryan, 1958],and numer-
Chlorine atomsare efficienthydrogen atom abstractorsand
ous investigatorshave reportedthe influenceof trace metals
will undergosolutionreactionsanalogousto thoseof the hy
on the 802/8042-- system[e.g.,Brimblecombe and Spedding,
droxyl radical. Among thesewill be
1974b;Barrie and Georgii, 1976; Judeikiset al., 1978; Penkett
CI' + H2_•o C1- + H3O+ q-H. (106) et al., 1979b; Kaplan et al., 1981]. Two recent studieshave
comparedthe importanceof thesemetal-catalyzedpathways
C1.+ HO2'.•o C1-+ 02 q-H30+ (107) to other sulfate production mechanisms[Miiller, 1980; Mid-
C1.+ OH-_•o C1-+ O- + H30+ (108) dletonet al., 1980]. In the following paragraphswe will con-
sider the role of transition metals as both homogeneousand
CI' + H202.•o C1-+ HO2'q-H3O+ (109) heterogeneouscatalystsof atmosphericprocesses.
CI' + CO32- • C1- + CO3-' (ll0) b. Homogeneouscatalysis. Homogeneous catalysis, as
usedhere, meansthat both the reactant and the catalystare in
CI' + HCO3-.•o C1-+ CO3-' + H3O+ (lll) the samephase.Severalimportantfactorsmustbe considered
CI' + 8032- • C1- + SO3- (112) in evaluating transition metals as potential homogeneous
catalysts:(1) the abundanceof the transitionmetal in atmo-
CI' + NO2- '-> C1- + NO2 (ll3) sphericaerosols,(2) the various chemical forms of the metal
in the aerosol(minerals,oxides,hydroxides,complexes,etc.),
C1.+ HNO3.•o C1-+ NO3'q-H3O+ (ll4)
(3) the solubilitylimits that apply to the metal in aqueousso-
The presenceof chlorinein aqueoussolutionsthus enhances lution, (4) the stableoxidation statesthat are available to the
the spectrumof radical processes
that may occur. metal, (5) the ability of the metal to form complexes,and (6)
c. Bromide and iodide chemistry. Bromide and iodide the availability of ligandsin the aerosolto complexthe metal.
ion• are common constituentsof marine aerosols[Moyers and c. •4bundanceof transitionmetalsin aerosols. Of the tran-
Duce, 19728, b; Kritz and Rancher, 1980]. Their participation sition metals,the first-row transitionelementsmake by far the
in aqueousatmosphericchemistryis thus assured.The equi- largestcontribution to the atmosphericaerosol.Table 2 lists
librium and reactionprocessesthat occurfor chloridein aque- typical rangesreportedfor the atmosphericconcentrationsof
ous solutionare generallyreplicatedby bromide and iodide the first-row transition elements and subclassifies these ele-
[Seddonand Sutton,1963;Thomas,1967;Zehaviand Rabani, ments into four groupswith respectto these concentrations.
1972]and will not be repeatedhere. They may be sourcesfor (The enrichmentclassifications, also presentedin this table,
gaseousHBr and HI in the atmosphere; thesespecieshave are discussedbelow.) Iron has the largestconcentrationvalue
been detectedby Rahn et al. [1976]. of the elements in Table 2 and has, in fact, been determined to
d. Summary of chlorine chemistry. Although chloride be the seventhmost abundant element in an analyzed group
saltsare major constituentsof atmospheric their role of atmospheric
aerosols, aerosols(500-2000ng/m3 [Blosserand Henry,
in aerosolchemistryappearsto be disproportionatelysmall. 1971]). Cobalt has the smallestconcentrationvalue in the
The conversion of chloride ions to chlorine atoms leads to a group,with a rangeof 0.3-3.0 ng/m3.
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 5 17

TABLE 3. Maximum Solubilities for SelectedMetal Hydroxides

Concentration, mol/1

Hydroxide gsp
a pH 2 pH 3 pH 4 pH 5 pH 6 pH 7 pH 8
Fe(OH)2 8 X 10-16 8 X 108 8 X 106 8 X 104 8 X 102 8 8 X 10-2 8 X 10-n
Fe(OH)3 6 X 10-38 6 X 10-2 6 x 10-5 6 x 10-8 6 x 10-II 6 x 10-14 6 X 10-17 6 X 10-20
Cu2(O)
½ 1.2x 10-15b 1.2x 10-3 1.2x 10-4 1.2x 10-5 1.2x 10-6 1.2X 10-7 1.2x 10-8 1.2x 10-ø
Cu(OH)2 2.2X 10-2ø 2.2x l0n 2.2 X 102 2.2 2.2 X 10-2 2.2 x 10-n 2.2 x 10-6 2.2 x 10-8
Zn(OH)2 7 x 10-18 7 x 106 7 x l04 7 x 102 7 7 x 10-2 7 x 10-4 7 x 10-6
Ti203a I x 10-4øb I x 10-4 I X 10-7 1 X 10-1ø I X 10-13 1 X 10-16 1 X 10-19 I X 10-22
TiO(OH)2* I x 10-3ø* 1x 10-6 I x 10-8 I x 10-1ø I x 10-12 1 x 10-14 I x 10-16 I x 10-18
Mn(OH)2 1.6x 10-13 1.6x 1011 1.6x 109 1.6X 107 1.6x 105 1.6x 103 1.6x 101 1.6x 10-I
Ni(OH)2 2 X l0-15 2 X 109 2 X 107 2 x 105 2x 103 2 x 101 2 x 10-1 2 x 10-3
Cr(OH)3 7 X 10-31 7 X 105 7 X 102 7 X 10-l 7X 10-4 7 X 10-7 7 X 10-!ø 7 X 10-13
Cd(OH)2 2.8x 10-14 2.8x 101ø 2.8x 10s 2.8x 106 2.8x l04 2.8x 102 2.8 2.8x 10-2
Co(OH)2 2 X 10-16 2 x 108 2 X 106 2 x l04 2x 102 2 2 x 10-2 2 x 10-4
Co(OH)3 I x 10-43 I • 10-7 I X 10-1ø I X 10-13 IX 10-16 I X 10-19 I X 10-22 I X 10-25
HgOf 3 X 10-26 3 x 10-2 3 x 10-4 3 x 10-6 3x 10-8 3 x 10-1ø 3 X 10-12 3 x 10-14
Ag20g 2.6 x 10-8 2.6x 10n 2.6 x 103 2.6X 102 2.6 x 101 2.6 2.6 x 10-I 2.6 X 10-2
AI(OH)3 1.9x 10-33• 1.9x 103 1.9 1.9x 10-3 1.9x 10-6 1.9x 10-ø 1.9x 10-12 1.9x 10-15
a Unless otherwiseindicated, from King [1959].
/' FromLatimerandHildebrand[1951].
cCu20, K,p-- [Cu+][OH-].
aTi203,K,v = [Ti+++][OH-]
3.
eTiO(OH)2' Ksp = [TiO++][OH-]2.
• HgO,K,v= [Hg++][OH-] 2.
gAg20,K,v -- [Ag+][OH-].

d. Chemicalforms of the transitionmetals. The majority agents the solutionpH determinesthe upper concentration
of the publicationscontainingatmosphericconcentrations for limits (with respectto the hydroxides)of the transition metal
transitionmetals simply report elementalanalyses,and, for ions.Table 3 liststhe solubilityproductsfor the hydroxidesof
obviousreasonsof analytical complexity,do not identify the the most abundant transition metal ions as well as the maxi-
actual chemicalforms in which theseelementsare present.To mum concentrationsof the metal aquo ions in the pH range
a large extent the chemical form of a transition metal in the from 2 to 8. In thisœH rangethe solubilitylimits imposedon a
aerosoldependson the originsof the metal. The element can numberof the metalions(FeTM,Ti TM,Ti TM,CoTM,Hgn, andto a
come primarily from natural sources,from anthropogenic lesserextentCu• and CrTM)are so severethat theseions are
sources, or from some combination of the two. Source unlikely to make a significantcontribution as homogeneous
strengthscan be estimatedby comparingthe concentrationof catalysts.It shouldbe noted that this approachconsidersonly
an element in an atmosphericaerosolto its concentrationin the aquo ion and providesno information on intermediatehy-
the earth'scrustor the sea(the concentrations
are normalized droxideions.For example,in the caseof Fe(OH)3 the solubil-
to an element with a predominantlynatural source,for ex- ity productenablesus to calculatethe aqueousconcentration
ample, aluminum). Rahn [1976] has compiled such ratios, of Fem but not the concentrations
of Fe(OH)2+or Fe(OH)2+.
termed enrichment factors, for a large number of elements Detailed treatment of such systemsis complex and requires
and proceedsto classifyelementsas 'enriched,''intermediate,' knowledge of the equilibrium constantsrelating each of the
or 'nonenriched.' These enrichment classifications are also in- individual hydroxy complexes;these values are not always
cluded in Table 2. Transition metals that are nonenriched available. A recent paper by Zafiriou and True [1980], dis-
(i.e., have predominantlynatural sources)are likely to be cussingequilibriabetweenvariousiron hydroxycomplexesin
presentin the aerosolas oxide componentsof soft,clay, or seawater,illustratesstill further complicationsencounteredin
mineral particles.Transition metals that are enrichedlikely suchan approach.Consideringthe problemsassociatedwith a
enter the aerosolas a result of smelting,refining, combustion, detailedtreatment,hydroxideK,• valuesprovidea quick and
incineration, wear, corrosion,etc. As a first approximation, simple estimateof the limits of metal ion solubility.
enriched metals, because of their more recent origins, are f. Available oxidationstates. The stable oxidation states
likelyto bepresent
in a chemical
formthatis moresoluble of the most abundant transition metals are listed in Table 4. A
and more reactive than the chemical form of nonenriched
key feature of an aqueousredox catalystis its ability to exist
metals.Consequently,Ti and Sc (nonenriched)are expected in solutionin more than one oxidation state[Basoloand Pear-
to contribute little to the homogeneoussolution chemistry; son, 1968].Applying this criterion, Zn, Cd, and Sc, which ex-
significantfractionsof V, Cr, Mn, Fe, and Co (intermediate) hibit only a single oxidation state, are unlikely to function as
are presentin insolublemineral particles,etc.;and Ni, Cu, Zn, efficient redox catalysts.
Ag, Cd, and Hg (enriched)are likely presentin more reactive The oxidationstateof a transitionmetalis alsoquiteimpor-
chemical forms. tant in controllingthe aqueoussolubilityof a species.Prime
e. Aqueoussolubilityof transitionmetal hydroxides. For a examplesare the solubility differencesbetween ferrous and
number of transition metal ions the most important limit on ferric hydroxidesor betweencobaltousand cobaltichydrox-
aqueousconcentrationsis the solubility of their hydroxides. ides (seeTable 3).
By definition, the solubility product is a number which the A numberof the oxidationstateslistedin Table 4, though
productof the ion concentrations in solutioncanneverexceed importantin the chemistryof the element,are unlikely to be
at equilibrium.The solutionpH determinesthe hydroxideion encounteredin the aqueousportion of atmosphericaerosols.
concentration. Thus in the absence of strong complexing For example,the free Cut ion can existin aqueoussolution
518 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

only in trace concentrations, and cuprous salts such as atmosphericaerosols,in order of decreasingabundance,are
Cu2SOnare immediately decomposedby water to yield ele- SOn2-(HSOn
-) > NOs- > El- > NH3 • CO32-(HCO•
-) •
mentalCu and Cull species[Cottonand Wilkinson,1980].Fen, OH- • SO2 > H2S(HS-). In general, chargedligands are ex-
V It, V Ill, and CrIt ionsare eachreadily oxidizedby molecular pectedto give strongercomplexesthan are neutral ligandsbe-
oxygen in air-saturatedsolutions.No simple Ni lit salts are causeof the greater interaction between a positive metal ion
known. These oxidation statesare found under specialcondi- and a negativeligand. It is alsogenerallytrue that an increase
tions but are not likely to be encounteredin air-equilibrated in the basicilyof the ligand increasesthe stability of the metal
solutions. complex.(Of the first-rowtransitionmetals,thisis particularly
g. Ability of various transition metals to form com- true for Sc, Ti, V, Cr, Mn, and Zn.) A rough order of the ten-
plexes. A secondarybut still importantpropertyfor a redox dency of the speciesabove to function as ligands is NH3 >
catalystis its ability to form complexes[Basoloand Pearson, H20 > OH- > NO3- > C1- > SOn2- > H2S.(It mustbe em-
1968].Often, complexationof a substrateby a transitionmetal phasizedthat this order can changewith differentmetals and
promotesthe oxidation of the substrate.In somecases,transi- with differentoxidationstatesof the samemetal.) If all of the
tion metal complexesmay coordinateand 'activate' molecular potentialligandsin aerosolswere presentat similarconcentra-
oxygen. The subjectof transition metal complexesis a vast tions, ordering considerationswould be important. In actual-
area extensivelycoveredin a number of texts [e.g., Cottonand ity, the ligands commonly encounteredin aerosolsare not
Wilkinson,1980;Basoloand Pearson,1968].The stability of a present at concentrationssufficientto displacewater as the
complex dependsin an intricate fashion on both the ligand dominant molecule in the coordinationsphereof the metal
(the moleculecoordinatedto the metal ion) and the metal ion. ion. In addition,none of the ligandscommonlyavailable(in-
There are synergisticeffectsthat prevent one from simply or- cludingwater) form exceptionallystrongcomplexeswith tran-
dering ligands (see below) or metal ions in terms of com- sition metals.This is in contrastto certain multidentatelig-
plexingability. For metal ions,there is a socalled'natural or- ands (ligandsthat bind to the metal through more than one
der'; the stability constantsfor divalent ions of Mn through functionalgroup), such as EDTA, which form very strong
Zn with ligandsthat contain nitrogen donor atoms fall in the complexesand effectivelyremovethe metal from the chemical
order Mn II < FeII < CoIt < Ni n < CUll > ZnII [Cottonand system.A number of polyols (specieswith multiple alcohol
Wilkinson, 1980]. However, even this restrictedsequencecan functionality)have been reportedin aerosols[Wauterset al.,
be scrambledby ligands that do not contain nitrogen donor 1979;Grosjeanet al., 1978]and have the ability to functionas
atoms. For the purposeof this discussionit is sufficientto say multidentateligands.However,it doesnot appearthat any of
that transition metal complexesformed by Cr, Mn, Fe, Co, thesespeciesare presentat sufficientlyhigh concentrationsin
Ni, and Cu are much more numerous and that these elements the aqueousphaseof the aerosolto significantlyaffectthe cat-
have much richer aqueouschemistriesthan do the other met- alytic activity of transitionmetals.
als in Table 2. i. Potential homogeneous redox catalysts. Considering
In consideringcatalytic activity the rate at which a metal- the factorsoutlinedabove,we can estimatethe potentialfor a
ligand bond is broken or formed (lablilly) is as important as given transitionmetal to function as a homogeneous redox
the strengthof the bond (stability). For example,both chro- catalystin aqueousatmospheric aerosols.We proceedin order
mium (III) and cobalt(III) form stablecomplexeswith a wide of reportedabundance(Table2). Iron is an unlikelyhomoge-
variety of ligands. However, the rate at which ligand sub- neouscatalystbecauseof the rapid rate at which the ferrous
stitution occursin these complexesis extremely slow (these ion, in air-saturated solution, is oxidized to the ferric ion. The
complexesare classifiedas 'inert'). This severelyimpairs their ferric ion, in turn, has extremelylimited solubilityeven in
abilityto serveas redoxcatalysts, sincethe rate of substrate moderatelyacidic solutions.Copper has catalyticpotential.
turnover is minimal. Zinc is incapableof redoxcatalysissinceit hasonly onestable
h. Availability of ligandsin the aerosolto complexthe oxidationstate.Titanium is an unlikelycatalystowingto hy-
metal. The most common ligand in aqueous atmospheric droxide-imposed solubilitylimits. Manganesehas catalytic
aerosols is water itself. Transition metal ions dissolved in wa- potential.Vanadiumhascatalyticpotential,althoughthe ions
ter are already complexed;that is, water moleculesare coordi- stablein an air-equilibrated solution(VTMandV v) arelimited
nated to the metal ion. The other ligandslikely to be found in in their ability to form complexes. Nickel is an unlikelycata-
lyst becauseonly one oxidation state is readily available.
TABLE 4. Stable Oxidation States of the More Common Chromiumcatalysisis unlikelysincechromousspecies will be
Transition Metals
rapidly oxidized,chromium(VI) existsonly in oxo species,
Element Oxidation and chromium(III) complexeshave extremelyslowratesof
ligand exchange.Cadmium is incapableof redox catalysis
Fe Fell,F½Illa
Cu CuI, CuiI a sinceit hasonly one stableoxidationstate.Cobalt, scandium,
Zn Zni! a mercury,and silverare eachunlikelycatalystsbecausethey
Ti Ti m, TilV a are normallypresentin small amountsin atmosphericaero-
Mn Mnn,a Mn TM,Mn TM,Mn vI, MnVII sols.In summary,copper,manganese, and perhapsvanadium
V VII, VIII, VlV, V v a and nickel each have potential as homogeneous redox cata-
Ni NiH,a Ni TM
Cr CrlI,a CrlII,a CrTM lystsin aqueousatmospheric systems.Of thesefour, manga-
Cd CdlI a neseis probablythe mostimportantbecauseof its multiple
Co Con? CoTM oxidation states.
So ScllI a
j. Heterogeneous catalysis. Heterogeneouscatalysis,as
Hg HgI, HgHa
Ag AgIa
usedhere,meansthat the reactantand the catalystare in two
separatephases.Consequently,the solubilityof the transition
Most stable state.
metal is an unimportantfactorfor heterogeneous processes;
 GRAEDEL
ANDWESCHLER:
AEROSOL
ANDRAINDROP
CHEMISTRY 519

TABLE 5. Initial Homogeneous

Gas PhaseReactionRates for of theparticles
is 2.2 g/cm3 [Judeikis
andSiegel,1973].For a
SelectedAtmosphericGases real-world aerosolthat has a 'dirty' surface,a reasonableup-
-d[G]ldt,molecules
s-! m-3 perlimit on theaccommodationcoefficienta is 0.03(see,for
example,Heicklen[1976]or Chodes
et al. [1974]).An average
Species GasPhase
Reactant Urban Rural value for the molecularweight of the gasis 40 amu or 0.040
H202 h•, 5 X 1012 2 X l0l! kg/mole.Theseestimates yield
CO HO' 3 X 1013 4 X 10l!
NO 03 4 X 1015 4 X 1013 rateof collision+ incorporation
= 4.2 x 10-316
'] s-1 (117)
NO2 ht, I X 1016 2 X 1013 Henceforatmospheric
concentrations
rangingfrom2.5x 1015
H2S HO' I X l0l! 5 X 109
SO2 HO' 6 X l0II 1X 10lø to 2.5 x 1017molecules/m 3 (--•0.1-10ppb), reasonableupper
CU4 UO. 3 x l0l! I X l0ll limitsfor the rate of collisionand incorporation are 1 x 1013
CH3CH2CH3 HO' 2 X 1012 2 X l0l! to 1 x 1015molecules s-l m -3.
CH2CHCH3 HO' 2 X 1013 3 X l0l! The nextstepin thisevaluationprocess
is to comparethe
CH2CHCH2CH3 HO' 2 X 1012 3 x l0l!
HCHO hp I X 1013 4 X l0 l! upperlimitsjustderived
fortherateof collision
andincorpo-
CH3CHO hp 3 x 1012 6 x 10lø ration with that for reaction at the transition metal surface.

Rate constantsare from Graedel[1978].Concentrations

of atmo-
For a redoxprocess
a reasonable
upperlimit on the catalytic
spheric
gases
arefromTable8 andGraedel
[1978]. activity
(therateperunitareaatwhichmolecules
react)is 10TM
molecules
s-! cm-•- (see,for example,Sleight[1980,andrefer-
theability
ofthemetal
toformcomplexes
andtheavailability
ences
therein]
orGlasstone
etal.[1941]).
Toestimate
thecata-
ofligandsforsuch
complexesarealsofarless
important
in lyticsurface
areaofthetransition
metal,
assume
themetal
is
heterogeneous
processes
thanin homogeneous
ones.
How- present
intheatmosphere
ata concentration
ofI/•g/m3(ap-
ever,theotherfactors
considered inthepreceding
paragraphs proximately
theatmosphericconcentrationof iron),hasa
onhomogeneous catalysis
(transition
metal
abundance,chem-density of5 g/cm3(similar
toFe203),andexistsas0.1-/zm-di-
icalform,andavailable oxidation
states)
areof significance.ameter
spheres(anassumption
thatwillgiveanexaggeratedly
A redoxprocessthatisheterogeneously
catalyzedbya tran- highvalue
forthesurface
area,consistent
withanupper limit
sitionmetalwithinan aqueous atmospheric
aerosolmaybe estimate). Usingthesevalues,
thetotalcatalytic
surface area
separated
intoasmany assevensteps:
(1)transport
ofthere- ofthetransition
metal
would be--•0.1
cm2percubicmeter of
actant(s)
to thegas-liquid
interface,
(2) transport
of react-air.Theproduct
ofthisvalue andthecatalytic
activity
yields
ant(s)
acrosstheinterface
andthroughtheliquidtothepar- a rateof1013
molecules
s-l m-3asanupperlimitforreaction
ticle surface,(3) adsorption
of reactant(s)
at the particle at thetransition
metalsurface.
surface,
(4)reaction
onthesurface,
(5)desorptionof prod- Fromtheabove calculations
weconcludethatforgaseous
uct(s)
fromtheparticlesurface,
(6) transport
of product(s)
concentrations
greaterthan0.1ppbthemaximum rateforan
throughtheliquid
andacross
thegas-liquid
interface,
and(7) atmospheric
reactionheterogeneously
catalyzedbya transi-
transport
of product(s)
fromtheinterface
intothebulkgas tionmetal
islikelytobedeterminedbytherateofreaction
at
phase. themetal
surface
andisoftheorder
of1013
molecules
s-! m-3.
Thepotential
importance
of transition
metals
ashetero-Atgaseous
concentrations
below0.1ppbthemaximum rateis
geneous
catalysts
depends
ontherateofthecatalyzed
reac-likely
tobedetermined
bytherateofcollision
andincorpora-
tionascompared
withtherateofthenoncatalyzed
reactions.
tionandisgivenbyexpression
(117).
Tomake
such
comparisons,
it isuseful
toestimate
anupper Table5 presents
rates
ofdisappearance
forselected
atmo-
limitfortherateof theformerreaction.
Therate-determining
spheric
gases
asa consequence
of homogeneous
gasphase
re-
stepina heterogeneous
reaction
involving
a gasanda transi-actions.
Comparisonsofthese
rates
withthevalues
estimated
tionmetalismost
likelytobeeither
steps
1and'2(collectively
abovereveal
thatforcertain
processes,
heterogeneous
path-
considered
astherateofcollision
andincorporation)
orstep4 wayscannot
compete
withhomogeneous
ones(e.g.,theoxida-
(therateof reaction
at theparticle
surface).
Thefollowing
tionofNOorthedecomposition
ofNO2).
However,
forthe
paragraphs
estimate
upper limitvalues
foreach
process. majorityofthereactions,
heterogeneous
catalysis
bytransi-
The rate of collisionbetweena gasmoleculeand an aerosol tion metalshasthe potentialto makea significantcontribu-
[Present,1958]is givenby tion.Amongtheseprocesses aretheoxidationof SO: andfor-
maldehyde,
the decomposition
of hydrogenperoxide,and
rateof collision= (8RT/½rMG)I/2(A/4)[G] (115) perhaps the oxidationof carbonmonoxide (considering the
whereR is the gasconstant,T is the temperature,
MG is the respective
atmospheric concentrations
and the ratesof the
molecular
weight,A isthesurface perunit vol- corresponding
areaof aerosol homogeneous reactions).Synergisticeffects
umeofspace,
and[G]istheconcentration
ofthegas
molecule.
maybeimportant
intheaboveprocesses
(forexample,
the
Onlyafraction
ofthesecollisions
willlead
toincorporation
of heterogeneous
oxidation
ofSO:issignificantly
influenced
by
thegas
molecule
intotheaerosol: trace
quantities
ofNO:[Barbarayetal.,1978;Cofer
etal.,
1980]).
rate of collision + incorporation -- k. Summaryof transitionmetal chemistry. Transition
(aT/2,rrMv)l/2(,,t)[G]a (116) metalshavethe potentialto serveas bothhomogeneous
and
where a is the 'accommodationcoefficient,'that is, the frac- heterogeneous.
catalysts.
The metalionsmostlikelyto be ef-
tion of moleculesimpingingon the aerosolthat are incorpo- fectivehomogeneous
catalystsare copper,manganese,
and
rated(seesection
El). To evaluate thatin a (perhaps)
(116),consider vanadium.
The othertransition
metalsarelimited
typical
particle
sizedistribution
thetotalsurface
areaof the intheirability
tofunction
ashomogeneous
catalysts
because
aerosol
perunitvolume,
A,isapproximately
0.0014
m2/m 3if oftheirsolubility,
available
oxidation
states,
oratmospheric
theaerosol
concentration
is 100/•g/m
3andthemeandensity abundance.
Solubility
isunimportant
forheterogeneous
cata-
520 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

lysis.Consequently,the list of metalsthat haveheterogeneouscles under favorable photochemicalcircumstances. These

catalyticpotentialis longer:iron, copper,titanium, manga- skinsmay form relativelylate in the lifetimesof the particles,
nese, vanadium, and (perhaps)chromium.Examinationof' 'effectivelysealingin the aqueousconstituents whichdominate
rates for noncatalyzedgas phasereactionsindicatesthat het- aerosolchemistry.
erogeneouslycatalyzed pathways are most likely to make a
2. Alkanes
significantcontribution to the oxidation of sulfur dioxide, for-
maldehyde,and perhapscarbon monoxide,as well as to the Alkanes are very commonaerosolconstituents.Those with
decompositionof hydrogenperoxide. C > 5 are generallypresent[Appelet al., 1975;Eichmannet al.,
1979];the range of alkanesoften extendsto carbon numbers
of at least 30 [Hauser and Pattison, 1972; Cautreelsand Van
D. ORGANIC AEROSOL AND RAINDROP CHEMISTRY
Cauwenberghe, 1976;Eichmannet al., 1979].A major source,
1. Introduction at leastin urban areas,is aerosolizedlubricating oil from mo-
tor vehicle exhaust [Duboiset al., 1970; Cukor et al., 1972].
Organic aerosolchemistryhas generallybeen given short Alkanes are rather insolublein water and seemlikely to be
shrift in comparisonwith the inorganicanalog.This neglect major constituentsof the organicfilms found on many aerosol
has been largely a function of the complexityof the system particles. The initial reaction of dissolvedalkane molecules
and the shortageof kineticdata rather than lack of its impor- will be abstractionof a hydrogenatom (for simplicity,we as-
tance:both Duce [1978] and Jaenicke[1978] have noted that sume that this occurson a terminal carbon):
the production of organic particles is of the same order of
magnitudeas the productionof soft-derivedaerosols,sea salt, RCH3 + OH'--> RCH2' + H20 (118)
and sulfates.
RCH3 + C1 ß--> RCH2' + HCI (119)
The massof organiccompoundsin aerosolsis substantial.It
varieswith locationand seasonand can be particularlyhigh The alkyl radicals will then add molecular oxygen at rates
in forestedregions[Goetz, 1960].In arid regionsthe organic that are at or near diffusioncontrol [Howard, 1973;Rabani et
contentof the soil is reflectedin an organiccomponentof the al., 1974]:
wind-erosion-generated soft-derivedaerosol[Delanyand Zen-
chelsky,1976].In urbanareas,at least,the organiccomponent RCH2' q- 0 2'•> RCH202 ß (120)
of the aerosolcan to someextentbe relatedto photochemical
The peroxyl radical may react with another alkane molecule
activity (seeFigure 5). A generalestimateis that the organic
to form a hydroperoxide[Ingold, 1973]:
component constitutessome 10-30 wt % of the total atmo-
sphericparticulatematter [Grosjeanet al., 1976;Ketseridisand
R•CH202' q- R2H--> R•CH202H q- R2' (!21)
Eichmann, 1978].
A very large number of organic compoundshave been whichwill promptlyphotodissociate to producethe associated
identified as aerosolcomponents[Graedel, 1978; Karasek et alkoxyl radical [Livingstonand Zeldes, 1966]:
al., 1978]. The properties and reactivities of the individual
chemical groupsare discussedbelow. It is useful to note here RlCH202H •-•RlCH20' + OH. (122)
that they are sometimeschemically divided into bases,acids,
and neutral compounds,typical weight percentages of these The alkoxylradicalwill presumablyreactwith molecularoxy-
types of compoundsbeing •8, •27, and •64 [Ketseridisand gen to form the carbonyl derivative:
Eichmann,1978;Hahn, 1980].Organic compoundsare found
in rain and snowas well; detailedanalyseshave been reported RlCH20' q- 02 --> R,CHO + HO2' (123)
by Gallowayet al. [1976] and by Lunde et al. [1977].
If the initial organic radical is of the a-hydroxyl type, carbo-
Several investigators suggestthat at least some organic
molecules are found on the outer surfaces of aerosols rather
nyl compoundswill be formed directly [Downesand Sutton,
1973; Carter et al., 1979]'
than beingdistributedthroughoutthe aqueousphase[e.g.,Rip-
pertonandJeffries,1971;Bigget al., 1974b;Husarand$hu, 1975]. RCH(OH). + 02 --> RCHO + HO2' (124)
This is a natural consequenceof the low aqueoussolubilities
and surfactantcharacterof many organiccompounds.If Alkanesin solutionare thusexpectedto providecarbonyl
close-packedlayersof organicmolecules
formon atmosphericcompounds which,as seenbelow,are susceptible
to further
aerosolparticles,
theeffectwouldbe threefold:
evaporation
of oxidation.
interior volatiles would be inhibited [Chang and Hill, 1980], 3. Alkenes
diffusionof water-soluble(largelyinorganic)compoundsinto
the chemically active solution [c.f. Hales, 1972;Strathdeeand A number of alkeneshave been detectedin aerosols[Appel
Given, 1977]would be inhibited, and the presenceof organic et al., 1975;Kunenet al., 1976].The atmosphericlifetimesof
molecules on the exterior of the aerosol would reduce the ul- alkenes are considerablyshorter than are those of the corre-
traviolet flux reachingthe interior. Giddingsand Baker [1977] spondingalkanes [Graedel, 1978]. It thus seemslikely that
suggestthat most atmosphericorganicshave surfaceenerget- most of the compoundsdetectedhad their originsin automo-
ics that are unfavorable for the formation of close-packed tive exhaustor someother anthropogenicsourcethat allowed
films. This seems inconsistent with the observation of 'elastic direct aerosolization.
skins' on aerosols[Husar and Shu, 1975]; it is worth noting Alkenesreact in solutionby addition of the hydroxyl radi-
that Garfias[1979]haspresentedtheoreticalargumentsin sup- cal at the point of unsaturation:for ethylene [Thomas,1967],
port of the formation of a stablesurfacelayer in which only
CH2--CH2 + OH.--> HOCH2CH2 ß (125)
half of the surfacemoleculesare organic. It thus seemslikely
that surface'skins'are presenton at least someaerosolparti- By analogy with the favored reaction of the methanol
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 521

(HOCH2 ') radical in solution[Rabaniet al., 1974],addition of

molecularoxygenis anticipatedfor the ethanol radical:
HOCH2CH2' + O2 --> HOCH2CH202 ß (126) 03 o
O•HO HO
o//"'--
with subsequenttransition to the hydroxyaldehydethrough
chainsanalogousto thosefor the alkane derivatives.
In addition to the structures shown, structures in which the
Alkenes in solution react readily with ozone. The mecha-
-CHO group was replacedby-CH2OH or-COOH were com-
nisms and products can be quite complex [e.g., Bailey and
mon. Nitrites and nitrates were also detected. These structures
Lane, 1967;Murray, 1968;Murray and Suzui, 1973],but recent
are consistentwith initial attackby ozoneover a doublebond,
work suggests that the ozonolysisproceedsthrougha Criegee-
followedby a variety of oxidation,addition, and elimination
type cleavageof the double bond. For example, Griesbaum
reactions.Detailed mechanismsin the gas phase have been
and Hofmann [1976] deducethe following partial mechanism
for the solutionozonolysisof trans-2,3-dichloro-2-butene:
suggestedby Graedel[1979];thosein aqueoussolutionseem
likely to be similar both to the gasphaseoxidationprocesses
and to solutionprocessesfor alkenesand aromatics.
CH
3-C(C•,)
=C(C•,)-CH
3 ?3 • Hp.O
• CH3COC•.• CH3COOH
CH3C+
(Cl)-00- HC•, '5. Aromatics

Peroxideand epoxideproductsare alsoproduced.The mech- Most of the common substituted benzenes and substituted
anism has marked similaritiesto the gas phaseozonolysisof naphthaleneshave been identified as aerosol components
cyclicalkenes(seediscussionbelow (sectionD 11) on organic [Schuetzleet al., 1975;Kunenet al., 1976].In addition,a wide
radicals).It is notablethat a principal productis a carboxylic spectrumof polynucleararomatic hydrocarbonsare present
acid, a classof compoundscommonly found in aerosolsand [Lao et al., 1973;Bj6rsethet al., 1979].The apparentsourcesof
raindrops. thesecompoundsare a wide variety of natural and anthropo-
geniccombustionprocesses.
4. Terpenes Methylated benzenesreact with the hydroxyl radical in
Terpeneshave long been regardedas a potential sourceof neutral or mildly acidic solution[Sehestedet al., 1975].Add-
'blue haze' aerosolsover forestedregions[Went, 1960],in part itoh occurs,with the eventualproductbeing an alcoholor cre-
becauseaerosolsare commonproductsof terpenesmogcham- sol [Kochi, 1973]:
ber studies[Stephensand Price, 1970;Lillian, 1972; Ripperton I
et al., 1972].Terpeneshave not beenidentifiedas aerosolcon-
stituents,but severalterpene derivativeshave been. Terpene
gas phase lifetimes are of the order of a few hours, and it OH HOp_- OH
seemsreasonableto supposethat at least the initial oxidation A smallerpercentageof the time, hydrogenatom abstraction
step occursin the gas phase,producingderivativesthat are from an alkyl group by hydroxyl or chlorine radicalswill oc-
more solublein aqueoussolutionsthan are the terpenesthem- cur [Sehestedet al., 1975],initiating a chain that resultsin car-
selves[Graedel, 1979]. boxylic acid formation:
The most common of the terpenesand the most widely CH2* CH202- C(O)OH
studiedis a-pinene (StructureI below). Two of its derivatives,
pinonic acid (Structure II) and nor-pinonic acid (Structure
III), have been detectedin both laboratory-generated aerosols
[Wilsonet al., 1972]and natural aerosols[Wilsonet al., 1972; H20 HC•
Cronn et al., 1977].
The polynucleararomatichydrocarbons are moderatelyre-
activein aqueousenvironmentalsolutions[Falk et al., 1956],

• 03=
I
O•/jCOOH
O••i•CO0
H •
and their oxidation,perhapsby the O2('A)producedin ozone
photolysis(reaction (9)), is expectedto lead to formation of
endoperoxides [Fatiadi, 1967; Committeeon BiologicEffects
of Environmental Pollutants,1972;Fox and Olive, 1979].Thus
What portionof the oxidationoccursin the gasphasehasnot for anthracene,
beendetermined;a-pineneis known to autoxidizein the pres- H

enceof water and sunlight,however,to producesuchproducts

as verbenone(StructureIV) and verbenol (StructureV) [de (129)
Mayo, 1959]. 02

••o ••L•
OH If the bridgeheadcarbonatomsare also bondedto hydrogen
atoms, conversionto quinonesoccursrapidly [Committeeon
BiologicEffects of EnvironmentalPollutants, 1972; Barofsky
and Baum, 1976]'

The productsof photochemicalreactionsof limonene and

terpinolene in a smog chamber containing ozone and NO,•
have been studied by Schuetzleand Rasmussen[1978]. For (130)
limonene(StructureI, below) they found the principal prod-
uctsto be ketonesand substitutedketones(StructuresII-IV).
522 GRAEDEL AND WESCHLER.' AEROSOL AND RAINDROP
Oxidation can also take place by oxygen addition to a satu-
rated C-H bond [Committeeon BiologicEffects of Environ-
mental Pollutants,1972;Korfmacheret al., 1980]:for fluorene,
H2 0 ily than do ketones [Noller, 1958]. Thus numerous linear
•C• [0]
••
An alternative processfor the polycyclic aromatic com-
poundsis nitrosation.Pitts and colleagues[Pitts, 1979]have
demonstratedthat particulate benzo (a) pyrene reacts with
gaseousNO2, particularly in the presenceof HNO3 or H2SO4,
to producethe nitro derivative:
O• + NO2
(g) H
N03
(g)O•
OR
=---
H2S04(g)
The generalityof suchprocesses
remainsto be established.
6. Alcohols
Two classesof alcoholsoccur with reasonablefrequencyin
aqueousatmosphericsystems.The first is composedof ali-
phatic alcoholswith C _• 5, which are often found in combi-
nation with aldehydicor acidic forms of the samecompounds
[Schuetzleet aL, 1975; Cronn et aL, 1977]. The secondclass
consistsof the aromatic phenols and cresols[Schuetzle,1972;
Cautreelsand Van Cauwenberghe,1976]. These compounds
have many direct sources[Graedel, 1978] but may result as
well from reactions in the gas phase and in solution (see
above). A number of polyolshave also been identified [Wau-
terset aL, 1979].
Aliphatic and aromatic alcoholsare readily oxidized to al-
dehydesor ketonesin solution.The processis generallywrit-
ten in chemistrytektbooksas
RCH2OH • RCHO
where [O] indicates'any suitableoxidizing agent.' In aqueous
atmosphericsystemsthe processbeginswith hydrogen atom
abstraction [Asrnuset al., 1973]:
RCH2OH + OH .---• RCHOH. + H20
RCH2OH + C1 .---• RCHOH. + HC1
followed by [Downesand Sutton, 1973; Carter et aL, 1979]
RCHOH. + 02 • RCHO + HO2'
7. Carbonyls
A number of carbonyl compoundshave been detected on
aerosols.The most common are aliphatic and olefinic alde-
hydes and dialdehydeswith 5 _• C _• 7 [Schuetzleet al., 1975;
Cronn et al., 1977], although a number of aliphatic ketones
and aromaticcarbonylsincludingbenzaldehydeand quinones
are also present [e.g., Graedel, 1978, 1980]. No direct sourceis
known for most of thesecompounds,and it is generally be-
lieved that they are chemically formed by atmosphericreac-
tions in either the gasor the liquid phase.
The predominant common gaseouscarbonyl compoundin
the atmosphereis formaldehyde,which has recently been de-
tected in both aerosolsand raindrops [Kliœœel and Warneck,
1978].Sincecarbonylcompoundsare generallywater-soluble,
one should anticipate that other compoundsknown to be
CHEMISTRY
present in the atmosphereas gases(acetaldehyde,acetone,
etc.) will be presentin aqueousatmosphericsystemsas well.
Aldehydesundergo oxidation in solutionmuch more read-
chain organic acids (which result from aldehyde oxidation)
(131) are observedon aerosols,but branched chain organic acids
(which would result from ketone oxidation) are not [Graedel,
1978]. In solution, the aldehydesare in equilibrium with re-
lated glycols:
H20
RCHO • RCH(OHh (137)
--H20
Formaldehydeis almostentirely in the glycolform in aqueous
solution [Walker, 1964;Funderburket al., 1978];the equilib-
NO2
(132)
rium for someof the more complexaldehydesis much further
to the left. The most efficient solution oxidation route for for-
maldehydemay be hydrogen atom abstractionfrom the gly-
col, followed by rearrangementand a secondabstractionto
give the carboxylicacid:
C!-, OH- 02
RC(OH)zH
[ • RC(OH)
z-• RC(OH)HO.
• RC(O)OH
HC•"
H20 H02ø (138)
It is uncertainwhetherphotochemical processes
play a sig-
nificantrole in the aerosolchemistryof carbonylcompounds.
This uncertaintyarisesbecauseof the small overlapbetween
the availablesolarultravioletflux and the absorptionspectra
of the carbonyl compoundsin aqueoussolutionand because
vibrational deactivation of excited molecules in solution is
rapid and alternative processescompete effectively [Coyle
and Carless, 1972]. Two distinct topics are of interest;first,
photochemicallyexcited reactionsof carbonyl compounds
that are otherwiseforbidden,and second,the potential of
thesereactionsto significantlyaffectthe solutionchemistryof
(133) other aerosolspecies.
The solarirradiancein the troposphere decreasessharplyat
wavelengthsbelow 320 nm [Greenet al., 1974]as a result of
absorptionby ozonein the stratosphere, becomingnegligible
at •290 nm. In contrast,aliphaticcarbonylcompoundsare
(134) only beginningto absorbat suchwavelengths.Encinaset al.
[1980]point out that aliphaticketonesdo not absorbappre-
(135) ciably in aqueoussolutionat X _>337 nm. At X _<300-310 nm,
however,acetone[Porteret al., 1971]and larger aliphaticcar-
bonyl compounds[Yang and Feit, 1968; Chen et al., 1973;
(136) Blank et al., 1974]begin to demonstrateappreciableabsorp-
tion. Without quantitativeabsorptionspectrafor the carbonyl
compoundsin aqueoussolutionit is not possibleto assess with
certaintythe overlapof speciesabsorptionand solarradiation
or what photoprocesses may be active.It is useful,however,to
discussa few of the common atmosphericcarbonyl com-
poundsindividually.
Formaldehyde,the only Cl carbonyl compound,existsin
solutionin glycolform, which doesnot absorblight at tropo-
sphericwavelengths. Acetaldehyde,the only C2 carbonyl,ab-
sorbslight within the 300 nm _<X _<350 nm band in aqueous
solution [Blank and Fischer, 1973]. Alpha cleavageat these
wavelengthsdoesnot occur [Yang, 1967;Henne and Fischer,
1975],but the speciesdoesundergoH abstraction.The sameis
true of propanal[Blank et al., 1975],althoughin thiscasesome
alphacleavagemay occurin the 290 nm _<X _<310 nm region
[Chen et al., 1973]. Acetone in aqueoussolution also under-
goesH atom abstractionfollowing irradiation at 300 nm _<X
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY
0.2
•c• OA OHC(CH
O
o•
z<u""
z PEAKIO
3 9.
o,,'<0.2
•õ•, o.•
HR OF DAY (PST)
Fig. 6. Diurnal variation of aldehydicnitrate and acidic nitrate
aerosolcompounds in WestCovina,California,July23-24, 1973[af-
ter Aœœel
et aL, 1975].The data suggest
the oxidationof aldehydesto
acidswithin the aqueousaerosolsolution.
_<350 nm [Henne and Fisher, 1975]. For C >_4 carbonyls,H
atom abstractionand alpha cleavagehave both been observed
in variouscasesand with,variousirradiation techniques[Yang
and Feit, 1968; Blank et al., 1974, 1975; Fallis, 1975; Encinas et
al., 1980].Cleavagehas generallybeen seenonly for hydroxy-
substitutedcarbonyls or using irradiations with significant The subsequentreaction stepshave not been characterized
powerat wavelengths3,< 300 nm. Followingcleavagethe al- but would be expectedto yield a variety of oxygenatedderiva-
koxyl radicalsare expectedto abstracthydrogento form alde- tives.
hydes [Shafferet al., 1972; Bak et al., 1977] as in
0
•k",,hv•C(O)'
RH•CHO CH$. R*
To summarize,the casefor carbonylphotochemistryin at-
toosphericaerosolsis tenuous.If suchprocesses do occur,they
seem likely to be those leading to the eventual formation of
carboxylicacidsof the samecarbonnumber rather than to the
productionof small radical fragmentsthat could have a much
wider chemical influence.
8. CarboxylicAcids
Carboxylic acids are perhapsthe most common of the or-
ganic constituentsof aerosolsand raindrops.Formic and ace-
tic acids(the smallestpossiblealiphatic carboxylicacids) are
possibly,thoughnot certainly,present[Dawsonet al., 1980].A
wide variety of carboxylicacidswith C >_3 is found in urban
aerosols[Schuetzleet al., 1975; Cronn et al., 1977; Grosjeanet
al., 1978],in marine aerosols[Bargerand Garrett, 1976;Marty
et al., 1979], and in precipitation [Gallowayet al., 1976;Lunde
et al., 1977].The fatty acidsare widely presentin nature in the
marine surfacelayer and as volatile plant constituents,so that
direct injection is almost certianly responsiblefor at least a
portion of the carboxylicacids in aqueousaerosols.Several
lines of independentevidenceindicate the presenceof chem-
ical formation mechanismsfor lower molecular weight car-
boxylic acids. These include the precursor-productstudiesof
Grosjean [Committeeon Medical and BiologicEffectsof Envi-
ronmental Pollutants, 1977], the occurrencerelationships of
oxygenated organic compoundson aerosols[Graedel, 1978],
and the diurnal pattern relationshipsnoted by Appel et al.
[1975] betweenurban aldehydesand carboxylicacids.The lat-
ter are reproducedin Figure 6.
Carboxylic acids are partly dissociatedin solution:
H20
RC(O)OH • H30+ + RC(O)O-
•H20
523
and thus provide a small degreeof acid bufferingto aqueous
atmosphericsystems.They do not absorb radiation at the
wavelengthspresent in the troposphere[Kaiser and Fischer,
19791.
Organic Bases
As discussedin the introduction to this section, some 8 wt %
of the organic compoundson aerosolsare basic in nature. At
the pH of a typical aqueousaerosol,a significantpercentage
of thesebaseswill be protonated.The speciesinvolved include
aminesand heterocyclicnitrogen compounds[Novakovet al.,
1972].As with other organics,data from aqueoussolutionex-
perimentssuggest that reactionswith the hydroxylradicalpro-
vide the most likely mechanismsfor chemical degradation.
The most completedata are for indole, which adds the hy-
droxyl radical [Shetiyaet al., 1972]to the aromaticsystemin
reactions of the form
N N
OH*
= j0 (141)
10. Other OrganicCompounds
The potential exists[e.g., Chawlaand Fessenden,1975] for
the formationof sulfur-containingorganicaddition products.
Although chemicaldetailsare lacking,the detectionof sulfur-
containingorganicaerosolcompoundsin laboratoryexperi-
ments [Hirose et al., 1975; $chultenand $churath, 1975b] and
on aerosols[Panterand Penzhorn,1980]is evidencefor the ex-
istenceof suchchainsin atmosphericsystems.
The reactionsof a number of complexorganiccompounds
foundin aqueoussolutionhavebeendiscussed by Mabey and
Mill [1978]. They emphasizehydrolysis,which they define as
'the reactionof a compoundin water with net exchangeof
some group X with OH at the reaction center:
RX + H20--> ROH + HX. (142)
The detailedmechanismmay involvea protonatedor anionic
intermediateor a carboniumion, or any combinationof these
intermediates.'The chemicalgroupswith which they deal
(halides, haloalkanes,epoxides,esters,amides, carbamates,
phosphoric andphosphonic acidesters,acylatingand alkylat-
ing agents,and pesticides)are found more often in freshwater
streamsand riversthan in the atmosphere; it thusappearsap-
propriate merely to note this source of information rather
than to discussthe subjectin detail in this review.
11. Organic Radicals
A number of oxygenatedorganicradicalsare formed in the
atmosphereby gas phase chemical reactions.These radicals
may be relativelysimple,suchas the methylperoxylradical
formed by
OH- 02
CH4
(g)• CH3ø(g
)• CH30,•ø
(g) (143)
H20
or they may be complex, such as the structuresproposedby
Grosjean [Committeeon Medical and BiologicEffectsof Envi-
(140) ronmentalPollutants,1977]to accountfor the productsformed
upon photoxidation of cyclic alkenes:
524 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

eousfilm which is set up by the gas-liquid interface and rein-

forced by the presenceof wake effectsaround the droplet
(;'AS
FLOW FIELD,,,
[Parker, 1977].The moleculemust next traversethe interface
and the liquid interfacefilm. This film may consistlargely of a
'skin' of organicmolecules,which could have the effect of in-
hibiting transport. Another potential inhibiting effect is the
volatilization of dissolved gases as a result of gas-particle
equilibria [e.g., Tang, 1980]. Finally, circulation within the
aqueousphasemust be consideredif it is significantlyslower
than the chemicalreactiontime scale.Experimentsby McRae
et al. [1978]suggest,however,that liquid phasereactionveloc-
ities, and not diffusion times, control chemical processesoc-
curring in aerosolsolution.
The complexities involved in quantitative treatment of
theseprocesses are sufficientthat evaluationcurrently appears
theoreticallyintractable [Hales, 1972]. It is possible,however,
to accuratelycompute the gas phase diffusion portion of the
problem and to parameterizethe film transportand interfacial
Fig. 7. Mechanismsof transportin an atmosphericaerosoldrop- transport processesinto an 'accommodation coefficient' a.
let. Note that the presenceof an insolublecore will alter the circula- The rate of incorporationof a gaseousspeciesi into the atmo-
tion patternsshownhere.(Figure is from Hales [1972].Reprintedby sphericaerosolis then the product of that speciesconcentra-
permissionof PergamonPress.) tion and of the 'effective flux' of that speciesto the aerosol
0-0 surface.Fuchsand Sutugin[1971] have shown that the latter
may be expressedfor the speciesas
o • Clio
2
•( +03 g) (g)
•
--IZm
qh II 1+
• L ..IcH0 (144)
,, 1+fiKndD, v (g) 3a-----•---i-'
Kn (146)
The parameters in (146) are definedasfollows:Nr is the num-

+OH*•,•0U 02'e,.,,-CU0
u (145)
L ..•HO
v (g) NO v (g)
g) (g)
ber of aerosolparticlesof diameterDr in a cubiccentimeterof
air at the time of the calculation;Pminand Pmaxare the limits
within which significant surface area is found; Kn is the
In any case,it can be expectedthat oxygcnatcdradicalswill Knudsennumberof theparticle(Kn -- )•i/rr, where)•iisthe ef-
havea reasonableaffinityfor waterand will enterinto aqueous fectivemean free path for the condensingspeciesi in air); fi is
atmosphericchemistryupon incorporationinto aerosolsor a parameter given [Fuchs and $utugin, 1971] by the inter-
raindrops.The radicalchemistryis expectedto parallelthe re- polation formula
actions outlined in sections D2-D10.
fi = (1.333+ 0.71Kn-')/(l •- Kn-') (147)
12. Summary
ai is the accommodation coefficient, that is, that fraction of
Althoughextensiveresearchremainsto be doneon the oxi-
moleculesimpinging upon a surfacethat undergo incorpora-
dation of organicmoleculesin aqueousatmosphericsystems,
tion; and Di is the moleculardiffusionconstant,given approx-
the broad outlinesof the processseemclear, in part because
imately by [Kennard, 1938]
Mill [1980]has recentlypresentedan excellentdiscussion of
the currentinformationregardingthe reactionsand processes
involved.The oxidationinitiator for mostorganicmoleculesis 3 '/• I M,+M.k (148),
likelyto beOH -, althoughO3and•O•_ mayoccasionally serve
this function. The potential sourcesof OH- are the dis- where N. is the number densityof air moleculesat the altitude
sociationof dissolvedO3 and the photodissociation of dis- of concern,Mi and M. arc the massesof the speciesof interest
solvedH•_O•_. The organicradicalformedby the initiator reac- and of air; and S• is the 'reducedsurfacearea,' given by
tion will add O•_to form a peroxy radical, which can then
enter into a variety of propagationand terminationreactions s, = [,fro,+ 0.)'-]/4
to producehydroperoxides, alcohols•and ketones.
where o•and o. arc the effectivediametersof the speciesof in-
tcrcst and of air.
E. THERMODYNAMIC AND KINETIC PROCESSES
To performthe calculations required,it is necessary
to spec-
TransportBetweenGaseous
andLiquidPhases
ify the diffusionconstants(or effectivediameters)and the ac-
In orderfor atmospheric gases
to enterintochemicalreac- commodation coefficients
of eachof thechemical
species,plus
tionswithinthe aqueousaerosolparticle,theymustbe incor- the aerosolnumberdistributionas a functionof time of day.
poratedintothebulkliquidsurrounding theparticlecore.The Diffusionconstants or diametersare generallyavailablefor
stepsinvolvedin thisprocess havebeenreviewedby Hales thespeciesof interest;
if not,theyarecalculated
by [ Wilkeand
[1972].Initially,of course,
themolecule mustbein motionin Lee, 1955]
the gasphasein a directionsuchthat it will interceptthe par-
ticle.Then,asshownin Figure7, it mustpassthroughthegas- o•= 1.18(GMgV•./p•)
•/3 (150)
 GRAEDEL AND WESCHLER: AEROSOLAND RAINDROP CHEMISTRY 525

whereGMW•is the appropriategrammolecularweightand Pi providethe mostusefulquantitative informationon inter-

the density. facialtransport
rates,
at least
for the forseeable
future.
The remainingparameterrequiringspecification
is the ac-
2. ScavengingofAerosols byRaindrops
commodationcoefficient.In the generalcase,a may be ex-
pectedto be a functionof species
concentration
(because
of Raindropchemistry is complicated by the fact that the
saturation effects),of time of day (becauseof the anticipated dropsscavenge aerosol particles
duringtheirfall [e.g.,Gon-
diurnaltimedependence of theorganiccoatingdevelopment), zalesandMurr, 1977],as do snowflakes [e.g.,Magonoet al.,
and perhapsof otheratmospheric variables.To begin,con- 1979].Scavenged particles arealmostcertainly thesourceof
siderthe caseof unsaturatedsolutionsand negligibleorganic theionsof sodium,potassium, calcium,andothermetalsthat
coatings. The maximumpossible value of a is unity, and are sooftenfoundin raindrops[Likenset al., 1979;Liljestrand
Heicklen[1976]hasarguedthat sucha valueoftenprevails andMorgan,1981].The complexities of the scavengingproc-
when moleculesof one substanceapproachdropletsof the essaremany.The subject hasrecentlybeentreatedin detail
samesubstancein uncontaminatedsystems(i.e., in the ab- by Slinn[1977],Lai et al. [1978],andPruppacher andKlett
senceof surfacecoatings,etc.).A carefullyacquiredexperi- [1978], however; someof theresults arebrieflystatedbelow.
mentalvalue for watervaporon water droplets,however,is The lossof aerosolsto raindropsis generallydescribedby
aI-12o
-- 0.033[Chodes etal.,1974].
Thisappears tobeanabso- definingthe scavenging coefficient
A by
luteupperlimit to the truevalueunderlaminarflowcondi-
tions.In the atmosphere the presenceof wakeand interfacial A(r, t) -- K(r, a)na(a,t) da (152)
effectswill producea lowervaluewhichcannotbe derived
from extant data. The accommodationcoefficientwill always whereK is the collectionkernel(a functionof drop radiusa
begreater thanor equalto thecollisional reactionprobability, andparticleradiusr) andnaisthenumberof dropsperunit
since the latter is the fraction of moleculesthat are incorpo- volume of air at time t in the size interval a to a + da. For
rated and also react. Baldwin and Golden[1979, 1980] have smallparticles
(r •<0.01gm),Browniandiffusion
to the drops
measuredcollisionalreactionprobabilities¾for severalspe- is thecontrolling
process.
For largeparticles
(r •> 1 gm),iner-
ciesat surfuricacidsurfaces.
Amongtheir resultsare ¾I-12o-- tial impactiondominates.
Betweentheseextremes it appears
0.002,¾i•o•= 8 x 10-n,¾i•o.
= 5 x 10-n,and¾NI•3 > 0.001. thatphoretic,
turbulent,
andelectrical
processes
achieve
com-
Definingthe accommodation as a functionof parable
coefficient ornear-comparable
scavenging
[Pruppacher
andKlett,
speciesconcentration comprises1978],although
in thegasandliquidphases no definitive
treatment
of thetotalproblem
the firstlevelof sophistlcation ap- yet exists.
overthe semiempirical
proachoutlinedabove.For unreactive
species
in equilibrium, Sinceit appearsthat A is onlya weakfunctionof r, it is
it is generallysuitableto utilizeHenry'slaw: possible
to definea valueof Am,,,,independent of r, thatap-
proximates the net scavenging coefficient.
Pruppacher and
g, = H,li (151) Klett[1978]demonstrate thatif thedropsfollowa Marshall
i in thegasphase,li is andPalmer[1948]sizespectrum,
wheregiis themolefractionof species the net scavenging coeffi-
i in theliquidphase,andHi is the cient can be expressedas
themolefractionof species
Henry'slaw constant.Evenif equilibrium conditions
prevail, Amax(s
-l) • 4.2x 10-n/•R0'79 (153)
Hi valueshavenotbeendetermined for manyspecies
of atmo-
sphericinterestanddonotappearcalculable bycurrenttech- where œ is the characteristiccollisionefficiencyfor drop-par-
niquesfor aqueous [Gotoh,1976].In addition,the ticleinteractionandR is the rain rate(millimetersperhour).
solutions
interesthereis on species
that are reactivein evolvingatmo- In summary, recentexperimental andtheoretical advances
sphericaqueous media.In thesecases,experimental determi- enablethescavenging of aerosol particlesby raindrops to be
mustbemade estimatedwith moderateaccuracy,at leastfor ensembleaver-
nationsof Hi areverydifficult,sincecorrections
for species
removalfromthesystem by dissociation
andteac- ageassessments.
Thephysicalcomplexity of theproblem ap-
tion.Asa result,
measurements
oftheaqueous
solubilities
of pears
to render
detailed
analyses
of individual
events
intrac-
low concentrations
of ammonia[HalesandDrewes,1979],car- tableat present.
In anycase,it is clearthatsuchscavenging
bon monoxide[Meadowsand Spedding,1974],and sulfur can be reflectedin chemicalprocesses in raindropsand that
dioxide[Brimblecombe and Spedding,1974a]under atmo- scavenging willinvolve themechanically generatedsoilparti-
spheric conditions giveresults thatareoftendifficultto inter- clesas well as the smallerparticlesproducedby nucleation,
pret.It appears preferable at thisstageof investigation
to de- coagulation,and accretionprocesses.
scribethetransport of suchspecies by analogywithunreactive
compounds andto attemptto treatthechemistry in somede- 3. AqueousSolubilities
tail ratherthanto defineHi valuesthat inextricablyincorpo- The participation of an atmospheric chemicalspecies in
rate both effects. aerosolchemistry is heavilyinfluencedby thedegreeto which
In summary,it is possibleto calculatethe flux of a gas it is soluble. In Table 6 we list bulk solubility data for the
phasemolecule to thevicinityof an aerosolor raindropsur- principal tracegases of theatmosphere. Asis apparent fror
face. Transportacrossthe air-surfaceinterfacecannotbe theequilibria presented in Table7, mostof thesolubilities
are
treated
withrigor,however.
It islikelythattheprocess
variespH-dependent.
Themoststriking
values
in Table6 arethose
withthedegreeofairturbulenceneartheinterface,
thepres- for ammonia,
whicharehigherby abouta factorof 4 than
enceandcharacter
of the surface
coating,andthe chemical thoseof the next mostsolublegas,HC1.Formaldehyde
is
natureof thegasphase molecule.
Innovative
laboratory
ex-' nearly
assoluble.
SO,_,
thenextinline,ismorethananorderof
perimentsarenowbeginningtoprovide
results
thatrepresentmagnitude
moresolublethanall theremaininggasesin the
thesumof theselatterprocesses;
suchresults
seemlikelyto table.CO,_,
H2S,andOCSforma trioof moderately soluble
526 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 6. AqueousSolubility of SelectedGasesat One trates the solutionconcentrationwill often be determinedby

Atmosphere Pressure
the amountof water associated with the aerosol.In a pure salt
Temperature, øC aerosolat any humidity or a salt-containingaerosolat low rel-
0 10 20 25 30 ative humidity, the ionic concentrations will be very high, and
there will be significantdeviation from ideal solution behav-
02a 0.0489 0.0380 0.0310 0.0283 0.0261
03b'c 0.0184 0.0140 0.0098 0.0065 0.0036 ior. The greaterthe chargeof the ionic species,the greaterthe
H2a 0.0214 0.0193 0.0178 0.0171 0.0163 deviation (for example, H2SOn displays a larger deviation
CO2a 1.71 1.18 0.860 0.738 0.642 than HC1). An accuratedescriptionof suchsolutionsrequires
CO a .0352 0.0278 0.0227 0.0208 0.0192 the useof the activitiesof the variousionic speciesin solution.
NH3d 5234. 3369. 2235. 1840. 1524.
NO a 0.0738 0.0571 0.0471 0.0430 0.0400
(Activity may be thought of as an effectiveconcentration).
NO2 e 0.269 Unfortunately, relating activitiesto concentrationsis a tedious
H2 Sa 4.37 3.59 2.91 2.61 2.33 task, particularly over a large range of solution ionic
SO2a 79.79 56.65 39.37 32.79 27.16 strengths.Doing so in a realisticway remainsa taskfor the fu-
CS2a 0.601 0.572 0.528 0.498 0.457
ture. We note alsothat Table 8 assumesequilibrium between
OCS a 1.33 0.836 0.561 0.468 0.403
HC1•' 505. 430. 413. the aqueousand gas phasesin the atmosphere;such an as-
HCHO s 180. sumptionis likely to be muchlessvalid for raindropsthan for
aerosols.
Solubilitiesare givenascubiccentimeters
of gasper cubiccentime-
ter of water. 4. Ionization Constants
a Stephenand Stephen[1963].
bNemeth[1975]. Many of the chemicalprocesses in aqueoussolutiondepend
c Weast [ 1971]. upon the degreeto which a speciesof interestis ionized. Ac-
a HalesandDrewes[1979]. cordingly, in Table 7 we presentionization constantsfor at-
e Schwartz [1980]; see section C4 for discussion.
• Klippeland Warneck[1980]. mosphericallyimportant species.Where available, rate con-
stantsfor forward and back reactionsare included to suggest
the speedat which a given systemequilibrates.(The rate of
compounds,followedby NO2. Other species,including02, are diffusion-limitedproton transfer is assumedto be approxi-
relatively lesssoluble. mately5 x 10TM M -• s-• if no valueis givenin the literature.)
The.principal trace gaseshave atmosphericconcentrations In addition to ionization constants,Table 7 also includeshy-
that result in relatively dilute solutions in aqueous atmo- drolysis constantsfor a number of important reactionsin-
sphericaerosols.These solutionconcentrations can be esti- volvingsulfurdioxideand carbondioxide.As noted,the tabu-
mated by taking measurementsof trace gas concentrations lated values are for 25øC. Ionization constants are
typical of the urban and remotetroposphereand performing temperature-dependent and can typicallyvary 40% from 0øC
Henry's law calculationsusingthe solubilitiesgivenin Table to 50øC [Weast, 1971],but few data are available for the sys-
6. For H202 and HNO3, both of which are infinitely solublein tems of interest here.
water, we utilize raindrop concentrationmeasurements.The In order to get a picture of the ionic compositionof atmo-
resultsare presentedin Table 8. Becauseof the low concentra- sphericsolutions,selecteddata of Table 7 have been used to
tions of thesedissolvedgaseousspeciesthere is little deviation prepareionicequilibriumplotsasa functionofpH. (The tech-
from idealsolutionbehavior.This is not the case,however,for nique is describedby Kaesche[1970]).Theseplotsappearin
the principal inorganic electrolytes that constitute atmo- Figure 8 and demonstratethe influenceofpH over many as-
sphericaerosols.For saltssuchas sulfates,chlorides,and hi- pects of the aqueouschemicalsystems.At the pH of the

TABLE 7. Ionization Constantsin AqueousAtmosphericAerosol Systems

Reaction K25oc t,f kr Reference

2H20 • H3O+ q- OH- 1.008X 10-•'* M 2 1.3 X 10-3 M s-• 1.3 X 10• M -• s-• Eigen et al. [ 1964]
H202 • H + + HO2- 1.5 X 10-•2 M '"7.5 X 10-2 s-• '"5 X 10mM -• s-• Cottonand Wilkinson[ 1980]
H2SOn• H + + HSOn- > 1M >5 X 10•øs-• '•5 X 10•øM -• s-• Cottonand Wilkinson[1980]
HSO,,- • H + + SOn2- '•10-2M 1 X 109s-• 1 X 10• M -• s-• Eigenet al. [ 1964]
SO2'xH20 • H + + HSO3- 1.7X 10-2 M 3.4 X 106s-•a 2.0 X 108M -• s-• Eigenet al. [ 1964]
HSO3- • H + + SO32- 6.2 X 10-8 M 3 X 103s-• 5 X 10•øM -• s-• King [1959]
HNO3 • H + + NO3- > 1M >5 X 10m s-• '"5 X l0 w M -• s-• Cottonand Wilkinson[ 1980]
HNO2 •- H + + NO2- 6.0 X 10-6 M --'3 X 105s-• '"5 X 10TM M -• s-• Cottonand Wilkinson[ 1980]
NH3' H20 • NHn+ + OH- 1.8x 10-5 M 6 x 105s-• a 3.4 X 10•øM -• s-• Eigen et al. [ 1964]
HC1 • H + + C1- >1M >5 x 10 •ø s-• -•5 x 10 •ø M -• s-• Cottonand Wilkinson[1980]
H2CO3• H + + HCO3- 2 x 10-n M -• 1 x 107 S-• "•5 X 10M -• s-• Cottonand Wilkinson[1980]
HCO3- • H + + CO32- 4.84 X 10-• M "2.5 s-• "•5 X 10•øM -• s-• Cottonand Wilkinson[1980]
H2S • H + + HS- 5.7 X 10-8 M 4.3 X 103 S-• 7.5 X 10•øM -• s-• Eigenet al. [1964]
HS- • H + + S2- 1.3 X 10-•3 M --,6.5 X 10-3 S-• '•5 X 10•øM -• s-• King [1959]
HCOOH • H + + HCOO- 1.7 X 10-n M 8.6 X 106 s-• '"5 X 10•øM -• s-• Eigen et al. [1964]
CH3COOH • H + + CH3COO- 1.6 X 10-5 M 7.8 X 105s-• '•5 X 10•øM -• s-• Eigen et al. [ 1964]
H2SO3• SO2+ H20 1.9 X 10• 6.3 X 107s-• 3.4 X 106s-• Eigen et al. [ 1964]
SO2+ H20 • HSO3- + H + 1.7 X 10-2 M 3.4 X 106s-• 2 X 108M -• s-• Eigenet al. [1964]
H2CO3• CO2 q-H20 3.5 X 102 15s-• 4.3 X 10-2 s-• a Eigenet al. [1964]
CO2 + H20 • HCO3- + H + 7.7 x 10-7 M 0.043 s-• 5.6 x 10nM -• s-• Eigen et al. [ 1964]
HCO3- • CO2 + OH- 7.1 x 10-9 M 1 x 10-4 s-• 1.4 x 10nM -• s-• Eigen et al. [1964]
"This value representsa pseudo-first-orderrate constant.
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 527

TABLE 8. Typical Concentrationsof SelectedGasesin the Atmosphereand in the Aqueous Phase of

Atmospheric Aerosolsat 25øC
Urban Rural

Gas Aqueous Gas Aqueous

Concentration, Concentration, Concentration, Concentration,
Species ppb Reference M ppb Reference M

02 2 x 108 3X 10-4 2 x 108 3X 10-4

03 70 1 2X 10-ll 30 1 9X 10-12
H2 2 X 103 1 2X 10-9 600 1 5x 10-lø
H202 20 2, 3 3X 10-6 I 4, 5 3X 10-7
CO 8 X 103 I 7 X 10-9 120 I I x 10-lø
CO2 5 x 105 6 2 x 10-5 3.3 x 105 7 1 x 10-5
NO 10 I 2 X 10-11 0.1 I 2 X 10--13
HNO3 I 1, 8 5X 10-5 0.3 1, 8 IX 10-6
NH3 25 I 2x 10-6 1.5 I Ix 10-7
H2S 2 I 2X 10-10 0.1 I IX 10-11
CS2 0.15 9 3x 10-•2 0.04 9 9X 10--13
OCS 0.6 10 I x 10-ll 0.6 10 1 x 10-ll
SO2 50 I 7 x 10-8 1 1 2 x 10-9
HCI 6 I I x 10-7 0.7 I I x 10-8
HCHO 6 11 5 x 10-8 0.2 11 2 x 10-ø

Referencesare to the gas phase concentrationexcept for H202 and HNO3, where referencesto both
gasphaseand aqueousphaseconcentrations are given:(1) Graedel[1980],(2) Kok et al. [1978],(3) Kok
[1980],(4) Kelly et al. [1979],(5) Bufaliniet al. [1979],(6) McRae and Graede![1979],(7) Woodwell[1978],
(8) Likens et al. [1979], (9) Maroulis and Bandy [1980], (10) Torreset al. [1980], (11) Platt et al. [1979].

freshly generatedoceanicaerosol(•8) the solutionwill con- 5. Photochemical Data

tain primarily HCO3-, NHnOH, NO2-, HS-, SO32-, and a. Introduction. A number of photochemicalprocesses
SO42-.At thepH of an uncontaminated
raindropequilibrated have been identifiedin earlier sectionsas having the potential
with atmosphericcarbondioxide (•5.6) the solutionwill con- to occur in aerosolsand raindrops.In this sectionwe present
tain primarily HCO3-, NHnOH, both HNO2 and NO2-, H2S, the quantitative information available on suchprocesses. For
aso3-, and SO42-.At the pH of an acidifiedurban aerosol each we provide the absorption spectrum and associated
(•3) the solutionwill containprimarily H2CO3,NH4+, HNO2, cross-section data. If available,quantum yieldsare also given.
H2S, HSO3-, and SO42-.In all cases,any nitric and hydro- The latter are actually effectivecrosssectionsfor the processes
chloric acid moleculespresentwill be almost completelyion- of interest;that is, they refer to processes
that result in actual
ized, and any hydrogenperoxidemoleculespresentwill be al- chemical change rather than in mere energy transfer to the
most completelyunionized.In addition to the obviouseffects solvent.The data can thusbe directly utilized in computations
of the different degreesof ionization on thermochemistry dealing with the photoprocesses discussedherein, provided
within the solutions,photochemistryis affectedas well, since the influenceofpH on the degreeof ionization of many of the
HNO2 and NO2- are photosensitiveto different degreesand moleculesand the pH dependenceof the tautomericforms of
have different product chains. the carbonyl compoundsare properly taken into account.
b. Ozone. The absorptionspectrumfor ozonein aqueous
solutionis given in Table 9. No net reactionis producedby ir-
400 ....

TABLE 9. AbsorptionCrossSectionsof Ozonein AqueousSolution

X, nm o, (cm2/molecule)
X 1021
% •,H;, (d)
o
290
300
1500
500
305 270
310 140
313 100
(b) 320 42
330 13
340 3.3
480 1.2
500 2.8
520 3.8
540 5.5
546 6.0
560 7.1
580 8.0
I 3 5 7 9 590 8.5
pH pH 600 7.6
625 5.5
Fig. 8. Equilibrium diagramsfor ion-moleculesystemsof interest 650 4.2
in atmospheric aerosol and raindrop chemistry: (a) H2CO3, (b) 675 2.7
NHnOH, (c) HNO2, (d) H2S, (e) H2803, and (1) HSO4-.
528 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 10. AbsorptionCrossSectionsof HydrogenPeroxideand TABLE 12. AbsorptionCrossSectionsof NitrousAcid in Aqueous

Hydroperoxyl Ion in Aqueous Solution Solution

X,nm o,(cm2/molecule)
X 1023 ]k,nm o,(cm2/molecule)
X 1020
290 760 305-310 1.50
300 380 310-315 4.26
310 180 315-320 4.16
320 88 320-325 4.26
330 41 325-330 4.62
340 19 330-335 5.41
350 8.3 335-340 6.29
360 3.7 340-345 7.44
370 1.6 j245-350 9.18
380 0.80 350-355 9.01
390 0.66 355-360 12.3
360-365 9.73
365-370 10.2
radiation within the visible band, so the ultraviolet band is the 370-375 11.8
one of primary interest. 375-380 6.29
380-385 5.63
The quantumyield for the H202 productionprocesswasde-
385-390 5.76
termined by Taube [1957] to be 0.23 at 310 nm. 390-395 2.41
c. Hydrogenperoxide. The absorptionspectrumof H202 395-400 0.63
in solution has been extensivelystudied over the years, with 400-405 0.21
405-410 0.10
perhaps the most complete data on absorption coefficients
being thoseof Taylor and Cross[1949] and of Phibbsand Gi-
gudre[1951].At low H202 concentrationsthe resultingabsorp- on the absorptionspectrumof aqueousnitric acid, in part be-
tion crosssectionsare those presentedin Table 10. As was causeit is almostentirely ionized. Hayon and Saito [1965] ir-
pointedout by Molina et al. [1977],the gasphaseand aqueous radiated HNO3 solutions with a mercury arc and found no
phasevaluesare very similar. dissociationat 314 nm, their observedchemical effectsbeing
The quantumyieldsfor OH. productionby H202 photodis- producedby molecularcleavageresultingfrom the absorption
sociationhave been studiedby Hunt and Taube[1952] and by of 254-nm radiation. This suggeststhat the HNO3 absorption
Baxendale and Wilson [1957]. The irradiations in each case spectrumin solutionresemblesthat in the gasphase,which is
wereat 254nm with a smallflux alsoat 314nm. Bothpairsof presentedby Hudson[1979].The quantumyieldsin solution
investigatorsreport observedquantum yields near unity but are undetermined;those in the gas phase are of the order of
infer that a chain reaction is involved and that the true pri- unity [Hampsonet al., 1973]. By analogy with the solution
mary effectivequantum yield is 0.50 _+0.01. They assumeq•254 photochemistryof nitrous acid we therefore anticipate an ef-
"- (•)314' fectivequantumyield for solventcageescapeof HNO3 photo-
d. Hydroperoxylion. Baxendaleand Wilson[1957]report lysisproductsof q•• 0.10.
that the absorptionspectrumand effectivequantum yield of h. Nitrite ion. The absorptionspectrumof the nitrite ion
HO:- are identical with those of H:O:; these are given in in aqueoussolution has been determined by $trickler and
Table 10. Kasha [1963] and is given in Table 13. The spectrumpeaksat
e. Nitrogen dioxide. Nitrogen dioxide has an absorption 350 nm, well within the range of solar radiation in the tropo-
spectrumin aqueoussolutionthat is similar to that in the gas sphere.
phase(Table 11). As discussedearlier, it is uncertain at pres- The effectivequantum yield for NO production has been
ent whether photodissociationoccursand, if so, what the ef- investigatedby Zafiriou and True [1979a],who find a value of
fective quantum yield of the processmay be. q• ~ 0.05 over the troposphericirradiation spectrum. This
f. Nitrousacid. The absorptionspectrumfor nitrousacid value reflectsthe probability of escapeof productsfrom the
in aqueoussolutionis presentedin Table 12. Over the band solvent cage, since the quantum yield of the formation of
300-400 nm, Rettich [1978] givesq•-- 0.095 _+0.005 for photo- productswithin the cagehas been estimatedby Treinin [1970]
dissociationfollowed by escape of the products from the to be near unity.
solvent cage.
g. Nitric acid. Little experimental work has been done TABLE 13. AbsorptionCrossSectionsof Nitrite Ion in Aqueous
Solution

TABLE11. Absorption
Cross
Sections
of Nitrogen
Dioxide
in X,nm o,(cm2/molecule)x
1021
Aqueous
Solution 290 15
h,nm o,(cm2/molecule)
X 1019 300
310
15
16
290 8.18 320 17
300 6.94 330 23
320 5.74 340 29
330 5.93 350 36
340 5.96 360 37
360 5.70 370 27
370 6.41 380 15
380 7.54 390 8.6
400 7.50 400 1.8
420 7.13 410 0.17
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 529

TABLE 14. AbsorptionCrossSectionsof Nitrate Ion in Aqueous et al. [1980] have recently estimatedthe total [OH.] concen-
Solution
trationsin freshwatersystemsas 1 x 10-•7 M, which is of the
2•,nm o, (cm2/molecule)
x 1020 same order of magnitude that we derive from preliminary
290 0.95 modeling studies. Computing the photolysis as described
295 1.1 above gives
300 1.2
305 1.2 [OH' ]koH.,H202
= 4 X 10-•øs-•
310 1.0
315 0.81 hVl-i2o•
-- 5 X 10-6 s-•
320 0.55
325 0.28
and the photolysisis seento be dominant. The situation for
330 0.15 HO2-, a dissociationproduct of H202, will be similar.
HNO2 and NO2- photodissociations competewith OH. re-
actions. In the case of HNO2 the photolysis rate is high
L Nitrate ion. The nitrate ion absorptionspectrumpeaks enoughthat it dominatesthe OH. reaction.For NO2- the two
at about 300 nm and extendsto about 340 nm [Meyersteinand rates are approximately equivalent.
Treinin, 1961;Rotlevi and Treinin, 1965]. It is shownin Table The assessment of relative importanceof photoprocesses for
14. The quantumyield for photolysisfollowedby productes- other speciesis hamperedby a lack of informationconcerning
cape from the solventcageis about q•= 0.04 over the 290-340 the competing processes.For NO3- no significant non-
nm band [Danielset al., 1968;Baylissand Bucat, 1975]. photochemicalreactionshave been identified. For NO2 and
j. Nitrogen trioxide radical. The aqueous absorption NO3 the only known competingreactionsare with other NOx
spectrumof NO3' has been determined by Martin et al. species;the ratesfor thesereactionsin aerosolsand raindrops
[1963]. It is a complex banded structuregiven in Table 15, will doubtless be small.
which wasconstructed by convertingthe opticaldensityval- In summary, photolysisin solution is important or domi-
ues of Martin et al. [1963] to crosssectionsreferencedto the nant for H202 and HNO2 and for their dissocationproducts.It
smoothedgasphasedata of Wayneet al. [1978]at 550 and 635 appearsto be unimportantfor 03. More data are required to
rim.
assessthe solution photochemistryof the NOx compounds
The effectivequantum yields for NO3' photolysisin aque- (and of the carbonylcompounds;seesectionD7), but the un-
ous solutionwill be much lower than in the gasphasebecause certaintiesseem unlikely to distort the general picture of at-
of solventcageeffects.By analogywith the gasphasebranch- mosphericsolutionchemistrypresentedin this review.
ing ratio and with HNO2 aqueousphotolysisquantumyields,
we suggestq• • 0.01 and q•2• 0.09 as appropriateband-aver- 6. Reaction Rate Parameter Data
aged estimates. Previous sectionsof this paper have discussedthe mecha-
k. Importanceof photochemical processes. The intent of nisms of the chemical reactions that occur in atmospheric
this sectionis to evaluatethe ratesof the photochemicalproc- aerosols. In this section we review the information available
essesdescribed above in order to assessthe importance of
these reactions relative to other chemical processesin solu- TABLE 15. AbsorptionCross Sectionsof Nitrogen Trioxide in
tion. To do so requiresa knowledgeof both the rate parame- Aqueous Solution
ters and the reactant concentrationsfor each processof inter-
2•,nm o, (cm2/molecule)
X 10•8
est. The rate parameters are generally available; species
concentrations are taken from Table 8. 535-540 1.03
540-545 1.33
Ozonephotolysisin solutioncompeteswith ozonescaveng- 545-550 1.69
ing by OH- and HSO3-. In a solutionofpH 5 we have [OH-] 550-555 2.12
= 10-9 M. A rate constant of 106 M -• s-• for the reaction of 555-560 2.65
OH- and O3 appearsto be a reasonableestimatein view of 560-565 3.01
565-570 3.14
the solutiondata. For [HSO3-] we have7 x 10-8 M. The pro-
570-575 3.28
ductionof O(•D) by ozonephotolysisin the sunlitnoonatmo- 575-580 3.42
sphereat latitude41øN proceedswith a rate of --•3x 10-5 s-•, 580-585 3.71
a value computedby multiplying the absorptioncrosssections 585-590 4.03
of Table 9 by the quantumyield for the ozonephotolysisreac- 590-595 4.54
595-600 4.73
tion and by the incident solar flux [Peterson,1976] and in- 600-605 4.54
tegrating the result over the troposphericspectrum.Com- 605-610 4.19
paringthe ratesof the threeprocesses gives 610-615 4.03
615-620 4.03
[OH-]koH-,O3--
1 X 10-3 s-• 620-625 4.37
625-630 5.11
[HSO3-]kHso3_,o3
= 2 X 10-2 S-l 630-635 5.96
635-640 5.74
hvo•= 3 X 10-5 s-• 640-645 4.37
645-650 3.14
and clearly, photolysishas only a minor effect on 03 concen- 650-655 2.03
tration in aerosols. 655-660 1.53
For hydrogen peroxide, only the solution reactions with 660-665 1.77
trace ions and radicalscompetesignificantlywith photolysis. 665-670 3.01
670-675 3.71
The reaction processmost easily assessedis that with OH.,
675-680 2.43
for which a measured rate constant at 25 øC is available. Mill
530 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 16. Rate Constantsfor Reactionsof Oxygen-HydrogenCompoundsin AqueousSolution

Reaction k23oc Reference
O-- q' 02 "-> 03-- (3.6 + 0.9) X 109 FR
03--"-> O-- q- 02 (5.0+ 1.3)x 103 BeharandCzapski[1968]
H' + 02 --'>H O2' (2.6 + 0.7) x 10TM •4nbaret al. [1975]
O- q- H20 "->OH- + OH. (1.8 + 0.4) x 106 FR
O- + HO2---> OH- + 02- (3.9 + 1.0)x 108 FR
O- + H•O2--> 02- + H20 (8.0 q-0.8) x 109 FR
027 + OH.--> OH- + 02 (8.0 + 1.0)x 109 FR
02- + HO2' --> HO2- + O2 (1.0+ 0.5) x 108 Bielski[1977]
Oi- + H202--> OH- + OH + 02 (1.3 + 0.7) x 10-1 WeinsteinandBidski [1979]
OH' + OH'--> H202 (5.2 + 0.5) x 109 FR
OH' + OH---> O- + H20 (6.2 + 1.5)x 108 Hayon[1965]
OH' + H2--> H' + H20 (3.5 + 0.9) x 107 FR
OH' + HO2'--> H20 + 02 (3.1 + 0.8) x 109 FR
OH' + H202--> HO2' + H20 (4.5 + 1.1)x 107 FR
HO2' + HO2' --> H202 +02 (7.6 + 1.9) x 105 FR
HO2' + H202--> OH' + 02 + H20 (5.0 + 0.9) x 10-1 Weinstein andBidski[1979]
FR denotesFarhatazizand Ross[1977].Units are 1 mole-l s-l for bimolecularreactionsand s-l for
unimolecular reactions.

on the ratesof thesereactions.In accordancewith the general cies, reactions,and processes.Our inferences,although less
practicein solutionkinetics,rate constantsfor bimolecularre- buttressedby evidencethan is desirable,identify a number of
actionsare expressedin units of litersper mole per second.For atmosphericand laboratory studiesto which attention might
unimolecularreactions,units of s-• are used. Although a usefullybe directed.
number of the reactionsdoubtlesshave significanttemper- The physicalpicture of an atmosphericaerosolparticle at
ature dependence,the available data were virtually all ac- moderateto high humidities,or of a raindrop in general,can
quired at room temperature; the rate parameters are thus be schematicallysummarizedas shown in Figure 9. Several
given at T~ 23øC. aspectsof the diagram deservemention. The first is the in-
The chemistryof the compoundscomprisingoxygen and solublecore,which is generallypresentand which may be in-
hydrogenis the beststudiedof the inorganicaqueoussystems. volved catalytically in someof the chemical reactionsthat oc-
Of particular interest to laboratory kineticistshave been the cur. Second,the core is envelopedin a aqueoussolutionthat
reactionsof the hydroxyl radical ahd of hydrogenperoxide. accountsfor 30% of the total weight. This solution contains
Table 16 listsreactionsin the O-H systemfor which rate con- significantamounts of dissolvedinorganic and organic com-
stants have been experimentally determined. Those for in- pounds.Third, the solutionis generallycoveredwith a film of
organic carbon compoundsare presentedin Table 17, those organicmaterial, with any polar portionsof the organicmole-
for inorganicnitrogen compoundsin Table 18, and those for culespreferentiallyorientedtoward the core as a result of so-
inorganic sulfur compoundsin Table 19. In the last caseit is lution bonding. This picture bears a striking resemblanceto
significantthat laboratorystudiesare thusfar unable to define thoseof micelies[e.g., Fendler, 1980],the electricallycharged
the mechanisticdetails of the transformationinto sulfate of colloidal particleswhich are the subjectof much recent bio-
lesshighly oxidizedsulfur-containing species.Table 20 pre- chemicallyorientedresearch.It is prematureto applythe re-
sentsthe rate constantdata for halogenated
compounds, which sultsof micelieresearchto atmosphericproblems,but we con-
are disappointinglymeagerin view of the ubiquitouspresence siderthe prospecta promisingone.
of halogenatedcompoundsin aerosolsand raindrops. The organicfilm that coatsthe aerosolparticlespresumably
Rate constantdata for organicreactionsare given in Table coalescesand thickens as the particles reside in the atmo-
21. With few exceptionsthe table containsdata for the initial sphere.The effect of this film on moleculartransferacrossit
hydroxyl reactiononly. It will be necessaryto acquiremuch probablyvaries with the moleculeunder consideration.Be-
more productand rate constantdata for thesesystemsbefore causeof the film's presence,one might expect the rate of
the role of organicchemistryin aerosolsand raindropscan be transferof water-solublecompoundsacrossthe air-solution
properly assessed. interface to decreasewith particle lifetime. Conversely,the
A comparisonof the reactionslistedwith thoseof the above loweringof surfacetensionmay increasethe rate, particularly
sectionsdemonstratesthat the rate parametersfor a number for nonpolar molecules.As particlesage, they may thus be-
of reactionsof potential interest remain to be determined. A1- come increasinglyeffective sinks for organic molecules.
thoughtechniquesexistin somecasesfor estimatingundeter- The presenceof a vigorousand complex chemistrywithin
mined rate constants[e.g.,Benson,1976],it is to be hopedthat
continuedexperimentalwork will providemany of the needed TABLE 17. Rate Constants for Reactions of Inorganic Carbon
values in years to come. Compoundsin AqueousSolution
Reaction k23o
C Reference
F. DISCUSSION
0 2-- q- HCO3- -'->CO3- q- HO2- (1.5+ 0.5) X 106 FR
The previoussectionsof this paperhave attemptedto pres- OH' + HCO3- --->CO3- + H20 (3.6 + 0.3) x 107 FR
ent, in a comprehensiveway, the scientificinformation rele- OH. + CO32- ----->
CO3 q- OH- (3.7+ 0.9) x 108 FR
vant to aerosoland raindrop chemistry.In the presentsection OH' + CO--> CO2 + H. (8.7 q-2.2) x 108 FR
OH' + CO2--> HCO3' <106 FR
we leave this relatively solid ground and use the information
to draw inferencesconcerningthe importanceof certain spe- FR denotesFarhatazizand Ross[1977].Units are 1 mole-l s-l.
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 531

TABLE 18. Rate Constantsfor Reactionsof Nitrogen Compoundsin AqueousSolution

Reaction k2aoc Reference

H20
O- + NO2- --> 2OH- + NO2 (3.6 :!:0.9) x 108 FR
C1- + NO3'--• products (1.0 + 0.3) x 108 RossandNeta [1979]
OH- + HNO2--• NO2- + H20 ~1 x 10•ø Rettich[1978]
OH. + NO2- '•> OH- + NO 2 (1.0+ 0.3) x 10•ø FR
OH. + NO3- --> OH- + NO 3 <5 x 105 FR
OH. + NO--• H. + NO2 (1.0 + 0.3) x 10•ø FR
OH' + NO 2 -•> HNO3 (1.3 + 0.3) x 109 FR
OH' + NH2' --• NH2OH (9.5+ 2.4) x 109 FR
OH' + NH3 --• NH2' + H20 (3.6 + 0.9) x 107 FR
OH' + HNO2--• NO2 + H20 ~1 x 109 Rettich[1978]
03 + NH3 --• products (2.0 + 0.1) x 10 Hoign• and Bader [1978]
HO2' + NO2 '-• HO2NO2 (4.0 + 1.0)x 109 Sutton[1975]
HO2NO2 '-• HO2' + NO2 (1.4 + 0.2) x 10-2 Suttonet al. [1978]
NO 2 -[- NO 2 .•> N20 4 (4.5+ 1.0)x 108 Grdtzelet al. [1969]
3 H20
N204 '-> 2H30 + + NO2- + NO3- (1.0 + 0.1) x 103 Grdtzelet al. [1969]
FR denotesFarhatazizand Ross[1977].Units are 1 mole-• s-• for bimolecularreactionsand s-• for
unimolecular reactions.

TABLE 19. Rate Constantsfor Reactionsof Sulfur Compoundsin Aqueous Solution

Reaction k23o
C Reference
H20
O-+ SO32---• SO3- + 2OH- (3.0 + 0.8) x 108 FR
OH' + H2S--• HS. + H20 (1.5+ 0.4) x 10lø FR
OH. + HS---• OH- + HS. (8.4 + 2.1) x 109 FR
OH. + CS2-•, CS2OH ' (8.0 + 2.0) x 109 FR
OH' + CH3SCH3--• CH3S(OH)CH3 ß (5.2 + 1.3)x 109 FR
OH' + CH3S---> OH- + CH3S' (6.0+ 0.9) X 109 FR
OH' + CH3SSCH3--• OH- + CH3SSCH3+ (1.7+ 0.3)x 10•ø FR
OH' + HSO3- --• SO3- + H20 (9.5+ 2.4) x 109 FR
OH' + HSO4--• 804-- '[' H20 (1.6 + 0.4) x 106 FR
OH' + SO32---•products (5.5 + 1.4)x 109 FR
03 + SO2--• H2SO4+ 02 <3 + 103 Ericksonet al. [1977]
03 + HSO3- '-> HSO 4- + 02 (3.1 + 0.2) x 105 Ericksonet al. [1977]
0 3 -[-SO32--
.•>SO42--
-[-0 2 (2.2 + 0.4) x 109 Ericksonet al. [1977]
H202+ HSO3-H30• + H2804 pH-dependent Martin andDamschen. [1981]
2H20
SO3- + 02--• SO5- <1.0 x 109 RossandNeta [1979]
FR denotesFarhatazizandRoss[1977].Units are 1mole-• s-•.

TABLE 20. Rate Constantsfor Reactionsof HalogenatedCompoundsin AqueousSolution

Reaction k23o
C Reference
OH. + C1---• CIOH- (4.3 + 0.4) x 109 Jaysonet al. [1973]
C1OH---• OH- + C1. (6.1 + 0.8)x 109 Jaysonet al. [1973]
OH' + Br- --• BrOH- (1.1 4-0.1)X 10•ø Zehavi and Rabani [ 1972]
BrOH---• OH. + Br- (3.3 4-0.4) X 107 Zehavi and Rabani [1972]
OH. + CH3I--• CH3OH + I. (1.4 4-0.4) x 109 Farhataziz and Ross[1977]
Units are 1 mole -• s-• for bimolecular reactions and s-• for unimolecular reactions.

the aqueoussolutionscan readilybe demonstrated: the start- 5. The activereducingagentpresentin greatestconcentra-

ing point is to estimatethe concentrationsof variousspecies tion is suffurdioxide.
within the solutions,ashasbeendonein Table 8. Severallea- From the standpointof redoxchemistryit thusappearsthat
turesof the aqueousconcentration valuesareimmediatelyap- H202 is potentiallymuch more importantthan 03 and that
parent: SO2is highly important. CO•, HC1, NH3, and HNO3 influence
1. Molecular oxygenis abundantin solution,exceeding thepH of the solution,but theixreactionsare probablynot of
theconcentrations of CO• andHNO3, thenextmostabundant significance. The concentrations and reactivitiesof the other
species,by factorsof 1-270. speciessuggestthat they are not of chemicalimportancein
2. Hydrogenperoxideand ammoniaare the most abun- aqueousatmospheric aerosolsand raindrops.
dant of the specieswhosechemistryis of interest. Althoughthe species listedaboveappearto be the mostsig-
3. The solutionconcentrationsof formaldehydeand sul- nificantfor our discussion,this review has discussed evidence
fur dioxideare comparable. for the ubiquitouspresence of perhaps100compounds within
4. The activeoxidizingagentpresentin greatestconcen- typicalaerosolparticles.Most of thesespecies reactpreferen-
tration is hydrogenperoxide. tially with the hydroxylradical,which thus has the potential
532 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY

TABLE 21. Rate Constantsfor Reactionsof OrganicCompoundsin AqueousSolution

Reaction k23oc Reference
CH 3 ß+ 02 --> CH302 ß (4.7& 0.7)X 109 Thomas[1967]
R' + 02--> R02' ~3 X 109 Howard[1973]
HCHO + H20 '-> CH2(OH)2 (9.8 :!:0.8) Suttonand Downes[1972]
HOCH202 ß--> HCHO + H02' (9.9 :!:2.5) Downesand Sutton[1973]
OH' + CH 4--> CH 3 ß+ H20 (1.2 :!:0.4) x 108 FR
OH' + HCHO--• CHO' + H20 (6.9:!:1.7)x 108 FR
OH' + CH30H --• CH20H' + H20 (9.4 :!:2.3) x 108 FR
OH' + CH2=CH2--> HOCH2CH 2 ß (4.8:!:1.2)x 109 FR
OH' + CH3CHO---> products (5.0 :!:1.2)x 108 FR
OH' + CH3CH20H --> CH3CHOH ß+ H20 (1.8 + 0.5) X 109 FR
OH' + CH3C(O)CH3 --> products (9.7 :t:2.4)x 10? FR
OH. +/fiX,CHO-->1
.o,/•o (7.0 :!:1.8)X 109 FR
OH' +/X,ø•--•/•,.ø"+ H20 (3.0 :!:0.8) x 109 FR
oH-+ ,o•/X,o•-->products (2.0 -I-0.5) X 109 FR
OH. + ,/fiN/• products (7.7 :!:1.9)x 109 FR
OH. + ,/jx•._>products (7.7 + 1.9)x 109 FR
OH. +/•7o ._>products
o
(3.8 :!:1.0)x 109 FR
OH-+,fi•,/--•products (9.0 :!:2.2) x 108 FR
OH. +/•'o•-• products (4.6 :!:1.2)x 109 FR
OH. +/X/X, ø•-->products (5.5 + 1.4)X 109 FR
OH.+ [•] -->[•. + H20 (3.0:!:0.8)x 109 FR
OH'+ /X/•/'o• -->products (5.9 :!:1.5)x 109 FR
OH. + "øx/X/X/Xo..
• products (4.6:!:1.2)x 109 FR
OHß+0'---}•+H20 (8.8 m2.2) x 109 FR

OH'+•_..}:•o. (5.1 :!:1.3)x 109 FR

OH + (1.8 :!:0.5) x 10•ø FR
• •H0 • v

OH. + •½H0..•
products (4.4:!:1.1)x 109 FR

(3.0 :!:0.7) x 109 FR

OH.+ •--• products (6.7:!:1.7)x 109 FR

OH.
+[•--•products (7.5 :t:1.9)x 109 FR

OH.+• --•products (7.0 :!:1.8)x 109 FR

OH.+• OH --•products (1.1 + 0.3)X 10•ø FR

OH.+.o•--• products (1.2 + 0.2) X 10•ø FR

OH-+
I••-•products n_ o
(4.4 :t:0.5) x 109 $teenkenand O'Neill [1979]

(3.6 :!:0.9) x 109

OH..:•r• products $teenkenand O'Neill [1979]

FR denotesFarhatazizand Ross[1977].Units are 1 mole-l s-I for bimolecularreactionsand s-• for

unimolecular reactions.

to be as central to atmosphericcondensedphasechemistryas ORGANIC

it is to atmosphericgas phasechemistry,if its concentrations $U R FACE
INSOLUB
CORE
LE FILM
are sufficientlyhigh.
A detailed assessment of chemicalprocessesin atmospheric
aerosolsis hampered by a scarcityof relevant data. The dis-
cussionin sectionE demonstratesthat many solubilitiesand
rate parametersneedto be determinedand that the kineticsof
transfer across the interface at the aerosol surface are uncer-
tain; their elucidationwill require innovativeexperimentalap- NONPoLAR
PART OF ORGANIC
proaches. MOLECULE
Notwithstandingthe above, the chemicalsystemsof atmo-
spheric aerosolsand raindrops can at least be describedin AQUEOUS POLAR PART OF
SOLUTION ORGANICMOLECULE
broad overview.Becausechemicalprocesses in natural aque-
ous systemssharemany common attributes,the information Fig. 9. Schematicdiagram of the possiblestructureof aged atmo-
presentedhere is potentially applicableas well to lake and sphericaerosols.
 GRAEDEL AND WESCHLER: AEROSOL AND RAINDROP CHEMISTRY 533

oceansurfacewaters.The startingmaterialsavafiableto fresh- absorptionof sufiurdioxideby water dropscontainingheavy metal

ly generatedaerosolscan be specified,and chemicalreaction ions, Atmos. Environ., 10, 743-749, 1976.
Basolo, F., and R. G. Pearson, Mechanismsof Inorganic Reactions,
chains for the formation of inorganic surfate, inorganic ni-
2nd ed., John Wiley, New York, 1968.
trate, carboxylicacids,and other productsof interestcan be Bayliss,N. S., and R. B. Bucat,The photolysis
of aqueousnitrateso-
written. A full understandingof atmosphericchemistrywill lutions, Aust. J. Chem., 28, 1865-1878, 1975.
nonetheless require closecooperationand dedicatedwork by Baxendale,J. H., and J. A. Wilson, The photolysisof hydrogen per-
experimentaland theoreticalscientistsin the comingyears. oxide at high light intensities,Trans. Faraday $oc., 53, 344-356,
1957.
Behar,D., and G. Czapski,Flash photolysisof hydrogenperoxide,I,
Acknowledgments,Aspectsof the structureof aerosolparticlesde-
The reactionof ozonidewith hydrogenperoxide,Isr. J. Chem., 6,
pictedin Figure 9 were originallysuggested to us by the late Lyman
43-51, 1968.
Ripperton. Commentson variousaspectsof this work by E. Deutsch,
Behar,D., G. Czapski,and I. Duchovny,Carbonateradical in flash
R. S. Freund,D. Grosjean,P. C. Milner, S. E. Schwartz,J. W. Suggs,
photolysis and pulseradiolysisof aqueouscarbonatesolutions,J.
R. P. Turco, and O. C. Zafiriou have been most helfpul.
Phys. Chem., 74, 2206-2210, 1970.
Beilke S., and G. Gravenhorst,HeterogeneousSO2-oxidationin the
dropletphase,Atmos.Environ.,12, 231-239, 1978.
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