Preface xxv

1 The Atmosphere 1
1.1 History and Evolution of the Earth'sAtmosphere 1
1.2 Climate 4
1.3 The Layersof theAtmosphere 6
1.4 Variationof Pressurewith Height in the Atmosphere 9
1.5 Large-ScaleMotion of the Atmosphere 10
1.5.1 The GeneralCirculation 10
1.5.2 Troposphere-Stratosphere Transport 14
1.6 TemperatureandWaterVapor 16
1.7 ExpressingtheAmount of a Substancein the Atmosphere 18
1.8 Compositionof theAtmosphere 21
1.9 Radiation 23
1.9.1 SolarandTerrestrialRadiation 26
1.9.2 Absorptionof Radiationby Gases 29
1.10 EnergyBalancefor Earth andAtmosphere 33
1.10.1 SolarVariability 37
1.10.2 Earth'sEnergyBalance 38
1.11 SpatialandTemporalScalesof AtmosphericProcesses 40
Appendix 1 Derivation of the GeostrophicWind Speed 43
References 47
Problems 47

2 Atmospheric Composition, Global Cycles,and Lifetimes 49

2.1 AtmosphericResidenceTimes 50
2.1.1 ResidenceTime 51
2.2 Sulfur-ContainingCompounds 55
2.2.1 Dimethyl Sulfide (CH3SCH3) 61
2.2.2 CarbonylSulfide (OCS) 62
2.2.3 Sulfur Dioxide (SO2) 63
2.2.4 The AtmosphericSulfur Cycle 63
2.3 Nitrogen-ContainingCompounds 67
2.3.1 Nitrous Oxide (N2O) 67
2.3.2 Nitrogen Oxides(NOx = NO + NO;) 70
2.3.3 ReactiveOdd Nitrogen (NOy) 71

vii
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4 Chemistry of the Stratosphere

4.1 ChapmanMechanism 164
4.2 HO x Cycles 171
4.3 NO x Cycles 173
4.3.1 N2O StratosphericSourceof NO x 173
4.3.2 NOx Cycles 175
4.4 ClOx Cycles 177
4.5 ReservoirSpeciesand Coupling of the Cycles 180
4.6 StratosphericSpeciesObservationsand Predictions 184
4.6.1 Upper Stratosphere 184
4.6.2 Lower Stratosphere 186
4.7 OzoneHole 189
4.7.1 Polar StratosphericClouds 192
4.7.2 PSCsand the OzoneHole 194
4.7.3 Antarctic OzoneHole Measurements 198
4.7.4 Arctic OzoneHole 199
4.7.5 Summary 202
4.8 Heterogeneous (Nonpolar)StratosphericChemistry 203
4.8.1 Heterogeneous Hydrolysis ofN2Os 203
4.8.2 Effect of Volcanoeson StratosphericOzone 207
4.8.3 Summaryof Midlatitude andTropical Stratospheric
OzoneChemistry 210
4.9 TransportBetweenthe Tropical andMidlatitude
Stratosphere 210
4.10 Ozone-DepletingPotentialof Halocarbons 212
4.11 Effect of Aircraft Emissionson StratosphericOzone 215
4.12 CarbonylSulfide (OCS)and the Stratospheric
Aerosol Layer 216
4.12.1 AtmosphericChemistryofOCS and
OCSLifetime 217
4.12.2 StratosphericAerosol Layer 217
4.13 Projectionsof FutureOzoneChange 218
Appendix 4 Sensitivity/UncertaintyAnalysis of Atmospheric
ChemicalMechanisms 219
4.A.l SensitivityCoefficients 222
4.A.2 The Direct DecoupledMethod 223
4.A.3 Adjoint Methods 224
4.A.4 Green'sFunctionMethods 224
References 226
Problems 230

5 Chemistry of the Troposphere

5.1 Basic PhotochemicalCycle of N02, NO, and03 235
5.2 AtmosphericChemistryof CarbonMonoxide andNOx 239
5.3 AtmosphericChemistryof FonnaldehydeandNOx 244
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5.15 AtmosphericChemistry(GasPhase)of Sulfur Compounds 314

5.15.1 Sulfur Oxides 314
5.15.2 ReducedSulfur Compounds(Dimethyl Sulfide) 315
5.16 TroposphericChemistryof HalogenCompounds 317
5.16.1 ChemicalCyclesof HalogenSpecies 318
5.16.2 TroposphericChemistryofCFC Replacements:
Hydrofluorocarbons(HFCs)and
Hydrochlorofluorocarbons
(HCFCs) 319
References 323
Problems 331

6 Chemistry of the Atmospheric Aqueous Phase 337

6.1 Liquid Waterin the Atmosphere 337
6.1.1 Cloud Typesand Liquid WaterContent 338
6.2 AbsorptionEquilibria and Henry's Law 340
6.2.1 Gas/Aqueous-Phase Distribution Factor 343
.6.3 Aqueous-Phase ChemicalEquilibria 344
6.3.1 Water 344
6.3.2 CarbonDioxide/WaterEquilibrium 345
6.3.3 Sulfur Dioxide 348
6.3.4 Ammonia/WaterEquilibrium 353
6.3.5 Nitric Acid/Water Equilibrium 355
6.3.6 Equilibrium of OtherImportantAtmosphericGases 356
6.4 Aqueous-Phase ReactionRates 361
6.5 S(IV) to S(VI) Transformationand Sulfur Chemistry 363
6.5.1 Oxidation of S(IV) by Dissolved03 363
6.5.2 Oxidation of S(IV) by HydrogenPeroxide 366
6.5.3 Oxidation of S(IV) by OrganicPeroxides 367
6.5.4 UncatalyzedOxidation of S(IV) by O2 368
6.5.5 Oxidationof S(IV) by 02 Catalyzedby
Iron andManganese 369
6.5.6 S(IV) Oxidationby the OH Radical 372
6.5.7 Oxidation ofS(IV) by Oxidesof Nitrogen 374
6.5.8 Reactionof DissolvedS02 with HCHO 376
6.5.9 Comparisonof Aqueous-Phase S(IV)
Oxidation Paths 378
6.6 Aqueous-Phase Nitrite andNitrate Chemistry 380
6.6.1 NOx Oxidation 380
6.6.2 Nitrogen Radicals 381
6.7 Aqueous-Phase OrganicChemistry 381
6.8 Oxygenand HydrogenChemistry 383
6.9 Dynamic Behaviorof Solutionswith Aqueous-Phase
ChemicalReactions 384
6.9.1 ClosedSystem 385
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 CONTENTS xiii

8.5.2 Aerosol Mobility andDrift Velocity 475

8.5.3 MeanFreePathof an Aerosol Particle 478
8.6 PhoreticEffects 480
8.6.1 Thermophoresis 480
8.6.2 Diffusiophoresis 483
8.6.3 Photophoresis 483
8.7 Aerosol andFluid Motion 484
8.7.1 Motion of a Particlein an IdealizedFlow
(900 Corner) 485
8.7.2 StopDistanceand StokesNumber 486
8.8 Diametersof NonsphericalParticles 488
References 488
Problems 489

9 Thermodynamics of Aerosols 491

9.1 ThermodynamicPrinciples 491
9.1.1 Internal Energyand ChemicalPotential 491
.
9.1.2 The GibbsFreeEnergy,G 493
9.1.3 Conditionsfor ChemicalEquilibrium 495
9.1.4 ChemicalPotentialsof Ideal Gasesand Ideal
GasMixtures 499
9.1.5 ChemicalPotentialof Solutions 501
9.1.6 The Equilibrium Constant 506
9.2 Aerosol Liquid WaterContent 507
9.2.1 ChemicalPotentialof Waterin AtmosphericParticles 508
9.2.2 TemperatureDependenceof the DRH 510
9.2.3 Deliquescenceof Mu1ticomponent Aerosols 514
9.2.4 Crystallizationof Single andMulticomponentSalts 519
9.3 Equilibrium VaporPressureOver a CurvedSurface:
The Kelvin Effect 519
9.4 Thermodynamicsof AtmosphericAerosol Systems 523
9.4.1 The H2SO4-H2OSystem 523
9.4.2 The Sulfuric Acid-Ammonia-Water System 529
9.4.3 The Ammonia-Nitric Acid-Water System 531
9.4.4 The Ammonia-Nitric Acid-Sulfuric
Acid-Water System 537
9.4.5 OtherInorganicAerosol Species 539
References 541
Problem 543

10 Nucleation 545

10.1 ClassicalTheory of HomogeneousNucleation:

KineticApproach 547
10.1.1 The ForwardRateConstant.Bi 550
10.1.2 The ReverseRateConstantYi 551
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 CONTENTS xv

11.2.5 CharacteristicTime for Aqueous-Phase

ChemicalReactions 617
11.3 MassTransportandAqueous-Phase Chemistry 617
11.3.1 Gas-Phase Diffusion andAqueous-Phase Reactions 618
11.3.2 Aqueous-Phase Diffusion and Reaction 620
11.3.3 Interfacial MassTransportandAqueous-Phase
Reactions 621
11.3.4 Application to the S(IV)-Ozone Reaction 623
11.3.5 Application to the S(IV)-Hydrogen Peroxide
Reaction 626
11.3.6 Calculationof Aqueous-Phase ReactionRates 627
11.3.7 An Aqueous-Phase Chemistry/Mass
TransportModel 634
11.4 MassTransferto Falling Drops 635
11.5 CharacteristicTime for AtmosphericAerosol Equilibrium 636
11.5.1 Solid Aerosol Particles 636
11.5.2 AqueousAerosol Particles 638
Appendix 11 Solution of the TransientGas-Phase Diffusion
ProblemEquations(11.4)to (11.7) 641
References 643
Problems 645

12 Dynamics of Aerosol Populations 648

12.1 MathematicalRepresentations of the Aerosol
SizeDistributions 648
12.1.1 DiscreteDistribution 648
12.1.2 ContinuousDistribution 649
12.2 Condensation 649
12.2.1 Solutionof the CondensationEquation 652
12.3 Coagulation 656
12.3.1 Brownian Coagulation 656
12.3.2 Coagulationin Laminar ShearFlow 664
12.3.3 Coagulationin TurbulentFlow 665
12.3.4 Coagulationfrom GravitationalSettling 665
12.3.5 Brownian Coagulationand ExternalForceFields 666
12.3.6 The CoagulationEquation 672
12.3.7 Solutionof the CoagulationEquation 676
12.4 The DiscreteGeneralDynamic Equation 680
12.5 The ContinuousGeneralDynamic Equation 682
12.6 Evolution of an Aerosol SizeDistribution During
Gas-to-ParticleConversion 684
12.6.1 Diffusion-ControlledGrowth 685
12.6.2 SurfaceReaction-ControlledGrowth 686
12.6.3 VolumeReaction-ControlledGrowth 688
12.6.4 DimensionlessSizeSpectraEvolution 689
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 CONTENTS xvii

14.1.2 TemperatureChangesof a Rising (or Falling)

Parcelof Air 770
14.2 AtmosphericStability 772
Problems 775

15 Cloud Physics 777

15.1 Propertiesof WaterandWaterSolutions 777
15.1.1 SpecificHeat of Waterand Ice 778
15.1.2 Latent Heatsof Evaporationand of Melting for Water 778
15.1.3 WaterSurfaceTension 779
15.2 WaterEquilibrium in theAtmosphere 780
15.2.1 Equilibrium of a Flat PureWaterSurface
with the Atmosphere 780
15.2.2 Equilibrium of a PureWaterDroplet 781
15.2.3 Equilibrium of a Flat WaterSolution 783
15.2.4 AtmosphericEquilibrium of an Aqueous
Solution Drop 784
15.2.5 AtmosphericEquilibrium of an AqueousSolution
Drop Containingan InsolubleSubstance 790
15.3 Cloud andFog Formation 793
15.3.1 IsobaricCooling 794
15.3.2 Adiabatic Cooling 795
15.3.3 Cooling with Entrainment 798
15.3.4 A Simplified MathematicalDescriptionof
Cloud Formation 799
15.4 Growth Rateof Individual Cloud Droplets 801
15.5 Growth of a Droplet Population 805
15.6 Cloud CondensationNuclei 809
15.7 Cloud Processingof Aerosols 812
15.7.1 NucleationScavengingof Aerosolsby Clouds 813
15.7.2 ChemicalCompositionof Cloud Droplets 814
15.7.3 NonrainingCloud Effectson Aerosol Concentrations 816
15.7.4 Interstitial Aerosol Scavengingby Cloud Droplets 821
15.7.5 Aerosol NucleationNear Clouds 823
15.8 OtherFormsof Waterin theAtmosphere 823
15.8.1 Ice Clouds 824
15.8.2 Rain 828
15.9 Cloud Climatology 832
References 834
Problems 839

16 Micrometeorology 841

16.1 BasicEquationsof AtmosphericFluid Mechanics 841

16.2 Turbulence 847 .
16.3 Equationsfor the Mean Quantities 849
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 CONTENTS xix

18.3 Summaryof GaussianPoint SourceDiffusion Fonnulas 923

18.4 DispersionParametersin GaussianModels 926
18.4.1 Correlationsfor uyand UzBasedon
Similarity Theory 926
18.4.2 Correlationsfor uyand UzBasedon
PasquillStability Classes 929
18.5 PlumeRise 931
18.6 Analytical Propertiesof the GaussianPlumeEquation 933
18.7 FunctionalFonns of MeanWind SpeedandEddy Diffusivities 938
18.7.1 MeanWindSpeed 938
18.7.2 Vertical Eddy Diffusion Coefficient Kzz 938
18.7.3 Horizontal Eddy Diffusion Coefficients Kxx and K yy 942
18.8 Solutionsof the Steady-State AtmosphericDiffusion Equation 943
18.8.1 Diffusion from a Point Source 943
18.8.2 Diffusion from a Line Source 944
References 947
Problems 949

19 Dry Deposition 958

19.1 DepositionVelocity 958
19.2 ResistanceModel for Dry Deposition 960
19.2.1 AerodynamicResistance 962
19.2.2 Quasi-LaminarResistance 963
19.2.3 Surfaceof CanopyResistance 965
19.2.4 RelativeMagnitudesof ra, rb, and rc 968
19.3 Dry Depositionof Particles 969
19.4 A Model for Dry DepositionCalculations 971
19.5 Measurementof Dry Deposition 977
19.5.1 Direct Methods 978
19.5.2 Indirect Methods 979
19.5.3 Comparisonof Methods 980
19.6 SomeCommentson Modeling andMeasurementof
Dry Deposition 980
19.7 InteractionBetweenEquilibration Processesand
Dry Deposition 982
19.1.1 Solutionof the Model Equations 987
19.7.2 TheDepositionRatio 988
19.7.3 Effects of Equilibration Processeson
Dry andWet Deposition 989
References 993
Problems 995

20 Wet Deposition 997

20.1 GeneralRepresentation
of Atmospheric
Wet RemovalProcesses 997
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 CONTENTS xxi

22 Radiative Effects of Atmospheric Aerosols: Visibility and Climate

22.1 ScatteringandAbsorptionof Light by Small Particles 1114
22.1.1 RayleighScatteringRegime 1120
22.1.2 GeometricScatteringRegime 1122
22.1.3 ScatteringPhaseFunction 1123
22.1.4 Extinction by an Ensembleof Particles 1123
22.2 Visibility 1126
22.3 Scattering,Absorption,and Extinction Coefficientsfrom
Mie Theory 1131
22.4 CalculatedVisibility ReductionBasedon AtmosphericData 1135
22.5 Direct Effect of Aerosolson Climate 1139
22.5.1 Optical Depth 1143
22.5.2 UpscatterFraction 1146
22.5.3 ScatteringModel of an Aerosol Layer 1147
22.5.4 Cooling VersusHeatingof anAerosol Layer 1152
22.5.5 ScatteringModel of anAerosol Layer for a
NonabsorbingAerosol 1154
22.5.6 Direct AerosolForcing of Climateby
SulfateAerosols 1156
22.5.7 Effect of Mineral Dust on RadiativeForcing
of Climate 1160
22.5.8 Effect of Carbonaceous Aerosolson Radiative
Forcingof Climate 1166
22.5.9 Internaland ExternalMixtures 1166
22.6 Indirect Effect of Aerosolson Climate 1170
22.6.1 RadiativeModel for a Cloudy Atmosphere 1173
22.6.2 Sensitivityof Cloud Albedo to Cloud Drop
NumberConcentration 1175
22.6.3 Relationof Cloud Drop NumberConcentrationto
Aerosol Concentrations 1177
22.6.4 Estimatesof Indirect RadiativeForcing of Aerosols 1179
22.7 Summary:Estimatesof Contributionsto RadiativeForcing ~ 1180
22.8 Climate Responseto AnthropogenicAerosol Forcing 1182
Appendix 22 Calculationof ScatteringandExtinction Coefficients
by Mie Theory 1184
References 1185
Problems 1190

23 Atmospheric Chemical Transport Models

23.1 Introduction 1193
23.1.1 Model Types 1194
?~ 1 2 Tvne~of AtmosohericChemicalTransportModels 1195
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 CONTENTSxxiii

24.6 Alternative Formsof Air Quality Standards 1277

24.6.1 Evaluationof Alternative Formsof the OzoneAir Quality
Standardwith 1971Pasadena, California, Data 1279
24.6.2 Selectionof the AveragingTime 1281
24.7 RelatingCurrentandFutureAir Pollutant
StatisticalDistributions 1281
References 1283
Problems 1285

Appendix A Units and Physical Constants 1289

A.l SI BaseUnits 1289
A.2 SI Derived Units 1289
A.3 FundamentalPhysicalConstants 1292
A.4 Propertiesof theAtmosphereandWater 1293
A.5 Units for RepresentingChemicalReactions 1294
A.6 Concentrationsin the AqueousPhase 1295
A.7 Symbolsfor Concentration 1295
References 1295

Appendix B Rate Constantsof Atmospheric Chemical Reactions 1297

References 1307

Index 1309
 The study of atmospheric chemistry as a scientific discipline goes back to the 18th century,
when the principal issue was identifying the major chemical components of the atmos-
phere, nitrogen, oxygen, water, carbon dioxide, and the noble gases. In the late 19th and
early 20th centuries attention turned to the so-called trace gases,speciespresent at less than
1 part per million parts of air by volume (1 JLmol per mole). We now know that the atmos-
phere contains a myriad of trace species, some at levels as low as 1 part per trillion parts of
air. The role of trace species is disproportionate to their atmospheric abundance; they are
responsible for phenomena ranging from urban photochemical smog, to acid deposition, to
stratospheric ozone depletion, to potential climate change. Moreover, the composition of
the atmosphere is changing; analysis of air trapped in ice cores reveals a record of striking
increases in the long-lived so-called greenhouse gases, carbon dioxide (CO2), methane
(CH4), and nitrous oxide (N 20). Within the last century, concentrations of tropospheric
ozone (03), sulfate (SO~-), and carbonaceous aerosols in the Northern Hemisphere have
increased significantly. There is evidence that all these changes are altering the basic chem-
istry of the atmosphere.
Atmospheric chemistry occurs within a fabric of profoundly complicated atmospheric
dynamics. The results of this coupling of dynamics and chemistry are often unexpected:
witness the unique combination of dynamical forces that lead to a wintertime polar vortex
over Antarctica, with the concomitant formation of polar stratospheric clouds that serve as
sites for heterogeneous chemical reactions involving chlorine compounds resulting from
anthropogenic chlorofluorocarbons-all leading to the near total depletion of stratospheric
ozone over the South Pole each spring; witness the nonlinear, and counterintuitive, depen-
dence of the amount of ozone generated by reactions involving hydrocarbons and oxides of
nitrogen(NOx) at the urbanandregionalscale-although both hydrocarbonsandNOx are
ozoneprecursors,situationsexist wherecontinuing to emit more and more NO x actually
leads to less ozone.
The chemical constituents of the atmosphere do not go through their life cycles inde-
pendently; the cycles of the various species are linked together in a complex way. Thus a
perturbation of one component can lead to significant, and nonlinear, changes to other com-
ponents and to feedbacks that can amplify or damp the original perturbation.
In many respects, at once both the most important and the most paradoxical trace gas in
the atmosphere is ozone (03). High in the stratosphere ozone screens living organisms
from biologically harmful solar ultraviolet radiation; ozone at the surface, in the tropos-
phere, can produce adverse effects on human health and plants when present at levels ele-
vated above natural. At the urban and regional scale, significant policy issues concern how
to decreaseozone levels by controlling the ozone precursors-hydrocarbons and oxides of
nitrogen. At the global scale, understanding both the natural ozone chemistry of the tro-
posphere and the causes of continually increasing background tropospheric ozone levels is
a major goal.

xxv
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3;)Vd31ld JAxx
 PREFACE xxvii

for the benefit of the studentand the instructor.The designation(A) indicatesa problem
that involves a straightforwardapplicationof materialin the text. Thoseproblemsdenoted
(B) requiresomeextensionof the ideasin the text. Problemsdesignated(C) encouragethe
readerto apply conceptsfrom the book to currentproblemsin atmosphericscienceandgo
somewhatbeyondthe level of (B) problems.Finally, thoseproblemsdenoted(D) are of a
degreeof difficulty correspondingto (C) but generallyrequiredevelopmentof a computer
programfor their solution.
This book isa successorto John H. Seinfeld'sAtmosphericChemistryand Physicsof
Air Pollution (Wiley, 1986),which has been widely usedfor a decade.Substantialaddi-
tions havebeenmadein virtually all areascoveredby the earlier book, reflectingthe sig-
nificant increasein our understandingof atmosphericprocessesthat hasemergedover the
last decadeand reflecting the truly global scopeof the scienceof atmosphericchemistry
and physics.
We extendsincereappreciationto Marta GoodmanandLaura Shaheenwho providedso
much valuableassistancein making this book a reality and to Cecilia Lin who draftedthe
figuresso skillfully.

JOHN H. SEINFELD

SPYROSN. PANDIS
 1

1.1 HISTORY AND EVOLUTION OF THE EARTH'S ATMOSPHERE

It is generally believed that the solar system condensed out of an interstellar cloud of gas
and dust, referred to as the "primordial solar nebula," about 4.6 billion years ago. The at-
mospheres of the Earth and the other terrestrial planets, Venus and Mars, are thought to
have formed as a result of the release of trapped volatile compounds from the planet itself.
The early atmosphere of the Earth is believed to have been a mixture of carbon dioxide
(COz), nitrogen (Nz), and water vapor (HzO), with trace amounts of hydrogen (Hz), a
mixture similar to that emitted by present day volcanoes.
The composition of the present atmosphere bears little resemblance to the composition
of the early atmosphere. Most of the water vapor that outgassed from the Earth's interior
condensed out of the atmosphere to form the oceans. The predominance of the CO2 that
outgassed formed sedimentary carbonate rocks after dissolution in the ocean. It is esti-
mated that for each molecule of COz presently in the atmosphere, there are about 105 COz
molecules incorpor~ted as carbonates in sedimentary rocks. Since Nz is chemically inert,
non-water soluble, and noncondensable, most of the outgassed Nz accumulate~ in the at-
mosphere over geologic time to become the atmosphere's most abundant constituent.
The early atmosphere of the Earth was a mildly reducing chemical mixture, whereas the
present atmosphere is strongly oxidizing. The dramatic rise of oxygen (Oz) as an atmos-
pheric constituent over time was the result of the production of Oz as a by-product of pho-
tosynthetic activity. It has been estimated that the current level of Oz in the atmosphere was
achieved approximately 400 million years ago (Cloud, 1983). The present level of Oz is
maintained by a balance between production from photosynthesis and removal through
respiration and decay of organic carbon. If Oz were not replenished by photosynthesis, the
reservoir of surface organic carbon would be completely oxidized in about 20 years, at
which time the amount of Oz in the atmosphere would have decreased by less than 1%
(Walker, 1977). In the absenceof surface organic carbon to be oxidized, weathering of sed-
imentary rocks would consume the remaining O2 in the atmosphere, but it would take ap-
proximately 4 million years to do so.
The Earth's atmosphere is composed primarily of the gases Nz (78%), Oz (21%), and
Ar (1 %), whose abundancesare controlled over geologic time scales by the biosphere, up-
take and release from crustal material, and degassing of the interior. Water vapor is the next
most abundant constituent; it is found mainly in the lower atmosphere and its concentration
is highly variable, reaching concentrations as high as 3%. Evaporation and precipitation
control its abundance. The remaining gaseous constituents, the trace gases, comprise less
than 1% of the atmosphere. These trace gases playa crucial role in the Earth's radiative

1
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 HISTORY AND EVOLUTION OF THE EARTH'S ATMOSPHERE 3

The atmosphere is the recipient of many of the products of our technological society.
These effluents include products of combustion of fossil fuels and of the development of
new synthetic chemicals. Historically these emissions can lead to unforeseen consequences
in the atmosphere. Classical examples include the realization in the 1950s that motor vehi-
cle emissions could lead to urban smog and the realization in the 1970s that emissions of
chlorofluorocarbons from aerosol spray cans and refrigerators could cause the depletion of
stratospheric ozone.
The chemical fates of trace atmospheric species are often intertwined. The life cycles of
the trace species are inextricably coupled through the complex array of chemical and phys-
ical processesin the atmosphere. As a result of these couplings, a perturbation in the con-
centration of one species can lead to significant changes in the concentrations and lifetimes
of other trace species and to feedbacks that can either amplify or damp the original pertur-
bation. An example of this coupling is provided by methane. Methane is the predominant
organic molecule in the troposphere and it is the sec.ondmost important greenhouse gas af-
ter CO2. Methane sources such as rice paddies and cattle can be estimated and are increas-
ing. Methane is removed from the atmosphere by reaction with the hydroxyl (OH) radical,
at a rate that depends on the atmospheric concentration of OR. But, the OH concentration
dependson the amount of carbon monoxide (CO), which itself is a product of C~ oxida-
tion as well as a result of fossil fuel combustion and biomass burning. The hydroxyl con-
centration also depends on the concentration of ozone and oxides of nitrogen. Change in
C~ can affect the total amount of ozone in the troposphere, so methane itself affects the
concentration of the species, OR, that governs its removal.
Depending on their atmospheric lifetime, trace species can exhibit an enormous range
of spatial and temporal variability. Relatively long-lived species have a spatial uniformity
such that a handful of strategically located sampling sites around the globe are adequate to
characterize their spatial distribution and temporal trend. As species lifetimes become
shorter, their spatial and temporal distributions become more variable. Urban areas,for ex-
ample, can require tens of monitoring stations over an area of hundreds of square kilome-
ters in order to characterize the spatial and temporal distribution of their atmospheric
components.
The extraordinary pace of the recent increases in atmospheric trace gases can be seen
when current levels are compared with those of the distant past. Such comparisons can be
made for CO2 and C~, whose histories can be reconstructed from their concentrations in
bubbles of air trapped in ice in such perpetually cold places as Antarctica and Greenland.
With gasesthat are long-lived in the atmosphere and therefore distributed rather uniformly
over the globe, such as CO2 and C~, polar ice core samples reveal global average con-
centrations of previous eras. Analyses of bubbles in ice cores show that CO2 and C~ con-
centrations remained essentially unchanged from the end of the last ice age some 10,000
years ago until roughly 300 years ago, at mixing ratios close to 260 ppm by volume
and 0.7 ppm by volume, respectively. (See Section 1.4 for discussion of units.) About 300
years ago methane levels began to climb, and about 100 years ago levels of both gases be-
gan to increase markedly. Before the large-scale production of chlorofluorocarbons the nat-
ural level of chlorine in the stratosphere was 0.6 part per billion (ppb) by volume; now it is
3 ppb, a factor of 5 increase.
Activities of humans account for most of the rapid changes in the trace gases over the
past 200 years-combustion of fossil fuels (coal and oil) for energy and transportation, in-
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 CLIMATE 5

century. It has been estimated that a doubling of CO2 from its pre-Industrial Revolution
mixing ratio of 280 ppm by volume could lead to a rise in average global temperature of
1.5 to 4.5°C. A 2°C warming would produce the warmest climate seen on Earth in 6000
years. A 4.5°C rise would place the world in a temperature regime last experienced in the
Mesozoic Era-the age of dinosaurs.
Although an average global ~arming of a few degrees does not sound like much, it
could create dramatic changes in climatic extremes. It has been estimated, for example,
that, in the event of an average global warming of 1.7°C, the frequency of periods of 5 days
or more exceeding 35°C (95°F) in the Com Belt of the United States would increase three-
fold. Such conditions at critical stages of the growing season are known to harm com and
lead to reduced yields. With a doubling of CO2, the number of days exceeding 38°C
(100°F) and nights above 27°C (80°F) have been estimated to rise dramatically in many
major American cities. Changes in the timing and amount of precipitation would almost
certainly occur with a warmer climate. Soil moisture, critical during planting and early
growth periods, will change. Some regions would probably become more productive, oth-
ers less so. The North American Grain Belt, according to at least one climate model, will
shift northward into Canada as warming produces hotter, drier conditions in the American
Midwest.
Of all the effects of a global warming, perhaps none has captured more attention than
the prospect of rising sea levels. This would result from the melting of land-based glaciers
and volume expansion of ocean water as it warms. Prevailing opinion is that a sea level rise
of about 0.5 m could occur by 2100. In the most dramatic scenario, the West Antarctic ice
sheet, which rests on land that is below sea level, could slide into the sea if the buttress of
floating ice separating it from the ocean were to melt. This would raise the average sea
level 5 to 6 m (Bentley, 1997). Even a 0.3 m (1 foot) rise would have major effects on the
erosion of coastlines, salt water intrusion into the water supply of coastal areas, flooding of
marshes, and inland extent of surges from large storms.
To systematically approach the complex subject of climate, the scientific community
has divided the problem into two major parts, climate forcings and climate responses.
Climate forcings are changes in the energy balance of the Earth that are imposed upon it;
forcings are measured in units of heat flux-watts per square meter (W m-2). An example
of a forcing is a change in energy output from the sun. Responsesare the meteorological re-
sults of these forcings, reflected in temperatures, rainfall, extremes of weather, sea level
height, and so on.
Much of the variation in the predicted magnitude of potential climate effects resulting
from the increase in greenhouse gas levels hinges on estimates of the size and direction of
various feedbacks that may occur in response to an initial perturbation of the climate.
Negative feedbacks have an effect that damps the warming trend; positive feedbacks rein-
force the initial warming. One example of a greenhouse warming feedback mechanism in-
volves water vapor. As air warms, each cubic meter of air can hold more water vapor. Since
water vapor is a greenhouse gas, this increased concentration of water vapor further en-
hances greenhouse warming. In turn, the warmer air can hold more water, and so on. This
is an example of a positive feedback, providing a physical mechanism for multiplying the
original impetus for change beyond its initial amount.
Some mechanisms provide a negative feedback, which decreasesthe initial impetus. For
example, increasing the amount of water vapor in the air may lead to forming more clouds.
Low-level, white clouds reflect sunlight, thereby preventing sunlight from reaching the
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 'HE LAYERS OF THE ATMOSPHERE 7

Stratosphere. Extends from the tropopause to the stratopause (-45 to 55 kIn altitude);
temperature increases with altitude, leading to a layer in which vertical mixing is
slow.
Mesosphere. Extends from the stratopause to the mesopause (-80 to 90 kIn altitude);
temperature decreaseswith altitude to the mesopause, which is the coldest point in
the atmosphere; rapid vertical mixing.
Thermosphere. The region above the mesopause; characterized by high temperatures
as a result of absorption of short wavelength radiation by N2 and O2; rapid vertical
mixing. The ionosphere is a region of the upper mesosphereand lower thermosphere
where ions are produced by photoionization.
Exosphere. The outermost region of the atmosphere (>500 kIn altitude) where gas mol-
ecules with sufficient energy can escape from the Earth's gravitational attraction.
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 VARIATION OF PRESSURE WITH HEIGHT IN THE ATMOSPHERE 9

Absorption of solar ultraviolet radiation by 03 causesthe temperature in the stratosphereto

be much higher than expected, based on simply extending the troposphere's lapse rate into
the stratosphere.

1.4 VARIATION OF PRESSUREWITH HEIGHT

IN THE ATMOSPHERE

The variation of pressurewith height in the atmospherecan be addressedwith the hydro-

staticequation,!

dp(z) = .p(z)g (1.1)

dz

where p(z) is the massdensityof air at height z and g is the accelerationdue to gravity.
From the ideal gaslaw,

MairP(Z)
p(z)= (1.2)
RT(z)

where Mairis the averagemolecularweight of air (28.97g mol-I). Thus

dp(z) - Mairgp(z)
(1.3)
dz RT(z)

which we can rewrite as

d lnp(z) - -~
dz - H(z) (1.4)

where H(z) = RT(z)/ Mairg is a characteristic length scale for decrease of pressure with
height.
The temperaturein the atmospherevariesby lessthan a factor of 2, while the pressure
changesby six ordersof magnitude(seeTableA.8). If the temperaturecan be takento be
approximatelyconstant,just to obtain a simple approximateexpressionfor p(z), then the

'Units of pressure. Because instruments for measuring pressure, such as the manometer, often contain mercury,
commonly used units for pressure are based on the height of the mercury column (in millimeters) that the gas
pressure can support. The unit mm Hg is often called the Torr in honor of the scientist, Evangelista Torricelli. A
related unit for pressure is the standard atmosphere (abbreviated atm):
1 standard atmosphere = 1 atm = 760 mm Hg = 760 Torr

The unit of pressure in the International System of Units (SI) is newtons per meter squared (N m-'), which is
called the pascal (Pa). In terms of pascals, the standard atmosphere is 1.01325 x 10s Pa. Another commonly used
unit of pressure in atmospheric science is the millibar (mbar), which is equivalent to the hPa (see Tables A.5 and
AR) Thp .t"nti"rti "tmn.nhprP i. 101, ?~ mh"r
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 ARGE-SCALE MOTION OF THE ATMOSPHERE 11

to the tropics must pass through more atmosphere and intercept a larger surface area. The
uneven distribution of energy resulting from latitudinal variations in insolation and from
differences in absorptivity of the Earth's surface leads to the large-scale air motions of the
Earth. In particular, the tendency to transport energy from the tropics toward the pola( re-
gions, thereby redistributing energy inequalities on the Earth, is the overall factor govern-
ing the general circulation of the atmosphere.
In order to visualize the nature of the general circulation of the atmosphere, we can think
of the atmosphere over either hemisphere as a fluid enclosed within a long, shallow con-
tainer, heated at one end and cooled at the other. Because the horizontal dimension of the
"container" is so much greater than its vertical dimension, the curvature of the Earth can be
neglected, and the container can be considered to be rectangular. If such a container were
constructed in the laboratory and the ends differentially heated as described above, one
would observe a circulation of the fluid, consisting of rising motion along the heated wall
and descending motion along the cooled wall, flow in the direction of warm to cold at the
top of the box, and flow in the direction of cold to warm along the bottom of the box. In the
atmosphere, then, the tendency is for warm tropical air to rise and cold polar air to sink,
with poleward and equatorward flows to complete the circulation.
However, the general circulation of the atmosphere is not as simple as just described.
Another force arises because of the motion of the Earth, the Coriolis force. At the Earth's
surface an object at the equator has a greater tangential velocity than one in the temperate
zones. Air moving toward the south cannot acquire an increased eastward (the Earth rotates
from west to east) tangential velocity as it moves south and thus, to an observer on the
Earth, appears to acquire a velocity component in the westward direction. Thus air moving
south in the Northern Hemisphere appears to lag behind the Earth. To an observer on the
Earth it appears that the air has been influenced by a force in the westward direction. To an
observer in space, it would be clear that the air is merely trying to maintain straight-line
motion while the Earth turns below it. Friction between the wind and the ground dimin-
ishes this effect in the lower atmosphere.
From the standpoint of air motion, the atmosphere can be segmented vertically into two
layers. Extending from the ground up to about 1000 m is the planetary boundary laye!; the
zone in which the effect of the surface is felt and in which the wind speed and direction are
governed by horizontal pressure gradients, shear stresses, and Coriolis forces. Above the
planetary boundary layer is the geostrophic laye!; in which only horizontal pressure gradi-
ents and Coriolis forces influence the flow. .
To predict the general pattern of macroscale air circulation on the Earth we must con-
sider both the tendency for thermal circulation and the influence of Coriolis forces. Figure
1.2 shows the nature of the general circulation of the atmosphere. At either side of the equa-
tor is a thermal circulation, in which warm tropical air rises and cool northern air flows to-
ward the equator. The circulation does not extend all the way to the poles becauseradiative
cooling of the upper northward flow causesit to subside (fall) at about 30° Nand S latitude.
The Coriolis force acting on these cells leads to easterly winds, called the trade winds. The
same situation occurs in the polar regions, in which warm air from the temperate zones
moves northward in the upper levels, eventually cooling by radiation and subsiding at the
poles. The result is the polar easterlies.
In the temperate regions, between 40° and 55° latitude, influences of both tropical and
polar regions are felt. The major feature of the temperate regions is large-scale weather sys-
tems, which results in the circulation shown in Figure 1.2. The surface winds in the
Northern Hemisphere are westerlies because of the Coriolis force.
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 LARGE-SCALE MOTION OF THE ATMOSPHERE 15

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tropopause folds
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Pole Equator
Latitude
FIGURE 1.3 Dynamicalaspectsof stratosphere-troposphere exchange(Holton et al., 1995).The
tropopauseis shownby the thick line. Thin lines are surfacesof constantpotential temperature(in
kelvin units).(Potentialtemperaturewill be definedanddevelopedin Chapter14.For now,thesesur-
facescan be thought of as those on which horizontal transportoccurs.)The shadedregion of the
stratosphereis that within which so-called tropopausefolding occurs. (Tropopausefolding is a
processwherebya thin band of stratosphericair intrudesinto the tropospherealong strongly tilted
isentropes.Part of the stratosphericair in the fold returnsreversibly to the stratosphereand part is
drawnirreversiblyinto the troposphere.)The regionof the stratosphereaboveabout380 K potential
temperaturedoesnot havedirect stratosphere-troposphere exchangein the midlatitudes.The broad
arrowsindicatetransportby the global-scalecirculation,which is driven by the "extratropicalpump:'
The extratropicalstratosphereactspersistentlyon the tropical lower stratosphereasa kind of global-
scalesuction pump, the strengthof which varies seasonallyand interannuallyand in which air is
graduallywithdrawn from the tropical stratosphereandpushedpolewardandultimately downward.

exchange is that air is forced into the stratosphere by tropical cumulus convective turrets.
More consistent, however, is that the net flux from the tropical troposphere to the stratos-
phere is actually a result of the wave-driven pumping from the extratropical stratosphere
(the large horizontal arrows in Figure 1.3). It is this pumping that is the cause of the steady
ascent of air in the tropical stratosphere (Holton et al., 1995). The shaded region of the
stratosphere, the lowermost stratosphere, is the only part of the stratosphere that can re-
ceive material from the troposphere by transport along surfaces of constant potential tem-
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3~3HdSOW.LV3H.L 91
 TEMPERATURE AND WATER VAPOR

SOc
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Latitude
FIGURE 1.4 Meanatmospherictemperatureover the period 1980to 1989between1000mbarand
50 mbar averagedarounda latitude band(Salstein.1995).Data not availablein blackenedareas.

the averagetemperatureexceeds295 K. The annualmeantemperaturestructureis largely

symmetricabout the equator(although the highest temperatureoccursat about 10° N),
with the differencein meansurfacetemperaturebetweenthe tropics and the poles about
35°C.At the top of the troposphere,aboutthe 200 mbar level, the meridionaltemperature
gradientbeginsto reverse;at 100 mbar, for example,temperatureincreasespolewardby
about20°C.
Watervapor is distributedthroughoutthe lower troposphere,at highly variablelevels.
The watervaporcontentof the atmospherecanbe expressedin a variety of ways:

1. Mole (or volume) mixing ratio--moles of water vaporper mole of air (seeSection
1.7).
2. Amount of water vaporto dry air by mass[g H2O (kg dry air)-'].
3. Specifichumidity-proportion of watervapor to total air [g H2O (kg air)-'].
4. Relativehumidity-ratio of the specifichumidity to the maximumspecifichumid-
ity possibleat a given temperatureandpressure(dimensionless).(SeeSection1.7.)
5. Massconcentrationg H2O (m3air)-'.
6. Massmixing ratio g H2O (g air)-'.

Figure 1.5showsthe zonalmeanspecifichumidity for the period 1980to 1989.Maximum

specifichumidities are reachedin the tropics, about 16 g kg-I. By the 500 mbar altitude,
the valueover the tropics hasdecreasedto 2 g kg-I. This value of 2 g kg-I also holdsin
the northernand southernpolar regions.
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3~3HdSOW.LY3H.L 81
 EXPRESSING THE AMOUNT OF SUBSTANCE IN THE ATMOSPHERE 19

Thusthe mixing ratio ~i andthe molar concentrationarerelatedby

Cj
~j = -;;jiiT
(1.8)
-~=~
- pfRT p

where Pi is the partial pressure of i.

Concentration (mol m-3) depends on pressure and temperature through the ideal gas
law. Mixing ratios, which are just mole fractions, are therefore better suited than concen-
trations to describe abundances of species in air, particularly when spatial and temporal
variation is involved. The inclusion of water vapor in the totality of gaseous substancesin
a volume of air means that mixing ratio will vary with humidity. The variation can amount
to several percent. Sometimes, as a result, mixing ratios are defined with respect to dry air.
It has become common use in atmospheric chemistry to describe mixing ratios by the
following units:

partsper million (ppm) 10-6 .umolmol-l

partsper billion (ppb) 10-9 nmolmol-l
partsper trillion (ppt) 10-12 pmolmol-1

These quantities are sometimes distinguished by an added v (for volume) and m (for mass),
that is,

ppmv partsper million by volume

ppmm partsper million by mass

Unlessnotedotherwise,we will alwaysusemixing ratiosby volumeandnot usethe added

v. The parts per million, parts per billion, and partsper trillion measuresare not SI units;
the SI versionsare,asgiven above,JLmolmol-I, nmol mol-I, andpmol mol-I.
The concentrationof air moleculesat any temperatureand pressurecan be computed
from the ideal gaslaw (1.7).At T = 298 K andp = 1 atm, for example,the concentration,
expressedin moleculescm-3, is

.01325X 105 N/m2

= 40.897 mol
m3
mol' m3 6.022 X 1023 molecules
=
m3 ) 106cm3 mol
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 COMPOSITION OF THE ATMOSPHERE 21

1.8 COMPOSITION OF THE ATMOSPHERE

The atmosphere is composed primarily of nitrogen, oxygen, and several noble gases, the
concentrations of which have remained remarkably fixed over time. Also present are a
number of trace gases that occur in relatively small and sometimes highly variable
amounts.
In spite of its apparent unchanging nature, the atmosphere is in reality a dynamic sys-
tem, with its gaseous constituents continuously being exchanged with vegetation, the
oceans, and biological organisms. The so-called cycles of the atmospheric gasesinvolve a
number of physical and chemical processes. Gases are produced by chemical processes
within the atmosphere itself, by biological activity, volcanic exhalation, radioactive decay,
and human industrial activities. Gases are removed from the atmosphere by chemical reac-
tions in the atmosphere, by biological activity, by physical processes in the atmosphere
(such as particle formation), and by deposition and uptake by the oceans and earth. The av-
erage lifetime of a gas molecule introduced into the atmosphere can range from secondsto
millions of years, depending on the effectiveness of the removal processes. Most of the
species considered air pollutants (in a region in which their concentrations exceed substan-
tially the normal background levels) have natural as well as man-made sources. Therefore,
in order to assessthe effect man-made emissions may have on the atmosphere as a whole,
it is essential to understand the atmospheric"cycles of the trace gases,including natural and
anthropogenic sources as well as predominant removal mechanisms.
The important atmospheric gasesare listed in Table 1.1 arranged according to the nature
of their global cycles. The total quantity of a species both in the atmosphere and dissolved
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 RADIATION 23

erals at the Earth's surface. Thus the oxygen concentration in the atmosphere is probably a
result of both accumulation and geochemical cycles.
While in the air, a substancecan be chemically altered in one of two ways. First, the sun-
light itself may contain sufficient energy to break the molecule apart, a so-called photo-
chemical reaction. The more frequently occurring chemical alteration, however, takes
place when two molecules interact and undergo a chemical reaction to produce new
species. Atmospheric chemical transformations can occur homogeneously or heteroge-
neously. Homogeneous reactions occur entirely in one phase; heterogeneous reactions in-
volve more than one phase, such as a gas interacting with a liquid or with a solid surface.
During transport through the atmosphere, all but the most inert substancesare likely to
participate in some form of chemical reaction. This process can transform a chemical from
its original state, the physical (gas, liquid, or solid) and chemical form in which it first en-
ters the atmosphere, to another state that may have either similar or very different charac-
teristics. Transformation products can differ from their parent substance in their chemical
properties, toxicity, and other characteristics. These products may be removed from the at-
mosphere in a manner very different from that of their precursors. For example, when a
substancethat was originally emitted as a gas is transformed into a particle, the overall re-
moval is usually hastened since particles often tend to be removed from the air more
rapidly than gases.
In spite of the fact that the atmosphere is composed predominantly of relatively inert
molecules such as Nz and Oz, it is actually a rather efficient oxidizing medium. One reason
for the atmosphere's oxidizing capacity arises because the atmosphere contains minute
amounts of very reactive molecular fragments, called free radicals. The most important
free radical in the chemistry of the troposphere is the hydroxyl (OH) radical, which reacts
with nearly every molecular species in the atmosphere. In addition, the atmosphere con-
tains trace amounts of species less reactive than free radicals but nonetheless reactive
enough to attack a variety of airborne compounds. Ozone (03) is one important oxidizer,
which also participates in the formation of the hydroxyl radical.
Once emitted, species are converted at various rates into substances generally charac-
terized by higher chemical oxidation statesthan their parent substances.Frequently this ox-
idative transformation is accompanied by an increase in polarity (and hence water
solubility) or other physical and chemical changes from the precursor molecule. An exam-
ple is the conversion of sulfur dioxide (SOz) into sulfuric acid (HzS04). Sulfur dioxide is
moderately water soluble, but its oxidation product, sulfuric acid, is so water soluble that
even single molecules of sulfuric acid in air immediately become associated with water
molecules. The demise of one substance through a chemical transformation can become
another species in situ source. In general, then, a species emitted into the air can be trans-
formed by a chemical process to a product that may have markedly different physico-
chemical properties and a unique fate of its own.

1.9 RADIATION

Basically all the energy that reaches the Earth comes from the Sun. The absorption and loss
of radiant energy by the Earth and the atmosphere are almost totally responsible for the
Earth's weather, both on a global and local scale. The average temperature on the Earth re-
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 RADIATION 25

106m

104m
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High Frequencyr 102m

(Radio)
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Gamma. RHV~
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lO-lOcm

Cosmic Rays 1012cm

FIGURE 1.6 Electromagneticspectrum.

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 RADIATION 27

I I I I I I I

30

/ 300 K Blackbody
-'8 201
:j.
C'1
'8
~
~

~~
10

01
.' I I I I ~-,--,-,
0 10 20 30 40 50 60 70
Wavelength, ~m
FIGURE 1.8 Spectralirradiance(W m-2 p,m-l) of a blackbodyat 300 K.

As can be seenfrom Figures 1.7 and 1.8, the higher the temperature, the greater is the emis-
sive power (at all wavelengths). We also see that, as temperature increases, the maximum
value of FB(A) moves to shorter wavelengths. The wavelength at which the maximum
amount of radiation is emitted by a blackbody is found by differentiating (1.14) with re-
spect to A, setting the result equal to zero, and solving for A. The result with A expressed
in nm and T in kelvin units is

2.897 X 106
Amax= (1.15)
T

Thushot bodiesnot only radiatemore energythan cold ones,they do so at shorterwave-

lengths.The wavelengthsfor the maximaof solar andterrestrialradiationare480 nm and
about 10,000nm, respectively.The Sun, with an effective surfacetemperatureof about
6000 K, radiatesabout2 X 105more energyper squaremeterthan the Earth at 300 K.
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 RADIATION 29

If (1.14) is integratedover all wavelengths,the total emissivepower FB (W m-1 of a

blackbody is found to be

aT4 (1.16)

where u = 5.671 X 10-8 W m-2 K-4, the Stefan-Boltzmann constant.

1.9.2 Absorption of Radiation by Gases

Absorption of radiation by gases is one of the most important aspects of both global mete-
orology and atmospheric chemistry. The solar spectrum is radically altered by absorption
as the radiation traverses the atmosphere. It is important to note that the molecules that are
responsible for the most pronounced absorption of both solar and terrestrial radiation are
the minor constituents of the atmosphere, not N2 and O2. Thus ozone in the upper atmos-
phere effectively absorbs all solar radiation below 290 nm, whereas water vapor and car-
bon dioxide absorb much of the long-wave terrestrial radiation. The most significant
absorbing gasesin the atmosphere are O2, 03, H2O, and CO2, Figure 1.9 shows the solar ir-
radiance at the top of the atmosphere and that at sea level. The absorption spectra are quite
complex, but they do indicate that absorption is so strong in some spectral regions that no
solar energy in those regions reaches the surface of the Earth. For example, absorption by
O2 and 03 is responsible for removal of practically all the incident radiation with wave-
lengths shorter than 290 nm. However, atmospheric absorption is not strong from 300 to
about 800 nm, forming a "window" in the spectrum. About 40% of the solar energy is con-
centrated in the region of 400 to 700 nm. Water vapor absorbs in a complicated way, and
mostly in the region where the Sun's and Earth's radiation overlap. From 300 to 800 nm,
the atmosphere is essentially transparent. From 800 to 2000 nm, terrestrial long-wave radi-
ation is moderately absorbed by water vapor in the atmosphere. Table 1.2 summarizes the
attenuation of solar radiation by the atmosphere.
Figure 1.10 shows the penetration of radiation as a function of height in the atmosphere.
Wavelengths shorter than about 100 nm are absorbed by O2 and N2 and do not penetrate be-
low 100 krn. O2 absorbs strongly in the range 100 to 175 nm, the so-called
Schumann-Runge continuum, and also in the range 175 to 200 nm, the Schumann-Runge
bands. Wavelengths in the 200 to 245 nm range are absorbed in the stratosphere, mainly by
O2 (the weak Herzberg continuum). Wavelengths between 200 and 230 nm do penetrate as
low as 30 krn altitude. Ultraviolet absorption by ozone, which peaks near 254 nm (the
Hartley band of 03 absorption), attenuates solar radiation over the entire range of 230 to
300 nm. As a result, solar radiation of wavelengths shorter than about 290 to 300 nm does
not reach the Earth's surface.
Why molecules absorb in particular regions of the spectrum can be determined only
through quantum chemical calculations. In general, the geometry of the molecule explains,
for example, why H2O, CO2, and 03 interact strongly with radiation above 400 nm but N2
and O2 do not. In H2O, for instance, the center of the negative charge is shifted toward the
oxygen nucleus and the center of positive charge toward the hydrogen nuclei, leading to a
separation between the centers of positive and negative charge, a so-called electric dipole
moment. Molecules with dipole moments interact strongly with electromagnetic radiation
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200 ' I I I I I I

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Wavelength, nm
FIGURE 1.10 Depth of penetrationof solar radiation through the atmosphere.Altitudes corre-
spondto an attenuationof lIe (Kluwer AcademicPublishersAeronomyof the Middle Atmosphere,
1984,Brasseur,G. and Solomon,S. with kind permissionfrom Kluwer AcademicPublishers).

because the electric field of the wave causes oppositely directed forces and therefore ac-
celerations on electrons and nuclei at one end of the molecule as compared with the other.
Similar arguments hold for ozone; however, nitrogen and oxygen are symmetric and thus
are not strongly affected by radiation above 400 nm. The CO2 molecule is linear but can
easily be bent, leading to an induced dipole moment. A transverse vibrational mode exists
for CO2 at 15 JLm,just where the Earth emits most of its infrared radiation.
Considering the outgoing long-wave infrared radiation, the spectral region from about 7
to 13 JLmis also a window region; nearly 80% of the radiation emitted by the Earth in this
region escapesto space. Most of the non-CO2 greenhouse gases, including 03, CH4, N2O,
and the chlorofluorocarbons, all have strong absorption bands in this window region. For
this reason, relatively small changes in the concentrations of these gasescan produce a sig-
nificant change in the net radiative flux. As the concentration of a greenhouse gas contin-
ues to increase, it can absorb more of the radiation in its energy bands. Once an absorption
wavelength becomes saturated, further increases in the concentration of the gas have less
and less effect on radiative flux. This is called the band saturation effect. For CO2, for ex-
ample, the 15 JLmband is already close to saturated. In addition, if a gas absorbs at wave-
lengths that are also absorbed by other gases, then the effect of increasing concentrations
on radiative flux is less than in the absence of band overlap. For example, there is signifi-
cant overlap between some of the absorption bands of CH4 and N2O; this overlap must be
carefully accounted for when calculating the effect of these gases on radiative fluxes.
Even with the band saturation effect, it is incorrect to conclude that because there is al-
ready so much CO2 in the atmosphere, more CO2 can have no additional effect on absorp-
tion of outgoing radiation. When gases are present in small concentrations, doubling the
concentration of the gas will approximately double its absorption. When an absorbing gas
is present in high concentration the effect of further addition is not one-to-one but it is not
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 ENERGY BALANCE FOR EARTH AND ATMOSPHERE 33

in this portion of the spectrum. Away from this band, however, where CO2 is less strongly
absorbing, the increase in CO2 does have an effect. As more and more CO2 is added to the
atmosphere, more of its spectrum will become saturated, but there will always be regions
of the spectrum that remain unsaturated and thus capable of continuing to absorb infrared
radiation. For example, the 10 .urn absorption band is about 106times weaker than the peak
of the 15 .urn band, but its contribution to the irradiance change in the lower frame is im-
portant. And as CO2 concentrations increase, the importance of the 10 .urn band will con-
tinue to increase relative to the 15 .urn band.

1.10 ENERGY BALANCE FOR EARTH AND ATMOSPHERE

The Earth's climate is controlled by the amount of solar radiation intercepted by the planet
and the fraction of that energy that is absorbed. The flux density of solar energy, integrated
over all wavelengths, on a surface oriented perpendicular to the solar beam at the Earth's
orbit is about 1370 W m-2. This is called the solar constant.3 Let the solar constant be de-
noted by So = 1370 W m-2. The cross-sectional area of the Earth that intercepts the solar
beam is 1TR2,where R is the Earth's radius. The surface area of the Earth that receives the
radiation is 41TR2.Thus the fraction of the solar constant received per unit area of the Earth
is (1TR2/41TR1 = 1/4 of the solar constant, about 343 W m-2. Of this incoming solar radi-
ation, a fraction is reflected back to space; that fraction, which we can denote by Rp, is the
global mean planetary reflectance or albedo. Rp is about 0.3 (Ramanathan, 1987;
Ramanathanet al., 1989). Contributing to Rp are clouds, scattering by air molecules, scat-
tering by atmospheric aerosol particles, and reflection from the surface itself, the surface
albedo (the surface albedo is denoted as Rs). The fraction 1 - Rp represents that fraction
of solar short-wave radiation that is absorbed by the Earth-atmosphere system. For
Rp = 0.3, this corresponds to about 240 W m-2. This amount is matched, on an annual and
global average basis, by the long-wave infrared radiation emitted from the Earth-atmos-
phere system to space(Figure 1.12). The infrared radiative flux emitted at the surface of the
Earth, about 390 W m-2, substantially exceeds the outgoing infrared flux of 240 W m-2 at
the top of the atmosphere. Clouds, water vapor, and the greenhouse gases(GAGs) both ab-
sorb and emit infrared radiation. Since these atmospheric constituents are at temperatures
lower than that at the Earth's surface, they emit infrared radiation at a lower intensity than
if they were at the temperature of the Earth's surface and therefore are net absorbers of
energy.
The equilibrium temperature of the Earth can be estimated by a simple model that
equatesincoming and outgoing energy (Figure 1.13). Incoming solar energy at the surface
of the Earth is

So
Fs = -(1 - Rp) (1.17)
4

3Since the late 1970s, regular satellite measurements of the solar constant have been perfonned (Mecherikunnel
et aI., 1988). Maximum differences in the value of Soamong the instruments is about 2 W m-2, corresponding to
a little more than 0.1 % of the value of So. Over the period 1980 to 1986 the so-called SMM/ ACRIM instrument
measured an average value of So of about 1386 W m-2, whereas that on NIMBUS- 7 reported an average So of
about 1370 W m-2.
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 ENERGY BALANCE FOR EARTH AND ATMOSPHERE 35

Reflected

Emitted

For Rp = 0.30, this equation gives Te = 255 K. If the Earth were totally devoid of clouds,
then the global albedo would be about Rp = 0.15. With this value of Rp, the equilibrium
temperature Te = 268 K. This simple equation predicts that Te varies about 0.5 K for a
10 W m-2 (0.7%) variation in the solar constant, or for a reflectance variation around Rp =
0.3 of ~Rp = 0.005.
The net radiative energy input, F net = Fs - F L, is zero at equilibrium. If a perturbation
occurs then the change in net energy input is related to the changes in both solar and long-
wave components by

= ~Fs - ~FL (1.20)

To reestablish equilibrium, a temperature change ~T eresults, which can be related to ~F net

by a parameter }.O,

whereAo,having units K (W m-1-1 is called the climate sensitivityfactor. If we neglect

any feedbacksin the climate system,Aocanbe estimatedas (8Fe/8Te)-I,

Te
~=, 4FL
(1.22)
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 ENERGY BALANCE FOR EARTH AND ATMOSPHERE 37

Global climate changeis inducedby a forcing that disturbsthe equilibrium andleadsto

a nonzeroaveragedownwardnet flux at the top of the atmosphere(TOA),

So
-Foe! = -(1 - Rp) - FL (1.23)
4

It is customary to write (1.23) in terms of downward flux, -Fnet, at the TOA; an increase
of - F net corresponds to heating of the planet. Primary forcing can occur as a result of
changes of So,Rp, or FL, Changes in incoming solar radiation have resulted from changes
in the Earth's orbit and fromyariations in the Sun's output of energy. Changes in the plan-
etary albedo Rp can result from changes in surface reflectance from human activity (agri-
culture, deforestation), from changes in the aerosol content of the atmosphere from both
natural (volcanoes) and anthropogenic (industrial emissions, biomass burning) causes,and
to a lesser extent from changes in levels of gases that absorb solar wavelengths (e.g.,
ozone). Changes in the emitted long-wave flux F L result primarily from changes (increases)
of absorbing gasesin the atmosphere and to a lesser extent from changes in aerosols. As we
have seen, in the long-wave portion of the spectrum gasesand aerosols absorb much of the
radiation emitted by the surface and reemit radiation to space at their lower temperature.

1.10.1 Solar Variability

The amount of solar radiation reaching Earth and Earth's changing orientation to the Sun
have been the major causes for climatic change throughout its history. If the Sun's radia-
tion intensity declined 5 to 10% and there were no other compensating factors, ice would
engulf the planet in less than a century. Although no theory exists to predict future changes
in solar output, the effect of changes in Earth's orbit as it travels around the Sun is begin-
ning to be understood. During the past million years, Earth has experienced 10 major and
40 minor episodes of glaciation. All appear to have been controlled by three so-called or-
bital elements that vary cyclically over time.
First, Earth's tilt changes from 22° to 24.5° and back again every 41,000 years. Second,
the month when Earth is closest to the Sun also varies over cycles of 19,000 and 24,000
years. Currently, Earth is closest to the Sun in January. This month-of-closest-approach
factor can make a difference of 10% in the amount of solar radiation reaching a particular
location in a given season. Last, the shape of Earth's orbit varies from being nearly circu-
lar to being more elliptical with a period of 100,000 years. The climatic cycles caused by
these orbital factors are called Milankovitch cycles after the Serbian mathematician
Milutin Milankovitch, who first described them in 1920. Superimposed on the
Milankovitch cycles are changes in the Sun that occur over days or months or a few years.
Over the period 1979 to 1990, for example, total solar irradiance varied by about 0.1 %
(Hickey et al., 1988; Willson and Hudson, 1988).
Even though studies of ocean cores have shown that these orbital changes are the prin-
cipal determinant of the times of glaciation, the exact mechanisms by which Earth re-
sponds to the orbital changes have not been established. Orbital changes alone appear not
to have caused the vast climate shifts associated with glaciation and deglaciation.
Feedbacks, such as changes in Earth's reflectivity, amount of particles in the atmosphere,
and the carbon dioxide and methane content of the atmosphere, act together with orbital
changes to enhance global warming and cooling. The levels of carbon dioxide and
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 ENERGY BALANCE FOR EARTH AND ATMOSPHERE ~O

from the Earth, andnonradiativeprocesses.Of the 100units of incoming solar flux:

-26 units are absorbedwithin the atmosphere(-22 by cloud-free air and -4 by

clouds)
4 (- 7 from the cloud-free atmosphere, -17
- 30unitsarereflectedbackto space from
the cloudy atmosphere,and -6 from the Earth's surface)
-44 units absorbedby the Earth's surface

The Earth-atmosphere system emits thermal infrared radiation. The upward flux from the
Earth's surface is -115 units. The cloud-free atmosphere emits -33 units back to the
Earth's surface and -34 units out to space. The cloudy atmosphere emits -67 units back
to Earth and -36 units out to space. Thus -70 units of infrared radiation leave the top of
the atmosphere, balancing the net -70 units of solar radiation penetrating the top of the at-
mosphere.The net upward flux of infrared radiation at the surface of the Earth is -15 units,
consisting of -115 units emitted by the Earth and -100 units radiated back to Earth by the
cloud-free and cloudy atmosphere.
The incoming solar energy absorbed by the Earth is -44 units; this is balanced by the
net upward flux of infrared radiation of -15 units, plus -6 unit loss by sensible heat con-
duction, and - 23 unit loss by latent heat. The Earth emits -115 units of infrared radiation
to the atmosphere, whereas the atmosphere emits -170 units of infrared radiation, a net
deficit of -55 units. Since the atmosphere absorbs -26 units of solar radiation, the net ra-
diative loss from the atmosphere is -29 units; this is made up for by the sensible and latent
heat fluxes. The net radiative cooling of the atmosphere is thus balanced by the latent heat
of condensation released in precipitation processes and by the convection and conduction
of sensible heat from the surface.
The average annual ratio of sensible to latent heat loss at the surface is called the Bowen
ratio. With -6 units of sensible heat loss and -23 units of latent heat loss, the Bowen ra-
tio is -0.27.
Figure 1.16 shows the zonally annual averaged absorbed solar and emitted infrared
fluxes, as observed from satellites. We note a net gain of radiative energy between about
40° Nand 40° S, and a net loss of energy in the polar regions. This pattern results largely
from the decrease in insolation to the polar regions in winter and from the high surface
albedo in the polar regions. The outgoing infrared flux displays only a small latitudinal de-
pendence. The tendency for the outgoing infrared flux to be greatest in the tropics where
the surface temperature is largest is muted by the larger amount of atmospheric water va-
por and the higher and colder clouds in the tropics. As a result of the net gain of radiative
energy in the tropics and the net loss in the polar regions, an equator-to-pole temperature
gradient is generated.

'The average value of the albedo, the incoming radiation that is reflected or scattered back to space without ab-
sorption, is usually taken to be somewhere in the range of 30 to 34%. It is important to note that the albedo varies
considerably, depending on the surface of the Earth. For example, in the polar regions, which are covered by ice
and snow, the reflectivity of the surface is very high. On the other hand, in the equatorial regions, which are
largely covered with oceans, the reflectivity is low, and most of the incoming energy is absorbed by the surface.
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 SPATIAL AND TEMPORAL SCALES OF ATMOSPHERIC PROCESSES 41

Urban or Regional or Synoptic to

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FIGURE 1.17 Spatialandtemporalscalesof variability for atmosphericconstituents.

dimensions. Four rough categories have proved convenient to classify atmospheric scales
of motion:

1. Microscale. Phenomena occurringon scalesof the orderof 0 to 100m, suchasthe

meanderinganddispersionof a chimneyplumeandthe complicatedflow regimein
the wakeof a largebuilding.
2. Mesoscale. Phenomenaoccurring on scalesof tens to hundredsof kilometers,
such as land-seabreezes,mountain-valley winds, and migratory high- and low-
pressurefronts.
3. SynopticScale. Motions of whole weathersystems,on scalesof hundredsto thou-
sandsof kilometers.
4. Global Scale. Phenomenaoccurringon scalesexceeding5 X 103kin.

Spatial scales characteristic of various atmospheric chemical phenomena are given in

Table 1.3. Many of the phenomena in Table 1.3 overlap; for example, there is more or less
of a continuum between (1) urban and regional air pollution, (2) the aerosol haze associ-
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creases and stratospheric ozone depletion, and (4) tropospheric oxidative capacity and
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 DERIVATION OF THE GEOSTROPHIC WIND SPEED 43

atmosphere's scales of motion. Much of this book will be devoted to understanding the ex-
quisite interactions between chemical and transport processes in the atmosphere. In antici-
pation of much of the remainder of this book, Table 1.4 summarizes atmospheric effects of
trace gases.

APPENDIXl DERIVATION OF THE GEOSTROPffiC WIND SPEED

The direction of winds in the geostrophic layer is determined by horizontal pressure gradi-
ents and Coriolis forces. As we have discussed, an air parcel moving southward in the
Northern Hemisphere as a result of pressure gradients is accelerated toward the west by the
Coriolis force. We can actually compute the wind speed and direction at any latitude as a
function of the prevailing pressure gradient if we assume that only pressure and Coriolis
forces influence the flow.
It can be shown that the acceleration experienced by an object on the surface of the
Earth (or in the atmosphere) moving with a velocity vector u consists of two components,
-0 x (0 x r) and - 2(0 x D), where 0 is the angular rotation vector for the Earth and
r is the radius vector from the center of the Earth to the point in question. The first term is
simply the centrifugal force, in a direction that acts normal to the Earth's surface and is
counterbalanced by gravity. The second term, 0 x u, is the Coriolis force. This force
arisesonly when an object, suchas an air parcel,is moving; that is U :;t: O. Even though
the Coriolis force is of much smaller magnitude than the centrifugal force, only the Coriolis
force has a horizontal component. Since the winds are horizontal in the geostrophic layer,
the Coriolis acceleration is given by the horizontal component of the Coriolis term, namely,
2uGQ sin cf>,where Q is the rate of rotation of the Earth and cf> is the latitude.The direc-
tion of the Coriolis force is perpendicular to the wind velocity, as shown in Figure I.A.I.
Wind speed UG at latitude cf> lies in the horizontal plane.
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Ile ae ae
iCe xe Ie
11+ n+
ne ne ne
pUB
xe
(I'VOI)
ne
:}Ie P!ng e q:>ns l01 UO!!OW pUl1 A!!nU!!uo:> 10 suo!!enb:} :}q.L o'\\og Ieu!weI U! pUl1
(ss:}IUO!!:>P1) P!:>S!AU! S! :}l:}qdsow!e :}q! !eq! p:}wnsse :}q Aew !! l:}AeI :>!qdoI!so:}~ :}q! uI
';l)I';IUA!:nw 1\1 ';IU 1
~
 DERIVATION OF THE GEOSTROPHIC WIND SPEED 45

Low p

~ Parcel initially
at rest here
FIGURE 1.A.2 Approachto geostrophicequilibrium.

Weusuallydenote20 sin r/> by f, calledthe Coriolis parameter.From the continuity equa-

tion (I.A.I), we seethat au/ax = 0, since v = w = O.Thusfrom (I.A.5) op/ox = 0, and
the direction of flow is perpendicular to the pressure gradient op/oy. In addition, from
(I.A.6), we seethat the componentof the Coriolis force, -ju, is exactly balancedby the
pressuregradient, (1/ p) op/oy. Therefore the geostrophic wind speed UGis given by

Ua= apjay
(I.A.7)
2pQ sin 4>

The approach to the geostrophic equilibrium for an air parcel starting from rest, accelerated
by the pressure gradient and then affected by the Coriolis force, is shown in Figure I.A.2.
The geostrophic balance determines the wind direction at altitudes above about 500 m.
In order to describe the air motions at lower levels we must take into account the friction
of the Earth's surface. The presence of the surface induces a shear in the wind profile, as in
a turbulent boundary layer over a flat plate generated in a laboratory wind tunnel. In ana-
lyzing the geostrophic wind speed we found that for steady flow a balance exists between
the pressure force and the Coriolis force. Consequently, steady flow of air at levels near the
ground leads to a balance of three forces: pressure force, Coriolis force, and friction force
due to the Earth's surface. Thus, as shown in Figure 1.A.3, the net result of these three
forcesmust be zero for a nonacceleratingair parcel. Sincethe pressuregradientforce Fp
must be directed from high to low pressure, and the frictional force Ff must be directed op-
posite to the velocity u, a balance can be achieved only if the wind is directed at some an-
gle toward the region of low pressure. This angle between the wind direction and the
isobars increases as the ground is approached since the frictional force increases. At the
ground, over open terrain, the angle of the wind to the isobars is usually between 10° and
20°. Because of the relatively smooth boundary existing over this type of terrain, the wind
speedat a 10 m height (the height at which the so-called surface wind is usually measured)
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 PROBLEMS 47

REFERENCES

Bentley,C. R. (1997)Rapidsea-levelrise soonfrom WestAntarctic Ice Sheetcollapse?Science,275,

1077-1078.
Boering,K. A. et al. (1995) Measurements of stratosphericcarbondioxide andwater vapor at north-
ern midlatitudes:implications for troposphere-to-stratospheretransport,Geophys.Res.Lett., 22,
2737-2740.
Brasseur,G., and Solomon,S. (1984)Aeronomyof the Middle Atmosphere.Reidel, Dordrecht,The
Netherlands.
Cloud,P.(1983).The biosphere.Sci.Am., 249, 176-189.
Graedel,T. E., and Crutzen,P.J. (1989)The changingatmosphere,Sci.Am., 261,58-68.
Hickey,J. R., Alton, B. M., Kyle, H. L., andHoyt, D. (1988)Total solarirradiancemeasurements by
ERB/Nimbus-7:a review of nine years,SpaceSci. Rev.,48,321-342.
Holton, J. R., Haynes,P. H., McIntyre, M. E., Douglass,A. R., Rood, R. B., and Pfister,L. (1995)
Stratosphere-troposphere exchange,Rev.Geophys.,33,403-439.
IntergovernmentalPanel on Climate Change (IPCC) (1995) Climate Change 1994: Radiative
Forcing of ClimateChangeand an Evaluationof the 1PCCIS92 EmissionScenarios.Cambridge
University Press,Cambridge,UK.
Iqb~l, M. (1983)An Introduction to Solar Radiation.AcademicPress,Toronto.
Liou, K. N. (1992) Radiation and Cloud Processesin the Atmosphere.Oxford University Press,
Oxford, UK.
Mecherikunnel,A. T., Lee, R. B., Kyle, H. L., andMajor, E. R. (1988)Intercomparisonof solartotal
irradiancedatafrom recentspacecraftmeasurements, J. Geophys.Res.,93,9503-9509.
Prather,M., McElroy, M., Wofsy, S., Russell,G., and Rind, D. (1987) Chemistryof the global tro-
posphere:fluorocarbonsastracersof air motion, J. Geophys.Res.,92,6579-6613.
Ramanathan, V. (1987)The role of earthradiationbudgetstudiesin climate and generalcirculation
research,J. Geophys.Res.,92,4075-4095.
Ramanathan, V., Cess,R. D., Harrison,E. F., Minnis, P.,Barkstrom,B. R.,Ahmad,E., andHartmann,
D. (1989)Cloud-radiativeforcing andclimate:resultsfrom the earthradiationbudgetexperiment,
Science,243,57-63.
Salstein,D. A. (1995) Mean propertiesof the atmosphere,in Composition,Chemistry,and Climate
of theAtmosphere,editedby H. B. Singh.VanNostrandReinhold,New York, pp. 19-49.
Trenberth,K. E., andGuillemot, C. J. (1994)The total massof the atmosphere,J. Geophys.Res.,99,
23079-23088.
Walker,J. C. G. (1977)Evolution of theAtmosphere.Macmillan, New York.
Willson, R. C., and Hudson,H. S. (1988) Solar luminosity variationsin solarcycle 21, Nature,332,
810-812.

PROBLEMS

l.lA Calculatethe concentration(in moleculescm-3) andthe mixing ratio (in ppm) of wa-
ter vapor at groundlevel at T = 298 K at RH valuesof 50%, 60%, 70%, 80%, 90%,
95%, and 99%.
The vapor pressureof pure wateras a function of temperaturecanbe calculated
with the following correlation:

PH10(T)= Ps exp[13.3185a- .976a2- O.6445a3- O.1299a4]

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 2

Virtually every element in the periodic table is found in the atmosphere; however, when
classifying atmospheric species according to chemical composition it proves to be conve-
nient to use a small number of major groupings such as:

1. Sulfur-containing compounds.
2. Nitrogen-containing compounds.
3. Carbon-containing compounds.
4. Halogen-containing compounds.

Obviously these categories are not exclusive; many sulfur-containing compounds, for
example, also include atoms of carbon. And virtually all the atmospheric halogens involve
a carbon atom backbone. We do not include in the above list species of the general formula
HxOy; with the exception of water and hydrogen peroxide (H2O2), these are all radical
species (e.g., hydroxyl, OH) that play key roles in atmospheric chemistry but do not nec-
essarily require a separate category. Every substance emitted into the atmosphere is even-
tually removed so that a cycle of the elements in that substanceis established. This is called
the biogeochemical cycle of the element. The biogeochemical cycle of an element or a
compound refers to the transport of that substance among atmospheric, oceanic, bio-
spheric, and land compartments, the amounts contained in the different reservoirs, and the
rate of exchange among them. The circulation of water among oceans, atmosphere, and
continents is a prime example of a biogeochemical cycle. The term biogeochemical cycle
is often used to describe the global or regional cycles of the "life elements," C, 0, N, S, and
P, with reservoirs including the atmosphere, the ocean, the sediments, and living organisms
(Rodhe, 1992).
A condition of "air pollution" may be defined as a situation in which substancesthat re-
sult from anthropogenic activities are present at concentrations sufficiently high above
their normal ambient levels to produce a measurable effect on humans, animals, vegeta-
tion, or materials. This definition could include any substance, whether noxious or benign;
however, the implication is that the effects are undesirable. Traditionally, air pollution has
been viewed as a phenomenon characteristic only of large urban centers and industrialized
regions. It is now clear that dense urban centers are just "hotspots" in a continuum of trace
speciesconcentrations over the entire Earth. Both urban smogs and stratospheric ozone de-
pletion by chlorofluorocarbons are manifestations of what might be termed in the broadest
senseas air pollution.
The first recognized type of air pollution was that typified by high concentrations of sul-
fur compounds (S02 and sulfates) and particles, resulting from combustion of coal and
high-sulfur-containing fuels. Cities with this characteristic type of air pollution are often in
cold climates where electric power generation and domestic heating are major sources of
emissions. 49
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 ATMOSPHERIC RESIDENCE TIMES 51

from direct emissionsof particlesbut also from emissionsof certaingasesthat either con-
denseas particlesdirectly or undergochemicaltransformationto a speciesthat condenses
as a particle.A full descriptionof atmosphericparticlesrequiresspecificationof not only
their concentrationbut also their size,chemicalcomposition,phase(i.e., liquid or solid),
andmotphology.
Onceparticlesare in the atmo~phere, their size,number,and chemicalcompositionare
changedby severalmechanismsuntil ultimately they are removedby natural processes.
Someof the physicaland chemicalprocessesthat affect the "aging" of atmosphericparti-
cles are more effective in one regimeof particle size than another.In spite of the specific
processesthat affect particulateaging,the usualresidencetime of particlesin the lower at-
mospheredoesnot exceedseveralweeks.Very closeto the ground,the main mechanisms
for particle removalaresettling anddry depositionon surfaces;whereasat altitudesabove
about 100m, precipitationscavengingis the predominantremovalmechanism.
As air risesthrougha cloud andbecomesslightly supersaturated with water vapor (i.e.,
asits relative humidity exceeds100%),cloud dropletsform on condensationnuclei-usu-
ally solubleaerosolparticles(e.g., microscopicparticlesof various salts)that exist in the
atmosphereat concentrationsof 100 to .1000cm-3-and grow by condensationof water
vapor.As the droplets grow and collide with each other they becomeraindrops,which
grow rapidly asthey fall and accretecloud droplets.

2.1.1 Residence Time

The fundamental physical principle governing the behavior of a chemical in the atmos-
phere is conservation of mass. In any imaginary cube of air the following balance must
hold:

Rateof the Rateof the Rateof intro- Rateof Rateof accumu-

species species duction (emis- removal of = lation of the
+ - the species
flowing in flowing out sion) of the speciesin the
species imaginaryvolume

This balance must hold from the smallest cube of air all the way up to the entire
atmosphere.
If we let Q denotethe total massof the substancein the volume of air, Fin and Foulthe
massflow ratesof the substancein and out of the air volume,respectively,P the rateof in-
troductionof the speciesfrom sources,andR the rate of removalof the species,thencon-
servationof masscanbe expressedmathematicallyas

dQ (Fin - Fout)+ (P - R) (2.1)

dt

If the amountQ of the substancein the volume or reservoiris not changingwith time,
then Q is a constant and dQ/dt = O. In order for Q to be unchanging, all the sources of the
substanceto the reservoirmust be preciselybalancedby the sinks of the substance.This
meansthat
Fin + P = Foul+ R (2.2)
In such a case steadv-state conditions are said to hold
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 ATMOSPHERIC RESIDENCE llMES 53

The stratosphere can be considered well mixed vertically only for atmospheric species
with residence times greatly exceeding 50 years. In fact, one of the only examples of such
a long-lived species is He, which has its source at the Earth's surface and its sink as escape
through the very top of the atmosphere into space. Thus the stratosphere is poorly mixed
vertically for essentially all atmospheric trace constituents.
Frequently the rate at which a chemical is removed from the atmosphere is proportional
to its concentration (first-order loss)-the more that is present, the faster its rate of re-
moval. This is generally the case for both dry deposition at the Earth's surface and scav-
enging by cloud droplets. Consider a species for which steady-state conditions hold and
which is removed at a rate proportional to its concentration with a proportionality constant
A. Such a species is 85Kr,the only significant removal process for which is radioactive de-
cay. For 85Kr,then

Q 1
-)..Q -)..

Thus to estimate the residence time of 85Kr does not even require knowledge of its atmos-
pheric abundance Q, but only of the radioactive decay constant. Consequently, it does not
matter whether 85Kris uniformly mixed throughout the entire atmosphere or not to estimate
its lifetime. In a case where the removal process is first order, then even for a poorly mixed
species a simple and accurate estimate for its residence time can be obtained provided that
its removal rate constant can be accurately estimated.
Now consider a species with mass Q in the atmosphere that is removed by two inde-
pendent processes,the first at a rate kl Q and the second at a rate k2 Q, where kl and k2 are
the first-order removal coefficients. Its overall residence time is given by

or

~ = kl + k2
1:

Process1. for example.could be dry depositionand process2 cloud scavenging.We can

actually associatetime constantswith the two individual removalprocesses,

.. = - T2= -
kl k2
where ., canbe thoughtof asthe residencetime of the speciesif the only removalprocess
is process1, which is alsotrue for .2. From (2.8) and (2.9) we canexpressthe overall res-
idencetime. in termsof the two individual removaltimes ., and .2 by

..:.=..:.+..:. (2.10)
. .1 .2
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 SULFUR-CONTAINING COMPOUNDS 55

The loss processesare usually representedas first order; for example, Rt = kt Qi'
wherethe first-orderrate constants,which we will denoteby k's, must be specified.Thus
(2.13)becomes

dQi
dt
= p.n
, + p.Q
I + p.C
, - (k~
I + k!lJ
, + k'! , )Q,'
, + k~ (2.14)

If the concentration of the species is not changing, then a steady state may be presumed
in which

p.n+ p.a+ p.C-

, , ,
( kd
,
+ k!1'
,
+ k':
,
+ k~
I
) Q, ' = 0

The meanresidencetime of speciesj can be calculatedby either

-
.,.,=
kd, + k!V
, + k,:I + k~I

or

Qi
t";= (2.17)
p!'I + p.a
I + p.C
I

To use (2.16) the individual first-order rate constants for removal must be estimated,
whereas in (2.17), estimates for the total number of moles in the troposphere, which can be
derived from a concentration measurement, and for the source strength terms are needed.
If the k; values are difficult to specify, mean residence times are often estimated from
(2.17).

2.2 SULFUR.CONTAINING COMPOUNDS

Sulfur is present in the Earth's crust at a mixing ratio of less than 500 parts per million by
mass and in the Earth's atmosphere at a total volume mixing ratio of less than I ppm. Yet,
sulfur-containing compounds exert a profound influence on the chemistry of the atmo-
sphere and, likely, on climate. The main questions that we will seek to answer with respect
to sulfur compounds, and indeed for all classes of atmospheric compounds, are:

1. What are the species present in the atmosphere? What are their natural and anthro-
pogenic sources?
2. What chemical reactions do they undergo in the atmosphere? How fast are these re-
actions?
3. What are the products of atmospheric transformations?
4. What effect does the presence of the compound and its chemical transformation
products have on the atmosphere?

In this chapter we focus on the first question.

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 SULFUR-CONTAINING COMPOUNDS 61

TABLE 2.3 Observed Mixing Ratios of Atmospheric Sulfur Gases

CompoundandLocation Average Mixing Ratio (ppt)

H2S
Marine surfacelayer 3.6-7.5
Coastalregions 65
Forests 35-60
Wetlands 450-840
Urban areas 365
Freetroposphere(2-5 kin) 6-8.5
CH3SCH3
Marine surfacelayer 80-110
Continentalsurfacelayer 8-60
Freetroposphere(2-5 kin) 1.5-15
CS2
Marine surfacelayer 2-18
Continentalsurfacelayer 35-120
Freetroposphere(2-5 kin) 5-7
OCS
Total troposphere 500
Marine surfacelayer 500
Continentalsurfacelayer 545
SO2
Marine surfacelayer 20
Freetroposphere(>5 km)- 50
Europe/NorthSea/Arctic
North America cleancontinental 160
CoastalEurope 260
Pollutedcontinentalair 1500
Source: Berresheim et al. (1995) (detailed references given by the authors).

2.2.1 Dimethyl Sulfide (CH~CH3)

Dimethyl sulfide (DMS) is the dominant sulfur compound emitted from the world's
oceans. DMS was discovered in the surface ocean by Lovelock et al. (1972), who sug-
gested that DMS may be the biogenic sulfur species that was needed at the time to balance
the global sulfur budget.
DMS is produced in oceanic waters by both benthic and planktonic marine organisms
(Dacey and Wakeham, 1986), suggesting that it may be ubiquitous in the surface ocean
(Barnard et al., 1982). It is thought to originate from the decomposition of dimethyl-sulfo-
niopropionate produced by marine organisms, in particular, phytoplankton (Andreae,
1990). Its concentration in the upper layer of the ocean varies between a few nanograms of
S per liter to a few micrograms of S per liter (Lovelock et al., 1972; Barnard et al., 1982;
Andreae and Raemdonck, 1983; Cline and Bates, 1983; Nguyen et al., 1984, 1988). The
DMS surface seawater concentration is highly nonuniform; its average concentration is ap-
proximately 100 nanograms (ng) of S per liter. It has been observed that the concentration
of DMS is dependent on diurnal (Andreae and Barnard, 1984) and seasonal variations
(Turner and Liss, 1985), and on depth and location (Andreae and Raemdonck, 1983).
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 SULFUR-CONTAINING COMPOUNDS 63

- Continental Marine
Atmosphere Atmosphere
1.6 3.2

: Human "

" Artivity ..<

Soils and Lakes and

Land. Rivers
3x ! 300
Ocean Marine
9 Biota
1.3xlO ?,.

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FIGURE 2.2 Major reservoirsandburdensof sulfur, in Tg(S) (Charlsonet al., 1992).Reprintedby

permissionof AcademicPress.

and 0.57 Tg in the stratosphere.Basedon the estimatedglobal OCS sourcestrengthof

0.73Tg yr-I, the global atmosphericlifetime of OCS is estimatedto be about7 years.We
will return to the global cycle and chemistryof OCS in Chapter4 in connectionwith the
stratosphericaerosollayer.

2.2.3 Sulfur Dioxide (S02)

Sulfur dioxide is the predominant anthropogenic sulfur-containing air pollutant. Mixing ra-
tios of S02 in continental background air range from 20 ppt to over I ppb; in the unpolluted
marine boundary layer levels range between 20 and 50 ppt. Urban S02 mixing ratios can
attain values of several hundred parts per billion. We will consider the atmospheric chem-
istry of S02 in Chapter 5.

2.2.4 The Atmospheric Sulfur Cycle

Figure2.2 depicts the major reservoirsin the biogeochemicalcycle of sulfur. with esti-
matedquantities(in Tg(S» in eachreservoir.Directions of fluxes betweenthe reservoirs
areindicatedby arrows.The major pathwaysof sulfur compoundsin the atmosphereare
depictedin Figure 2.3. The numberson eacharrow refer to the descriptionof the process
givenin the captionto the figure (not to fluxes).All the processesindicatedschematically
in Figure2.3 will be studiedlater in this book.
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The meanresidencetime of SO"is

7:S02 = P;02QS02
+ PS02
a

k~o, + k~O2+ kso,

whereas that for sulfate is

1'SO.
= QSO4
kSO,QSO2

kSO4d+ kSO4

The meanresidencetime of a sulfur atom is

t's =
QSO2 + QSO4
P;O2+ P:~

which canbe expressedin termsof the two previousmeanresidencetimes as

1:S = 1:S02 + b1:s04 (2.23)

where

ksozQs~
b= (2.24)
PSOz
+ Ps~

the fraction of S convertedto SO~- beforebeingremoved.

We can alsodefineindividual characteristictimes suchas
'so,
d = (kso,
d'
.502= (ks02) d
t'SO4 = (kSO4,
d'

sothat

- ~ w
1"S04 1"S04 TSO,

We can also define the mean residence time of a sulfur atom before surface removal or pre.
cipitation scavengingby

d,w -- Qs~ + QS04

TS
kd,w Q + kd.w
SO, S02 SO.QS04
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 NITROGEN-CONTAINING COMPOUNDS 67

2.3 NITROGEN-CONTAINING COMPOUNDS

Aside from N2, which is extremely stable chemically and is not involved in the chemistry
of the troposphere or stratosphere, the important nitrogen-containing trace species in the
atmosphere are nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NOJ, nitric acid
(HNO3), and ammonia (NH3). The first of these, nitrous oxide (N2O), is a colorless gas that
is emitted almost totally by natural sources, principally by bacterial action in the soil. The
gas is employed as an anesthetic and is commonly referred to as "laughing gas." The sec-
ond, nitric oxide (NO), is emitted by both natural and anthropogenic sources. Nitrogen
dioxide (NOJ is emitted in small quantities from combustion processesalong with NO and
is also formed in the atmosphere by oxidation of NO. The sum of NO and NO2 is usually
designated as NOx' Nitric oxide is the major oxide of nitrogen formed during high-temper-
ature combustion, resulting from both the interaction of nitrogen in the fuel with oxygen
present in the air and the chemical conversion of atmospheric nitrogen and oxygen at the
high temperatures of combustion. Other oxides of nitrogen, such as NO3 and N20S, exist
in the atmosphere in relatively low concentrations but nonetheless participate importantly
in atmospheric chemistry. Nitric acid is an oxidation product of NO2 in the atmosphere.
Ammonia (NH3) is emitted primarily by natural sources. Finally, nitrate and ammonium
salts are not emitted in any significant quantities but result from the atmospheric conver-
sion of NO, NO2, and NH3'
Nitrogen is an essential nutrient for all living organisms. The primary source of this ni-
trogen is the atmosphere. However, N2 is not useful to most organisms until it is "fixed" or
converted to a form that can be chemically utilized by the organisms. (Nitrogen fixation
refers to the chemical conversion ofN2 to any other nitrogen compound.) The "natural" fix-
ation of N2 occurs by two types of processes.One is the action of a comparatively few mi-
croorganisms that are capable of converting N2 to ammonia, ammonium ion (NHt), and
organic nitrogen compounds. The other natural nitrogen fixation process occurs in the at-
mosphere by the action of ionizing phenomena, such as cosmic radiation or lightning, on
N2. This process leads to the formation of nitrogen oxides in the atmosphere, which are ul-
timately deposited on the Earth's surface as biologically useful nitrates.
In addition to natural nitrogen fixation, human activities have led to biological and in-
dustrial fixation and fixation by combustion. Humans have increased the cultivation of
legumes, which have a symbiotic relationship with certain microorganisms capable of ni-
trogen fixation. Legumes provide an increase in the soil nitrogen and serve as a valuable
food crop. Industrial nitrogen fixation consists primarily of the production of ammonia for
fertilizer use. Combustion can also lead to the fixation of nitrogen as NOx' In the process of
nitrification, ammonium is oxidized to N°"i and NO3 by microbial action. N2O and NO
are by-products of nitrification; the result is the release of N2O and NO to the atmosphere.
Reduction of NO3 to N2, NO2, N20, or NO is called denitrification. Denitrification is ac-
complished by a number of bacteria and is the process that continually replenishes the at-
mosphere's N2. Figure 2.4 depicts the atmospheric nitrogen cycle.

2.3.1 Nitrous Oxide (N2O)

Nitrous oxide (N2O) is an important atmospheric gas that is emitted predominantly by bio-
logical sources in soils and water. Although by comparison to CO2 and H2O, N2O has a far
lower concentration, it is an extremely influential greenhousegas. This is a result of its long
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 NITROGEN-CONTAINING COMPOUNDS 69

TABLE 2.4 Estimated Sourcesand Sinks of N2OTypical of the Last Decade

Sources Range(Tg(N) yr-l) Likely (Tg(N) yi

NATURAL

Oceans 1-5 3
Tropical soils
Wet forests 2.2-3.7 3
Dry savannas 0.5-2.0 1
Temperate soils
Forests 0.1-2.0
Grasslands 0.5-2.0
Total natural sources 9

ANTHROPOGENIC

Cultivated soils 1.8-5.3 3.5

Biomassburning 0.2-1.0 0.5
Industrial sources 0.7-1.8 1.3
Cattle and feedlots 0.2-0.5 0.4

Implied total sources

(atmospheric increase + total sinks)a
"The observed atmospheric increase implies that sources exceed sinks by 3.9 Tg(N) yr-i.

Source: IPCC (1995).

the stratosphere.We will return to this processin Chapter4. Sourcesof N2Oexceedesti-

matedsinksby 2.4 Tg(N) yr-i.
Estimatesfor the atmosphericlifetime of N2Ocomefrom stratosphericchemicaltrans-
port modelsthat havebeentestedagainstobservedN2Odistributions.The bestcurrentes-
timate for the lifetime ofN2O is 120 :t 30 years.Becauseof its long lifetime N2Oexhibits
more or lessuniform concentrationsthroughoutthe troposphere.Ice core recordsof N2O
show a preindustrialmixing ratio of about276 ppb. N2O levels haverisen approximately
15% since preindustrialtimes, reaching 311 ppb in 1992 (IPCC, 1995; Machida et al.,
1995)(Figure 2.5). This observedatmosphericincreaseis consistentwith a differenceof
3.9 Tg(N) yr-1 excessof sourcesover sinks, which is in reasonableagreement,given the
uncertainties,with the mismatchbasedon attemptingto estimatesourcesand sinks inde-
oendentlv.
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Detailedemissionsinventoriesareavailablefor Canada,the United States,and western

Europethat describethe spatialpatternsof NOxemissionsfrom combustionof fossil fuels
andfrom industrialprocesses(Lubkert andZierock, 1989;Placetet al., 1990).Between40
and 45% of all NOxemissionsin the United Statesareestimatedto comefrom transporta-
tion, 30 to 35% from power plants,and about20% from industrial sources.About half the
NOx emissionsassociatedwith transportationcome from light-duty gasolinetrucks and
carsand approximatelyone-quarterare from heavy-dutygasolineanddieselvehicles.3

2.3.3 Reactive Odd Nitrogen (NO,)

Reactive nitrogen, denoted NO" is defined as the sum of the two oxides of nitrogen
(NOx = NO + NOJ and all compounds that are products of the atmospheric oxidation of
NOx' These include nitric acid (HNO3), nitrous acid (HONO), the nitrate radical (NO3),
dinitrogen pentoxide (N2Os), peroxynitric acid (HNO4), peroxyacetyl nitrate (PAN)
(RC(O)OONOJ and its homologues, alkyl nitrates (RONOJ, and peroxyalkyl nitrates
(ROONOJ. Nitric acid (HNO3) is the major oxidation product of NOx in the atmosphere.
Because of its extreme water solubility, HNO3 is rapidly deposited on surfaces and in wa-
ter droplets. Also, in the presence of NH3, HNO3 can form an ammonium nitrate (NH4NO3)
aerosol. The nitrate radical (NO3) is an important constituent in the chemistry of the tro-
posphere, especially at night. NO3 is present at night at mixing ratios ranging up to 300 ppt
in the boundary layer. Nitrous oxide (N2O) and ammonia (NH3) are not considered in this
context as reactive nitrogen compounds.
Measurement of total NO, in the atmosphere provides an important measure of the total
oxidized nitrogen content. Concentrations of individual NO, species relative to the total in-
dicate the extent of interconversion among species. NO, is indeed closer to a conserved
quantity than any of its constituent species (Roberts, 1995).
There is a sizable body of data on the concentrations of NOx in the atmosphere, but cau-
tion must be exercised in drawing conclusions from these measurements. Many measure-
ments of NO x have been made by devices that convert NO2 to NO, which is then measured
by the phenomenon of chemiluminescence. Comparison of these measurements with more
specific techniques suggests that surface converters that can convert NO2 to NO also con-
vert other reactive nitrogen oxide species, such as peroxyacetyl nitrate (PAN), to NO,
thereby causing interference. In urban locations, where the local NO sources are typically
large, NO and NO2 are probably the dominant constituents of the total reactive nitrogen
NO,. Thus, in urban areas, interference from PAN and other oxides of nitrogen is believed
to be relatively small. In rural and remote locations, however, the interference can be sub-
stantial. For this reason, all nonurban NOx measurements made with surface converters
must be considered upper limits (biased toward a high measurement).
Given the dominant role of anthropogenic emissions in the budget of atmospheric NOx
and the fact that the sources of these emissions tend to be located in or near urban areas,el-
evated concentrations of NOx are to be expected in these locations. Observations of NOx
support this expectation. The range and variability of NOx measurements are reflected in
measurements made in 29 cities across the eastern and southern United States during the

3It is estimated that in 1994 there were 147,000,000 light-duty motor vehicles in the United States, 48,000,000
trucks (85% light-duty), and 676,000 buses. Total vehicle miles traveled were estimated as 235 X 10'2, with
1.4 X 10'igallons of gasoline consumed.
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 NITROGEN-CONTAINING COMPOUNDS 73

TABLE 2.6 Typical Boundary Layer NOx

Mixing Ratios

Urban-suburban
Rural
Remotetropical forest
Remotemarine
Source: National Research Council (1991).

rural sites and generally range from a few tenths to 1 ppb. Measurements of NOx in the at-
mospheric boundary layer and lower free troposphere in remote maritime locations have
generally yielded mixing ratios of 0.02 to 0.04 ppb (20 to 40 ppt). Although the databaseis
still quite sparse, mixing ratios in remote tropical forests (not under the direct influence of
biomass burning) appear to range from 0.02 to 0.08 ppb (20 to 80 ppt); the somewhat
higher NOx concentrations found in remote tropical forests, as compared with those ob-
served in remote marine locations, could result from biogenic NOx emissions from soil.
A summary of the NOx measurements made in the four regions of the globe mentioned
above is presented in Table 2.6. It can be seen that NOx concentrations decreasesharply as
one moves from urban and suburban to rural sites in the United States and then to remote
sites over the ocean and tropical forests. The striking difference of three orders of magni-
tude or more between NOx concentrations in urban-suburban areas and remote locations is
compelling evidence for the dominant role of anthropogenic emissions of NOx over strong
anthropogenic source regions such as North America. Because the ability to measure Nay
was developed only recently, the rural and remote Nay databaseis even more limited than
that for NOx' However, there are enough data to establish a rough indication of the Nay dis-
tribution. Average Nay concentrations observed at many sites in the United States are quite
similar; median mixing ratio values range from 3 to 10 ppb. These are somewhat lower
than NOx mixing ratios typically observed in urban and suburban locations, which range
from 10 to 1000 ppb.
The contrast in Nay concentrations found in rural areas of the continental United States
with those observed in the remote troposphere is illustrated in Figure 2.7. The measure-
ment sites are Scotia, Pennsylvania, a rural site in the eastern United States; Niwot Ridge,
Colorado, an isolated inland site in the western United States; Point Arena, California, a
site on the West Coast that often receives air from the Pacific Ocean; and Mauna Loa,
Hawaii, a remote maritime site. Two of the sites, Mauna Loa and Niwot Ridge, are at high
elevations (approximately 3 kin), and thus the air sampled there is not necessarily repre-
sentative of the boundary layer. There is a progressive decreasein the contribution of NOx
to Nay as one moves toward more remote regions. On average, NOx at Scotia accounted for
59% of the observed Nay. At Niwot Ridge in 1987, NOx accounted for 32% of the Nay,
and at Mauna Loa, NOx accounted for only 15% of the Nay. Because Nay enters the at-
mosphere as NOx, the decrease in the ratio of NOx to Nay as one moves to more remote
sites can be understood in terms of the increasing chemical conversion of NOx to organic
nitrates (principally PAN) and to inorganic nitrates (principally HNO3) with increasing dis-
tance of the site from major anthropogenic sources.The most remote sites are characterized
by the lowest ratios of NOxINOv' Those sites at hi.e:haltitudes have the lar.e:estratio of
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 CARBON-CONTAINING COMPOUNDS 75

TABLE 2.7 Estimated Global Ammonia Emissions

Emission
Sourceof Ammonia (Tg(N) yr-1

,NTHROPOGENIC

Dairy cattle 5.5

Beef cattle/buffalo 8.7
Pigs 2.8
Horses 1.2
Sheep/goats 2.5
Poultry 1.3
Fertilizer 6.4
Biomassburning 2.0
Subtotal 3OA
NATURAL
Wild animals 2.5
Vegetation 5.1
Ocean -1.:Q
Subtotal 1.4,.Q
Total 45.0

Source: Dentener and Crutzen (1994).

are animal waste, ammonification of humus followed by emission from soils, losses of
NH3-based fertilizers from soils, and industrial emissions (Table 2.7). The ammonium
(NHt) ion is an important component of the continental tropospheric aerosol. Because
NH3 is readily absorbed by surfaces such as water and soil, its residence time in the lower
atmosphere is expected to be quite short, about 10 days. Wet and dry deposition of NH3 are
the main atmospheric removal mechanisms for NH3' In fact, deposition of atmospheric
NH3 and NH: may represent an important nutrient to the biosphere in some areas.
Atmospheric concentrations ofNH3 are quite variable, depending on proximity to a source-
rich region. NH3 mixing ratios over continents range typically between 0.1 and 10 ppb.

2.4 CARBON-CONTAINING COMPOUNDS

2.4.1 Classification of Hydrocarbons

Let us review briefly the classifications of carbon-containing compounds, particularly
those of interest in atmospheric chemistry. The carbon atom has four valence electrons and
can therefore share bonds with from one to four other atoms. The nature of the carbon-car-
bon bonding in a hydrocarbon molecule basically governs the properties (as well as the
nomenclature) of the molecule.
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Moleculeswith two doublebondsarecalled alkadienes,an exampleof which is

CH2=CH-CH=CH2
1,3-Butadiene

Moleculeswith a singletriple bond areknown asalkynes,the first in the seriesof which

is acetylene,HC ~ CR.
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molecules,of which the basicunit is benzene,

H
/C, "
HC CH
or
CH
HC,/
C
H

is calledaromatics.Other commonaromaticsare

CH3 CH3 CH3

6
Toluene
arCH3

a-Xylene m-Xylene
9 CH3
p-Xylene

Hydrocarbonsmay acquireone or more oxygen atoms.Of the oxygenatedhydrocar-

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joined by a doublebond.Aldehydeshavethe generalform

0
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whereas ketones have the structure

0
II

R-C-R

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TABLE 2.9 Estimated Sourcesand Sinks of Methane (Tg(CH4) yr-1

Identified Sources Individual Estimate Total

NATURAL

Wetlands 115(55-150)
Termites 20 (10-50)
Oceans 10 (5-50)
Other 15 (10-40)
Total identified natural sources 160 (110-210)D

ANTHROPOGENIC

Fossil-fuelrelatedsources
Natural gas 40 (25-50)
Coal mines 30 (15-45)
Petroleumindustry 15 (5-30)
Coal combustion ?(1-30)
Total fossil-fuel related 100(70-120)b
Biosphericcarbon
Enteric fermentation 85 (65-100)
Rice paddies 60 (20-100)
Biomassburning 40 (20-80)
Landfills 40 (20-70)
Animal waste 25 (20-30)
Domesticsewage 25 (15-80)
Total biospheric 275 (200-350)
~

Total identified anthropogenic sources 375 (300-450)"

Total identified sources

Sinks
TroposphericOH 445 (360-530)
Stratosphere 40 (32-48)
Soils 30 (15-45)

Total sinks 515 (430-600)

Total global burden:4850Tg (C~)

aA preindustrial level of 700 ppb would have required a source of2l0 Tg(CH.) yr-1 if the lifetime has remained
constant, and 280 Tg (CH.) yr-1 if current tropospheric chemical feedbacks can be extrapolated back. The total
anthropogenic emissions of CH. based on identified sources, 375 (300--450), is slightly higher than the inferred
range from preindustrial levels, 270-340, but is well within the uncertainties.
bpractional source from fossil carbon based on a measure of the atmospheric ratio of "CH. to 12CH..
Note: The observed increases in methane show that sources exceed sinks by about 35 to 40 Tg each year. All data
are rounded to the nearest 5 Tg.
Source: IPCC (1995).
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 CARBON-CONTAINING COMPOUNDS 81

TABLE 2.10 Estimated Global Anthropogenic Emissionsof

NonmethaneVolatile Organic Compounds

FUEL PRODUCTION/DISTRIBUTION

Petroleum 8
Natural gas 2
Oil refining 5
Gasoline distribution 2.5

FUEL CONSUMPTION

Coal 3.5
Wood 25
Crop residues(including waste) 14.5
Charcoal 2.5
Dung cakes 3
Roadtransport 36
Chemicalindustry 2
Solventuse 20
Uncontrolledwasteburning 8

OTHER 10

Total 142

Source: Middleton (1995).

pogenic VOC emissions included, for example, about 600 different compounds (Placet
et al., 1990).
Motor vehicles are the dominant contributor to VOC emissions in the United States.
VOCs emitted from motor vehicles are mainly hydrocarbons that result from the incom-
plete combustion of fuel or from its vaporization. These contributions are generally cate-
gorized and reported as exhaust and evaporative emissions. Within the exhaust emissions
category are included the unburned and partially burned fuel and lubricating oil in the ex-
haust and gases that leak from the engine. The evaporative emissions category includes
fuel vapor emitted from the engine and fuel system that can be attributed to several sources:
vaporization of fuel as a result of the heating of the fuel tank, vaporization of fuel from the
heat of the engine after it has been turned off (hot-soak emissions), vaporization of fuel
from the (uel system while the vehicle is operating (running losses), fuel losses due to leaks
and diffusion through containment materials (resting losses), and fuel vapor displacement
as a result of filling fuel tanks (refueling losses). Motor vehicles are the major sources of
alkane and aromatic emissions.
Estimates of global anthropogenic nonmethane VOC emissions in 1990 are given in
Table 2.10. In general, a breakdown by chemical compound is not yet available for global
anthropogenic VOC emissions. As seen in Table 2.10, transportation is the largest source
ofVOC emissions worldwide, with solvent use following as the second largest source.
As an illustration of the large number of organic compounds identified in the atmos-
phere, Table 2.11 lists the median concentrations of the 25 most abundant nonmethane or-
ganic species measured in the 1987 Southern California Air Quality Study.
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 TABLE 2.12 Organic CompoundsEmitted by Vegetation"

Isoprene =~>== a-Pinene

~
Camphene
f3-Pinene
IlJ
2-Carene
Sabinene

3
~ -Carene

a-Terpinene

d-Limonene

y-Terpinene

Myrcene

/\. Terpinolene

Ocimene

f:J-Phellandrene

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p-Cymene
/"\

"In the simplified molecular structures here bonds between carbon atoms are shown. Vertices represent carbon
atoms. Hydrogen atoms bonded to the carbons are not explicitly indicated.
83
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 CARBON-CONTAINING COMPOUNDS 85

TABLE 2.13 Global Biogenic VOC Emission Rate Estimates by Sourceand

Class of Compound (Tg yr-1

821
120
194
5
9

127 260
.Other reactive biogenic VOCs (ORVOC).
bThese totals include additional non-reactive VOCs not reflected in the columns to the left.
Source: Guenther et al. (1995).

biogenic hydrocarbon emissions in the southeastern United States is predicted to be as

large as that in the tropics. An estimate of global biogenic VOC emissions appears in Table
2.13. On a global basis, biogenic hydrocarbon emissions far exceed those of anthropogenic
hydrocarbons.

2.4.5 Carbon Monoxide

The global sources and sinks of CO are given in Table 2.14. Methane oxidation (by OH)
is a major source of CO, as are technological processes (combustion and industrial
processes), biomass burning, and the oxidation of nonmethane hydrocarbons. Un-
certainties in each of these estimated sources are large. It is estimated that about two-thirds

TABLE 2.14 Estimated Sourcesand Sinks of CO

Typical of the Last Decade

Technological
Biomassburning
Biogenics
Oceans
Methaneoxidation
NMHC oxidation

Sinks
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 HALOGEN-CONTAINING COMPOUNDS 87

As a group of atmospheric chemicals, halogen-containing compounds have a wide vari-

ety of anthropogenic and natural sources. They are produced by biological processesin the
oceans, from sea salt, from biomass burning, and from industrial synthesis. Their atmo-
spheric lifetimes vary considerably depending on their mechanism of removal, ranging
from a few days to several centuries.
Table 2.15 lists atmospheric halogenated organic species with global average concen-
trations, atmospheric burdens, lifetimes, sources, and sinks.4 Of the exclusively man-made
organic halogenated species, the chlorofluorocarbons are used as refrigerants (CFC-12,
HCFC-22), blowing agents (CFC-ll, HCFC-22), and cleaning agents (CFC-113). Methyl
chloroform (CH3CCI3), methylene chloride (CHzClz), and tetrachloroethene (CzCI4) are
used as degreasersand as dry cleaning and industrial solvents. Methyl bromide (CH3Br) is
a widely used agricultural and space fumigant. All the monomethyl halides in Table 2.15
have natural sources. Methyl chloride (CH3Cl) and CH3Br are also products of biomass
burning.
Lovelock (1971) first detected SF6 and CFCl3 in the atmosphere using the electron cap-
ture detector. In landmark work in atmospheric chemistry for which they received the 1995
Nobel Prize in Chemistry, Molina and Rowland (1974) showed that CFCs that are im-
mune to removal in the troposphere could decompose photolytically in the stratosphere to
release Cl atoms capable of catalytic destruction of stratospheric ozone. The very lack of
chemical reactivity that makes chlorofluorocarbon molecules so intrinsically useful also al-
lows them to survive unchanged in most commercial applications and eventually to be re-
leased to the atmosphere in their original gaseous form. The usual tropospheric sinks of
oxidation, photodissociation, and wet and dry deposition are ineffective with the chloroflu-
orocarbons. The only important sink for CFC13and CFzClz is photodissociation in the mid-
stratosphere (25 to 40 kill) by solar ultraviolet radiation with wavelengths shorter than
230 nm. These same CFCs that lead to stratospheric ozone depletion are efficient absorbers
of infrared radiation and potentially important greenhouse gases.
There is a sharp demarcation in atmospheric behavior between fully halogenated halo-
carbons and those containing one or more atoms of hydrogen. Halocarbons containing at
least one hydrogen atom, such as CFzHCl, CHCI3, and CH3CCI3, are effectively broken
down in the troposphere by reaction with the hydroxyl radical before they can reach the
stratosphere. Atmospheric lifetimes of these species range from months to decades. Some
of these gases also react with seawater; it is estimated that 5 to 10% of the removal of
CH3CCl3 occurs by absorption into the ocean. The hydrohalogenated species such as

'The tenD hydrochlorofluorocarbons is the collective name given to a series of chemicals with varying number of
carbon, hydrogen, chlorine, and fluorine atoms. The somewhat arcane system of numbering these compounds was
proposed by the American Society of Heating and Refrigeration Engineers in 1957. For the simpler hydrochloro-
fluorocarbons, the numbering system may be summarized as follows:

1. The first digit on the right is the number of fluorine (F) atoms in the compound.
2. The second digit from the right is one more than the number of hydrogen (H) atoms in the compound.
3. The third digit from the right, plus one, is the number of carbon (C) atoms in the compound. When this
digit is zero (i.e., only one carbon atom in the compound), it is omitted from the number.
4. The number of chlorine (CI) atoms in the compound is found by subtracting the sum of the fluorine and
hydrogen atoms from the total number of atoms that can be connected to the carbon atoms.

CCI2F2 C2CI2F4 CHCIF2. CCI3F

CFC-12 CFCI-114 CFC-22 CFC-II
 88

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 HALOGEN-CONTAINING COMPOUNDS 89

800
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1972 1976 1980 1984 1988 1992
Year
FIGURE 2.9 Annual emissionsof industrially important halocarbonsfrom 1972to 1992(IPCC.
1995).

methyl chloroform (CH3CCI3) and the HCFCs are also significant infrared absorbers but
their shorter atmospheric lifetimes reduce their radiative impact relative to the fully halo-
genated CFCs.
Discovery of the stratospheric ozone-depleting potential of CFCs in the mid-1970s led
to a ban in the United States (announced in 1976 and effective in 1978) on the use ofCFCs
as aerosol propellants and to similar restrictions in Canada and Scandinavia. When the
Antarctic ozone hole was discovered, subsequently, an international protocol outlining pro-
posed actions to protect the stratospheric ozone layer was signed in Montreal in September
1987. The so-called Montreal Protocol specifies a 20% reduction from 1986 emissions of
fully halogenated CFCs by 1994 and a further 30% reduction by 1999. Global emissions of
CFCI3, CF2CI2, C2F3C13,CF2HC1, and CH3CC13up to 1992 are shown in Figure 2.9. The
turn-down in emission rates reflects the results of the Montreal Protocol.
Atmospheric levels of CF2CI2, CFCI3, and CH3CC13from 1978 to 1992 are shown in
Figure 2.10. Mixing ratios increased steadily until about 1990. Methyl chloride (CH3Cl), at
an atmospheric abundance of about 600 ppt, is the dominant halogen compound in the at-
mosphere. To maintain the steady-state CH3Cl concentration, with an atmospheric lifetime
of order 2 years, requires a source strength of about 3.5 Tg yr-1 , most of which comes from
the ocean. Southern Hemisphere (SH) CFC concentrations lag behind those in the Northern
Hemisphere (NH) by about 1 year, reflecting the predominant source of CFCs in the NH
and the approximate 1 year mixing time between the NH troposphere and the SH tropo-
sphere.
At present, the atmosphere contains approximately 20 ppt of bromine, about half of
which is methyl bromide (CH3Br). Methyl bromide is an ubiquitous component of the at-
mosphere, arising from both man-made and natural sources.A calculated atmospheric life-
time of 1.7 to 1.9 years, based solely on removal by reaction with OH radicals, is consistent
with a global source of 90 to 110 Gg (109 g) yr-l (Singh and Kanakidou, 1993). A shorter
lifetime of about 1.3 years (see Table 2.15) results if deposition/hydrolysis losses are also
considered. Available data provide an estimate of global sources of CH3Br that divide 35%
(20 to 50%) man-made and 65% (80 to 50%) natural. Oceans are supersaturated with
CH3Br and constitute the major natural source of CH3Br of about 60 Gg yr-1, which could
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 ATMOSPHERIC OZONE 91

range from 40 to 80 Gg yr-l. CH3Br mixing ratios in the Northern Hemisphere ar,ound
1992 were about 14 ppt, with a ratio of NH to SH mixing ratios varying between 1.2 and
1.4 depending on season.The seasonalvariation is a result of source strength and OH vari-
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the stratosphere and contribute to halogen-induced stratospheric ozone depletion.

2.6 ATMOSPHERIC OZONE

Ozone(03) is a reactiveoxidant gasproducednaturally in traceamountsin the Earth's at-

mosphere.Ozonewas discoveredby C. F. Schonbeinin the middle of the last century;he
alsowas first to detectozonein air (Schonbein,1840,1854).Schonbein(1840) suggested
the presenceof an atmosphericgashaving a peculiarodor (the Greekword for "to smell"
is ozein).Spectroscopicstudiesin the late 19th century showedthat ozoneis presentat a
higher mixing ratio in the upper atmosphericlayersthan closeto the ground.Attemptsto
explainthe chemicalbasisof existenceof ozonein the upperatmospherebegannearly 70
yearsago.Within the last 30 years,however,while increasedunderstandingof the role of
other trace atmosphericspeciesin stratosphericozonewas unfolding, it becameapparent
that anthropogenicallyemitted substanceshave the potential to seriouslydepletethe nat-
ural levels of ozonein the stratosphere. At aboutthe sameperiod, ironically, it was real-
ized that anthropogenicemissionscould lead to ozone increasesin the troposphere.
Whereasstratosphericozoneis essentialfor screeningof solar ultraviolet radiation,ozone
at groundlevel can,at elevatedconcentrations,lead to respiratoryeffectsin humans.This
paradoxicaldual role of ozonein the atmospherehas, on occasion,led to the dubbing of
stratosphericozoneas "good" ozoneandtroposphericozoneas "bad" ozone.
Most of the Earth's atmosphericozone(about90%) is found in the stratospherewhere
it plays a critical role in absorbingultraviolet radiation emitted by the Sun. Figure 2.11
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 ATMOSPHERIC OZONE 93

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Latitude
FIGURE 2.12 Annual latitudinal variation of the total ozonefrom January1979to May 1991or
February1994,as indicated(IPCC, 1995).

from 1979to 1991have shownthat broadly similar midlatitudelosseshavealso occurred

at equivalentlatitudesin the SouthernHemisphere(IPCC, 1995).Figure 2.12 showsthe
annual,latitudinal variation of the total ozonetrendscalculatedfrom the Dobsonground-
basedmeasurementrecord and satellite observations.The effect of the Antarctic ozone
hole is seenin the data from 60° S to 90° S. Analysis of the total ozonemappingspec-
trometer(TOMS) dataover the period 1979to 1989between69° S and69° N revealsa to-
tal global averageozonedecreaseof 3.5% over that 11year period (Hermanet al., 1991).
Statisticaily significant decreasesin total ozoneare now being observedin all seasonsin
both the Northernand SouthernHemispheresat middle andhigh latitudes(Stolarskiet al.,
1992).

2.6.2 Ozone Flux from the Stratosphere to the Troposphere

Ozone from the stratosphere is transported down across the tropopause by so-called
tropopause folding events (Danielson, 1968) in which tongues of stratospheric air intrude
into the troposphere, usually at extratropicallatitudes (recall Figure 1.3 and associated dis-
cussion). Estimates of the amount of 03 transported from the stratosphere to the tropos-
phere on an annual basis rely on measurements of conserved tracers or on general
circulation models but are quite uncertain. In the NH ozone fluxes seem to maximize in
spring, being as much as five times the value in the fall. The NH stratosphere-to-
troposphere ozone flux has been estimated to fall in the range of (3 to 8) X 1010molecules
cm-2 S-l (Crutzen, 1995). The SH flux may be about half as large. An estimate for the to-
tal 03 production in the stratosphere is about 5 X 1013molecules cm-2 S-I; only about
0.1 % of all 03 produced in the stratosphere leaks down to the troposphere (Crutzen, 1995).
The estimated global 03 loss from photolysis in the troposphere is 14 X 1010molecules
cm-2 S-I, which generously exceeds the amount of 03 from stratosphere-to-troposphere
exchange.
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FIGURE 2.13 Selectedannual meansof ozone balloon soundingsover Payeme,Switzerland
(StaehelinandSchmid,1991).The annualmeanaltitudeof the tropopauseat Payemeis about 10kIn,
varying from about 8 kIn in winter to 12 km in summer.(Reprintedfrom Atmos. Environ., 25A,
Staehelin,J. and Schmid,W., Trend analysisof troposphericozoneconcentrationsutilizing the 20-
year data set of balloon soundingsover Payeme(Switzerland),p. 1739,1991,with kind permission
from ElsevierScienceLtd, The Boulevard,Langford Lane, Kid1ingtonOX5 1GB,UK.)

downwind of large urban areas,under certain meteorological conditions, emissions of NO x

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urban-suburban locations to rural locations and then to remote locations. Daily maximum
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urban-suburban atmosphere, where maxima well above 200 ppb have been observed
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ceed 150 ppb. In remote locations, ozone concentrations typically range from 20 to 40 ppb.

2.7 PARTICULATE MATTER (AEROSOLS)

Particles in the atmosphere arise from natural sources, such as windbome dust, sea spray,
and volcanoes, and from anthropogenic activities, such as combustion of fuels. Whereas an
aerosol is technically defined as a suspension of fine solid or liquid particles in a gas, com-
mon usage refers to the aerosol as the particulate component only (Table 2.17). Emitted di-
rectly as particles (primary aerosol) or formed in the atmosphere by gas-to-particle
conversion processes (secondary aerosol), atmospheric aerosols are generally considered
to be the particles that range in size from a few nanometers (nm) to tens of micrometers

TABLE 2.17 Terminology Relating to Atmospheric Particles

Aerosols,aerocolloids, Tiny particles dispersed in gases

aerodispersesystems
Dusts Suspensions of solid particlesproducedby mechanicaldisintegrationof
materialsuchascrushing,grinding, andblasting.Dp > I JLm.
Fog A looseterm appliedto visible aerosolsin which the dispersedphaseis
liquid. Usually,a dispersionof water or ice, closeto the ground.
The solid particlesgeneratedby condensationfrom the vapor state,gen-
erally after volatilization from meltedsubstances,and often accompa-
nied by a chemicalreactionsuchas oxidation.Often the material
involved is noxious.Dp < I JLm.
An aerosolthat impedesvision and may consistof a combinationof wa-
ter droplets,pollutants,and dust.Dp < 1 JLm.
Mists Liquid, usually water in the form of particlessuspendedin the atmos-
phereat or nearthe surfaceof the Earth; small water dropletsfloating
or falling, approachingthe form of rain, and sometimesdistinguished
from fog asbeing more transparentor as havingparticlesperceptibly
moving downward.Dp > I JLm.
Particle An aerosolparticle may consistof a single continuousunit of solid or
liquid containingmany moleculesheld togetherby intermolecular
forcesandprimarily largerthan moleculardimensions(> 0.001 JLm).
A particle may alsobe consideredto consistof two or more suchunit
structuresheld togetherby interparticleadhesiveforcessuchthat it
behavesas a singleunit in suspensionor upondeposit.
A term derivedfrom smokeand fog, appliedto extensivecontamination
by aerosols.Now sometimesusedloosely for any contaminationof
the air.
Small gas-borneparticlesresultingfrom incompletecombustion,con-
sistingpredominantlyof carbonandother combustiblematerial,and
presentin sufficientquantity to be observableindependentlyof the
presenceof other solids.Dp 2: 0.01 JLm.
Soot Agglomerationsof particlesof carbonimpregnatedwith "tar," formed
in the incompletecombustionof carbonaceous material.
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 PARTICULATE MATrER (AEROSOLS) 99

Remote
(11 areas)a
Nonurbancontinental 15 5 24 II 4 37
(14 areas)a
Urban 32 9 31 8 6 28
(19 areas)a
Rubidoux,Califomiab 87.4 18 6 20 6
(1986 annualaverage)
"Heintzenberg (1989).
bSolomon et aI. (1989).

to atmospheric aerosol have increased dramatically over the past century and have been
implicated in human health effects (Dockery et al., 1993), in visibility reduction in urban
and regional areas (see Chapter 22), in acid deposition (see Chapter 20), and in perturbing
the Earth's radiation balance (see Chapter 22).
Table 2.18 presents data summarized by Heintzenberg (1989) and Solomon et al. (1989)
on aerosol mass concentrations and composition in different regions of the troposphere. It
is interesting to note that average total fine particle mass (that associated with particles of
diameter less than about 2 .urn) in nonurban continental, (i.e., regional) aerosols is only a
factor of 2 lower than urban values. This reflects the relatively long residence time of par-
ticles. Correspondingly, the average compositions of nonurban continental and urban
aerosols are roughly the same. The average mass concentration of remote aerosols is a fac-
tor of 3 lower than that of nonurban continental aerosols. The elemental carbon component,
a direct indicator of anthropogenic combustion sources, drops to 0.3% in the remote
aerosols, but sulfate is still a major component. This is attributable to a global average con-
centration of non-sea-salt sulfate of about 0.5 .ugm-3. Rubidoux, California, located about
100 km east of downtown Los Angeles, routinely experiences some of the highest particu-
late matter concentrations in the United States.

2.7.3 Cloud CondensationNuclei (CCN)

Aerosols are essential to the atmosphere as we know it; if the Earth's atmosphere were to-
tally devoid of particles, clouds could not form. Particles that can become activated to grow
to fog or cloud droplets in the presence of a supersaturation of water vapor are termed
cloud condensation nuclei (CCN). At a given mass of soluble material in the particle there
is a critical value of the ambient water vapor supersaturation below which the particle ex-
ists in a stable state and above which it spontaneously grows to become a cloud droplet of
10 JLmor more diameter. The number of particles from a given aerosol population that can
act as CCN is thus a function of the water supersaturation. For marine stratiform clouds, for
which supersaturations are in the range of 0.1 to 0.5%, the minimum CCN particle diame-
ter is 0.05 to 0.14 tLm. CCN number concentrations vary from fewer than 100 cm-3 in re-
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 PARTICULATEMAnER (AEROSOLS) 101

Chemical Conversion
of Gasesto Low
IHot Vapor
Volatility Vapors
"
Condensation
-~
Volatility
Vaoor

r-' Homogeneous
Coagulation Nucleation

Chain Condensation
..
Growth, Nuclei 'ind Blown Dust
+
Emissions
+
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+
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Coagulation Plant ~articles I

,.I,.

&--- ,

WII~hrult mental
.J"
-
0.001
-
0.01 0.1 1
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Particle Diameter, ~m
- Transient Nuclei or
Aitken Nuclei Range
+ Accumulation

Range
Mechanically

Aerosol
Generated-

Range

Fine Particles Coarse Particles-

FIGURE 2.15 Idealized schematicof the distribution of particle surfaceareaof an atmospheric
aerosol(Whitby and Cantrell, 1976).Principal modes,sources,and particle formation and removal
mechanismsareindicated.

roads, wind erosion of cropland, construction, etc.), and transportatIon sources (automo-
biles, etc.).
Fugitive particles are those not emitted from a definable point such as a stack. Industrial
fugitive dust emissions result from wind erosion of storage piles and unpaved plant roads
and from vehicular traffic over plant roads. Fugitive process emissions result from indus-
try-related operations such as materials handling, loading, and transfer operations. Three
broad categories account for nearly all of the potential process fugitive emissions-mineral
products, food and agriculture, and primary metals. Nonindustrial fugitive particulate
emissions, commonly termedfugitive dust, are caused by traffic entrainment of dust from
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 EMISSIONSINVENTORIES 103

Atmospheric particulate matter samples can be analyzed routinely for more than 50
trace elements. Trace element emissions arise from a large number of different source types
in urban areas.For example, motor vehicles burning leaded fuel, electric arc steel furnaces,
Kraft recovery boilers, and secondary lead smelters contribute to atmospheric lead con-
centrations. The wide spectrum of sources, together with the fact that trace metals often are
only a minor fraction of the mass emissions from each source, obscure the relative impor-
tance of the contributors to atmospheric trace element levels.
As with all atmospheric species, trace metal emissions undergo atmospheric transport
and dilution before they reach a particular receptor site. Mathematical models can be con-
structed based on the fundamentals of atmospheric chemistry and physics that will track
the contributions from many emission sources as they undergo atmospheric transport.
Indeed, the development of such models will receive considerable attention in this book. In
the case of particulate emissions, an alternative is available. It is possible to attack the
source contribution identification problem in reverse order, proceeding from measured par-
ticulate concentrations at a receptor site backward to the responsible emission sources (see
Chapter 24). The unique metals content of the emissions from each source type is viewed
as a fingerprint for the presence of material from that source in an ambient aerosol sample.

2.7.6 Carbonaceous Particles

Carbonaceous particles in the atmosphere consist of two major components-graphitic or
black carbon (sometimes referred to as elemental or free carbon) and organic material. The
latter can be directly emitted from sources or produced from atmospheric reactions involv-
ing gaseous organic precursors. Elemental carbon can be produced only in a combustion
process and is therefore solely primary. Graphitic carbon particles are the most abundant
light-absorbing aerosol species in the atmosphere. Particulate organic matter is a complex
mixture of many classes of compounds (Daisey, 1980). A major reason for the study of par-
ticulate organic matter has been the possibility that such compounds pose a health hazard.
Specifically, certain fractions of particulate organic matter, especially those containing
polycyclic aromatic hydrocarbons (PAHs), have been shown to be carcinogenic in animals
and mutagenic in in vitro bioassays.

2.8 EMISSIONS INVENTORIES

An estimate of emissions of a species from a source is based on a technique that uses

"emission factors," which are based on source-specific emission measurements as a func-
tion of activity level (e.g., amount of annual production at an industrial facility) with regard
to each source. For example, suppose one wants to sample a power plant's emissions of
SO2 or NOx at the stack. The plant's boiler design and its BTU (British thermal unit) con-
sumption rate are known. The sulfur and nitrogen content of fuel burned can be used to cal-
culate an emissions factor of kilograms (kg) of SO2 or NOx emitted per metric ton (Mg) of
fuel consumed.
The U.S. Environmental Protection Agency (EPA) has compiled emission factors for a
variety of sources and activity levels (such as production or consumption), reporting the re-
sults since 1972 in "AP-42 Compilation of Air Pollutant Emission Factors," for which sup-
olements are issued regularly. Emission factors currently in use are developed from only a
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 AIR POLLUTION LEGISLATION 105

lationship that requires the U.S. Environmental Protection Agency (EPA) to develop
National AmbientAir-Quality Standards(NAAQS) andempowersthe statesto implement
and enforceregulationsto attain them. The act also requiresthe EPA to set NAAQS for
commonand widespreadpollutantsafter preparingcriteria documentssummarizingscien-
tific knowledgeof their detrimentaleffects.The EPAhasestablishedNAAQS for eachof
six criteria pollutants:sulfur dioxide, particulatematter,nitrogendioxide, carbonmonox-
ide, ozone,and lead.At certainconcentrationsand length of exposurethesepollutantsare
anticipatedto endangerpublic healthor welfare.The NAAQS arethresholdconcentrations
basedon a detailedreview of the scientific information relatedto effects.Concentrations
below the NAAQS are expectedto have no adverseeffects for humansand the environ-
ment. Table 2.20 presentsthe U.S. national primary and secondaryambient air-quality
standardsfor ozone,carbonmonoxide,nitrogendioxide, sulfur dioxide, suspendedpartic-
ulate matter,and lead.
In the CleanAir Act Amendmentsof 1970,Congressset 1975asthe deadlinefor meet-
ing the NAAQS. By 1977,2 yearsafter this deadline,many areaswere still in violation of
the ozoneNAAQS. The 1977amendmentsto the CleanAir Act delayedcompliancewith
the ozone and carbon monoxide NAAQS until 1982, and areasthat demonstratedthey
could not meetthe 1982deadlineweregiven extensionsuntil 1987.The 1990amendments
classify nonattainmentareasaccordingto degreeof noncompliancewith the NAAQS. The
classificationsareextreme,severe,serious,moderate,or marginal,dependingon the area's
ozone design value and the percentageby which the value is greaterthan the NAAQS.
Ozonedesign valuesare ozoneconcentrationsthat are statistically determinedfrom air-
quality measurements for eachnonattainmentarea.If monitoring datafor an areaarecom-
plete,the designvalue is the fourth highestmonitor readingover the past 3 years.Design
valuesareusedto determinethe extentof control neededfor an areato reachattainment.
The 1990amendmentsof the CleanAir Act establishan interstateozonetransportre-
gion extendingfrom the Washington,DC metropolitanareato Maine. In this denselypop-
ulated region, ozone violations in one area are caused,at least in part, by emissionsin
upwind areas.A transportcommissionis authorizedto coordinatecontrol measureswithin
the interstatetransportregion and to recommendto the EPAwhen additionalcontrol mea-
suresshouldbe appliedin all or part of the region in order to bring any areain the region
into attainment.Henceareaswithin the transportregion that arein attainmentof the ozone
NAAQS might becomesubjectto the controlsrequiredfor nonattainmentareasin that re-
gion.
The CleanAir Act requireseachstateto adopta plan, a so-calledStateImplementation
Plan (SIP), that provides for the implementation,maintenance,and enforcementof the
NAAQS. It is, of course,emissionreductionsthat will abateair pollution. Thus the states'
plansmust containlegally enforceableemissionlimitations, schedules,and timetablesfor
compliancewith suchlimitations. The control strategymust consistof a combinationof
measuresdesignedto achievethe total reductionof emissionsnecessaryfor the attainment
of the air-quality standards.The control strategymay include,for example,suchmeasures
asemissionlimitations, emissionchargesor taxes,closing or relocationof commercialor
industrial facilities, periodic inspectionandtestingof motor vehicle emissioncontrol sys-
tems,mandatoryinstallationof control deviceson motor vehicles,meansto reducemotor
vehicle traffic, including suchmeasuresas parking restrictionsand carpool laneson free-
ways,and expansionandpromotionof the useof masstransportationfacilities.
 901

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 HAZARDOUS AIR POLLUTANTS (AIR TOXICS) 107

2.11 HAZARDOUS AIR POLLUTANTS (AIR TOXICS)

Hazardousair pollutantsor toxic air contaminants("air toxics") refer to any substancesthat

may causeor contributeto an increasein mortality or in seriousillness,or that may posea
presentor potentialhazardto humanhealth.Title III of the CleanAir Act Amendmentsof
1990completelyoverhauledthe existing hazardousair emissionprogram.Section 112of
theAmendmentsdefinesa new processfor controlling air toxics that includesthe listing of
189 substances,the developmentand promulgation of Maximum Achievable Control
Technology(MACT) standards,and the assessment of residualrisk after the implementa-
tion of MACT. Any stationary sourceemitting in excessof 10 tons yr-1 of any listed
hazardoussubstance,or 25 tonsyr-1 or moreof any combinationof hazardousair contam-
inants,is a major sourcefor the purposeof Title III and is subjectto regulation.Congress
establisheda list of 189 hazardousair pollutants in the CAA itself. It includes organic
chemicals,pesticides,metals,coke-ovenemissions,fine mineral fibers, and radionuclides
(including radon).This initial list may be revisedby the EPAto either add or removesub-
stances.The EPA is required to add pollutants to the list if they are shown to present,
throughinhalationor other routesof exposure,a threatof adversehumanhealtheffectsor
adverseenvironmentaleffects,whetherthroughambientconcentrations,bioaccumulation,
deposition,or otherwise.
Congressdirectedthe EPA to list by 15 November 1995,the categoriesand subcate-
goriesof sourcesthat represent90% of the aggregateemissionsof:

.. Alkylatedleadcompounds
Polycylicorganicmatter
.. Hexachlorobenzene
Mercury
.. Polychlorinatedbiphenyls
2,3,7,8-Tetrachlorodibenzofuran
. 2,3,7,8-Tetrachlorodibenzo-p-dioxin

Congress further directed the EPA to establish and promulgate emissions standards for
such sources by 15 November 2000. The emissions standards must effect the maximum de-
gree of reduction in the listed substance, including the potential for a prohibition on such
emissions, taking into consideration costs, any non-air-quality health and environmental
impacts, and energy requirements. In establishing these emissions standards, the EPA may
also consider health threshold levels, which may be established for particular hazardous air
pollutants. Each state may develop and submit to the EPA for approval a program for the
implementation and enforcement of emission standards and other requirements for haz-
ardous air pollutants or requirements for the prevention and mitigation of accidental re-
leases of hazardous substances.
The California Air Resources Board (ARB) (1989) has developed a list of substancesof
concern in California, called "Status of Toxic Air Contaminant Identification." This list and
the organization of substances within it are subject to periodic revision, as needed. The
February 1989 Status List groups substances into three categories. Category I includes
identified toxic air contaminants: asbestos,benzene, cadmium, carbon tetrachloride, chlo-
rinated dioxins and dibenzofurans (15 species), chromium (VI), ethylene dlbromide and
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 COMPARTMENTALMODELS OF GLOBAL BIOGEOCHEMICAL CYCLES 113

Comparablebalanceson the two stratospherecompartmentsyield

0 =- (k~H/SH+ k~rT + k~H) Q~H + klH/NHQ~H + k~rsQ~H (2.A.5)

0 = - (k~H/NH+ k~fT + k~H) Q~H+ k~H/SHQ~H
+ k~~SQrH (2.A.6)

Equations (2.A.3) to (2.A.6) constitute four equations in the four unknowns Q~H' Q~H'
Q~H' and Q~H' It is useful to rewrite these equations as

0 = -alQI +a2Q2 +a3Q3 + PI (2oA.7)

0 = -a4Q2 + asQI + a6Q4 + P2 (2.A.8)

0 = -CX7Q3 + CXSQ4+ CX9QI (2.A.9)

0 = -aloQ4 + all Q3 + al2Q2 (2.A.IO)

where QI = Q~H' Qz = Q~H'Q3= Q~H'Q4= Q~H'PI = PNH,andPz= PsH.Also,

at -- kNH/SH
T + kTIS
NH + kTNH a2 = k§H/NH a3 = kNH
I: SIT

a4 -- kSH/NH
T + kTIS
SH + k SH
T a5 = k~/SH a6 = k SH
SIT

a7 -- NH/SH + kSIT
ks NH + kS
NH as = k~H/NH a9 = k NH
TIS

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S all-
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Equations(2.A.9) and (2.A.lO) can be solvedsimultaneouslyto obtain Q3and Q4in terms

ofQ. and Q2'
Q3 = .81 Qz + .8ZQI (2.A.II)
Q4 = .83QZ+ .84QI (2.A.I2)
where

The resultingequationsfor QI and Q2are

0 = (a3.82- at)Qt + (a2 + a3.8t)Q2 + PI (2.A.I3)

0 = (a~ + a"BJJ.)01 + (a"B~ - aJJ.)O,+ P, (2.A.14)
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 COMPARTMENTALMODELS OF GLOBAL BIOGEOCHEMICAL CYCLES 115

It can be assumedthat thesemassesdivide equally betweenthe NH and SH. With the av-
eragemolecularweight of air, Mair= 28.9 g mol-I, the troposphericmassof a substanceof
molecularweight M that hasa troposphericmixing ratio of ~ T is

(2.A.19)

Similarly, for the stratosphere,

s
QS= ~~sM (2.A.20)
Mair

(2.A.21)

If the troposphericmassis divided into Q~Hand QIH'

(2.A.22)

Q SH
T - - -Wa{r/2t:T
SSHM (2.A.23)
Mair

As an example,the averagemixing ratios of OCS in the troposphereand stratosphere

are (Chin andDavis, 1995)

~Jcs = 490 ppt = 490 x 10-12

~JcS = 380 ppt = 380 X 10-12

The total atmosphericmassofOCS is (Mocs = 60 g mol-I)

4.56 X 1021 0.72 X 1021

Q (490 x 10-11+
, 28.9 28.9
= 4.63 x 1012g + 0.57 x 1012g
= 4.63Tg + 0.57Tg
5.2Tg

2.A.2 Application of the Compartment Model to Methyl Chloroform (CH3CCI3)

Methyl chloroform is a man-made substance, the total emissions of which to the atmos-
phere are reasonably well known. Its atmospheric degradation occurs almost entirely by
hydroxyl radical reaction. The CH3CCl3 mixing ratio in the atmosphere is well established;
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 REFERENCES117

REFERENCES

Andreae,M. O. (1990) Ocean-atmosphereinteractionsin the global biogeochemicalsulfur cycle,

Marine Chem.,30, 1-29.
Andreae,M. 0., andBarnard,W. R. (1984)The marinechemistryof dimethylsulfide,Marine Chem.,
14,267-279.
Andreae,M. 0., and Crutzen,P.J. (1997)Atmosphericaerosols:biogeochemicalsourcesandrole in
atmosphericchemistry,Science,276, 1052-1058.
Andreae,M. 0., and Raemdonck,H. (1983)Dimethylsulfidein the surfaceoceanand the marineat-
mosphere:a global view, Science,221,744-747.
Andreae,M. 0., et at. (1992) Ozoneand aitken nuclei over equatorialAfrica: airborneobservations
during DECAFE 88, J. Geophys.Res.,97,6137-6148.
Arnts, R. R., and Meeks,S. (1981)Biogenic hydrocarboncontribution to the ambientair of selected
areas,Atmos.Environ., 15, 1643-1651.
Barnard,W. R., Andreae,M. 0., Watkins,W. E., Bingemer,H., and Georgii, H. W. (1982)The flux
of dimethylsulfidefrom the oceansto the atmosphere,J. Geophys.Res.,87, 8787-8793.
Barnes,R. A., Holland, A. C., and Kirchhoff, V. W. J. H. (1987) Equatorialozoneprofiles from the
groundto 52-km during the SouthernHemisphereautumn,J. Geophys.Res.,92, 5573-5583.
Baugues,K. (1986)A review of NMOC, NOx,and NMOC/NOxratios measuredin 1984and 1985.
U.S. EnvironmentalProtectionAgency report EPA-450/4-86-015,ResearchTrianglePark,NC.
Berresheim,H., Wine, P. H., and Davis, D. D. (1995) Sulfur in the atmosphere,in Composition,
Chemistry,and Climateof the Atmosphere,editedby H. B. Singh.Van NostrandReinhold,New
York, pp. 251-307.
Bojkov, R. D. (1988) Ozone changesat the surfaceand in the free troposphere,in Tropospheric
Ozone,editedby I. S. A. Isaksen.Reidel, Dordrecht,pp. 83-96.
Bouwman,A. F., Vander Hoeck,K. W., andOlivier, J. G. J. (1995)Uncertaintiesin the global source
distribution of nitrous oxide,J. Geophys.Res.,100, 2785-2800.
Browell, E. V., Gregory,G. L., Harriss,R. C., and Kirchhoff, V. W. J. H. (1988)Troposphericozone
and aerosoldistributionsacrossthe Amazon.J. Geophys.Res.,93, 1431-1451.
California Air ResourcesBoard (1989) Information on substancesfor review as toxic air contami-
nants.ReportNo. ARB/SSD/89-01,Sacramento,CA.
Charlson, R. J., Anderson, T. L., and McDuff, R. E. (1992) The sulfur cycle, in Global
BiogeochemicalCycles,edited by S. S. Butcher,R. J. Charlson,G. H. Oriana,and G. V. Wolfe.
AcademicPress,New York, pp. 285-300.
Chin, M., andDavis, D. D. (1995) A reanalysisof carbonylsulfideasa sourceof stratospheri'4back-
groundsulfur aerosol,J. Geophys.Res.,100, 8993-9005.
Cline, J. D., andBates,T. S. (1983)Dimethyl sulfidein the equatorialPacificOcean:a naturalsource
of sulfur to the atmosphere,Geophys.Res.Lett., 10, 949-952.
Crutzen, P. J., (1988) Troposphericozone: a review, in TroposphericOzone,edited by I. S. A.
Isaksen.Reidel,Dordrecht,pp. 3-32.
Crutzen, P. J. (1995) Ozone in the troposphere,in Composition,Chemistry,and Climate of the
Atmosphere,editedby H. B. Singh.Van NostrandReinhold,New York, pp. 349-393.
Dacey,J. W. H., andWakeham,S. G. (1986) Oceanicdimethylsulfide:productionduring zooplank-
ton grazingon phytoplankton,Science,233, 1314-1316.
Daisey,J. M. (1980) Organiccompoundsin urbanaerosols,Ann. N. }: Acad. Sci., 338, 50-69.
Danielson,E. F. (1968)Stratosphere-troposphere exchangebasedon radioactivity,ozoneandpoten-
tial vorticitv. .1.Atma.'!. .S'ci..25.502-518.
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 REFERENCES 119

Lamb, B., Guenther,A., Gay, D., and Westberg,H. (1987)A national inventoryof biogenic hydro-
carbonemissions,Atmos.Environ.,21, 1695-1705.
Lamb, B., Westberg,H., and Allwine, G. (1985) Biogenic hydrocarbonemissionsfrom deciduous
andconiferoustreesin the United States,J. Geophys.Res.,90, 2380-2390.
Lamb, B., Westberg,H., andAllwine, G. (1986) Isopreneemissionfluxes determinedby an atmos-
pheric tracertechnique,Atmos.Environ., 20, 1-8.
Logan,J. A. (1989)Ozonein rural areasof the United States,J. Geophys.Res.,94,8511-8532.
Lovelock, J. E. (1971)Atmosphericfluorinecompoundsasindicatorsof air movements,Nature,230,
379.
Lovelock, J. E., Maggs, R. J., and Rasmussen,R. A. (1972) Atmosphericdimethyl sulfide and the
naturalsulfur cycle, Nature,237,452-453.
Lubkert, B., and Zierock, K. H. (1989) Europeanemissioninventories-a proposalof international
worksharing,Atmos.Environ., 23,37-48.
Lurmann,F. W., andMain, H. H. (1992) Analysis of the ambientVOC datacollectedin the Southern
California Air Quality Study. Final Report. ARB Contract No. A832-130, California Air
ResourcesBoard,Sacramento,CA.
Machida,T., Nakazawa,T., Fujii, Y., Aoki, S., andWatanabe,O. (1995) Increasein the atmospheric
nitrous oxide concentrationduring the last 250 years,Geophys.Res.Lett., 22,2921-2924.
Middleton, P. (1995) Sourcesof air pollutants, in Composition, Chemistry,and Climate of the
Atmosphere,editedby H. B. Singh.Van NostrandReinhold,New York, pp. 88-119.
Molina, M. J., andRowland,F. S. (1974) Stratosphericsink for chlorofluoromethanes: chlorineatom
catalyzeddestructionof ozone,Nature,249, 810-812.
Monson,R., Jaeger,C., Adams,W., Driggers,E., Silver, G., andFall, R. (1992)Relationshipsamong
isopreneemissionrate, photosynthesis,and isoprenesynthaseactivity as influencedby tempera-
ture, PlantPhysiol., 92, 1175-1180.
Montzka, S. A., Trainer, M., Angevine, W. M., and Fehsenfeld,F. C. (1995) Measurementsof 3-
methyl furan, methyl vinyl ketone,and methacroleinat a rural forestedsite in the southeastern
United States,J. Geophys.Res.,100, 11393-11401.
Montzka, S. A., Trainer,M., Goldan,P.D., Kuster,W. C., and Fehsenfeld,F. C. (1993)Isopreneand
its oxidationproducts,methyl vinyl ketoneandmethacrolein,in the rural atmosphere, J. Geophys.
Res.,98, 1101-1111.
National ResearchCouncil (1991) Rethinking the Ozone Problem in Urban and Regional Air
Pollution. NationalAcademyPress,Washington,DC.
Nguyen,B. C., Beloriso,S., Mihalopoulos,N., Gostan,J., andNival, P.(1988) Dimethyl sulfidepro-
duction during naturalphytoplanktonicblooms,Mal: Chem.,24, 133-141.
Nguyen, B. C., Bergeret,C., and Lambert, G. (1984) Exchangeratesof dimethyl sulfide between
oceanandatmosphere,in Gas Transferat WaterSurfaces,editedby W. BrunsaertandG. H. Jirka.
Reidel, Dordrecht,pp. 539-545.
Oltmans,S. J., and Levy, H. II (1994) Surfaceozonemeasurements from a global network,Armos.
Environ., 28, 9-24.
Placet,M., Battye, R. E., Fehsenfeld,F. C., and Bassett,G. W. (1990) EmissionsInvolved in Acidic
Deposition Processes.State-of-SciencelTechnology Report I. National Acid Precipitation
Assessment Program.U.S. GovernmentPrinting Office, Washington,DC.
Prinn, R., et al. (1992) Global averageconcentrationand trend for hydroxyl radicalsdeducedfrom
ACF/GAGE trichloroethane(methyl chloroform) data from 1978-1990,J. Geophys.Res.,97,
2445-2461.
Rasmussen,R. A. (1970) Isoprene:identified as a forest-typeemissionto the atmosphere,Environ.
Sci. Technol.,4,669-673.
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 PROBLEMS 121

Went,F.W. (1960)Organicmatterin the atmosphereandits possiblerelationto petroleumformation,

Proc. Natl. Acad. Sci. (USA),46,212-221.
Whitby, K. T., and Cantrell, B. (1976) Fine particles,in InternationalConferenceon Environmental
SensingandAssessment,Las Vegas,NV, Institute of Electrical and ElectronicEngineers.
Winer, A. M., Arey, J., Aschmann,S. M., Atkinson, R., Long, W. D., Morrison, L. C., and Olszyk,
D. M. (1989)Hydrocarbonemissionsfrom vegetationfound in California's CentralValley.Final
Report.ContractNo. A 732-155.California Air ResourcesBoard, Sacramento,CA.
World Meteorological Organization (WMO) (1986) Atmospheric Ozone 1985. Global Ozone
ResearchandMonitoring Project:ReportNo. 16, Geneva.
World MeteorologicalOrganization(WMO) (1990)Reportof the InternationalOzoneTrendsPanel:
1988.Global OzoneResearchand Monitoring Project:ReportNo. 18,Geneva.
Yokouchi,Y. (1994) Seasonaland diurnal variation of isopreneand its reactionproductsin a semi-
rural area.Atmos.Environ.,28,2651-2658.
Yvon, S. A., Saltzman,E. S., Cooper,D. J., Bates,T. S., and Thompson,A. M. (1996)Atmosphere
sulfur cycling in the tropical Pacificmarineboundarylayer (120S, 1350W): a comparisonoffield
dataand modelresults I. Dimethylsulfide,J. Geophys.Res.,101,6899-6909.
Zimmerman,P.(1979) Testingof hydrocarbonemissionsfrom vegetation,leaf litter andaquaticsur-
faces, and development of a method for compiling biogenic emission inventories. U.S.
EnvironmentalProtectionAgency Report,EPA-450-4-70-004,ResearchTrianglePark,NC.
Zimmerman,P.,Greenberg,J., andWestberg,C. (1988) Measurements of atmospherichydrocarbons
and biogenicemissionfluxes in the Amazonboundarylayer,J. Geophys.Res.,93, 1407-1416.

PROBLEMS

2.1A In the simplified calculationof the atmosphericsulfur cycle in Section2.2.4, if the

valueof c, the S02 fraction of the total sulfur, is takenas0.5, a sulfur atomresidence
time of 50 hoursis estimated.What is the value of b, the fraction of sulfur converted
to SO~- beforebeing removed,that is consistentwith this choiceof c?
2.2A Preparea plot of ozonemixing ratio versusaltitudefrom groundlevel to 50 km. Total
molecularnumberdensity of air can be obtainedfrom TableA.8, and 03 molecular
numberdensity is given in Figure 2.11. Why do the molecularnumberdensity and
mixing ratio peakat different altitudes?
2.3A One Dobsonunit correspondsto 2.69 X 1016molecules03 cm-2 integratedover a
vertical column to the top of the atmosphere.Show how vertical ozonecolumn data
canbe convertedto Dobsonunits.
2.4A Calculatethe changein total ozonecolumn, as measuredin Dobsonunits, between
1969and 1988for the ozoneprofiles in Figure 2.13.
2.5A Confirm the calculationspresentedin Section2.A.2 on the concentrationandlifetime
of methyl chloroform.
2.6B Derive the balanceequationsfor a substancethat is completelyremovedin the tro-
posphere,but for which two tropospheric reservoirs should be considered(see
Appendix 2). Apply the balanceto CO using the sourceand sink data from Table
2.14.As a first approximation,assumethat anthropogenicsourcesaretotally concen-
tratedin the NorthernHemisphereandthat biomassburning sourcesaretotally in the
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 PROBLEMS 123

atmosphericresidencetime. = p-l. Given valuesof land r,p canbe calculated

from 1= rf(r + p) sincethesespecieshave beenemitted long enoughso that
rt» 1. Plot/versusp (and .) for r = 0.15 yr-1 showingpoints corresponding
to the threecompounds.
c. Let us now assumethat the tropospherecan be divided into Northern and
SouthernHemisphereswith an interhemisphericfractionalmixing rateof m yr-i.
The rate of removal from the atmosphere,p yr-l, is assumedto be the samein
both hemispheres.If all the manufactureand releaseof the compoundare as-
sumedto occur in the NorthernHemisphere,then let us find the ratio of concen-
trations,R, betweenthe Northernand SouthernHemispheresat any time t. Let

MN = massof speciesin NorthernHemisphere

Ms = mass of species in Southern Hemisphere

Showthat the hemisphericmaterialbalancesare

dMN= Poert
- pMN + m(Ms - MN)
dt
dMs = m(MN- Ms)- pMs
dt
MN(O)= Ms(O) 0

MN + Ms = _(err
Po - e-pt)
r+p

show that

e-pt

R= MN(t) --2(r +2me,t

p + m)ert - (r + p + 2m)e-pt - (r + p)e-(2m+p)1
- (r + p + 2m)e-pt+ (r + p)e-(2m+p)t
Ms(t)

For err »

R~ + r+p
m
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3 Atmospheric Photochemistry
and Chemical Kinetics

3.1 RADIATIVE FLUX IN THE ATMOSPHERE

The essentialenergyflux in atmosphericchemistryis the flux of solarradiation.The radi-

antflux densityF is the radiantenergyflux acrossany surfaceelement,without considera-
tion of the direction; F is measuredin watts per squaremeter (W m-1. The radiant flux
densityis called the irradiance E when the radiation is receivedon a surface.Thus F and
E are often usedinterchangeably.We will use F in generaland E when we are referring
specificallyto the radiantflux densityon a surface.The radianceL is the radiantflux as a
function of the solid angled{J)crossinga surfaceperpendicularto the axis of the radiation
beam;L is measuredin wattsper squaremeterper steradian(W m-2 sr-I). The radianceas
a function of direction gives a completedescriptionof the radiativefield.
Considera beamof radiation of radianceL crossinga surfacedS with the beamaxis
making an angle e to the normal to dS (Figure 3.1). dS projectsasdS cos e perpendicular
to the beamaxis of the radiation,and the radiantflux densitydF on dS is

dF = Lcos(J dw

The radiant flux density,or irradiance,on the surfacedS is obtainedby integratingthe ra-
dianceover all angles,

E = f L case dw
When the radianceL is independentof direction, the radiative field is called isotropic. In
this case,(3.2) canbe integratedover the half space,n = 271; andthe relation betweenthe
irradianceandthe radianceis

E = JrL

12-"
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 RADIATIVE FLUX IN THE ATMOSPHERE 127

Sometimesthe spectralradiant flux density is expressedas a function of frequency v,

that is, F(v). Becausethe frequency v of radiation is relatedto its wavelengthby (1.13),
v = ciA, F(A) andF( v) can be interrelated.Sincethe flux of energyin a small interval of
wavelengthdA mustbe equalto that in a small interval of correspondingfrequencyd v,

F()') d)' = F(v) dv

Since dv = (cj)..2) Id)..l,

F()') = ~)F(V)
-;;)F(v)
V2

Generally we will deal with wavelengthas the variable rather than frequency,although
they can easily be interrelatedasindicatedin (3.6).

3.1.1 Solar Radiation Received on Earth

Light absorption and scattering by atmospheric constituents attenuate the solar radiation as
it passes through the atmosphere. The amount of attenuation depends on the nature and
concentration of gases and particles and on the pathlength through which the solar beam
passes.The pathlength is a function of the angle of the Sun, which depends on time of day,
latitude, and date. Also, reflection of radiation from the Earth's surface contributes to the
radiation at any point in the atmosphere.
Table 3.1 gives the solar spectral irradiance, normalized to a solar constant of 1367
W m-z. Solar UV radiation, expressed in units of photons cm-z S-I nm-l, at the surface
(0 kIn), 20, 30, 40, and 50 kIn is shown in Figure 3.3. (A discussion of the processesthat
lead to the progressive attenuation of radiation was given in Chapter 1 in association with
Figure 1.9.) Usually radiative transfer through the atmosphere is calculated by radiative
transfer models that divide the atmosphere into layers and the radiative spectrum into
wavelength intervals (Goody and Yung, 1989; Liou, 1992; Lenoble, 1993). The vertical
distribution of trace gasesand particles and the surface albedo serve as inputs to such mod-
els. Near the Earth's surface the spectral distribution shows a steep cutoff, when moving
from longer to shorter wavelengths, beginning at about 320 nm. Radiation below 290 nm
does not reach the Earth's surface; as noted in Chapter 1, this cutoff is the result of absorp-
tion of solar radiation by stratospheric ozone. There is no overlap between the absorption
cross section of the major atmospheric gases,Nz, Oz, COz, and HzO, and the solar spectrum
at the Earth's surface. Overlap does exist, however, with a number of trace gases that are
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 RADIATIVE FLUX IN THE ATMOSPHERE 129

TABLE 3.1 (Continued)

F(A) f;F(A')dA'
F(A)
(W m -2 -I,
J;F(X)dX (W m-2)
om (W m-1 A (nm) (W m-2 nm-1
A (nm)
1120 0.066 1313
0.438
1140 0.054 1319
0.387
0.353 1159 0.047 1325
1176 0.041 1329
0.323
0.296 1191 0.036 1332
1205 0.031 1336
0.273
1218 0.024 1342
0.247
1230 0.019 1346
0.234
1241 0.015 1349
0.217
0.187 1251 0.012 1353
1260 0.010 1355
0.169
1267 0.008 1357
0.148
1274 0.005 1360
0.133
1281 0.003 1362
0.126
1287 0.002 1364
0.116
1298 0.001 1366
0.093
0.075 1307 0.000 1367

Source: Frohlich and London (1986).

important in troposphericchemistry.In spite of its stratosphericabsorption,a sufficient

overlap exists betweenthe solar UV spectrumat the Earth's surfaceand the absorption
crosssectionof ozonethat 03 photolysisis also importantin troposphericchemistry.

3.1.2 Earth Geometry for Solar Radiation

Because of the rotation of the Earth around the Sun and its daily rotation around itself, the
solar irradiance actually received at a given location on Earth depends on the location on
the Earth, the date of the year, and the time of day. The Earth describes an ellipse around
the Sun. The shortest distance between the Earth and Sun, occurring around January 3, is
1.471 X 108kIn, and the largest distance, around July 4, is 1.521 X 108kIn. The mean dis-
tance, the average of the two extremes, is 1.496 X 108kIn.
The Earth rotates in an eastward direction around the polar axis, which is inclined at
23 °27' from the normal to the ecliptic plane. The line joining the center of the Earth to the
center of the Sun makes an angle 11with the equatorial plane, which is called the Sun dec-
lination with the equatorial plane. 11reaches its maximum value of + 23 °27' at the summer
solstice around June 21; it reaches its minimum value of -23°27' at the winter solstice,
around December 21, and is zero at the spring and fall equinoxes. 11can be computed at any
day of the year by 11(in radians) = -0.4cos[27r(dn + 10)/365], where dn = 1 for January
1,2 for January2, andsoon.
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 RADIATIVE FLUX IN mE ATMOSPHERE 131

FIGURE 3.4 Definition of latitudeand

longitudeof a point M on the Earth. Oz
is the local vertical.

The period of the Earth's rotation is constant and is measured by the interval of time be-
tween two successive passagesof a star in the observer's meridian. This is called the side-
real day. The interval of time between two successive passagesof the Sun in the observer's
meridian, the solar day, is slightly longer (by about 4 minutes) than the sidereal day. Also,
becauseof the ellipticity of the orbit and the inclination of the axis, the solar day is not con-
stant throughout the year. For practical purposes, we use a mean solar day divided into 24
hours. Local mean time (LMT) noon is defined on this basis. The real Sun passes in the
meridian either earlier or later than the average Sun. The passageof the real Sun in the ob-
server's meridian defines the local true solar time (TST) noon. The difference between the
true solar time and the local mean time is ET = TST - LMT, which varies between :t 15

FIGURE 3.5 Horizontal coordinatesof the

Sun: eo= solar zenith angle; h = altitude
angle; <Po = azimuthalangle.
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 ABSORPTION COEFFICIENT AND ABSORPTION CROSS SECTION 133

3.2 ABSORPTION COEFFICIENT AND ABSORPTION

CROSSSECTION

Considerthe propagationof radiationthrougha mediumand selecta layer of thicknessdx

perpendicularto a beamof intensity F (Figure 3.7). The lossof intensity F over the infini-
tesimalslice dx as a result of light absorptionis

dF = -baF dx (3.10)
where ba is the absorption coefficient (m-l) of the medium. For a finite path between Xl and
X2,integration of (3.10) gives
F(X2) = F(x,) exp( -8a)

where
ba{x) dx (3.12)

is the absorption optical thickness (dimensionless) between Xl and X2' If the medium is ho-
mogeneous,ba(x) = ba,independentof X, and

F(xV = F(XI)eXp[-ba(X2 -XI)] (3.13)

This resultis known asthe Beer-Lambertlaw of extinction.Whenx is measuredvertically

in the atmospherethe optical thicknessis called the optical depth.
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I definedby
F(xV = exp( -b'a)
'f=~

Ildx

.. .
F(x.; F(~
FIGURE 3.7 Propagationof radiationthrougha medium.
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 ACTINICFLUX 137

As indicated,the quantity on the R.H.S. multiplying nA is jA. The spectralactinic flux is

then the radiative quantity that drives the photodissociation,that is, the quantity that mul-
tiplies rPA(A)aA(A)to producea product that when integratedover all wavelengthspro-
ducesthe photodissociationrate coefficient.
The spectralactinic flux I (A) is then

I(J..) = !L(J..,(},</» dw
w

= ff L(A, 0, 4» sinO dO d4>

(3.23)

t/> IJ

The spectral irradiance E()") is the radiant energy crossing a surface (per unit surface area,
time, and wavelength) and is calculated from L()", 0, 4» by (3.4),

E()") = ff L()", e, 4» cose sine de d4> (3.24)

"'9

The factor cos () reflects the change in the projected area of the surface as the angle of in-
cidence is varied. This factor does not appear in the expression for the actinic flux because
the projected area and the pathlengths offset exactly. As the angle of incidence is changed
from overhead «() = 0°) to nearly glancing «() -+ 90°), the energy (irradiance) incident
upon the layer decreases,but the actinic flux remains unchanged because the lower inten-
sity is exactly compensated for by the longer pathlength of light through the layer.
Two special casesexist, collimated and isotropic light, in which simple relationships ex-
ist between actinic flux and irradiance (Madronich, 1987). These two limiting cases often
can be used to approximate atmospheric situations. Collimated light can be considered to
be parallel, having originated from a very small solid angle Ll(JJ(j.An example is the direct
solar beam, which subtends Ll(JJ(j~ 7 X 10-5 sr at the Earth. Over this small solid angle
the radiance may be taken as constant, while at all other solid angles it equals zero:
=
L«(}"p) Lo = constant over the solid angle Ll(JJ(jcentered about «(}o,CPo).In this case
(3.23) and (3.24) become

10 = Lo~~ (3.25)
Eo= Locas(Jo~~ (3.26)

Thus, if Lois the extraterrestrial solar radiance, Eo is the solar irradiance at the top of the at-
mosphere.
The other special case is that of isotropic radiation, L«(J,4» = Ll = constant. In this
case

I = 21TLI (3.27)
E = 1TL. (3.28)

Equation(3.28)is identicalto (3.3).

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 ACTINICFLUX 139

TABLE 3.2 Relation Betweenthe Slant Path Optical

Depth m and sec 80for a Standard Rayleigh Atmosphere

SOUIre: Kasten and Young (1989).

If Foo(A)is the spectralradiantflux densityat the top of the atmosphere(TOA), that at

groundlevel on a planeperpendicularto the solarbeamcanbe determinedfrom an exten-
sion 0(3.11),

F(A) = Foo(A)exp[-m8(A)] (3.37)

where 8(A) is the total atmospheric optical depth at wavelength A, and m is the ratio be-
tween the slant path optical depth for the actual solar zenith angle (Joand the overhead Sun
optical depth (Figure 3.8). When the Sun is directly overhead «(Jo= 0°), m = 1.0andat-
mospheric attenuation is at its minimum. As the Sun approaches the horizon, (Joincreases
toward 90°, m increases and the attenuation of sunlight increases as a result of the increased
pathlength. When the sphericity of the Earth can be neglected,

m= - 1
= secf}o (3.38)
coseo
This relation holds for eo less than about 75°. For larger values of eo, m has to be com-
puted, taking into account the path through the spherical atmospheric layers, the vertical
profile of absorbing and scattering species, and the curvature of the optical rays as a result
of refraction. Values of m are given in Table 3.2 for the molecular atmosphere, that is, the
Rayleigh scattering optical depth!

2The TOA radiative flux can be estimated by measuring E()..) on a surface at ground level for various solar zenith
angles (Jo and plotting In E()..) versus m and extrapolating to m = O. The slope of the best-fit straight line is 8()..)

This method of calculating E-C)..) is called the Bouguer-Langley method. Integrating E_()..) over all wavelengths
producesthe solarconstantSo'
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 ATMOSPHERICPHOTOCHEMISTRY 141

of radiation can only occur if an upper energy level of the molecule exists that is separated
from the lower level by an energy equal to that of the incident photon. Small molecules
generally exhibit intense electronic absorption at wavelengths shorter than do larger mol-
ecules. For example, N2 and H2 absorb significantly at wavelengths less than 100 nm, while
O2 absorbs strongly for A < 200 nm, H2O for A < 180 nm, and CO2 for A < 165 nm.
As radiation penetrates deeper into the atmosphere the shorter wavelengths are progres-
sively removed (recall Figure 1.10; also Figure 3.3). Photochemistry in the troposphere is
confined to molecules that absorb radiation of wavelengths exceeding about 290 nm.
The primary step of a photochemical reaction may be written

A+hv~A*

where A * is an electronically excited state of the molecule A. The excited molecule A * may
subsequently partake in:
I
Dissociation A*--+-B1 + B2
2
Direct Reaction A* + B--+-CI + C2
3
Fluorescence A*--+-A+hv
4
Collisional deactivation A* +M--+-A+M
5
Ionization A*--+-A+ +e
The quantumyield for a specificprocessinvolving A * is definedasthe ratio of the num-
ber of molecules of A * undergoing that process to the number of photons absorbed. Since
the total number of A * molecules formed equals the number of photons absorbed, the
quantum yield cf>ifor a specific process i, say, dissociation, is just the fraction of the A *
molecules that participate in path i. The sum of the quantum yields for all possible
processesmust equal 1.
The rate of formation of A * is equal to the rate of photon absorption and is written4

d[A *] = ;A [A]
(3.41)
dt

where jA, having units S-I, is the first-order rate constantfor photolysisor the so-called
specificabsorptionrate; jA is normally takento be independentof [A]. The rateof forma-
tion of B 1 in step I is

~ =cf>tjA [A] (3.42)

dt

where cf>lis the quantum yield of step 1.

Photodissociation of a molecule can occur when the energy of the incoming photon ex-
ceeds the binding energy of the particular chemical bond. Thus the excited species A * can
lie energetically above the dissociation threshold of the molecule. One or more of the prod-

'In writing chemical reaction rate equations we will generally use [A] to denote the concentration of species A,
r..thpr th.." r.
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 ATMOSPHERICPHOTOCHEMISTRY 143

where the overbar denotes an average over a wavelength interval ~>"i centered at >"i.The
width of the wavelength intervals ~>"i is usually dictated by the available resolution for the
actinic flux /(>"). A typical size of ~>"i is 5 nm from 290 nm to over 400 nm, and 10 nm be-
yond 400 nm.5 Values of (1(>..)and 4>(>")may not be available on precisely the same inter-
vals as for /(>..),so some interpolation may be necessary.
Table 3.3 summarizes important light-absorbing molecules in atmospheric chemistry.
Photodissociation of molecular oxygen is key to stratospheric chemistry and will be ad-

TABLE 3.3 SomePhotochemicalReactionsof Importance in Atmospheric Chemistry"

Reaction Comments
O2 +hv ~O + O('D) > 50km Photodissociationof molecularoxygenresultspri-
~O+O marily from absorptionof solar radiationin the
200-220 nm wavelengthregion.The 185-200nm
region, the O2Schumann-Rungebandspectral
range,is also importantsincesolarradiationpene-
tratesefficiently into the stratosphereat those
wavelengths.Recommendedabsorptioncrosssec-
tions are given by DeMoreet al. (1994).
I
03 + hV--02 + 0 03 absorptioncrosssectionsare given in WMO
2 ReportNo. 16 (1986) and DeMoreet al. (1994).
-- O2+ 0(10)
DeMore et al. (1994) presenta polynomialex-
pressionfor the quantumyield forO(ID) produc-
tion, cP(OID),as a function of Ii and T in the range
305-320 nm. The upperlimiting value of cP(OID)
is takenas 0.95 at 305 nm. Discrepanciesexist be-
tweenpublishedO(ID) quantumyields, which can
be separated into two groups: those that show cf> to
drop to zero at about315 nm (DeMoreet al.,
1994)andthosethat exhibit a "tail" extendingbe-
yond 320 nm (Michelsenet al., 1994).In evaluat-
ing ambientdataagainstboth groupsof quantum
yields, Hofzumahauset al. (1995) found that the
cf> dataexhibiting a tail above315 nm betterrepre-

sent observed data. As noted in the text, the impli-

cation of this finding is that solar photolysis of 03
at wavelengths longer than 310 nm contributes
significantly more to tropospheric O(ID) forma-
tion than that based on the recommended correla-
tion of DeMore et al. (1994).

h = 10-3 S-I at 40 kID

h = 10-5s-t at 10 kID

continued

SMadronich and Weller (1990) calculated tropospheric photolysis rate constants for N02, 03, HONO, HCHO, and
CH3CHO using high spectral resolution (~A = 0.1 nm) and compared these to values calculated with ~A = I,
2,4,6,8, and 10 nm. Depending on the molecule, substantial errors were found to be introduced with the coarser
resolution calculations.
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TABLE 3.3 (Continued)
Reaction Comments
I
HCHO + hv--+- H + HCO Formaldehydephotolysisis a significantsourceof
2 free radicalsin the troposphere.Absorptioncross
--+- H, + CO sectionsfor HCHO aregiven by DeMore et al.
(1994). DeMore et al. (1994) give quantumyields,
cf>1 andcf>20from301to 356nm.Channellpre-
dominatesat shorterwavelengthsand channel2 at
longer wavelengths.
CH3OOH+ hv--products Absorptioncrosssectionsfor CH3OOHfrom 210 to
360 nm aregiven by DeMore et al. (1994).
Cl2+ hv~CI + CI Absorption cross sections for Clz from 260 to
470 nm are given by DeMore et al. (1994).
ClOG + hv-+CIO + 0 Absorption cross sections for ciao from 220 to
280 nm aregiven by DeMore et aI. (1994).
OCIO + hv--'O + CIO Absorption cross sections for OCIO from 272 to
475 nm aregiven by DeMore et al. (1994).
HOCI + hv OH + CI Absorptioncrosssectionsfor HOCI from 200 to 380
nm are given by DeMore et aI. (1994).
1
CIONO2 + hv-+CI +NO3 Absorptioncrosssectionsfor CIONOzfrom 196to
2 414 nm are given by DeMoreet aI. (1994).The
-+CIO + NO2 preferred yieldvaIuesarecf>1 =
quantum
0.6(). < 308nm), cf>.= 1.0(). > 364nm),
and cf>z= I - cf>1'

CCl3F + hv--+products Absorptioncrosssectionsfor CCI3Ffrom 170to 260

nm are given by DeMore et al. (1994).
CCl2F2
+ hjl~products Absorptioncrosssectionsfor CClzFzfrom 170to
240 nm aregiven by DeMore et aI. (1994).
OCS + hv~CO + S Absorptioncrosssectionsfor OCS from 186to 296
nm are given by DeMore et al. (1994).The rec-
ommendedquantumyield for photodissociation
is 0.72.
I
CH3CHO+ hv--+CH4 + CO Absorptioncrosssectionsfor acetaldehydehave
2 beenmeasuredby Martinez et al. (1992)at 300 :t
--+CH3 + HCO 2 K over the wavelengthregion 200-366 nm.
Recommended quantumyields for channelsI and
2 havebeentabulatedby Atkinson et al. (1992).
CH3C(O)CH3
+ hv-CH3 + CH3CO Absorptioncrosssectionsandquantumyields for
acetonehavebeensummarizedby Atkinson et al.
(1992).An averagephotodissociationquantum
yield for CH3COformation is about0.33 over the
wavelengthregion 280-330 nm.
"Many of the rateconstantsfor reactionsimportantin atmosphericchemistryaresurveyedperiodicallyby a group
organized through the Jet Propulsion Laboratory (JPL), Pasadena, CA. The latest report is that of De More et aI.
(1997) Evaluation No. 12, JPL Publication 97-4. Recommended values of rate constants, absorption cross sec-
tions, and quantum yields appear in these reports.

145
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 ATMOSPHERICPHOTOCHEMISTRY 147

Photolysis Wavelength, nm
320 300 280 260 240
I ' I-' I.' I ' I '
--
-0 1.0 """"""",.c',.""".'...' '
& -~
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Photolysis Energy, cm-l

FIGURE 3.10 Primaryquantumyield for 0(10) formationfrom 03 photolysisat 298 K. Summary
of datapresentedby Michelsenet al. (1994).
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 ATMOSPHERICPHOTOCHEMISTRY 149

IL, nm
FIGURE 3.12 Primaryquantumyield for 0 formationfrom NO2photolysis,ascorrelatedby
Demerjian
et al. (1980).

wavelengths, there is insufficient energy to promote bond cleavage. The point at which dis-
sociation fails to occur is not sharp becausethe individual molecules of NO2 do not possess
a precise amount of ground-state energy prior to absorption. The gradual transition area
(370 to 420 nm) corresponds to a variation in ground-state energy of about 40 kJ mol-I.
This transition curve can be shifted slightly to longer wavelengths by increasing the tem-
perature and therefore increasing the ground-state energy of the system. Table 3.5 gives
tabulated values of the NO2 absorption cross section and quantum yield at 273 and 298 K,
and Table 3.6 illustrates the calculation of the photolysis rate jN02 for noon, July 1, at
40oN.

Example 3.2 Atmospheric Heating Rates: The Chapman Function The natureof
the attenuationthat occursasradiationpenetratesthe atmospherecan be seenby consider-
ing the Beer-Lambertlaw of light absorptionfor a singleabsorbingcomponent,

dF(A) = -a(A)NF(A) dx (3.47)

where a(A) is the absorptioncross section(cm2 molecule-'), N is the concentrationof

the species(moleculescm- 3), F( A) is the spectralradiant flux density at wavelengthA
(W m-2 nm-I), and dx is an incrementof optical path. If the absorbingspeciesis uni-
formly mixed in the atmosphere,that is, it has a uniform mixing ratio, its concentration
can be written as

N = Nt~ (3.48)
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 ATMOSPHERICPHOTOCHEMISTRY 151

TABLE 3.6 Calculation of the Photolysis Rate of NO2 at Ground Level, July 1,
Noon, 40° N, 298 K

3.14 X 1012 1.22 0.9976

3.35 X 1013 1.43 0.9966
1.24 X 1014 1.74 0.9954
2.87 X 1014 2.02 0.9944
4.02 X 1014 2.33 0.9934
5.08 X 1014 2.65 0.9924
7.34 X 1014 2.97 0.9914
7.79 X 1014 3.28 0.9904
7.72 X 1014 3.61 0.9894
8.33 X 1014 3.91 0.9884
8.32 X 1014 4.18 0.9874
9.45 X 1014 4.51 0.9864
8.71 X 1014 4.75 0.9848
9.65 X 1014 5.00 0.9834
1.19 X 1015 5.23 0.9818
1.07 X 1015 5.41 0.9798
1.20 X 1015 5.57 0.9762
9.91 X 1014 5.69 0.9711
1.09 X 1015 5.84 0.9636
1.13 X 1015 5.86 0.9360
1.36 X 1015 5.93 0.7850
1.64 X 1015 5.86 0.4925
1.84 X 1015 5.89 0.2258
1.94 X 1015 5.78 0.0914
1.97 X 1015 5.73 0.0354
9.69 X 1014 5.78 0.0188
Total jNO2 = 8.14 X 10-3 S-l
jNO2 = 0.488min-1
a Actinic flux from Finlayson-Pitts and Pitts (1986).
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 CHEMICALKINETICS 153

where Nj is the number concentration of species i (cm-3), (8kT /;rmij)1/2 is the root-
mean-square relative speed of the i and j molecules, k is the Boltzmann constant,
mij = mimj/(mi + mj) is the reducedmass,and ;rUi} is the so-calledcollision crosssec-
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in a gas are close enough to interact is brief, on the order of 10-12 to 10-13 s. At ambient
temperature and pressure the mean time between molecular collisions can be shown from
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time between collisions.
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ergy per mole, and we use exp( -E/ RT), where R is the universal gas constant. The rate
of reaction is expressed in a form that accounts for both the frequency of collisions and the
fraction that exceed the required energy,

(3.54)

The preexponentialfactor A(T) may dependon temperaturesincethe translationalkinetic

energyand internal degreesof freedomof the moleculesinfluencethe probability of reac-
tion in any collision event.
The rate of reactionis usually written as r = kcjcj, wherethe parameterk is calledthe
rate constant,6

k = A(T) exp( - E' (3.55)

RT

If A(T) is independent of T, we have the Arrhenius form, k =A exp( - E / RT). The max-
imum possible value of the rate constant of a bimolecular reaction is achieved if every mol-
ecular collision between molecules of i and j results in reaction. This is called the
gas-kinetic collision rate, and the corresponding value of the second-order rate constant k
at room temperature is about 2 X 10-10 cm3 molecule S-I. Most reactions have rate con-
stants less than this. First, the activation energy E must be overcome for the reaction to pro-
ceed. Second, molecules that are geometrically complex may have to be aligned properly
at the point of collision for reaction to take place and perfect alignment is not achieved in
every collision.
Consider the potential energy surface for the bimolecular reaction (most elementary re-
actions can be considered to be reversible)

f
A+BC~AB +C
b

~e rate constant k is not to be confused with the Boltzmann constant. The latter will always appear as a product
with T in this context.
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 CHEMICAL KINETICS 155

moleculedenotedby A *, followed by decompositionof A * to give B + C,

A*~B + c
Note that A * may return to A by collision and transfer of its excess energy to an M. The rate
equationsfor this mechanismare

d[A]
= -k(f[A][M] + k1b[A*][M]
dt

The reactive intennediate in this mechanism is A *. The PSSA states that the rate of gener-
ation of A * is equal to its rate of disappearance; physically, what this means is that A * is so
reactive that, as soon as an A * molecule is fonned, it reacts by one of its two paths. Thus
the PSSA gives

kIf [A] [M] - k1b[A*][M] - k2[A*] = 0 (3.59)

From this we find the concentrationof A * in terms of the concentrationsof the stable
moleculesA and M,

[A*] = k1f[A][M]
k1b[M] + k2

This expressioncan be usedin (3.57) to give

d[A] -- - klfk2[M][A]
k1b[M]+ k2 (3.61)
dt

We see that the single overall reaction A -+ B + C with a rate given by (3.61) depends
on the concentration of M. If the background species M is in such excess that its concen-
tration is effectively constant, the overall rate can be expressed as d[A]/dt = -k[A],
where k = k1fkz[M]/(k1b[M] + kz) is a constant. If k1b[M] »kz then d[A]/dt =
-k[A], with k = k1fkz/k1b. On the other hand, if k1b[M] «kz, then d[A]/dt =
-k]f[M][A], and the rate of the reaction depends on the concentration of M.
One comment is in order. The PSSA is based on the presumption that the rates of for-
mation and disappearanceof a reactive intermediate are equal. A consequenceof this state-
ment is that d[A*]/dt = 0 from (3.58). This should not, however, be interpreted to mean
that [A*] does not change with time. [A*] is at steady state with respect to [A] and [M].
We can, in fact, compute d[A*]/dt. It is

d[A*] -- ~ k)f[A][M]
dt k)b[M] + k2 (3.62)
dt
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 :HEMICAL KINETICS 1-"7

The time behaviorof 0 following irradiation beginningat t 0 is

Rl
[0] [Mj (1 exp(-k3[OZ] [M]t)) (3.64)
k3[O2]

At 80 km, T = 200 K, at which k3 = 1.4 X 10-33cm6molecule-2S-I. The exponential

term in (3.64) is <0.01 for t ~ 1.8 X 105s (50 h). Thus the time neededfor 0 to establish
a steady-stateconcentrationis much longer than that over which the solarintensity varies,
and 0 is neverin steadystateat this altitude in the atmosphere.The reasonwhy, at this al-
titude, 0(10) achievesa steadystateand0 doesnot, is basedon the relativeratesof the re-
moval reactions.That for 0('0) is sufficientlyfast; that for 0 is too slow to "keepup with"
the formation step.In the lower regionsof the atmosphere,wherethe pressureis large,and
hencethe concentrationof third bodies, M, is large, removal reactionsfor both 0 and
0(10) are, under all conditions,sufficiently fast that steadystatesare rapidly established
for both species.

3.5.2 PressureDependenceof Reactions

Certain reactionshave an order that is variable with pressure;they are third order at low
pressureand secondorder at high pressure.Consider,for example,the combinationof two
oxygenatoms(0(3p) in the triplet- P ground state,which we will denotesimply by 0) to
form O2,Upon collision the newly formed O2moleculepossesses the combinationenergy
of 0 + O. Unlesssomeenergyis removedwithin the time of one vibrational period, the
freshly formed O2 will decomposeback to 0 + O. The excessenergyis removedby the
third body,M. The overall reactionis written as

O+O+M-+O'J+M

But the elementarystepsare

0+0 ot2

+O,+M
wherethe dagger-denotes
vibrational excitation.The rateof formation of a productAB in
the generalsystem

A+B ABt

ABO M +AB+M

d[AB] kaks[A][B][M]
3.65)
dt ks[M] + kr

If the newly formed moleculeis larger than diatomic, there are severalvibrational modes
into which the bond combinationenergycan be converted.In sucha case,the lifetime of
the newly formed moleculecan extendover severalvibrational neriodsheforethe critical
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 CHEMICAL KINETICS 159

Actual experimental data on the pressure variation of the pseudo-second-order rate con-
stant k do not conform with (3.71). The reason is that the elementary rate constants ka, kr,
and k.,should have been defined for each individual quantized vibrational level of ABt, and
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convert in the newly formed molecule. A widely used modification of the treatment of pres-
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(3.71) is multiplied by a broadening factor F that is itself a function of ko/ koo'

(3.72)

Third-order reactionsoften exhibit decreasingrate with increasingtemperature.The

higher the temperature,the larger the thermalkinetic energypossessed by the reactantsA
and B, andthe largerthe internal vibrationalenergystoredin theABt molecule.The larger
this energy,the higher the chanceof recombinationand the largerthe value of kr. The rate
constantskaand ksdo not dependstrongly on temperature,so in the low-pressureregime
sincekr increasesas T increases,the overall rate constantdecreases.
This temperaturede-
pendenceof kois frequentlyrepresentedempirically by a factor Tn in the overall ratecon-
stant(seeAppendix B).
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 PROBLEMS 161

Hofzumahaus,A., Kraus, A., and Milller, M. (1995) Comparisonof troposphericphotolysis fre-

quency data J(O'D) measuredsimultaneouslyby chemical actinometryand spectroradiometry:
test of laboratoryO(ID) quantumyield data,in TroposphericOxidation Mechanisms,edited by
K. H. Becker.EuropeanCommission,ReportEUR 16171EN,Luxembourg,pp. 71-76.
Kasten,F., andYoung,A. T. (1989)Revisedoptical air masstablesandapproximationformula,Appl.
Opt. 28,4735-4738.
Lenoble,J. (1993)AtmosphericRadiativeTransfer:A. DeepakPublishing,Hampton,VA.
Liou, K. N. (1992) Radiation and Cloud Processesin the Atmosphere.Oxford University Press,
Oxford, UK.
Madronich, S. (1987) Photodissociationin the atmosphereI. Actinic flux and the effectsof ground
reflectionsand clouds,J. Geophys.Res.,92,9740-9752.
Madronjch, S., and Weller, G. (1990) Numerical integrationerrors in calculatedtroposphericpho-
todissociationrate coefficients,J. Atmos.Chem.,10, 283-300.
Martinez, R. D., Buitrago,A. A., Howell, N. W., Hearn,C. H., andJoens,J. A. (1992)The nearUV
absorption-spectra of severalaliphatic aldehydesand ketones,Atmos.Environ., 26, 785-792.
Merienne,M. F., Jenouvrier,A., andCoquart,B. (1995)The N02 absorptionspectrum.I. Absorption
cross-sections at ambienttemperaturesin the 300-500 nm region,J. Atmos.Chem.,20, 281-297.
Michelsen,H. A., Salawitch,R. J., Wennberg,P.O., andAnderson,J. G. (1994)ProductionofO(ID)
from photolysisof 03, Geophys.Res.Left., 21,2227-2230.
Troe, J. (1983) Specific rate constantsk(E, 1) for unimolecularbond fissions,J. Chem.Phys.,79,
6017-6029.
Wayne,R. P.(1991) Chemistryof Atmospheres,2nd ed. Oxford University Press,Oxford, UK.
World Meteorological Organization (WMO) (1986) Atmospheric Ozone 1985. Global Ozone
ResearchandMonitoring Project,ReportNo. 16,Geneva.

PROBLEMS
3.1B Considerthe following reactionsystem

A~B
B+M~C
AssumeM is presentin great excess,so that [M] ~ constant.The concentrationsof
B and C arezero at t = O.
8. Derive analyticalexpressionsfor the exactdynamicbehaviorof this systemover
time. Show mathematicallyunder what conditions the pseudo-steady-state ap-
proximation (PSSA)can be madefor [B].
b. Use the PSSAto derive a simpler setof equationsfor the concentrationsof A, B,
andC.
3.28 The most importantoxidizing speciesfor troposphericcompoundsis usuallythe hy-
droxyl (OH) radical. A standard way of determining the OH rate constant of a com-
pound is to measure its decay in a reactor in the presence of OH relative to the decay
of a second compound, the OH rate constant of which is known. Consider two com-
pounds A and B, A being the one for which the OH rate constant is to be determined
and B the reference compound for which its OH rate constant is known. Show that the
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 BASIC PHOTOCHEMICAL CYCLE OF N02, NO, AND 0, 235

5.1 BASIC PHOTOCHEMICAL CYCLE OF N02, NO, AND 03

When NO and NOz are presentin sunlight,ozoneformation occursas a result of the pho-
tolysis of NOz at wavelengths< 424 nm,

NO2+hv ~ NO+O (5.1)

O+O2+M~O3+M (5.2)

whereM representsN2 or O2or anotherthird moleculethat absorbsthe excessvibrational

energyand therebystabilizesthe 03 moleculeformed.Thereare no significantsourcesof
ozonein the atmosphereother than reaction5.2. Once formed, 03 reactswith NO to re-
generateN02,
03 + NO -- N02 + O2
Let us consider for a moment the dynamics of a system in which only these three reac-
tions are taking place. Let us assume that known initial concentrations of NO and NO2,
[NO]o and [NO2]o, in air are placed in a reactor of constant volume at constant temperature
and irradiated. The rate of change of the concentration of NO2 after the irradiation begins
is given by

d[NO2] - j5.1[NO2] + k5.3[O3][NO]

dt

Treating [02] as constant,there are four speciesin the system:N02, NO, 0, and 03, We
could write the dynamicequationsfor NO, 0, and03 just aswe havedonefor N02. For ex-
ample,the equationfor [0] is

d[O] = j5.I[NO2] - k5.2[O][O2][M]

dt

However,if we were to evaluatethe right-handside numerically we would find that it is

very closeto zero.Physically,this meansthat the oxygenatom is so reactivethat it disap-
pearsby reaction5.2 virtually asfast asit is formedby reaction5.1. In dealingwith highly
reactivespeciessuchasthe oxygenatom,it is customary,as notedin Chapter3, to invoke
the pseudo-steady-state approximation(PSSA)and therebyassumethat the rate of forma-
tion is exactly equalto the rateof disappearance,for example,

jS.1 [NO2] = kS.2[O][O2][M]

The steady-stateoxygenatomconcentrationin this systemis then given by

jS.1 [NOz]
[0]88=
ks.z[Oz][M]
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~
 BASIC PHOTOCHEMICAL CYCLE OF N02. NO. AND 0, 237

ing ratio of N02 with [03]0 = [NO]o = 0:

100
1000

If, on the other hand, [NOz]o = [03]0 = 0, then [03] = O. This is clear since with no N02
there is no means to produce atomic oxygen and therefore ozone. Thus the maximum
steady-state ozone concentration would be achieved with an initial charge of pure NOz.
The mixing ratios of ozone attained in urban and regional atmospheres are often greater
than those in the sample calculation. Since most of the NOx emitted is in the form of NO
and not NOz, the concentration of ozone reached, if governed solely by reactions 5.1 to 5.3,
would be far too low to account for the actual observed concentrations. It must be con-
cluded that reactions other than 5.1 to 5.3 are important in tropospheric air in which rela-
tively high ozone concentrations occur. Shortly we will see what those reactions are.

Example 5.1 Measurement of the Photolysis Rate of NOz The photolysis of NOz is
a key atmospheric reaction. Its photodissociation rate can be calculated if the actinic flux
I (A)-is known. However, such measurementsrequire specialized apparatus that is complex
and expensive. A method that allows one to determine the NOz photodissociation rate, j5.1,
directly circumvents the need for elaborate measurementsof the radiation intensity. By ex-
posing a mixture of NOz and Nz to sunlight one can determine the value of j5.1 by com-
paring the measured NOz decay as a function of time with that obtained by integration of
the rate equations. To integrate the rate equations it is necessary to assume a value for j5.1.
The desired value of j51 is that which produces agreement between the observed and pre-
dicted NOz decay.
In the previous analysis we considered only reactions 5.1 to 5.3. There are several other
reactions that occur in the NOx-Nz system that should be included for a more complete
analysis. These are'

0 + N02 -+ NO + 02 (5. 11)

0+N02 +M -+ N03 +M (5. 12)
NO+ N03 -+ 2N02 (5. 13)
0 + NO + M -+ N02 + M (5. 14)
N02 + N03 + M -+ N20S +M (5. 15)
N20S+ M -+ N02 + N03 + M (5. 16)

I Actually in the presence of sunlight NO3 photolyzes very rapidly (see Section 5.6) so that we do not expect day-
light NO, levels to be appreciable. NO, is added to the mechanism at this point largely for completeness.
31I3HdSOdO~.L3H.L dO J..~SIW3HJ 8fZ
 ATMOSPHERIC CHEMISTRY OF CARBON MONOXIDE AND NO, 239

6.0. I I I I I I

5.0
4. ~2 = 1 atm
6 3.0
.~ k I = 0.14min-
~
OJ) 2.0 . .
=
><
. . .
~
kl = 0.32 min-
N
0
Z 1.0 0
0,8 Experimental data 0 0
~ Integrationof mechanism 0
0
0.61 I I I I I I ~
01 23 4 56 7
Irradiation Time, min
FIGURE 5.1 NO2mixing ratio asa function of time in a systeminitially comprising5 ppm NO2in
N2. Experimentaldata and the predictionsof the mechanismin the text are shownfor two light in-
tensities(Holmeset al., 1973).

5.2 ATMOSPHERIC CHEMISTRY OF CARBON MONOXIDE AND NO,

We noted that in order to explain frequently observed atmospheric ozone levels it is neces-
sary that reactions other than 5.1 to 5.3 must be invoked. For these we must turn to the next
major class of tropospheric compounds, carbon-containing species. In some respects the
simplest atmospheric carbon-containing species is CO. Carbon monoxide does not, how-
ever, react readily with any of the species present in the NOx-air system.
We already know from Section 4.2 that ozone photolysis to produce both ground-state
(0) and excited singlet (O(ID)) oxygen atoms is important in both the stratosphere and tro-
posphere,
03 +hv -+- 0+02 (5.21a)
-+- 0(10) + 02 (5.21b)

The ground-state0 atom combinesrapidly with O2by reaction5.2 to reform 03, so reac-
tion 5.21afollowed by reaction5.2 has no net chemicaleffect. However,when 0('0) is
produced,sincethe 0('0) ~ 0 transition is forbidden,it must react with anotheratmos-

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 ATMOSPHERIC CHEMISTRY OF CARBON MONOXIDE AND NO, 241

The atmosphericoxidation of CO can be summarizedasfollows:

~
CO+OH. ~ CO2+ HO2'
HO2.+NO ~ NO2+0H.
NO2+hv ~ NO+O

O+O2+M~O3+M
Net co + 202 + hv--+ CO2+ 0,
Note that neitherOH nor H02 is consumedin this reactioncycle, which can be viewed as
a catalytic oxidation of CO to CO2-Net formation of 03 occursbecausethe conversionof
NO to N02 is accomplishedby the H02 radicalratherthanby 03 itself. This setof reactions
can occur repeatedlyuntil one of the moleculesis removedin a terminationreaction.
Terminationof the chain can occur when OH and N02 reactto form nitric acid,

OH. +NO2+M -+ HNO3 +M (5.26)

Again, we have already encountered this reaction in the stratosphere. (Termination can also
occur when HO2 reacts with itself, but at this point we assumethat NOx concentrations are
sufficiently large that the self-reaction of HO2 is not favored.)
In analyzing this mechanism, the PSSA, as applied to this system, can be represented in
terms of the rates of the nine reactions as2'

[0]88
Rs.I - RS.2+ RS.22 0 =
jS.1[N02] - kS.2[0] [02] [M] + kS.22
[M] [0(10)] = 0

RS.21b- RS.22+ RS.23= 0

[O(IO)]SS
kS.21b
[03] - kS.22[M][0(10)] - kS.23
[H2O] [0(10)] = 0

[OH]ss
2Rs.23- RS.24
+ RS.2S =0
- RS.26
RS.24 - Rs.2s= 0
[HO2]ss
2kS.23[H2O] [O( 1D)] - kS.26[OH] [N02] = 0

RS.2 - RS.3- RS.21= 0

[03]88
kS.2[0] [02] [M] - kS.3[03] [NO] - kS.21b
[03] = {\

2In writing rate equations for reactions of the type A + B + M ~ AB + M, for example, reaction 5.26, one must
decide whether to express the rate of the reaction as k[A)[B][M] or k[A)[B]. This is simply an issue of notation,
since the value of the rate constant k will depend on the concentration of the third body M through its appropriate
formula, as given in Appendix B. We will often choose not to explicitly indicate [M] in the rate equation for such
three-body reactions, keeping in mind that the value of the rate constant will depend on [M] through its appropri-
ate formula.
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=v
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u!l:l~qo ~M Suo!~Bnb~ ~AOqB ~q~ 3'U!AI0S (.uo!~Bnb~ SS[HOJ ~q~ U! 0 = ~z'~N - Irz'~N
3'u!sn ,(q P~~BU!W!I~ SBM SS[ZOHJ .suMoWlun JnoJ q:I!M suo!1Bnb~ mol ~ABq ~A\
~HHdSOdO}il Hffi dO A~.LSIWHHJ 'Z'n
 ATMOSPHERIC CHEMISTRY OF CARBON MONOXIDE AND NO. 243

The qualitative featuresof the set of CO/NOxreactionscan be describedas follows.

PhotolysisofN02 producesNO ando. The 0 atomimmediatelycombineswith an oxygen
moleculeto form 03, Ozonethen reactsmainly with NO to regenerateN02oThe cycle of
thesethreereactionscan be representedconciselyas (whereO2is not indicated)

hv
NO2 ~ NO+O3

The characteristictime of this cycle is usually shortenoughrelativeto the competingreac-

tions so that a steadystateis achievedquickly. The concentrationof 03 at sucha steady-
statecondition is given by the photostation~ staterelation (5.8). If we now considerthe
reactionsresulting when CO is present,we seethat the simple reversiblecycle aboveis
modified to be3
hv
NOz~ NO+03
r HOz I

The HO2radical that convertsNO back to NO2is convertedin the processto OH, which
then is availableto react with anothermoleculeof CO. Thus we obtain two interwoven
cycles,a "fast" cycle and a "slow" cycle,

hv
NOz ~ NO + 01
.

CO+ qH-E~
.
NO
.
The CO/NOxreaction mechanismis a chain reaction with OH as the chain carrier. The
chain length Lc of sucha reactionis definedas the numberof propagationstepsoccurring
for eachterminationstep,

Lr = RS.2S
= RS.24 kS.Z4[CO]
(5.31)
RS.26 RS.26 kS.z6[NOz]

Since the steady-state 03 concentration achieved in the fast cycle is proportional to the ra-
tio of [N02] to [NO], the effect of the slow CO cycle is to slowly convert NO to N02 and
therefore to increase the steady-state 03 concentration. Thus, because of the rapidity of the
N02/O3 cycle, an independent path that changes the ratio of [N02] to [NO] indirectly con-
trols the ozone concentration. It is common to refer to such oxidation chains that are driven
by sunlight as photooxidations.
The basic reaction mechanism of the CO/NOx system exhibits many of the key features
of those involving much more complex organic molecules. In particular, the role of OH as

-' The presence of water is also necessary to provide a path for formation of hydroxyl radicals after ozone photo]
ysis to give O('D).
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 CHEMISTRY OF THE BACKGROUND TROPOSPHERE 245

The rate equations for the photooxidation of a mixture of NO2, NO, and HCHO are, as a re-
sult,

[HCHO]

The chain length of the HCHO photooxidationis given by

R5.25
Lc=
RS.Z6

2jS.32a + RS.33

RS.z6

1 + kS.33[HCHO]

kS.Z6[NOz]
We seethat Lc is alwaysgreaterthan one as long asHCHO is presentin the system.Each
moleculeof HCHO that photolyzesvia reaction5.32aleadsto the conversionof two mol-
eculesof NO to N02 and at the sametime generatestwo OH radicals.The HCHO-OH
reaction,on the other hand,leadsto one NO to N02 conversionand producesa singleOH
radical.
The reactivity of the systemis controlled by the amountof HCHO. Upon photolysis,
HCHO providestwo H02 radicalson one pathandnoneon the other.Sincethesepathsare
roughly comparablein rate, we can sayapproximatelythat eachHCHO moleculeleadsto
one H02 molecule.(It leadsto exactly one in the OH reaction.)The conversionof NO to
N02 andthe formation of 03 arethereforedriven by HCHO throughits productionof H02.
Thus the theoreticalmaximumamountof 03 that could be producedin this systemis

[03] = [HCHO]o + [N02]o

When all the NOx is converted to HNO3, the system ceasesreacting.

5.4 CHEMISTRY OF THE BACKGROUND TROPOSPHERE

We have begun a systematic development of the chemistry of the troposphere. We began

with carbon monoxide since its atmospheric chemistry is the simplest, while exhibiting
some of the essential elements of hydroxyl radical attack, formation of the hydroperoxyl
radical, and conversion of NO to NO2. We then proceeded to formaldehyde, the atmos-
pheric chemistry of which is slightly more complex than that of carbon monoxide. The next
logical step would be to consider the simplest alkane, methane (CH4), and that is, in fact,
what we will now do. It turns out, moreover, that methane is the principal hydrocarbon
species in the chemistry of the background troposphere. Thus, in studying the atmospheric
chemistry of methane, we are led naturally to the chemistry of the background troposphere.
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 CHEMISTRY OF THE BACKGROUND TROPOSPHERE 247

Methyl peroxynitrate,CH3OONObthermally dissociatesback to the reactantswith a life-

time with respectto thermaldecompositionof 1 secondat room temperatureand atmos-
~

phericpressure,which increasesto ~2 daysfor the temperatureandpressureconditionsin

the upper troposphere(Atkinson et aI., 1989;Atkinson, 1990).Methyl peroxynitratecan
act asa temporaryreservoirof NO2andCH3O2radicalsin the uppertroposphere.
The reactionof CH3O2with the HO2radicaIleadsto the formation of methyl hydroper-
oxide,
CH302' + H02' ~ CH300H + 02 (5.42)

which can photolyzeor reactwith the OH radical

CH300H + hv --+- CH30, + OH. (5.43)

CH300H+ OH, ~ H2O + CH3O2' (5.44a)
~ H2O+ CH200H (5.44b)
-!- fast
HCHO + OH.

wherethe fractional splits indicatedare thoseat 298 K. The lifetime of methyl hydroper-
oxide in the troposphereresultingfrom photolysisandreactionwith the OH radical is cal-
culatedto be - 2 days.Methyl hydroperoxideis thena temporarysink of radicals,with its
wet or dry depositionbeing a troposphericloss processfor radicals.
The only important reactionfor the methoxy radical under troposphericconditionsis
with O2to form formaldehydeandthe H02 radical,

CH30.+ 02 ~ HCHO+ H02' (5.45)

Formaldehydeis a "first-generation"productthat reactsfurther, by photolysisby reac-
tions 5.32aand5.32bandwith the OH radical,reaction5.33.Formaldehydeis the first ma-
jor product of C~ oxidation with a lifetime longer than a few seconds.The lifetimes of
HCHO resulting from photolysisand OH radical reactionare -4 hours and 1.5 days,re-
spectively,leadingto an overall lifetime of -3 hoursfor overheadsunconditions.
Major chain-terminatingstepsin C~ oxidationincludenitric acid andhydrogenperox-
ide formation,4
OH. + N02 + M -+ HN03+ M (5.26)
H02. + H02. -+ H202 + 02 (5.46)
4 The recommendedrateconstantfor reaction5.46 is (Stockwell, 1995):
kS46 = (kc + kp)fw
kc = 2 X 10-13 exp(600/T)
kp = 1.7 X 10-33 [M] exp(IOOO/T)
fw = 1 + 1.4 X 10-21 [H2O] exp(2200/T)

where Tis in K and [M] and [H2O] are in molecules cm-3. kc is the bimolecular term, kp is the pressure-dependent
term, andfw is a water-vapor-dependent factor. Stockwell (1995) has shown that the contribution of the water-de-
pendent term can be very important; at the surface the value of kS46in air saturated with water vapor is over twice
the value of kS46in dry air. Above about 15 km the water-dependent contribution is negligible and above 25 km
the reaction is almost completely bimolecular.
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 CHEMISTRY OF THE BACKGROUND TROPOSPHERE 249

dation and assumingthat the photostationarystateholds at any instant, the local rate of
formation of 03 as a result of the abovecycle is

po] = {kS.2s[HO2]+ kS.4o[CH302]} [NO]

As a result of peroxy radical-NO reactions,the photostationarystaterelation must be

adjustedto (Parrishet al., 1986;Ridley et aI., 1992;Cantrell et aI., 1993)

[NO2]
-- kS.3[O3] + kS.2S[HO2]
+ kS.4o[CH302]
[NO] j5.

Measurements made during the spring of 1988 at Mauna Loa, Hawaii, indicated that per-
oxy radical mixing ratios of 60 ppt or so were required to account for observations of this
ratio (Ridley et al., 1992).
Production of 03 in the CH4 oxidation chain is interrupted if the peroxy radicals H02
and CH3O2react with something other than NO, for example, themselves, N02, or 03 itself,
or if NOx is removed from the active cycle by reaction with OH to form HN03. For the H02
radical, besides reaction 5.46, another important reaction is

H02' + 03 -+- OH. + 202 (5.47)

Reaction 5.46 is the principal gas-phasesource of H2O2in the atmosphere.

5.4.3 Hydrogen Peroxide

Hydrogen peroxide is the dominant oxidant in clouds, fogs, or rain in the atmosphere.
Photochemical activity largely determines the diurnal, seasonal, and latitudinal variations
of the H2O2concentration. H2O21evelshave been found to be higher in the afternoon, dur-
ing the summer, and in the southern latitudes (Sakugawa et al., 1990). The major gas-phase
destruction pathways for H2O2are its reaction with OH and its photolysis,

H202+ OR. ~ H2O+ H02 (5.48)

H202 +hv ~ 2 OR. (5.49)

The destruction of H2O2 in the aqueous phase, mainly by reacting with dissolved S02,
is considered in Chapter 6. Van Valin et al. (1990), Boatman et al. (1990), and Daum et al.
(1990) reported continuous airborne measurements of H2O2 over the northeastern United
States in June 1987. The range of H2O2mixing ratios was < 0.2 to 37 ppb, with an aver-
age of 2 to 4 ppb. H2O2 concentrations are typically low near the surface, rise to a maxi-
mum at the top of the boundary layer, then slowly decrease with height. 'Photochemical
model predictions indicate the H2O2levels depend on whether the atmosphere is in a high
or low NOx regime, according to whether radical production is greater or less than the NOx
emission rate (Kleinman, 1991). In the low NOx regime, more radicals are formed that can
react with NOx, and the "excess" radicals are removed by radical-radical reactions that are
the source of peroxides (e.g., reaction 5.46). In this regime, peroxide formation is nearly
proportional to the difference between radical source strength and NOx emission rate. In the
high NOx regime, peroxide formation is suppressed.
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 THE HYDROXYL RADICAL 251

Because the temperature dependences of these two rate constants are quite close, the at-
mospheric oxidation rate ofCH4 can be scaled to that ofCH3CCI3. An atmospheric CH4 de-
struction rate' of 440 :t 50 Tg yr-1 can be inferred in this way. From the current
atmospheric loading of CH4 of about 4850 Tg, a mean atmospheric lifetime of 11 (:t 10%)
years is derived based solely on OH reaction. When loss in the stratosphere and removal in
soils are also considered, the lifetime shortens to about 10 years.
Only in the past few years have reliable direct measurementsbeen made of lower tropos-
pheric OH radical concentrations (e.g., see, Felton et al., 1990; Eisele and Tanner, 1991;
Hofzumahaus et al., 1991; Comes et al., 1992; Hard et al., 1992; Mount and Eisele, 1992;
Eisele, 1995). These measurement show that, as expected, OH radical concentrations exhibit
a diurnal profile, with daytime maximum concentrations of several 106molecules cm-3.
Ehhalt et al. (1991) have evaluated the extent of agreement between calculated and mea-
sured OH concentrations on May 20, 1983, 0908 to 1130 hours, at Deuselbach, a rural area
in Germany, assuming that OH and HO2 levels were governed by the CH4 oxidation cycle.
Figure 5.3 shows the calculated concentrations and fluxes between species. Since inter-

,,°2
hv
1.5 x 107 HCHO: 0.5 x 106
t
HZ : 0.4 x 106
"-
N2;O2
OCD) °3 : 0.3 x 106
1.9x 10-2 80Z : 0.1 x 106

H;O Ux ~106 ;
1.9x
'/ '.':'::::::::::\

l::)
',".,' 'v-' . ',,'

~ - --,
-'
':""""HO:':'

~
0" () :::::: . . 2:7:
')3.9xl0;~ :-:.:8.2
.. x 10.:
~/ I-. '-.
~. /
"'~ °3: 2.2 x lO~
."'.
o"i NO2 bt OH
" 1.8x106 ~/ 4
A -;S'"
.~')~/ 3.5 x 10
'"104 -~.~
HNO3 .b~
-\\O');
1.5x1011
Kaiiiout I
HeterogeneousRemoval Rainout
1.8x 106 1.3 x 104

~ ~
FIGURE 5.3 Concentrationsand fluxes betweenOH and HO2(Ehhalt et al., 1991).The calcula-
tion simulatesan airmassobservedbetween0908 and 1130hours, May 20, 1983 at Deuselbach,
Germany.Numbersin boxesarecalculatedconcentrations(moleculescm-3); numberson arrowsare
conversionratesofOH and HO" (moleculescm-3s-').
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 THE NITRATE RADICAL 253

5.6 THE NITRATE RADICAL

We recall from Chapter 4 that the gaseous NO3 radical is formed via the reactions (see
Atkinson, 1991, Wayne et al., 1991, and Platt and Heintz, 1994, for comprehensive reviews
of the nitrate radical),

N02 + 03 -+ N03 + 02 (5.52)

M
N02 + N03 ~ N20S (5.15,5.16)

with N2Os being in a relatively rapid (characteristic time to reach equilibrium -1 minute at
298 K) equilibrium with N02 and the N03 radical. Nitrate radicals were first detected in the
troposphere in 1980. N03 is a strong oxidizing agent and reacts with a number of other at-
mospheric species. The prerequisite for N03 radical production is the simultaneous pres-
ence ofN02 and 03 in the same airmass, as reaction 5.52 is the only primary source ofN03
in the troposphere. The equilibrium with N2Os,reactions 5.15 and 5.16, is an important fea-
ture ofN03 chemistry.
During daytime N03 radicals photolyze rapidly via two paths (see Table 3.3),

N03 + hV(A < 700 om) -+ NO + O2 (5.53a)

N03 + hV(A < 580 om) -+ N02 + 0 (5.53b)

with a noontimelifetime of -5 seconds,andreactwith NO,

NO3+ NO ~ 2NO2 (5.13)

sufficiently rapidly that NO andN03 cannotcoexistat mixing ratiosof a few partsper tril-
lion (ppt) or higher. For typical daytime conditionsof [N02] = 40 ppb, [03] = 50 ppb,
and [NO] = 40 ppb, the maximumN03 mixing ratio will be 0.6 ppt. At nighttime,how-
ever,when NO concentrationsdrop nearzero,dueto reactionwith 03, the N03 mixing ra-
tio can reach 100 ppt. Under conditionstypical of rural areasin industrializedcountries
(N02 mixing ratio of -1 ppb), N03 andN2Osconcentrationsareroughly the sameorderof
magnitude.Whereashomogeneousreactionsof N2Oswith water vapor and other trace
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 THE OZONE BUDGET OF THE TROPOSPHERE AND THE ROLE OF NO. 255

]
...r
fo
Q)
x

Latitude
FIGURE 5.4 Meridianal crosssectionof 03 (in ppb) obtainedduring March and April 1987via
ozonesondes releasedfrom the researchvesselPolarsternon a northerncruisein theAtlantic, mostly
along 30° W. Approximate location of the tropopauseis shown with crosses.(Figure presentedin
Monthly Update,Departmentof EnergyAtmosphericChemistry Program,originally presentedby
Smit et al., in Ozonein the Atmosphere,edited by R. D. Bojkov and P. Fabian,DeepakPublishing,
1989.)

5.7.1 Tropospheric Sinks of Ozone

The principal photochemicalsink of 03 in the troposphereis reactions5.21b, 5.22, and
5.23.Becausethis removalpath dependson the concentrationof watervapor,it is mostef-
fective in low latitudesat low altitudes,wherethe radiationis intenseand the humidity is
high. An estimateof the magnitudeof the local rate of 03 destructionby reactions5.21b,
5.22,and5.23 canbe obtainedby assumingthat [O(ID)] is in a pseudo-steady stateasa re-
sult of thesethreereactions.The pseudo-steady-state concentrationof O(ID) is given by

[0(10)]88= j5.2Ib[O3]
ks.zz[M] + kS.Z3[HzO]

Ozonedestructionoccurswheneveran OrO) reactswith H2O,sincethis removesOrO)

from the system;otherwise0(10) is just quenchedback to 0 in reaction5.22, and 0 im-
mediatelyreforms03 by reaction5.2.Thusthe rateof 03 removalby reactions5.2Ib, 5.22,
and 5.23 is

d[O3] = -kS.23[O('D)][H2O]
dt

= k5.Z3 [HZO]j5.Z1b[O3]
k, ""fMl + k, "'tfH,,Ol
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 THE OZONE BUDGET OF THE TROPOSPHERE AND THE ROLE OF NO. 257

The fractional 03 photochemical loss in Figure 5.5 can be converted into absolute 24-
hour averages of the normalized 03 destruction rate (in S-I) by multiplying the fractions in
Figure 5.5 by the 24-hour average of j5.21b. For example, at 10° S at the surface,
j5.21b~ 7 X 10-6 S-l, and a photolysis lifetime of 03 is estimated as about 11 days. In con-
trast, the lifetime of 03 resulting from dry deposition to the surface of the ocean can be es-
timated as about 35 days on the b~sis of assuming a dry deposition velocity of 0.05 cm S-1
(see Chapter 19) (Smit et al., 1989). Since reactions other than photolysis also contribute to
photochemical 03 loss, such as reaction 5.47, one concludes that photochemistry is likely
the major sink for 03 in the boundary layer at 10° S and not dry deposition (Ayers et al.,
1992). In fact, ozone destruction by the photochemical processes 5.21b, 5.22, and 5.23 is
estimated to account for roughly 75% of the tropospheric loss of 03 by gas-phase routes;
the remainder is primarily the result of reaction 5.47. This conclusion is strengthened by
the lack of observed 03 decreaseat night, which would occur if dry deposition to the ocean
were having a noticeable effect on 03, since photochemical destruction occurs only during
daytime and dry deposition operates both day and night. (Over land the 03 dry deposition
velocity may be as much as an order of magnitude larger than that over the ocean, and with
a nighttime boundary layer generally shallower than that over the ocean, dry deposition of
ozone may compete effectively with chemical removal.)

5.7.2 Tropospheric Sourceof Ozone

The principal in situ chemical sourceof ozone in the troposphereis photochemicalpro-
duction through the methaneoxidation chain. The level of NO is critical in this chain in
dictating the fate of the HO2radical. Reaction5.25,

+NO~ NO2+0H. (5.25)

leadsto 03 production;reaction5.47,

+03 ~ OH-+202 (5.47)

destroys ozone. The break-even concentration of NO, below which 03 is destroyed and
above which it is produced, depends on the local 03 concentration. Tropospheric air may
be called NOx rich when NO mixing ratios exceed those of 03 by more than the ratio of the
rate constants of reactions 5.47 and 5.25. The ratio of the rates of these two reactions is

RS.47
= --kS.47[03]
RS.2S kS.2S[NO]

The rate constant ratio, k5.47/k5.25~ 2.5 x 10-4. The 03 mixing ratio near the Earth's sur-
face in the remote continental troposphere is about 20 ppb. Then R5.25> R5.47for NO mix-
ing ratios exceeding about 5 ppt. This amount of NO is roughly equivalent to 15 to 20 ppt
NOx. A competition also exists between NO and the H02 radical for reaction with the
CH3O2 radical, and the preferred route depends on the concentrations of H02 radicals and
NO. The rate constants for the reaction of the CH3O2radicals with NO (reaction 5.40) and
H02 radicals (reaction 5.42) are of comparable magnitude (see Table B.l). Based on ex-
pected H02 radical concentrations in the troposphere, Logan et al. (1981) calculated that
the reaction of the CH3O2radical with NO dominates over that with H02 for NO mixing ra-
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 THE OZONE BUDGET OF THE TROPOSPHERE AND THE ROLE OF NO- 259

-'~
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FIGURE 5.6 Calculated24 hour average03 production and loss rates for the free troposphere
aboveHawaii during the MLOPEX as a function of the NOxmixing ratio (Liu et al., 1992).

of the reduced solar intensity. At 20° N, for example, it is estimated that 03 lifetimes at the
surface are about 5 days in summer and 17 days in winter, whereas at 40° N these increase
to 8 days in summer and 100 days in winter. At 20° N, at 10 kIn altitude, estimated summer
and winter 03 lifetimes are 30 days and 90 days, respectively, increasing by about a factor
of 6 from those at the surface.
The key to understanding background tropospheric ozone is to determine whether a re-
gion is in a local 03-producing or 03-destroying condition. Because of the critical role
played by NOx, assessing the effect of anthropogenic NOx emissions on background tro-
pospheric NOx is one of the major issues in tropospheric chemistry. Increasing NOx weak-
ens the net photochemical sink of 03 in the background troposphere, leading to an overall
increase of 0,.

5.7.3 Fate of NO.,

At first glanceit might appearthat NOx releasedin urban and regional areaswill have a
lifetime too shortto permit its transportto the remotetroposphereto influencebackground
03. For typical OH levels,reaction5.26,

N02 + OH. + M -+ HN03+ M (5.26)

leads to NO2 lifetimes of a day or so, with HNO3 subsequently removed by dry and wet de-
position, typically in about a week. Because NO and NO2 are relatively insoluble in pre-
cipitation, however, they can be vented to the upper troposphere by storms, where reaction
5.26 still occurs but the HNO3 is not subject to dry deposition and generally not to wet de-
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 THE OZONE BUDGET OF THE TROPOSPHERE AND THE ROLE OF NO. 261

moval is indeed occurring, predicted HNO3 concentrations and the HNO3/ NOx ratio can
be reduced to a value close to those measured.
The heterogeneous hydrolysis of N2Os,reaction 5.54, has been suggestedto play an im-
portant role in tropospheric chemistry (Dentener and Crutzen, 1993). Particles on which
HNO3 has formed can be transported to the dry upper troposphere, where it is expected that
most water and HNO3 would evaporate. From the point of view of explaining the reason
for the mismatch in predicted and observed HNO3/ NOx ratios, reaction 5.54 does not help;
if the HNO3 is indeed released the result should be, more or less, equivalent to that if the
original NO2 were simply converted to HNO3 by OH. Understanding the relationship be-
tween HNO3 and NOx in the upper troposphere remains as an outstanding problem in at-
mospheric chemistry.

5.7.4 OzoneBudget of the Troposphere

The global tropospheric balance on ozone includes the following:
Production: transport from stratosphere; in situ chemical production
Loss: dry deposition at Earth's surface; in situ chemical destruction

Transport from the stratosphere and dry deposition rates can be estimated. The estimated
downward flux of 03 from the stratosphere is (3-8) X 1010molecules cm-2 S-I. Loss of 03
by dry deposition on the Earth's surface is estimated at about 8 X 1010molecules cm-2 S-I
(Galbally and Roy, 1980). The principal mechanism for in situ chemical destruction of 03
is photolysis and subsequent reaction of 0(10) with H2O, estimated also to be about 8 X
1010molecules cm-2 S-I (Lelieveld et al., 1993). The most difficult term to estimate, of the
four, is the average rate of in situ chemical production. We know that in situ production of
03 on the global scale is driven by the oxidation of CO and CH4. Thus a good starting point
is to estimate the amount of 03 that can be produced globally from the oxidation of CO and
C~. Average destruction rates of CO and CH4 by OH reaction are 3 X 1011molecules
cm-2 S-I and 1 X lOll molecules cm-2 S-I, respectively (Lelieveld et al., 1993). If all the
CO and CH4 oxidation were to occur in NOx-rich environments, yielding one 03 molecule
per each CO and 2.7 03 molecules for each C~ (this number accounts for oxidation of the
formaldehyde formed as a product of C~ oxidation), the average global production rate6
of 03 would be 3 X 1011+ 2.7 X lOll ~ 6 X 1011molecules cm-2 S-I. This production rate
exceeds substantially the amount of 03 that can be destroyed by reactions 5.21b and 5.23
and that which can be removed by deposition at the Earth's surface. The conclusion one
reaches is that large portions of the troposphere must contain so little NOx that these re-
gions lie below the NO crossover concentration with respect to 03 formation. At present,
the tropospheric 03 budget can be calculated by global chemical models, but the validity of
such calculations must be assessedby careful comparisons with field data that provide all
inportant components of production and loss. Nonetheless, there is little doubt that pro-
duction and loss of tropospheric ozone are dominated by in situ chemistry and not by
downward transport of 03 from the stratosphere.
Manzerall et al. (1996) have quantified the ozone budget over remote high northern lat-
itudes in summer using chemical and meteorological measurements between 0 and 6 kIn

"Globally, the methane oxidation chain has been estimated to result in a net annual loss of about 0.22 molecules
of OH for every CH. molecule destroyed (Tie et aI., 1992). The associated average annual yield of CO from
methane oxidation is about 0.82 molecule of CO per molecule of CH. destroyed. The global methane oxidation
chain is estimated to produce, as a result, about 1.15 molecules of ozone for each molecule of CH. destroyed.
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 THE OZONE BUDGET OF THE TROPOSPHERE AND THE ROLE OF NO, 263

downdraft. Cumulonimbus clouds are classified by their cells, organization, and life cycles.
Ordinary cumulonimbi contain a single cell that has a life cycle of 45 minutes to an hour.
Many thunderstorms are composed of a number of cells, each having lifetimes of 45 to 60
minutes. These multicell storms can last for several hours and vertically redistribute large
quantities of ozone and its precursors. Supercell storms, composed of a single steady cell,
with strong updrafts and downdrafts, can last 2 to 6 hours and inject large quantities of pol-
lutants into the upper troposphere (Dickerson et aI., 1987; Pickering et aI., 1989). Not all
cases of convection cause such transport (e.g., convective clouds above a cold front;
Pickering et al., 1988). Convective redistribution of ozone precursors may lead to an in-
crease in the production rate of ozone averaged through the troposphere (Pickering et aI.,
1990).

Example 5.3 The Troposphere/StratosphereTransition The transitionfrom tropos-

phereto stratosphereis traditionally definedbasedon the reversalof the atmospherictem-
peratureprofile. That transitionis also dramaticallyreflectedin how the concentrationsof
tracespeciesvary with altitude below andabovethe tropopause.Of tracespecies.H02 and
OH exhibit perhapsthe mostprofounddifferencesacrossthe tropopause(Wennberget al.,
1995).In the lower stratosphereH02 andOH participatein HOxCycle 4, which is the pre-
dominant cycle involved in 03 removal in that portion of the stratosphere.We saw in
Chapter4 that in the lower stratospherethe H02/0H ratio is describedby

[HO2] k4.ll [03]

[OH] k4.36[NO] +k4.14 f03]

The presenceof NO short-circuitsHO" Cycle 4 by reconvertingH02 backto OH beforeit

hasa chanceto reactwith 03, This ratio variesfrom about4 to 7 anddecreases as [NO] in-
creases.[OH] itself is essentiaIlyindependentof [NO] and dependsalmostentirely on so-
lar zenith angle.This independence of OH on NO is a resultof the fact that the increaseof
OH that resultsfrom reaction4.36 is offset almostexactly by a decreaseof the ratesof re-
actionsthat generateOH, reactions4.14, 4.40, and4.41.This occursbecausethe HO2that
participatesin reaction4.36 is not otherwiseavailablefor reactions4.14 and4.40.
The behaviorof HO2and OH in the uppertroposphereis dominatedby CO chemistry.
(Becauseof its I to 3 month lifetime, CO is more or less uniformly mixed up to the
tropopause.Above the tropopause,CO faIls off with increasingaltitude. Becauseof the
much slower vertical transportrate in the stratosphere,the rate of the CO-OH reaction
competeswith the rateof vertical mixing.) TroposphericCO oxidationproceedsaccording
to reactions5.24 and 5.25,coupledto reactions5.1 to 5.3. (Note that 4.36 and5.25 arethe
samereaction.)From Section5.2 we canobtainan expressionfor the HO2/OH ratio in the
uppertroposphere.Basedon the steady-staterelation for HO2,we obtain

[HOz] k5.24[CO]
[OH] k.5.25, [ NO . ]

As one proceeds up in the troposphere, the NO2/NOx ratio decreases,achieving its low-
est value at the tropopause, and then increases moving into the stratosphere. The increase
of NOz relative to NO in the lower stratosphere is the result of reaction 4.36 (5.25). (The
NOx /NOy ratio is more or less constant in the upper troposphere, falling off as one goes
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'){:>t!ut! HO 0:1 ~Iq!:ld~:>sns S! ~Ut!){{t! ~q:I U! WO:lt! H AUY '"M '{t!:>!pt!l IA){{t! ~q:I ~:>npold 0:1
(L~'~) EONH + '"M +- EON + H"M
(9~'~) OZH + °"M+- °HO + H"M
'spuoq H-:J WOJ) u°!1:)~Jtsq~ WOt~-H ~!A p~~:)oJd SUO!t:)~~Jqtog .SUO!t!puo:) ~W!tf.~p J~p
-un ss~:)oJd SSO{:)!l~qdsowt~ ~ s~ ~:)u~odw! (%0 ( ::;:) JOU!W)O ~U!~q f.{~J~U~~ ss~:)oJd
J~tt~{ ~Q"!Q"!!M S~:)!p~J EON pu~ HO Q"!!M t:)~~J S~~){~ 'SU°!1!PUO:) :)!l~qdsodoJt J~PUfl
sauu}JIV {"8.S
'S~!:)OOS:)!U~glO ~S~qI JO f.I!s!W~q:) ~qI U! S~!1!X~Idwo:) p~pp~ ~qI
puu (suoqm:)OlpAq :)!1~WOm pUU 'S~U~){JtI'S~UU){JtI)s~ss~I:) Sn°!lP.A JO s::>OA AUUWJO ~:)u~
-s~ld ~q1 Jo ~sn~:)~q P~1~:)!Idwo:) ~lOW APUU:)y!Ug!S S! ~l~qdsodol1 I~UO!g~l puu uuqln ~qI
Jo f.I!S!W~q:) ~qI '~l~qdsodol1 p~1~U!W°p-~u~q1~w 'u~~I:) ~qI Jo f.I!S!W~q:) ~qI Jo UO!SU~1X~
UU '~Id!:)upd U! 'qgnOqlIV .s1:)npold UO!1~P~lg~P S1! puu ~u~q1~w Jo ~SOqll~AO ~1~U!WOP
SUO!SS!W~xON :)!U~gOdOlqlUU puu ::>OA :)!u~godol1puu puu :)!U~gO!qJo SUO!1:)~~lI~:)!W~q:)
~q1 's~~m uuqln U! AIJtI!:)~ds~ puu 's~~m ~U!1Spd 1S0W~ql1nq IJtI U! ~l~qdsodol1l~A\OI ~qI uI
:[H:mdSOdOH.L ~H.L NI SONflOdWO:J :JINVDHO
~NVH.L~WNON .!IOj\.H.LSIW~H:J 8.S
~3HdSOdO~ 3H.L dO A~SIW3HJ t9Z
 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 265

These alkyl peroxy radicals can be classed as primary, secondary, or tertiary depending on
the availability of H atoms: RCHzOO.(primary); RR'CHOO. (secondary); RR'RNCOO.
(tertiary). The alkyl radical-Oz addition occurs with a room-temperature rate constant of
~IO-IZ cm3 molecule-1 S-l at atmospheric pressure. Given the high concentration of Oz,
the R + Oz reaction can be considered as instantaneous relative to other reactions occur-
ring such as those that form R in the first place. Henceforth, the formation of an alkyl rad-
ical will be considered to be equivalent to the formation of an alkyl peroxy radical.
Under tropospheric conditions, these alkyl peroxy (ROz) radicals react with NO, via two
pathways,

RO2' + NO -- RO.+ NO2 (S.S9a)

M
-- RONO? (5.59b)

For alkyl peroxy radicals,reaction5.59acanform the correspondingalkoxy (RO.) rad-

ical togetherwith NO2,or the correspondingalkyl nitrate,reaction5.59b,with the yield of
the alkyl nitrate increasingwith increasingpressureand with decreasingtemperature.For
secondaryalkyl peroxy radicals at 298 K and 760 Torr total pressure,the alkyl nitrate
yields increasemonotonically from <0.014 for a C2 alkaneup to -0.33 for a Cg alkane
(Atkinson, 1990).The rateconstantfor the CH3O2'+ NO reactionis (seeTableB.l): kS.40
= 4.2 X 10-12exp(180/T) = 7.7 X 10-12cm3molecule-1S-I at 298 K. Rateconstantsfor
higher (;=:C2)alkyl peroxy radicalswith NO are taken as (Atkinson, 1994):kS.S9= 4.9 X
10-12exp( 180/ T) = 8.9 X 10-12cm3molecule-l S-I at 298 K.
Alkyl peroxy radicalsreactwith NO2by combinationto yield the peroxynitrates(recall
reaction5.41),

RO2' +NO2 + M -..ROONO2+ M (5.60)

Limiting high pressurerateconstantsfor ~C2 alkyl peroxyradicalsareidentical to that for

the C2HsO2, radical: kS.60= 9 X 10-12cm3molecule-I S-I, independentof temperature
over the range250 to 350 K,
Alkyl peroxy radicalsalsoreactwith HO2radicals,

R02' + H02' -+ ROOH + 02 (5.61)

or with otherRO2radicals.The self-reactionof RO2. andRO2.proceedsby the threepath.

ways

R(RzCHOz"+ R(RzCHOz"-+ 2 R(RzCHO"+ Oz (5.62a)

-+ R(RzCHOH+R)RzCO+Oz (5.62b)
-+ R)RzCHOOCHR)Rz+ Oz (5.62c)

Pathway 5.62b is not accessible for tertiary ROz radicals, and pathway 5.62c is expected to
be of negligible impcrtance. Under urban conditions, and indeed possibly for much of the
lower troposphere in anthropogenically influenced continental regions, reaction with NO is
the dominant reaction pathway for ROz radicals.
Alkoxy (RO.) radicals are formed in the reaction of alkyl peroxy (RO2') radicals with
NO, reaction 5.59a. Subsequent reactions of alkoxy radicals determine to a large extent the
 '(P661) UOSU!'PV,(q
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(99'~) "M(O):) I'M + "M ~ 'O:)"MI'M'M
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'IAuoq
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)l 86Z"!u 'I~OI x ~'6 =
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L'(17661'UOSU!)[IV)
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3'H3HdSOdO~l. 3Hl. dO J..&SIW3H:> 99Z
 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 267

The 2-pentoxyradical canthen reactwith 020decompose,or isomerize:

o.

Decomposition " Isomerization

/
CH3CHO+ CH3CHzCHz
or

CH3. + CH3CH2CH2CHO

CH3CH(OH)CH2CH2CH2'
CH3C(0)CH2CH2CH3 + H02 .

Rate constants for alkoxy radical isomerizations can be combined with rate constants for
alkoxy radical decomposition and reaction with O2 to predict the relative importance of the
three pathways (Atkinson. 1994). Alkoxy radicals can also react with NO and N02. but un-
der ambient tropospheric conditions these reactions are generally of negligible importance.
 ";}l;}q qll1d 111q1I:J;}lg;}U II!M ;}M Inq 'UO!I:Jl1l1Sql1WOII1-H
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}O U°!1:JI1;tl HO Il1Il;}AO ;}qI }O %~> lO} All1Il;}U;}g sIUnO:J:J11sdnOl2 EH;J- WOl} U°!1:Jl1l1Sql1 WOII1 U;}gOlpAHs
.O~HJ~HJOH + ~ON ~ ON + . ~O~HJ~HJOH
l88j
.zOzHJzHJOH+-- Zo + .zHJzHJOH
.ZH:)ZH:)OH ~ 'HO + 1'Hz:)
S1ws1~q:)~W U01!:)~aJHo-~u~q!~
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 269

CH3CH2CH (~.) CH3 CH3CH2CH2CH202'

NOI Nol -
r CH3CH2CH(ON02)CH3 r CH3CH2CH2CH20NO2

CH3CH2CH (0.) CH 3 CH3CH2CH2CH20.

,,- I ;onm
°2 I V2! ~ 102

ICH,CH.C(O) CH, I CHJCH2O2° + ICH3CHOI irH ,rH.rH.rHOI CH2(02.) CH2CH2CH2OH

+ ! NO + ! NO
H02" HO"
2

CH3CH20" CH2(0.) CH2CH2CH20H

i 02 fsom.

@~ CH2(OH) CH2CH2CHOH
+
H02.

+
H02"

FIGURE 5.7 Atmosphericphotooxidationmechanismfor n-butane.The only significantreaction

of n-butaneis with the hydroxyl radical. Approximately 85% of that reactioninvolves H-atom ab-
stractionfrom an internalcarbonatomand 15%from a terminalcarbonatom.In the terminalH-atom
abstractionpath,the CH3CH2CH2CH2O. alkoxy radical is estimatedto reactwith O225% of the time
and isomerize75% of the time. The secondisomerizationis estimatedto be a factor of 5 fasterthan
the first isomerizationof the CH3CH2CH2CH2 O. radical, so that competitionwith O2reactionis not
consideredat this step.The predominantfate of a-hydroxy radicalsis reactionwith O2,For example,
.CHzOH+Oz-+ HCHO+HOz', and CH3CHOH+Oz-+ CH3CHO+HOz', In the n-butane
mechanism,the a-hydroxy radical, CHz(OH)CHzCHzCHOHreactsrapidly with O2to form 4-hy-
droxy-l-butanal, CHz(OH)CHzCHzCHO.In the internal H-atom abstractionpath,the alkoxy radi-
cal CH3CH2CH(0.)CH3reactswith O2to yield methyl ethyl ketone(MEK), CH3CH2C(0)CH3,and
decomposesto form CH3CHOand CH3CH2.,which, after reactionwith O2 and NO and O2 again,
yields anothermoleculeof CH3CHOand H02.

The HOCH2CH20.radicalthen decomposesand reactswith O2:

HOCH2CH2O. ~ HCHO+ .CH20H

+02 ~ HOCH2CHO+ H02'
HOCH2CH20.

The numbers over the arrows indicate the fraction of the reactions that lead to the indicated
products at 298 K. Finally, the .CH2OH radical reacts with O2 to give formaldehyde and a
hydroperoxyl radical,

.CH20H + 02 --+ HCHO+ H02

fast
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£'M/ £'M/ '\I'M
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:(P661 '6861 'UOSU!:>nY) [B:>!PBJ [A)[{BAXOJpAq
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V £ Z I
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(,ZOH + OH::>zH::>OH)8ZO0+
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oz
.zOzH::>zH::>OH
-- . HO + ~z::>
to
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 271

followed by rapid addition of O2to yield the corresponding{3-hydroxyalkylperoxy radi-

cals,

OH OH 00.
RJ, " .
R~ R)",I I /R3
c-c
M
+ °2 -=-- :c-c
R/2 \R 4 R1
2
"R4
In the presence of NO, the {3-hydroxyalkyl peroxy radical reacts with NO to form either the
{3-hydroxylalkoxy radical plus NO2 or the {3-hydroxynitrate:9

RI2
OH 00'
RI" I I /R3
:c-c
\R 4
+ NO - NO2+
R/2
,c-c
R4
(5.69)

Rate constants for the reactions of f3-hydroxyalkyl peroxy radicals with NO are essentially
identical to those for the reaction of NO with more than C2 alkyl peroxy radicals formed
from alkanes (Atkinson, 1994).
The f3-hydroxyalkoxy radicals can then decompose, react with O2, or isomerize.
Available data show that, apart from ethene, for which reaction of the HOCH2CH20. radi-
cal with O2 and decomposition are competitive, the f3-hydroxyalkoxy radicals formed sub-
sequent to OH addition to ~C3 alkenes undergo decomposition and the reaction with O2 is
negligible.
The decomposition reaction is

08 O. OH 0
Rl~ I 1/ R1 RI" I II
,C-C" ,C. + R3CR4
RI2 R4 R1
2

Carbonylyields from alkene-OH reactionsare summarizedin Table5.1. The yields of

HCHO and RCHO arising from cleavage of the -C = C- bond of l-alkenes
RCH = CHz decreasemonotonically from ~0.90 for propeneand I-butene to 0.21 to
0.39 for l-octene.H-atom abstractionfrom the CHzgroupsin the l-alkenesis expectedto
accountfor an increasingfraction of the overall OH radical reactionasthe carbonnumber
of the l-alkenes increases,with about 15% of the I-heptenereactionbeing estimatedto
proceedby H-atom abstractionfrom the secondaryCHzgroups.The propene-OHreaction
mechanismis shownin Figure 5.8.

"The {3-hydroxynitrate formation pathway accounts for only -I to 1.5% of the overall NO reaction pathway at
298 K for propene (Shepson et aI., 1985). The yields of {3-hydroxynitrates from the propene-OH and 1-
butene-OH reactions are about a factor of 2 lower than those of alkyl nitrates from the propane-OH and n-bu-
tane-OH reactions. These observations suggest that the formation yields of {3-hydroxynitrates from the OH
reaction with higher l-alkenes could also be a factor of 2 lower than those from the reactions with the corre-
sDondinl! n-alkanes.
 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 271

followed by rapid addition of O2to yield the corresponding{3-hydroxyalkylperoxy radi-

cals,

OH R OR 00
RJ " .
R~ I", I II R'l
M
c-c + °2 -=-- .C-C.
R{ R4 R1
2 R4

In the presenceof NO, the f'-hydroxyalkyl peroxyradicalreactswith NO to form eitherthe

f'-hydroxylalkoxy radical plus NO2or the f'-hydroxynitrate:9

RI2
OH 00.
RI",! I/R3
:c-c
\R 4
+ NO - NO2+
R/2
:c-c
R4
(5.69)

Rate constants for the reactions of f3-hydroxyalkyl peroxy radicals with NO are essentially
identical to those for the reaction of NO with more than C2 alkyl peroxy radicals formed
from alkanes (Atkinson, 1994).
The {3-hydroxyalkoxy radicals can then decompose, react with O2, or isomerize.
Available data show that, apart from ethene, for which reaction of the HOCH2CH20. radi-
cal with O2 and decomposition are competitive, the f3-hydroxyalkoxy radicals formed sub-
sequent to OH addition to 2:C3 alkenes undergo decomposition and the reaction with O2 is
negligible.
The decomposition reaction is

Rl" I

RI2
08 O.

,C-C"
I / R1

R4
- 08
RI", I

R1
2
C. +
0
II
R'tCR,i

Carbonylyields from alkene-OH reactionsare summarizedin Table5.1. The yields of

HCHO and RCHO arising from cleavage of the -C = C- bond of 1-alkenes
RCH = CHz decreasemonotonically from ~0.90 for propeneand I-butene to 0.21 to
0.39 for l-octene.H-atom abstractionfrom the CHzgroupsin the 1-alkenesis expectedto
accountfor an increasingfraction of the overall OH radical reactionasthe carbonnumber
of the 1-alkenesincreases,with about 15% of the 1-heptenereactionbeing estimatedto
proceedby H-atom abstractionfrom the secondaryCHzgroups.The propene-OHreaction
mechanismis shownin Figure 5.8.

"The {3-hydroxynitrate formation pathway accounts for only -I to 1.5% of the overall NO reaction pathway at
298 K for propene (Shepson et aI., 1985). The yields of {3-hydroxynitrates from the propene-OH and 1-
butene-OH reactions are about a factor of 2 lower than those of alkyl nitrates from the propane-OH and n-bu-
tane-OH reactions. These observations suggest that the formation yields of {3-hydroxynitrates from the OH
reaction with higher l-alkenes could also be a factor of 2 lower than those from the reactions with the corre-
sponding n-alkanes.
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 273

This is followed by rapid O2addition:

ONO2 ONOz
R"",I /R3 RI" I /R3
R/
C-C
o""R
+°2- R/
C-C
I "R4
2 4 Z 00.

to producethe {3-nitratoalkylperoxy radical, subsequentreactionsof which are

+NO
- + NO2

(5.73)
ONO2 R
R}, I / 3
"c -C,
/ I "R4
R2 ONO2

The latter reactionis expectedto be minor.

Furtherreactionsof {3-nitratoalkoxyradicalsinclude

R ONOz R
I" I / 4
+°2- R /
C-C
II
+ HO.
2

z 0

if R3 = H

0 0
II II
R)CR2 + R3CR4 + NO2

ONO2
RI~ I /R3
C-C +NOZ
-
R/ - I~R
2 0. 4

of which the last reactionis expecedto be minor. Figure 5.9 showsthe mechanismof the
orooene-NO,reaction.
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 275

Atkinson, 1994;Horie et al., 1994a, b; Neebet al., 1995;Thomaset al., 1995;Neebet al.,
1996)and are reasonablywell understoodfor a large numberof the smalleralkenes.The
major mechanisticissueconcernsthe fate, under atmosphericconditions,of the initially
energy-richCriegeebiradical, which can be collisionally stabilized or can undergouni-
moleculardecomposition,

[RI CH2t(R2)O6]~ -+- RI CH2C(R2)O6 (stabilization) (5.76a)

-+- RICH2C(O)R2 + 0 (5.76b)
-+- [RICH2C(O)OR2]'" -+- decomposition (5.76c)
-+- [RICH = C(OOH)R2]'" -+- RICHC(O)R2 + OH. (5.76d)

At atmosphericpressure,0 atomsarenot formedin any appreciableamount,sopath5.76b

can generallybe neglected.
Hydroxyl radicalshave beenobservedto be formed from alkene-O3reactions,some-
times with close to a unit yield (1 molecule of OH per 1 molecule of alkene reacted)
(Atkinson andAschmann,1993).Atkinson et al. (1995a)reported.OH radical yields from
a seriesof alkene-O3reactions:
Alkene OH Yield
I-Pentene 0.37
I-Hexene 0.32
I-Heptene 0.27
l-Octene 0.18
2,3-Dimethyl-l-butene 0.50
Cyclopentene 0.61
I-Methylcyclohexene 0.90

(Estimateduncertaintiesin theseyields area factor of -1.5.)

At I atm, fractional yields of stabilizedbiradicalsareestimatedas (Atkinson, 1994):

Ethene 0.37
Propene 0.275
trans-2-Butene 0.18
2-Methylpropene 0.174
2,- 3-Dimethy 1-2-butene 0.30

The reactionpathwaysof Criegeebiradicalsare generallywell establishedfor the first

two compoundsin the seriesalthoughthe exactfractionsthat proceedvia eachindividual
pathare still opento question(Horie and Moortgat, 1991):

M
--+- CH200. (stabilization)
CO2+ H2
CO + H2O (5.77)
0,
2HO2. +CO2
HtO + OH.
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 277

5.8.3 Aromatics
Aromatic compounds are of great interest in the chemistry of the urban atmosphere be-
cause of their abundance in motor vehicle emissions and becauseof their reactivity with re-
spect to ozone and organic aerosol formation. Understanding the atmospheric oxidation
mechanisms of aromatics has long been cited as the most critical need in further develop-
ment of reaction mechanisms for the urban and regional atmosphere (National Research
Council, 1991). The major atmospheric sink for aromatics is reaction with the hydroxyl
radical. Whereas rate constants for the OR reaction with aromatics have been well charac-
terized (Atkinson, 1994), mechanisms of aromatic oxidation following the initial OR at-
tack have been highly uncertain. Aromatic compounds of concern in urban atmospheric
chemistry are given in Figure 5.10.

CH~ CH3 CH3 CH3

~ ~ A ,CH~ A A
~ ~ ~ ij
'CH~ y
CH3
Benzene Toluene 0 -Xylene -
m Xylene P - Xylene

C2Hs CH3 CH3

X A ~CH~ A
~
~ y CH3
CH3
,
'CR3

Ethyl benzene ,2,4 Trimethyl benzene ,3,5 Trimethyl benzene

0 - Ethyl toluene m - Ethyl toluene p - Ethyl toluene

FIGURE S.10 Aromatic compoundsof interestin troposphericchemistry.
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 279

The H-atom abstractionpathwayleadsmainly to the formation of aromaticaldehydes

6
oCHZ CH20. CHO

02 °2
6 6 + H028 (5.82)

Benzaldehyde

As noted above,this H-atom abstractionpathwayis minor, accountingfor <10% of the

overall OH radical reactionfor benzeneand the alkyl-substitutedaromatichydrocarbons.
The radicalsresultingfrom OH addition to the aromaticring are namedasfollows:

c
CH3 CH3 CH3
l
f~H 6~H C ~~H )
"-
H OH
Hydroxycyclohexadienyl Methyl hydroxycyclohexadienyl
radical radicals
(from benzene) (from toluene)

For toluene, and other aromatics, there are several possible sites of attack for the OH radi-
cal. Some sites are less sterically hindered than others or are favored because of stabiliza-
tions resulting from group interactions. Andino et al. (1996) have performed ab initio
calculations to determine the most energetically favored structures resulting from OH ad-
dition to aromatic compounds. For toluene the most favored structure is that resulting from
OH addition at the ortho position 1°:

CH3

6~H

100M addition to the meta and para positions of toluene yield structures that are only I to 2 kcal mol-I less favor-
able than addition at the ortho site and thus cannot be ruled out categorically. For our purposes, we will consider
OH addition at the ortho site only.
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 281

After bicyclic radical formation, O2rapidly addsto the radical, forming a bicyclic per-
oxy radical, for example,
CH3

.OO-&~H

This radical is then expectedto react with NO to form a bicyclic oxy radical and NO2,for
example,
CH3
.O_-r-;"~"~H '

~'OH

The only path for this bicyclic oxy radical is fragmentationvia favorable/3-scissionre-
actions.For the aboveradical, suchscissionwould produce

.0

H OH H
1
/' ~ - Scissi°!l.O~
O~
'(-1 /
Decomposition B

H H a H OH
1l H
OA~. + O~ 0 ~-../' + .~
yOH I(
a
'1(
0

Observedring-fragmentationproductsof the toluene-OH reactioninclude the follow

ing:
00 00 0II CH
I 30 II
0 0
II II /I /I II II
HCCH CH3CCH HCCH=C CH HC CH =CH CH
Glyoxal Methylglyoxal Methyl butenedial 1.4-Butenedial

5.8.4 Aldehydes
Aldehydes are important constituents of atmospheric chemistry. We have already seen the
role played by formaldehyde in the chemistry of the background troposphere. Aldehydes
are formed in the atmosphere from the photochemical degradation of other organic com-
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 283

Peroxyacetylnitrate, the first compoundin the seriesof PANs, which itself is usually
called PAN. is formedfrom the OH reactionwith acetaldehyde,

CH3CHO+ OH, -+- CH3CO+ H2O (5.92)

CH3CO+ O2-+- CH3C(0)02' (5.93)
CH3C(0)02' +N02 + M ~ CH3C(0)02N02 + M (5.94, 5.95)

Reaction5.94 must competewith the NO-to~NO2conversionreaction

CH3C(O)OZ. + NO -.-+- NOz + CH3C(O)O. (5.96)

followed by
CH~C(O)O. ~ CH3O2'+ CO2 (5.97)

Peroxyacetyl nitrate does not absorb radiation above 290 nm so this class of compounds
is not expected to photodissociate in the troposphere. Peroxyacetyl nitrate is not highly wa-
ter soluble; it is more soluble than NO and NO2 but considerably less soluble, for example,
than nitric acid. Thus aqueous-phasescavenging is not expected to be an important tropos-
pheric removal path for PANs.
Once thought to be of importance only in polluted urban atmospheres, PANs are now
recognized to be ubiquitous, having been detected in urban, rural, and global environments
(Roberts, 1990). By virtue of their photochemical inertness, relative insolubility in water,
and low OH rate constant, PANs can have an appreciable atmospheric lifetime. The princi-
pal loss mechanism is thermal decomposition by reaction 5.91 or 5.95 back to the peroxy-
acyl radical and NO2. The thermal decomposition is highly temperature dependent; at
temperatures of the upper troposphere PANs are quite stable and can be transported long
distances.
The thermal decomposition rate constant for PAN, reaction 5.95, is both temperature
and pressure dependent, being in the falloff region at room temperature at and below at-
mospheric pressure. Using the Troe falloff expression, over the temperature range 280 to
330K,

k= ko[M] F{I
ko[M] 'gJoko[M]/koof}"
(5.98)
1+-
koo

the specificvaluesfor PAN are

ko = 4.9 X 10-3exp(-12100/ T) cm3molecule-I S-I

koo = 4.0 X 1016exp( -13600/ T) S-I

F=0.3
Thus koo= 6.1 X 10-4 S-I at 298 K and kS.9s= 5.2 X 10-4 s-t at 298 K and760 Torr total
pressure. The decomposition rates of the higher peroxyacyl nitrates are expected to be sim-

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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 285

with 5.99abeing the major reactionpathway.Subsequentreactionof this particularradical

with NO leadsto

00. O.
I I
CH3CHC(0)CH3 + NO -.. N02 + CH3CHC(0)CH3

CH3C(0.)HC(0)CH3 -..CH3CHO+ CH3CO

The major reaction products from the atmospheric reactions of the ketones are aldehydes
and PAN precursors.
Acetone is an ubiquitous atmospheric species having a mixing ratio of about 1 ppb in
rural sites in a variety of locations (Singh et al., 1994, 1995). Under extremely clean con-
ditions, ground-level background mixing ratios of 550 ppt have been found throughout the
NH troposphere. In the free troposphere, acetone mixing ratios on the order of 500 ppt are
present at northern midlatitudes, declining to about 200 ppt at southern latitudes (Singh et
al., 1995). From atmospheric data and three-dimensional photochemical models, a global
acetone source of 40 to 60 T g yr-1 has been estimated, comprised of 51 % secondary for-
mation from the atmospheric oxidation of precursor hydrocarbons (principally propane,
isobutane, and isobutene), 26% direct emission from biomass burning, 21 % direct biogenic
emissions, and 3% primary anthropogenic emissions (Singh et al., 1994). Atmospheric re-
moval of acetone is estimated to result from photolysis (64%), OH reaction (24%), and de-
position (12%). Acetone photolysis, which produces the PAN-precursor CH3CO radical, is
estimated to contribute 40 to 50 ppt of PAN in the middle and upper troposphere of the
Northern Hemisphere. Based on tropospheric models, up to 50% of observed PAN may be
formed by this mechanism. The average lifetime of acetone in the atmosphere is estimated
to be 16 days (Singh et al., 1995).
By virtue of its photooxidation chemistry (Figure 5.11), acetone is a source of HOx rad-
icals in the upper troposphere. Under the dry conditions of the upper troposphere, where
0(10) + H2O is relatively slow, acetone makes an important additional contribution to
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 CHEMISTRY OF NONMETHANE ORGANIC COMPOUNDSIN THE TROPOSPHERE 287

with the first reaction pathway accountingfor -85% of the overall reaction at 298 K.
Since, as shown earlier, both the .CH20H andCH30. radicals react with O2 to yield
formaldehydeand H02, the overall methanol-OHreactioncan be written as
~
CH30H + OH. --+ H2O + HO2' + HCHO

The ethanol-OH reactionproceedsas follows:

OR. + CH3CH20H -.. H2O + CH2CH20H (-5%) (5.104a)

-.. H2O + CH3CHOH (-90% ) (5.104b)
-.. H2O + CH3CH20. (-5%) (5.104c)

wherethe branchingratios arethoseat 298 K. The secondtwo channelsresult in identical

productsunder atmosphericconditions,H02 + CH3CHO.The first channelforms the in-
termediateCH2CH20H, which, underatmosphericconditions,leadsto the sameproducts
as the OH + ethenereaction.Using the ethene-OHmechanismgiven earlier, the overall
ethanol-OH reactionmechanismcan be written as

C2HsOH+ OH. +0.05 NO -+ 0.05 NO2 + 0.014 HOCH2CHO+ 0.072 HCHO

+0.95 CH:1CHO + HO2. + H2O

with the principal products being acetaldehyde and the HO2 radical.
Free tropospheric concentrations of methanol range from about 700 ppt at northern mid-
latitudes to about 400 ppt at southern latitudes (Singh et al., 1995). In general, ethanol
abundance in the free troposphere is an order of magnitude lower than that of methanol.
Average lifetimes of CH3OH and C2HsOH in the atmosphere are on the order of 16 days
and 4 days, respectively.

5.8.10 Acids
The atmospheric sources of formic and acetic acid are still open to question. In the
Shenandoah Cloud and Photochemistry Experiment conducted during 1990 in the rural
continental atmosphere at a mountaintop (1014 m) in Virginia, median mixing ratios for
HCOOH and CH3COOH were 5.4 and 2.1 ppb, respectively (Talbot et al., 1995). Formic
acid mixing ratios often approached or exceeded 10 ppb. An observed lack of correlation
between HCOOH and CH3COOH with peroxide speciesargued against a significant source
from permutation reactions of peroxy radicals (e.g., reaction 5.61). A strong correlation be-
tween the mixing ratios of both acids was suggestive of a common source, although com-
bustion emissions could be ruled out. Correlation between the seasonalvariation of the two
acids and ambient temperature is consistent with a soil microbial source.
Together, the two acids contribute between 16 and 35% of the free acidity in North
American precipitation and between 25 and 98% of the free acidity in precipitation in re-
mote areas. Photochemical production of organic acids occurs in the gas phase from
ozone-alkene reactions and in cloud water by the hydrolysis of aldehydes followed by
aQueous-phasereaction with OH radicals (see Chapter 6). These routes can explain, in part,
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 THE SIZE DISTRIBUTION FUNCTION 409

TABLE 7.1 Example of SegregatedAerosol Size Information

0.001-0.01 100 100 11111

0.01-0.02 200 300 20000
0.02-0.03 30 330 3000
0.03-0.04 20 350 2000
0.04-0.08 40 390 1000
0.08-0.16 60 450 750
0.16-0.32 200 650 1250
0.32-0.64 180 830 563
0.64-1.25 60 890 117
1.25-2.5 20 910 160
2.5-5.0 5 915 80
5.0-10.0 1 916 2

250

200
",
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2001
-
t)
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c
0
~ 150
e
-
c i
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0.0 0.1 0.2
Co)
~
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E 50 I
:J
Z

n
¥
-
0 1 2 3 4 5
Diameter, JIm
FIGURE 7.1 Histogramof aerosolparticlenumberconcentrationsversusthe sizerangefor thedis-
tribution of Table7.1. The diameterrange0 to 0.2 ILm for the samedistribution is shownin the in-
set.
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 THE SIZE DISTRIBUTION FUNCTION 411

~
20000
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[
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U
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Z

01'1"1111 IIIIIIII I I'~

0.01 0.10 1.00

Diameter. J.1m
FIGURE 7.3 SameasFigure 7.2 but plotted versusthe logarithm of the diameter.

large-andsmall-particleregionsare depicted,but it now erroneouslyappearsthat the dis-

tribution consistsalmostexclusivelyof particlessmallerthan0.1 j.Lm.
Using a numberof sizebins to describean aerosolsizedistribution generallyresultsin
lossof information aboutthe distribution structureinside eachbin. While this may be ac-
ceptablefor someapplications,our goal in this chapteris to developa rigorousmathemat-
ical frameworkfor the descriptionof the aerosolsizedistribution.The issuesdiscussedin
the precedingexampleprovide valuableinsights into how we shouldexpressand present
ambientaerosolsizedistributions.

7.1.1 The Number Distribution nN(Dp)

In the previoussection,the valueof the aerosoldistribution nj for a sizeinterval i wasex-
pressedas the ratio of the absoluteaerosolconcentrationNj of this interval and the size
range ~Dp. The aerosolconcentrationcan then be calculatedby

Ni = ni ~Dp

The use of arbitrary intervals ~Dp can be confusing and makes the intercomparison of size
distributions difficult. To avoid these complications and to maintain all the information re-
garding the aerosol distribution, one can use smaller and smaller size bins, effectively tak-
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 THE SIZE DISTRIBUTION FUNCTION 413

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FIGURE 7.4 Atmosphericaerosolnumber,surface,and volume continuousdistributions versus
particlesize.The diameterrange0 to 0.5 JLmfor the numberdistributionis shownasan inset.

Example 7.1 For the distribution of Figure 7.4, how many particles of diameter 0.1 j),m
. ')
exist.

According to the inset of Figure 7.4, nN(O.1 fLm) = 13,000 fLm-l cm-3. However, this
is not the numberof particlesof diameter0.1 fLm (it evenhasthe wrong units). To calcu-
late the numberof particleswe needto multiply nN by the width of the size range ~Dp.
But if we are interested only in particles with Dp = 0.1 fLm this size range is zero and
thereforethereare zeroparticlesof diameterexactly equalto 0.1 fLm.
Let us try to rephrasethe abovequestion.

Example 7.2. For the distribution of Figure7.4, how manyparticleswith diameterin the
range 0.1 to 0.11 .urn exist?

The size distribution is practically constant over this narrow range with n N(0.1 JLm)
= 13,000JLm -I cm -3. The width of the region is 0.11 - 0.1 = 0.01 JLm and there are
0.0 I X 13,000 = 130 particles cm -3 with diameters between 0.1 and 0.11 JLm for this
size distribution.
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The total aerosolvolume per cm3 of air, V, is

andis equalto the areabelow the nv(Dp) curve in Figure 7.4.

If the particlesall havedepsity Pp (g cm-3) then the distribution of particle masswith
respectto particle size, nM(Dp), is

)
Pp nv(Dp)
,1"66 = Pp
.106
)("6, D~nN(Dp)
7r
(,ug ,um-l cm-3) (7.7)

where the factor 106is needed to convert the units of density Pp from g cm -:I to ILg ILm -:I,
and to maintain the units for nM(Dp) as ILg ILm -I cm -3.
Becauseparticle diameters in an aerosol population typically vary over several orders of
magnitude, use of the distribution functions, nN(Dp), ns(Dp), nv(Dp), and nM(Dp), is
often inconvenient. For example, all the structure of the number distribution depicted in
Figure 7.4 occurs in the region from a few nanometers to 0.3 ILm diameter, a small part of
the 0 to 10 ILm range of interest. To circumvent this scale problem the horizontal axis can
be scaled in logarithmic intervals so that several orders of magnitude in Dp can be clearly
seen (Figure 7.5). Plotting nN(Dp) on semilog axes gives, however, a somewhat dis-
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 THE SIZE DISTRIBUTION FUNCTION 417

Theunits of n~ (In Dp) arecm-3 sinceInDp is dimensionless.The total numberconcen-

trationof particles N is

N = {(X} n~(In Dp) d In Dp (cm-3) (7.8)

J -(X}

The limits of integration in (7.8) are from -00 to 00 as the independent variable is In Dp.
The surface area and volume distributions as functions of In Dp can be defined similarly
to thosewith respectto Dp,

n~(lnDp) = 11"D;nN(ln Dp) (,um2cm-3) (7.9)

(.um3cm-3) (7.10)

with

The aboveaerosoldistributionscan alsobe expressedas functionsof the base10 loga-

rithm log Dp, defining nN(log Dp), ns(log Dp), and ny(log Dp). Note that nN, nN' and
nN aredifferent mathematicalfunctions,and,for the samediameter Dp, they havediffer-
ent arguments,namely Dp,ln Dp, and log Dp. The expressionsrelating thesefunctions
will be derivedin the next section.
Using the notation dNjdSjdV = the differential number/surface/volume of particles
in the sizerange Dp to Dp + dDp we have

dN = nN(Dp) dDp = n~(ln Dp) d In Dp = n~(log Dp) d log Dp (7.13)

dS = ns(Dp) dDp = ns(lnDp) d InDp = ns(log Dp) d log Dp (7.14)
dV = ny(Dp) dDp = nt(ln Dp) d In Dp = ny(log Dp) d log Dp (7.15)
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(91'0
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 THE SIZE DISTRIBUTION FUNCTION 419

This procedurecanbe generalizedto relateany two sizedistributionfunctions n(u) and

n(v), whereboth u and v arerelatedto Dp. The generalizationof (7.17) is

n(u) du = n(v) dv (7.24)

and dividing both sides by dDp

(dvfdDp)
= n(v)(d~)
n(u) (7.25)

7.1.5 Properties of Size Distributions

It is often convenient to summarize the features of an aerosol distribution using one or two
of its properties (mean particle size, spread of distribution) than by using the full function
n N (D p) . Growth of particles corresponds to a shifting of parts of the distribution to larger
sizes or simply an increase of the mean particle size. These properties are called the mo-
ments of the distribution, and the two most often used are the mean and the variance.
Let us assume that we have a discrete distribution consisting of M groups of particles,
with diameters Dk and number concentrations Nk, k = 1,2, ..., M. The number concen-
tration of aerosols is therefore

M
N = L Nk (7.26)
k=l

The meanparticle diameter,Dp, of the populationis

M
Dp = ~~1
=;--.--NkDk = ~ L NkDk (7.27)
N k=1

The variance,0'2, a measureof the spreadof the distribution aroundthe meandiameter

Dp, is definedby
1 M
NL
k=l Nk(Dk
-D Pr (7.28)

A value of a2 equalto zero would meanthat every one of the particlesin the distribution
haspreciselydiameterDp. An increasinga2 indicatesthat the spreadof the distribution
aroundthe meandiameterDp is increasing.
We will usually deal with aerosoldistributionsin continuousform. Given the number
distribution nN(Dp), (7.27) and (7.28) can be written in continuousform to define the
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 THE SIZE DISTRIBUTION FUNCTION 421

7.1.6 The Log-Normal Distribution

A measured aerosol size distribution can be reported as a table of the distribution values for
dozens of diameters. For many applications carrying around hundreds or thousands of
aerosol distribution values is awkward. In these cases it is often convenient to use a rela-
tively simple mathematical function to describe the atmospheric aerosol distribution. These
functions are semiempirical in nature and have been chosen because they match well ob-
served shapes of ambient distributions (Hinds, 1982). Of tbe various mathematical func-
tions that have been proposed, the log-normal distribution (Aitchison and Brown, 1957)
often provides a good fit and is regularly used in atmospheric applications. A series of other
distributions are discussed in the next section.
The normal distribution for a quantity u defined from -00 < u < 00 is given by

(u - U)2
(7.31)
2a2
u

whereu is the meanof the distribution, a; is the variance,and

N= j OO
n(u) du (7.32)
-00

The normal distribution has the characteristic bell shape, with a maximum at Ii". The stan-
dard deviation, au, quantifies the width of the distribution, and 68% of the area below the
curve is in the range Ii"::!::au.
A quantity u is log-normally distributed if its logarithm is normally distributed. Either
the natural (In u) or the base 10 logarithm (log u) can be used, but since the former is more
common, we will express our results in terms of In Dp. An aerosol population is therefore
log-normally distributed if u = In Dp satisfies (7.31), or

where N is the total aerosolnumberconcentration,and Dpg and ag are for the time being
the two parametersof the distribution. Shortly we will discussthe physicalsignificanceof
theseparameters.The distribution nN(Dp) is often usedinsteadof nN(ln Dp)' Combining
(7.21)with (7.33)

A log-normal aerosol distribution with Dpg = 0.8,urn and O"g = 1.5 is depictedin Figure
7.7.
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 THE SIZE DISTRIBUTION FUNCTION 423

The error function erf z is definedas

erfz

anderf(O) = O.erf( 00) = 1. If we divide the integralin (7.37)into onefrom -00 to 0 and
thesecondfrom 0 to (In D; - In D pg) 1.J2 In (1g. thenthe first integralis seento be equal
to In 12 and the second to (In 12)erf[(ln D; -In Dpg)/.J2 In (1g].Thus for the log-
normaldistribution

For Dp Dpg. since erf(O) = 0

N
F(Dpg) = "2

and we seethat Dpg = Dmedis the median diametel; that is, the diameter for which exactly
one-half of the particles are smaller and one-half are larger. To understand the role of ug let
us consider the diameter Dp17for which Ug = Dp17 /Dpg. At that diameter, using (7.39),

1 1
F(Dp,,) = N 2"+ 2"erf "J2) = O.841N
( 1

Thus ag is the ratio of the diameterbelow which 84.1% of the particleslie to the median
diameterand is termedthe geometricstandarddeviation.A monodisperseaerosolpopula-
tion has ag = I. For any distribution, 67% of all particleslie in the rangefrom Dpg/ag to
Dpgagand 95% of all particleslie in the rangefrom Dpg/2ag to 2Dpgag.
Let us calculatethe meandiameterDp of a log-normally distributedaerosol.By defin-
ition, the meandiameteris found from

Dp
~ rooDpnN(Dp) dDp (7.42)
N Jo
which we wish to evaluatein the caseof nN(Dp) given by (7.34).Therefore
( (In Dp -In -Dpg) 2
exp - dDn
2 In2 a~

After evaluating the integral one finds that

Dp = Dpgexp

We seethat the meandiameterof a log-normaldistribution dependson both Dpg and D'g.

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 THE SIZE DISTRIBUTION FUNCTION 425

narrowdistribution and to a steepline in the log-probability graph (Figure 7.8). The geo-
~etric standarddeviation can be calculatedas the ratio of the diameter Dp+a for which
FN(Dp+a) = 0.84 to the mean diameter

ag = ~ (7.47)
15"

7.1.8 Properties of the Log-Normal Distrjbution

We have discussed the properties of the log-normal distribution for the number concentra-
tion. The next step is examination of the surface and volume distributions corresponding to
a log-normal number distribution given by (7.34). Since ns(Dp) = 1TD;nN(Dp) and
ny(Dp) = (1T/6)D~nN(Dp). let us determine the forms of ns(Dp) and ny(Dp) when
n(Dp) is log-normal. From (7.34) one gets
- 2
(In Dp -In Dpg)

"2i~
By letting D; = exp(2 In Dp), expandingthe exponential,and completingthe squarein
theexponent,(7.48)becomes

- 2 2
[In Dp - (In Dpg + 2 In Ug)]
x exp - 2 In2ug

Thus we see that if the number distribution nN(Dp) is log-normal, the surface distribution
ns(Dp) is also log-normal with the same geometric standard deviation C1gas the parent dis-
tribution and with the surface median diameter given by

- - 2
In Dpgs= In Dpg + 2 In Ug (7.50)

The abovecalculationscan be repeatedfor the volume distribution and one can show
that - 2
(In Dp -In Dpg)
exp( -

or by letting D~ = exp(3 In Dp), expandingthe exponential,andcompletingthe squarein

theexponent,(7.51) becomes

( [lnDp - (lnDpg + 3 In2ag)f

x exp - (7.51a)
2 In2ag
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 THE SIZE DISTRIBUTION FUNCfION 427

1
It)
I

E
U 10.2

~
Q.
Q

C)
.p. 10
'-"
o~
c:

10.6

10.8-
0.1 1.0 10.0
Diameter. ~
FIGURE 7.9 Power-lawdistributionsfor C = 0.001,anddifferent valuesof a

106 1000.0
c = 91.658
a = 3.746 c= 91.658
10'
, a = 3.746
/" ',/
,, 100.0 Q.
'" ~
I 10Z Q;
E
u 0
CO

10.0 ..,
t:J

~ 11
01
~
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"0
I
c..
10

10.6 0.1
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0.1 1.0 10.0 100.0 0.1 1.0 10.0 100.0
Diameter. IJtT1 Diameter. IJtT1
FIGURE 7.10 Fitting of an urban aerosol number distribution with a power-law distribution (left) and
comparison of the corresponding volume distributions (right). Even if the power-law distribution ap-
pears to match the number distribution, it fails to reproduce the volume distribution.
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 AMBIENT AEROSOL SIZE DISTRIBUTIONS 429

The Modified Gamma Distribution The modified gammadistribution (Deirrnendjian,

1969) has been proposedas another function that approximatesambient aerosol size
distributions,

nN(Dp) = AD; exp(-BD~) (7.55)

whereA, b, B, and c are all positive parameters.This distribution form providessignifi-

cant flexibility (Figure 7.11). but its use is often cumbersome.The total aerosolnumber
concentrationN is equalto

AB-(b+l)/c
N= c r(~
wherer is the gammafunction. The maximumof the distribution occursat diameter Dm.

) I/c

Dm= !!.-
Bc

7.2 AMBIENT AEROSOL SIZE DISTRIBUTIONS

Atmosphericaerosolsizedistributionsareoften describedasthe sumof n log-normaldis-

tributions,
( (log Dp -log -Dpj) 2
exp -
2 1 2
og aj

where Ni is the number concentration, Dpi is the mean diameter, and O"iis the standard de-
viation of the jib log-normal mode. In this case 3n parameters are necessary for the de-
scription of the full aerosol distribution. Characteristics of model aerosol distributions are
presentedin Table 7.3 following the suggestions of Jaenicke (1993).

7.2.1 Urban Aerosols

Urban aerosols are mixtures of primary particulate emissions from industries, transporta-
tion, power generation, and natural sources and secondary material formed by gas-to-par-
ticle conversion mechanisms. The number distribution is dominated by particles smaller
than 0.1 ILm, while most of the surface area is in the 0.1 to 0.5 ILm size range. On the con-
trary, the aerosol mass distribution has usually two distinct modes, one in the submicron
regime (referred to as the accumulation mode) and the other in the coarse particle regime
(Figure 7.12).
The aerosol size distribution is quite variable in an urban area. Extremely high concen-
trations of fine particles (less than 0.1 ILm in diameter) are found close to sources (e.g.,
highways), but their concentration decreasesrapidly with distance from the source (Figure
 Off'

~
~

~
8-
~
-
==
 AMBIENT AEROSOLSIZE DISTRIBUTIONS 431

0.01 0.10 1.00 10.00

Diameter, IJIn
FIGURE 7.12 Typical urbanaerosolnumber,surface,and volumedistributions.

7.13). Figure 7.13 describes the number of particles as a function of their diameter (both in
logarithmic scales) for a variety of environments. There are roughly an order of magnitude
more particles close to the freeway compared to the average urban concentration. Figure
7.14 illustrates the corresponding volume distributions. These distributions show that most
of the particles in an urban area are smaller than 0.1 JLm,while most of the particle mass is
found in particles with diameters larger than 0.1 JLm.
An important feature of atmospheric aerosol size distributions is their multimodal char-
acter. Mass distributions, measured in urban centers, are characterized by three modes with
a minimum between 1.0 and 3 JLm. The size range of particles larger than the minimum
(supermicron particles) is termed "coarse," while the smaller particles are called "fine."
The three modes present in the mass distribution of Figure 7.14 correspond to the nuclei
mode (particles below 0.1 JLm),accumulation mode (0.1 < Dp <' 1 JLm),and coarse mode
(Dp > 1 JLm) (Whitby and Sverdrup, 1980). Thus the fine particles include both accumu-
lation and nuclei modes. The boundaries between these sections are not precise (recall in
Chapter 2 that we divided fine and coarse modes at 2.5 JLmdiameter). Note that our defin-
ition of modes has been based on the mass (or volume distribution). The location of modes
may be different if they are based on the number or surface distribution.
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The mass concentrations of the accumulation and coarse particle modes are comparable
for most urban areas. The nuclei mode, with the exception of areas close to combustion
sources, contains negligible volume (Figures 7.12 and 7.14). Most of the aerosol surface
area is in particles of diameters 0.1 to 0.5 jJ.m in the accumulation mode (Figure 7.12).
Becauseof this availability of area, transfer of material from the gas phase during gas-to-
particle conversion occurs preferentially on them.
The sources and chemical compositions of the fine and coarse particles are different.
Coarse particles are generated by mechanical processesand consist of soil dust, seasalt, fly
ash, tire wear particles, and so on. Nuclei and accumulation mode particles contain primary
particles from combustion sources and secondary aerosol material (sulfate, nitrate, ammo-
nium, secondary organics) formed by chemical reactions resulting in gas-to-particle con-
version (see Chapters 9 and 13).
Th~ main mechanisms of transfer of particles from the nuclei to accumulation mode is
coagulation (Chapter 12) and growth by condensation of vapors formed by chemical reac-
tions (Chapter II) onto existing particles. Coagulation among accumulation mode particles
is a slow process and does not transfer particles to the coarse mode.
Processing of accumulation and coarse mode aerosols by clouds (Chapter 15) can also
modify the concentration and composition of these modes. Aqueous-phase chemical reac-
tions take place in cloud and fog droplets, and in aerosol particles at relative humidities ap-
proaching 100%. These reactions can lead to production of sulfate (Chapter 6) and after
evaporation of water, a larger aerosol particle is left in the atmosphere. This transformation
can lead to the formation of two modes in the 0.1 to I jJ.m size range, with the smaller one
called the condensation mode and the larger one the droplet mode (Hering and Friedlander,
1982; John et al., 1990; Meng and Seinfeld, 1994).
Terms often used to describe the aerosol mass concentration include total suspended
particulate matter (TSP) and PMx (particulate matter with diameter smaller than x jJ.m).
TSP refers to the mass concentration of atmospheric particles smaller than 40 to 50 jJ.m,
while PM2.s and PM 10are routinely monitored. For a description of the sampling issues
and problems related to the measurement of TSP, PM2.s, and PM 10the reader is referred to
the EPA Particulate Matter Criteria document (U.S. EPA, 1996).

7.2.2 Marine Aerosols

In the absence of significant transport of continental aerosols, particles over the remote
oceansare largely of marine origin (Savoie and Prospero, 1989). Marine atmospheric parti-
cle concentrations are normally in the range of 100 to 300 cm -3. Their size distribution is
usually characterized by three modes (Figure 7.15): the nuclei (Dp < D.l JLm) the accu-
mulation (D.l < Dp < D.6JLm), and the coarse (Dp > D.6JLm) (Fitzgerald, 1991).
Typically, the coarse particle mode, comprising 95% of the total mass but only 5 to ID% of
the particle number (Figure 7.16), results from the evaporation of sea spray produced by
bursting bubbles or wind-induced wave breaking (Blanchard and Woodcock, 1957;
Monahan et al., 1983). Typical sea-salt aerosol concentrations in the marine boundary layer
(MBL) are around 5 to 3D cm-3 (Blanchard and Cipriano, 1987; O'Dowd and Smith,
1993).
Figures 7.15 and 7.16 show number and volume aerosol distributions in clean maritime
air measuredby several investigators (Meszaros and Vissy, 1974; Hoppel et al., 1989; Haaf
andJaenicke,198D;De Leeuw, 1986) and a model marine aerosol size distribution. The dis-
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 AMBIENT AEROSOL SIZE DISTRIBUTIONS 435

fectsthe concentrationsof the largerparticles),or to uncertaintiesinherentin the different

measurement
methods.

7.2.3 Rural Continental Aerosols

Aerosols in rural areas are mainly of natural origin but with a moderate influence of an-
thropogenic sources (Hobbs et al., 1985). The number distribution is characterized by two
modes at diameters about 0.02 and 0.08 .urn, respectively (Jaenicke, 1993), while the mass
distribution is dominated by the coarse mode centered at around 7 .urn (Figure 7.17). The
mass distribution of continental aerosol not influenced by local sources has a small accu-
mulation mode and no nuclei mode. The PM 10concentration of rural aerosols is around
20 .ug m -3.

7.2.4RemoteContinental Aerosols
Primaryparticles (e.g., dust, pollens, plant waxes)and secondaryoxidation productsare
the main componentsof remote continental aerosol (Deepak and Gali, 1991).Aerosol
number concentrations average around 2000 to 10,000 cm -3 and PM 10concentrations are
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 AMBIENT AEROSOLSIZE DISTRIBUTIONS 437

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FIGURE 7.19 Typical free troposphericaerosolnumber,surface,and volume distributions.

particlesin the accumulationmoderelative to lower troposphericspectra,suggestingpre-

cipitation scavengingand depositionof smaller and larger particles (Leaitch and Isaac,
1991).

7.2.6 Polar Aerosols

Polar aerosols, found close to the surface in the Arctic and Antarctica, reflect their aged
character; their concentrations are very low. Collections of data from aerosol measure-
ments in the Arctic have been presented by a number of investigators (Rahn, 1981; Shaw,
1985; Heintzenberg, 1989; Ottar, 1989). The number distribution appears practically
monodisperse (Ito and I wai, 1981) with a mean diameter of approximately 0.15 J1.m;two
more modes at 0.75 and 8 J1.m(Shaw, 1986; Jaenicke et aI., 1992) (Figure 7.20) dominate
the mass distribution.
During the winter and early spring (February to April) the Arctic aerosol has been found
to be influenced significantly by anthropogenic sources, and the phenomenon is commonly
referred to as Arctic Haze (Barrie, 1986). During this period the aerosol number concen-
 AMBIENT AEROSOLSIZE DISTRIBUTIONS 437

0.01 0.10 1.00 10.00

Diameter. ~
FIGURE 7.19 Typical free troposphericaerosolnumber,surface,and volume distributions.

particlesin the accumulationmoderelative to lower troposphericspectra,suggestingpre-

cipitation scavengingand depositionof smaller and larger particles (Leaitch and Isaac,
1991).

7.2.6 Polar Aerosols

Polar aerosols, found close to the surface in the Arctic and Antarctica, reflect their aged
character; their concentrations are very low. Collections of data from aerosol measure-
ments in the Arctic have been presented by a number of investigators (Rahn, 1981; Shaw,
1985; Heintzenberg, 1989; attar, 1989). The number distribution appears practically
monodisperse (Ito and Iwai, 1981) with a mean diameter of approximately 0.15 ,urn; two
more modes at 0.75 and 8 ,urn (Shaw, 1986; Jaenicke et al., 1992) (Figure 7.20) dominate
the mass distribution.
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referred to as Arctic Haze (Barrie. 1986). During this period the aerosol numher cnnc~n-
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distribution.

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 AEROSOLCHEMICAL COMPOsmON 441

Aerodynamic Diameter. Dae. Jim

FIGURE 7.23 Measured size distributions of aerosol sulfate, nitrate, ammonium, chloride,
sodium,and hydrogenion in Claremont,CA (Wall et al., 1988).

fine particles. Crustal materials, including silicon, calcium, magnesium, aluminum, and
iron, and biogenic organic particles (pollen, spores, plant fragments) are usually in the
coarse aerosol fraction. Nitrate can be found in both the fine and coarse modes. Fine nitrate
is usually the result of the nitric acid/ammonia reaction for the formation of ammonium ni-
trate, while coarse nitrate is the product of coarse particle/nitric acid reactions.
A typical urban aerosol size/composition distribution is shown in Figure 7.23 (Wall et
al., 1988). These results indicate that sulfate, nitrate, and ammonium have two modes in the
0.1 to 1.0 Jl,m size range (the condensation and droplet modes), and a third one over 1 Jl,m
(coarse mode) (Figure 7.24). The condensation mode has a peak around 0.2 Jl,m and is the
result of condensation of secondary aerosol components from the gas phase. The droplet
mode peaks around 0.7 Jl,m in diameter and its existence is attributed to heterogeneous,
aqueous-phasereactions discussed in Chapter 6 (Meng and Seinfeld, 1994). More than half
of the nitrate is found in the coarse mode together with most of the sodium and chloride.
This coarse nitrate is the result of reactions of nitric acid with sodium chloride or aerosol
crustal material (see Chapter 9). This is an interesting case where secondary aerosol matter
(nitrate) is formed through the reaction of a naturally produced material (sea salt or dust)
and an anthropogenic pollutant (nitric acid).
More than 40 trace elements are routinely found in atmospheric particulate matter sam-
ples. These elements arise from dozens of different sources including combustion of coal,
oil, wood burning, steel furnaces, boilers, smelters, dust, waste incineration, and break
wear. Depending on their sources, these elements can be found in either the fine or the
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 AEROSOLCHEMICAL COMPOSITION 443

TABLE 7.7 Comparison of Ambient Fine and CoarseParticles

Formationpathways

Composition Resuspended dust

Coal and oil fly ash
Crustal element (Si, AI, Ti,
Fe) oxides
CaCO3, NaCI
Pollen, mold, spores
Plant, animal debris
Tire wear debris

Combustion(coal, oil,
gasoline,diesel,wood)
Gas-to-particleconversionof
NOx' S03' andVOCs
Smelters,mills, etc.

Source: Adapted from Wilson and Shuh (1997) and U.S. EPA (1996).

fonn of oxides (e.g., Fe203, Fe304, AI203), but their chemical fonn is in general un-
certain.
A summary of chemical infonnation regarding the coarse and fine modes is presented in
Table 7.7.
The composition of sea salt reflects the composition of seawater enriched in organic ma-
terial (marine-derived sterols, fatty alcohols, and fatty acids) that exists in the surface layer
of the oceans (Schneider and Gagosian, 1985). Seawater contains 3.5% by weight sea salt
and when first emitted the sea salt composition is the same as that of seawater (Table 7.8).
Reactions on sea salt particles modify its chemical composition; for example, sodium chlo-
ride reacts with sulfuric acid vapor to produce sodium sulfate and hydrochloric acid vapor

H2SO4(g) + 2NaCI ~ Na2S04+ 2 HCI(g)

leadingto an apparent"chloride deficit" in the marineaerosol.

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 VERTICAL VARIATION 445

and N B is the numberconcentrationof the backgroundaerosolaloft. For marine aerosol

H; varies from -290 to 440 m. Note that if H; is negative n = -I, and (7.60) can be
rewrittenas
-1
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NB

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 REFERENCES447

JaenickeR., Dreiling V., LehmannE., Koutsenogii,P. K., and Stingl, J. (1992) Condensationnuclei
at the GermanAntarctic StationVonneymayer,Tellus,44B, 311-317
John,W., Wall, S. M., Ondo,J. L., and Winklmayr, W. (1990) Modes in the size distributionsof at-
mosphericinorganicaerosol,Atmos.Environ., 24A,2349-2359.
Koutsenogii,P. K., and Jaenicke,R. (1994) Number concentrationand size distribution of atmos-
pheric aerosolin Siberia,J. AerosolSci., 25,377-383.
Koutsenogii, P. K., Bufetov, N. S., and Drosdova,V. I. (1993) Ion composition of atmospheric
aerosolnearLake Baikal, Atmos.Environ, 27A, 1629-1633.
Leaitch, W. R., and Isaac,G. A. (1991) Troposphericaerosolsize distributions from 1982to 1988
over EasternNorth America,Atmos.Environ., 25A,601-619.
Li, X., Maring, H., Savoie,D., Voss,K., and Prospero,J. M. (1996) Dominanceof mineral dust in
aerosollight scatteringin the North Atlantic tradewinds, Nature,380,416-419.
Meng, Z., and Seinfeld,J. H. (1994) On the sourceof the submicrometerdroplet modeof urbanand
regionalaerosols,AerosolSci. Technol.,20,253-265.
Meszaros,A., and Vissy, K. (1974) Concentration,size distribution and chemical natureof atmos-
pheric aerosolparticlesin remoteoceanareas,J. AerosolSci., 5, 101-109.
Monahan,E. C., Fairall, C. W., Davidson,K. L., andJones-Boyle,P.(1983)Observedinter-relation-
shipsamongst10-m-elevationwinds, oceanicwhitecaps,andmarineaerosols,Q. J. R. Meteorol.
Soc.,109, 379-392.
O'Dowd, C. D., andSmith, M. H. (1993)Physicochemicalpropertiesof aerosolsover the Northeast
Atlantic: evidencefor wind-speedrelated submicron sea-saltaerosolproduction, J. Geophys.
Res.,98, 1137-1149.
Ott, S. T., Ott, A., Martin, D. W., andYoung,J. A. (1991)Analysisof trans-Atlanticsaharandustout-
breakbasedon satelliteandGATE data,Mon. WeatherRev.,119, 1832-1850.
Ottar, B. (1989)Arctic air pollution: a Norwegianperspective,Atmos.Environ.,23,2349-2356.
Prospero,J. M. (1995)The atmospherictransportof particlesto the ocean,in SCOPEReport:Particle
Flux in the Ocean,Ittekkot, V., Honjo, S., Depetris,P.J. (Eds.),Wiley, New York, NY.
Prospero,J. M., Nees,R.T., andUematsu,M. (1987)Depositionrateof particulateanddissolvedalu-
minum derived from saharadust in precipitation in Miami, Florida, J. Geophys.Res., 92,
14723-14731.
Pruppacher,H. R., and Klett, J. D. (1980) Microphysics of Cloud and Precipitation, D. Reidel,
Dordrecht,The Netherlands.
Radke,L. F., Lyons, J. H., Hegg, D. A., and Hobbs, P. V. (1984) Airborne observationsof Arctic
aerosols.I: Characteristicsof Arctic haze, Geophys.Res.Lett., 11, 369-372.
Rahn, K. (1981) Relative importanceof North America and Eurasiaas sourcesof Arctic aerosol,
Atmos.Environ., 15,1447-1456.
Savoie,D. L., andProspero,J. M. (1989)Comparisonof oceanicandcontinental sourcesof non-sea-
salt sulfateover the Pacific ocean,Nature, 339, 685-687.
Schneider,J. K., and Gagosian,R. B. (1985) Particle size distribution of lipids in aerosolsoff the
coastof Peru,J. Geophys.Res.,90, 7889-7898.
Schroeder,W. H., Dobson,M., Kane,D. M., andJohnson,N. D. (1987)Toxic traceelementsassoci-
atedwith airborneparticulatematter:a review,J. Air Pollut. Cont.Assoc.,37,1267-1285.
Shaw,G. E. (1984) Microparticle sizespectrumof Arctic haze, Geophys.Res.Lett., 11,409-412.
Shaw, G. E. (1985) Aerosol measurementsin Central Alaska 1982-1984,Atmos. Environ., 19,
2025-2031.
Shaw,G. E. (1986) On physicalpropertiesof aerosolsat RossIsland,Antarctica,J. Aerosol Sci., 17,
937-945.
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 PROBLEMS 449

7.48 Showthatthe varianceof the sizedistributionof a log-nonnallydistributedaerosolis

7.SA Starting with semilogarithmicgraph paper,constructa log-probability coordinate

axis and showthat a log-normaldistribution plots as a straightline on thesecoordi-
nates.
7.6A The datagiven below were obtainedfor a log-normally distributedaerosolsizedis-
tribution:

SizeInterval GeometricMean of Numberof Particles

(,urn) SizeInterval (I/.m) in Intervalu
0.1-0.2 0.1414 50
0.2-0.4 0.2828 460
0.4-0.7 0.5292 1055
0.7-1.0 0.8367 980
1.0-2.0 1.414 1705
2.0-4.0 2.828 680
4.0-7.0 5.292 102
7.0-10 8.367 10
10-20 14.14 2
U Assume that the particles are spheres with density p = 1.5 g cm -3.

8. Completethe abovetable by computing the following quantities: ~Ni / ~Dpi.

~Ni/N~Dpi,~Si/~Dpi, ~Si/S~Dpi. ~Mi/~Dpi. ~Mi/M~Dpi,
~Ni / ~ log Dpi, ~Ni / N ~ log Dpi, ~ Si/ ~ log Dpi. ~ Si/ S ~ log Dpi, and
~Mi / ~ log Dpi, ~Mi / M ~ log Dpi, where M = particle mass.
b. Plot ~Ni / ~ log Dpi, ~Si / ~ log Dpi, and ~Mi / ~ log Dpi as histograms.
c. Determinethe geometricmeandiameterand geometricstandarddeviationof the
log-normaldistribution to which thesedataadhereandplot the continuousdistri-
butionson the threeplots from part (b).
7.78 For a log-normally distributedaerosoldifferent meandiameterscan be definedby
- - 2
DplI = Dpgexp(v In ag)

where v is a parameterthat definesthe particular meandiameterof interest.Show

that
Diameter v
Mode (mostfrequentvalue) -1
Geometricmeanor median 0
Number(arithmetic)mean 0.5
Surfaceareamean 1
Massmean 1.5
Surfaceareamedian 2
Volumemedian 3
 PROBLEMS 449

7.48 Showthatthe varianceof the sizedistributionof a log-normallydistributedaerosolis

7.SA Starting with semilogarithmicgraph paper,constructa log-probability coordinate

axis and showthat a log-normaldistribution plots asa straightline on thesecoordi-
nates.
7.6A The datagiven below were obtainedfor a log-normally distributedaerosolsizedis-
tribution:

SizeInterval GeometricMean of Numberof Particles

(,urn) SizeInterval (ILm) in Intervalu
0.1-0.2 0.1414 50
0.2-0.4 0.2828 460
0.4-0.7 0.5292 1055
0.7-1.0 0.8367 980
1.0-2.0 1.414 1705
2.0-4.0 2.828 680
4.0-7.0 5.292 102
7.0-10 8.367 10
10-20 14.14 2
U Assume that the particles are spheres with density p = 1.5 g cm -3.

8. Completethe abovetable by computing the following quantities: ~Ni / ~Dpi,

~Ni/N~Dpi,~Si/~Dpi, ~Si/S~Dpi, ~Mi/~Dpi, ~Mi/M~Dpi,
~Ni / ~ log Dpi, ~Ni / N ~ log Dpi, ~ Si/ ~ log Dpi, ~ Si/ S ~ log Dpi, and
~Mi / ~ log Dpi, ~Mi / M ~ log Dpi, where M = particle mass.
b. Plot ~Ni / ~ log Dpi, ~Si / ~ log Dpi, and ~Mi / ~ log Dpi as histograms.
c. Determinethe geometricmeandiameterand geometricstandarddeviationof the
log-normaldistribution to which thesedataadhereandplot the continuousdistri-
butionson the threeplots from part (b).
7.78 For a log-normally distributedaerosoldifferent meandiameterscan be definedby
- - 2
DplI = Dpgexp(vln ag)

where v is a parameterthat definesthe particular meandiameterof interest.Show

that
Diameter v
Mode (mostfrequentvalue) -1
Geometricmeanor median 0
Number(arithmetic)mean 0.5
Surfaceareamean 1
Massmean 1.5
Surfaceareamedian 2
Volumemedian 3
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 TEMPERATUREIN THE LOWER ATMOSPHERE 767

is referred to as stable. The stability condition of the atmosphere plays an important role in
determining the rate of dispersal of material.
The phenomenon of direct interest in predicting the dispersion of air pollutants is turbu-
lent diffusion. Actually, turbulent diffusion is something of a misnomer. The phrase refers
to the observed spreading of a cloud of marked particles in a turbulent fluid at a rate many
ordersof magnitude greater than that from molecular diffusion alone. The spreading is re-
ally not due to a "diffusion" phenomenon such as results from molecular collisions but
ratheris a result of the rapid, irregular motion of macroscopic lumps of fluid (called eddies)
in turbulence. Thus the scales of length in turbulent diffusion are much greater than in mol-
eculardiffusion, with the contribution of the latter to the dispersion of pollutants in turbu-
lence being virtually negligible. The lev~l of turbulence in the planetary boundary layer
increaseswith increased wind speed, surface roughness, and instability. Turbulence there-
fore arises from both mechanical forces (shear, surface friction) and thermal forces (buoy-
ancy).
Lower atmospheric temperature profiles determine in part the stability of the atmos-
phereor, in other words, the degree to which turbulence induced by wind, surface rough-
ness,or buoyancy will propagate through the layer. Under strongly stable conditions,
disturbancesare highly damped and mixing of species is strongly suppressed. It is under
such conditions that the worst air pollution episodes have occurred. The importance of
winds to the atmospheric aspectsof air pollution is clearly evident. Our discussion of winds
in this chapter will be largely qualitative; in Chapter 16 we shall treat air motion in the
lower atmosphere from a quantitative standpoint.

14.1 TEMPERATURE IN THE LOWER ATMOSPHERE

Thelayersof the atmospherecan be classifiedin a numberof ways, suchas by tempera-

ture,density,and chemicalcomposition.From the standpointof the dispersionof air pol-
lutants,the most importantclassificationis on the basisof temperature.

14.1.1 Pressure and Temperature Relationships in the Lower Atmosphere

We shall utilize the concept of an air parcel, a hypothetical mass of air that may deform as
it moves vertically in the atmosphere. The concept of an air parcel is a tenable one as long
asthe parcel is of such a size that the exchange of air molecules across its boundary is small
when compared with the total number of air molecules in the parcel. As such a parcel rises
in the atmosphere, it expands to accommodate the lowering pressure; however, it does so
in such a way that exchange of heat between the parcel and the surrounding air is negligi-
ble. As the parcel expands upon rising, its temperature decreases.The process of vertical
mixing in the atmosphere can, for simplicity, be envisioned as one involving a large num-
ber of parcels rising and falling. If there is no heat exchange between the parcel and the sur-
rounding air, the parcel and the surrounding air may be at different temperatures (but not
different pressures). The relation of the parcel's temperature to that of the air determines
whether the parcel will continue rising or falling or whether it will reach a point of equi-
librium. Therefore the variation of temperature with altitude in the atmosphere is a key
variable in determining the degree to which contaminant-bearing air parcels will mix ver-

tically.
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 TEMPERATUREIN THE LOWER ATMOSPHERE 771

conditions.Integrating(14.14)with respectto z gives

One might ask: Why does not the atmosphere always have an adiabatic lapse rate as its
actual profile? The reason it does not is that other processes such as winds and solar heat-
ing of the Earth's surface lead to dynamic temperature behavior in the lowest layers of the
atmospherethat is seldom adiabatic. These other processesexert a much stronger influence
on the prevailing temperature profile than does the adiabatic rising and falling of air

parcels.
Let us compute the temperature change with z of an isolated parcel of air (or possibly
other gas) as it rises or falls adiabatically through an atmosphere that is not adiabatic. We
assumethat conduction or convection of heat across the boundary of the parcel will be slow
compared with the rate of vertical motion. Thus an individual parcel is assumed to rise or
fall adiabatically, even when the surrounding air is nonadiabatic.
Let T denote the temperature of the air parcel and T' the temperature of the surround-
ing air. At any height z, the pressure is the same in the parcel as in the atmosphere. The rate
of change of T with p in the parcel is given by (14.4), and the rate of change of p with z
is given by (1.3). Combining these two relations, we find that

dT T
dz =-rr
Thereforethe rising air will cool at a greateror lesserratethanthe adiabatic,dependingon
whetherits temperatureis higher or lower than that of the adjacentatmosphere.
If A is the actuallapserate in the atmosphere,then at any height z

T'(z) = T~- Az (14.17)

Then,from (14.16)and (14.17),

dT T(z)
=-r 1:' - Az
(14.18)
dz 0

Integrating(14.18)with T(O) = To.the surfacetemperatureof the rising parcel

riA
T(z) = To .!i-=!:.3-
1:'
0

so that, in general,

(r-A)fA To
dT ~!!:!:.
=-r (14.20)
dz T~ "TJ
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 ATMOSPHERICSTABILITY 773

On the other hand, if A < r, a rising air parcel will cool more rapidly with height than
the surroundings and a point will be reached at which the temperature of the parcel equals
that of the surroundings. We see that, if A < r, the acceleration will oppose the motion of
a parcel. Thus any fluctuations in the temperature of an air parcel will cause it to rise or fall,
but only for a short distance. When A < r, the atmosphere is said to be stable.
Summarizing, the conditions are:

A = r, neutralstability
A > r. unstable(vertical motionsenhanced)
A < r. stable(vertical motionssuppressed)

These same arguments may be applied to the case of a moist atmosphere. Because of the
releaseof the latent heat of vaporization, a saturated parcel cools on rising at a slower rate
than a dry parcel, since

rdry> r wet

Thus a cloudy atmosphere is inherently less stable than a dry atmosphere, and a stable sit-
uation with reference to the dry adiabatic lapse rate may actually be unstable for upward
displacements of a saturated air parcel.
Figure 14.1 summarizes the types of temperature profiles found in the lower atmos-
phere, and Figure 14.2 shows a typical diurnal variation of temperature near the ground.
The airmass near the ground is adiabatic only under special circumstances. Adiabatic con-
ditions are reached usually when the sky is heavy with clouds and there is a moderate to
high wind. The clouds prevent radiation from reaching the surface and ensure that the tem-
peratureof the ground does not differ greatly from the air just above it. The wind serves to
mix the air, thereby smoothing out temperature differences. Vertical movement is then a re-

FIGURE 14.1 Temperature profiles in the atmosphere. (1) Adiabatic lapse rate (neutral stability,
about 1°C per 100m) T decreaseswith height such that any vertical movement imparted to an air par-
cel will result in the parcel maintaining the same T or density as the surrounding air. (2) Superadiabatic
(unstable): a rising air parcel will be warmer than its environment so it becomes more buoyant and con-
tinues rising. (3) Subadiabatic (stable): a rising air parcel is cooler than its surroundings so it
becomes less buoyant and subsides. (4) Isothermal (stable): temperature is constant with height.
(5) Inversion (extremely stable): temperature increases with height.
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 PROBLEMS 775

Figure 14.3showsmonthly averagediurnal and seasonalvariationsof the vertical ther-

malstructureof the planetaryboundarylayer at rural site nearSt. Louis, Missouri.

PROBLEMS

14.1A Showthat if the atmosphereis isothermalthetemperaturechangeof a parcelof air

rising adiabaticallyis

T(z) = Toe-rz/To
Where Toand T~are the temperaturesof the parcelat the surfaceand of the air at
the surface,respectively.
14.2A A rising parcel of air will cometo rest when its temperatureT equalsthat of the
surroundingair, T'. Showthat the height z wherethis occursis given by
. 1;,r 1{(r-A)
1 0
z= A
,~

What condition musthold for this result to be valid?

14.3A Show that the condition that the density of the atmospheredoesnot changewith
height is
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Clouds are one of the most significant elements of the atmospheric system, playing several
key roles.

1. Cloudsarea major factor in the Earth'sradiationbudget,reflectingsunlightbackto

spaceor blanketing the lower atmosphereand trapping infrared radiation emitted
by the Earth's surface.
2. Cloudsdeliver waterfrom the atmosphereto the Earth'ssurfaceasrain or snowand
arethus a key stepin the hydrologic cycle.
3. Clouds scavengegaseousand particulatematerialsand return them to the surface
(wet deposition).
4. Cloudsprovide a mediumfor aqueous-phase
chemicalreactionsandproductionof
secondaryspecies.
5. Cloudsaffect significantlyvertical transportin the atmosphere.Updraftsanddown-
draftsassociatedwith cloudsdeterminein a major way the vertical redistributionof
tracespeciesin the atmosphere.

Despite their great importance, clouds still remain one of the least understood compo-
nents of the weather and climate system. We begin our discussion of clouds by summariz-
ing the properties of their basic constituent, water. We then investigate the formation of
droplets in a cooling air parcel. The microphysics of a droplet population and the dynam-
ics of cloud formation are then examined. Finally, we revisit the chemical processestaking
place in clouds and fogs using the material already developed in Chapter 6. A comprehen-
sive discussion of cloud physics, beyond the scope of this book, can be found in
Pruppacher and Klett (1980).

15.1 PROPERTIES OF WATER AND WATER SOLUTIONS

Liquid water, H2O, is characterized by the strong hydrogen bonds between its molecules,
which give rise to a number of unique properties. Because of the strength of these bonds, a
relatively large amount of energy is required to evaporate a unit mass of water. Similarly,
the latent heat of freezing is also relatively large, as a result of further strong bonding in ice
crystals. The surface tension (surface free energy) is also large. Table 15.1 summarizes
thesephysical properties of water. In the following sections we discuss the atmospherically
relevant properties of water and and its solutions.

777
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 PROPERTIESOF WATERAND WATERSOLUTIONS 779

15.1.3 Water Surface Tension

Thesurfacetensionof water decreaseswith increasingtemperature.Pruppacherand Klett
(1980)recommenduseof the following function:

(Two = 0.0761- 55 x IO-4(T - 273)

for the temperature range -40 to 40°C, where awo is in J m -2. The surface tension of wa-
ter is 76.1 x 10-3 J m-2 at O°C, and decreases by 1.55 x 10-3 J m-2 for every 10°C.
Note that these values can be used for supercooled water also, that is, liquid water existing
at temp,eraturesbelow O°C.
The dissolution of other compounds in water alters its surface tension. Experimental
valuesof the variation of water solution surface tension with the solution concentration are
tabulatedin the Handbook of Physics and Chemistry. For salts like NaCI and (NH4)2S04
the dependence of the solution surface tension, aw, on the solution molarity is practically
linear over the range of atmospheric interest:

O"w(mNaCI, T) = O"wo(T)+ 1.62 x 10-3 mNaCI

O"w(m(N~n
so.' T) = O"wo(T)+2.17 x 10-3 m(NH.)2S0.

where uwo(T) is the surface tension of pure water and mNaCland m(N~nS04 are the mo-
larities of NaCI and (N~)2 SO4 in M, respectively. I
A last issue is the dependenceof the water surface tension on the size of the droplet. One
would expect that as the droplet surface tension is the result of attractive forces between
water molecules near the surface, a change in droplet diameter would change the number
of molecules interacting with the molecules at the surface, thus changing the surface ten-
sion.However, becauseof the small range of molecular interaction, this dependenceof Uwo
on size is significant only for extremely small drops, consisting merely of a few thousands
of molecules, and the exact dependence is still a subject of debate (Pruppacher and Klett,
1980).The change is probably smaller than 1% for water drops as small as 0.1 JLmand be-
comessignificant only at drop sizes less than 0.01 JLm. Therefore the dependence of sur-
facetension on droplet size can be neglected for atmospheric cloud applications.

]Because solutes alter the surface tension of water, one would expect variations of the concentrations of these
speciesnear the droplet-air interface. For example, as nature tries to reach states of lower energies, if a solute in-
creasesthe surface tension of water, this species at equilibrium should have lower concentrations at the interface
than in the bulk solution. The opposite should happen for a surface-active compound that lowers the surface ten-
sion. One would expect higher concentrations of this species near the interface than in the bulk. For a I M NaCI
solution this surface tension effect results in a NaCI deficiency at the interface of less than 1% (Pruppacher and
Klett, 1980). The same authors suggested that for drops with diameters larger than 0.2 JLm and NaCI concentra-
tions lower than I M, this concentration gradient due to surface tension is less than I % and can safely be ignored.
The effect of solution inhomogeneity due to surface tension will therefore be neglected for our discussion of at-
mospheric droplet formation.
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 WATEREQUILIBRIUM IN THE ATMOSPHERE 781

TABLE 15.2 Saturation Vapor Pressureof Water Vapor Over a Flat Pure
Water or Ice Surface

pO(mbar) = ao + a) T + a2T2 + a3T3 + a4T4 + asTs + a6T6 (T is in °C)

Water( -50 to +50°C) Ice (-50 to DOC)

ao = 6.107799961
al = 4.436518521 x 10-1
a2 = 1.428945805 x 10-2
a3 = 2.650648471 x 10-4
a4 = 3.031240396 x 10-6
as = 2.034080948 x 10-8
a6 = 6.136820929 x 10-11

Source: Lowe and Ficke (1974).

where ~Hv is the specific heat for water evaporation, Mw is the molecular weight of wa-
ter, and Vv and Vw are the molar volumes of water vapor and liquid water correspondingly.
Assuming that Vv » Vw and that water vapor satisfies the ideal gas law (pOvv = RT),
then (15.7) becomes (9.68),

dpO ""
~Hv(T)pOMw
dT RT2

Replacing in the above equation a function describing the temperature dependence of the
latent heat of evaporation (e.g., (15.3)), one can integrate and obtain an explicit expression
for pO(T). A series of such expressions exist in the literature (see Problem 1.1), and that
proposedby Lowe and Ficke (1974) is given in Table 15.2.

15.2.2 Equilibrium of a Pure Water Droplet

In Chapter 9 we showed that the vapor pressure over a curved interface always exceedsthat
of the same substance over a flat surface. The dependence of the water vapor pressure on
the droplet diameter is given by the Kelvin equation (9.86) as

E~ exp
(

~
4Mwaw"

pO

wherePw(Dp) is the water vaporpressureover the dropletof diameterDp, po is the water

vaporpressureover a flat surfaceat the sametemperature,Mw is the molecularweight of
water,O"wois the air-water surfacetension,and Pwis the water density.The equilibrium
watervaporconcentrationsat O°C and 20°C are shownin Figure 15.2asa function of the
dropletdiameter.Note that the effect of curvaturefor water dropletsbecomesimportant
only for Dp < 0.1 /.Lm.
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 WATEREQUILIBRIUM IN THE ATMOSPHERE 783

15.2.3 Equilibrium of a Flat Water Solution

Let us considera water solution (flat surface)at constanttemperatureT andpressurep in
equilibriumwith the atmosphere.Waterequilibrium betweenthe gasand aqueousphases
requiresequality of the correspondingwater chemical potentialsin the two phases(see
Chapter9):
,uw(g) = ,uw(aq) (15.10)

Water vapor behaves in the atmosphere as an ideal gas so its gas-phasechemical potential
is
.uw(g) = .u~(T)+ RTlnp~ (15.11)

wherep~ is the water vapor partial pressureover the solution.The chemicalpotential of

liquid water will be given by

JLw(aq) = JL~+ RTlnywxw (15.12)

whereYwis the water activity coefficient and Xw the mole fraction of water in solution.
Combining(15.10)to (15.12)we obtain
( /10 * '

~ = exp t"'w - .uw

(15.13)
YwXw RT

Theaboveequationdescribesthe behavior of the systemfor any solution composition.

Notethat the right-handside is a function of temperatureonly and thereforewill be equal
to a constant,K, for constanttemperature.Consideringthe caseof pure water (no solute)
wenotethat when Xw= I, Yw-+ 1 and p~ = po = K (T), wherepo is the vaporpressure
of waterover pure water.Therefore(15.13)canbe rewritten as

0 0
Ps = Yw Xw P (15.14)

Equation(15.14) is applicablefor any solution and does not assumeideal behavior.

'.~"'---". -" " Yw,
The mole fraction of water in a solution consistingof nw water moles and ns solute
molesis given by

Xw = nwnw
+ ns (15.15)

andtherefore the vapor pressure of water over its solution is given by

p; =. -
n... YwpO (15.16)
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 WATEREQUILIBRIUM IN THE ATMOSPHERE 787

Equations (15.21), (15.24), (15.26), and (15.27) are different forms of the Kohler equa-
tions (Kohler, 1921, 1926). These equations express the two effects that determine the va-
por pressure over an aqueous solution droplet-the Kelvin effect that tends to increase
vapor pressure and the solute effect that tends to decreasevapor pressure. For a pure water
drop there is no solute effect and the Kelvin effect results in higher vapor pressurescom-
pared to a flat interface. By contrast, the vapor pressure of an aqueous solution drop can be
larger or smaller than the vapor pressure over a pure water surface depending on the mag-
nitude of the solute effect term, BI D~, relative to the curvature term, AI Dp. Note that
both effects increase with decreasing droplet size but the solute effect increases much
faster. One should also note that a droplet may be in equilibrium in a subsaturatedenviron-
ment if D~A < B.
Figure 15.5 shows the water vapor pressure over NaCl and (NH4)2S04 drops. The A
term in the Kohler equations can be approximated by

4MwO"w 0.66
A= ::::: (in JLm) (15.28)
RTpw T

where T is in K, and the soluteterm,

(in JLm3) (15.29)

where ms is the solute mass (in g) per particle, Ms the solute molecular weight (in g
mol-I), and v is the numberof ions resultingfrom the dissociationof one solutemolecule.
For example,v = 2 for NaCI and NaN°3, while v = 3 for (NH4)2S04.

0.5I'] I I I I I II'I I I I I I I ~- - . (NH4)2S

NaCI I I ~ 4
II' ,

o. . .
,
. . D =0.05 .urn
~ 0.3 .
. p
,
a0 0.')1
.
.
:.j
=
0.1 J.l,m
~
+"
o.
=
~
100 0.0 - . ,-
~ ,
§'
f/) -0.
,
,
,
. , 10.5 Ji,m

-O.:t
,
,
"
., ,
- 0.3 III0 'I" "I ilill 1 I; 'I IIIIII 10 I I I IIIIIJ100

Wet Diameter. p,m

FIGURE 15.5 Kohler curves for NaCl and (NH4)ZSO4 particles with dry diameters 0.05, 0.1, and
0.5 ILm at 293 K (assuming spherical dry particles). The supersaturation is defined as the saturation
minus one. For example, a supersaturation of 1% corresponds to a relative humidity of 101%.
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 WATEREQUILIBRIUM IN THE ATMOSPHERE 789

Let us consider first a drop lying on the portion of the Kohler curve for which
Dp < Dpc. We assume that the atmospheric saturation is fixed at S. A drop will constantly
experience small perturbations caused by the gain or loss of a few molecules of water. Say
that the drop grows slightly due to the addition of a few molecules of water. At its momen-
tary larger size, its equilibrium vapor pressure is larger than the fixed ambient value and the
drop will evaporate water, eventually returning to its original equilibrium state. The same
phenomenon will be observed if the droplet loses a few molecules of water. Its equilibrium
vapor pressure will decrease,become less than the ambient, and water will condense on the
droplet returning it to its original size. Therefore drops in the rising part of the Kohler curve
are in stable equilibrium with their environment.
Now consider a drop on the portion of the curve for which DIJ > Dpc that experiences
a slight perturbation, causing it to grow by a few molecules of water. At its slightly larger
size its equilibrium vapor pressure is lower than the ambient. Thus water molecules will
continue to condense on the drop and it will grow even larger. Conversely, a slight shrink-
age leads to a drop that has a higher equilibrium vapor pressure than the ambient so the
drop continues to evaporate. If it is a drop of pure water, it will evaporate completely. If it
contains a solute, it will diminish in size until it intersects the ascending branch of the
Kohler curve that corresponds to stable equilibrium. In conclusion, the descending
branchesof the curves describe unstable equilibrium states.
If the ambient saturation ratio S is lower than the critical saturation Sc for a given par-
ticle, then the particle will be in equilibrium described by the ascending part of the curve.
If 1 < S < Sc, then there are two equilibrium states (two diameters corresponding to S).
One of them is a stable state and the other is unstable. The particle can reach stable equi-
librium only at the state corresponding to the smaller diameter.
If the ambient saturation ratio S happens to exceed the particle critical saturation Sc,
there is no feasible equilibrium size for the particle. For any particle diameter the ambient
saturation will exceed the saturation at the particle surface (equilibrium saturation), and the
particle will grow indefinitely. In such a way a droplet can grow to a size much larger than
the original size of the dry particle. It is, in fact, through this process that particles as small
as0.01 JLm in diameter can grow one billion times in mass to become 10 JLmcloud or fog
droplets. Moreover, in cloud physics a particle is not considered to be a cloud droplet un-
less its diameter exceeds its critical diameter Dpc.
The critical saturation Sc of a particle is an important property. If the environment has
reached a saturation larger than Sc, the particle is said to be activated and starts growing
rapidly, becoming a cloud droplet. For a spherical aerosol particle of diameter ds (dry di-
ameter), density Ps, and molecular weight Ms, the number of moles (after complete disso-
ciation) in the particle is given by

ns= V7rd; Ps
(15.33)
6Ms

andcombiningthis result with (15.32)we find that

1/2
In Sc= (15.34)
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 WATEREQUILIBRIUM IN THE ATMOSPHERE 791

(NH4)2S04, T= 20°C
.01 - No dissociation
- - -. Complete dissociation

1.009

1.007
s
.005 I
0.02 ~m--- I
I

~I
I
1.003
I
1.001 '?
0.04~m-
,
, , - --
I
0.999I
.
I
; . ~O.l
I I
~m
.
10.2 10.1 1 10

Wet Radius, Ilffi

FIGURE 15.7 Kohler curves for (NH4)2S04 assuming complete dissociation and no dissociation
of the salt in solution for dry radii of 0.02, 0.04, and0.1 ILm.
ts, all
at the
acti-
Our analysisfollows exactly Section15.2.4,until the derivationof the mole fraction of
ODOr water Xw in (15.19) and (15.20).The existenceof the insoluble material needsto be in-
v and cludedin theseequations.If the insoluble particle fraction is equivalentto a sphereof di-
ameterduothen the droplet volume will be
1 and
~(the D3 - - 1
e ab-
1 7r
6" p = nwvw+ nsvs+ 6"7rdu3 (15.35)

andthe mole fraction of water Xwin the solution will be given by

dig-
-- +
ns
= (15.36)
Xw nw
wa.
Substitutingthis expressioninto (15.18)we find

not
In = 4MwC1w + In Yw- In (15.37)
RTp:D;
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 CLOUD AND FOG FORMATION 793

ns analo-
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1.00 £ =0.01

'\.
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Dry Diameter, ,u,m
FIGURE 15.9 Critical supersaturationas a function of the particle dry diameterfor different con-
tentsof insolublematerial.The solublematerialis (NH4)2S04.
(15.39)

and (15.38) can be rewritten as a function of the particle soluble fraction and the initial par-
ticle diameter provided that the densities of soluble and insoluble material are known. The
number of moles of solute are in this case given not by (15.33) but by the following
expression:

(15.40)

Kohler curves for a particle consisting of various combinations of (NH4)2 SO4 and in-
soluble material are given in Figure 15.8. We see that the smaller the water-soluble fraction
the higher the supersaturation needed for activation of the same particle, and the lower the
critical diameter. Critical supersaturation as a function of the dry particle diameter is given
in Figure 15.9.

15.3 CLOUD AND FOG FORMATION

The ability of a given particle to becomeactivateddependson its size and chemicalcom-

position andon the maximumsupersaturation experiencedby the particle.If, for example,
the ambientRH doesnot exceed100%,no particle will be activatedanda cloud cannotbe
formed2. In this sectionwe will examinethe mechanismsby which cloudsare createdin

ontaining 2The classic Kohler formulation does not consider the cases of solutes that are not completely soluble or soluble
Ible mass gases, both of which influence the solute effect term in (15.27). In such cases cloud droplets can exists at S < 1
since B/D~ > A/Dp.

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S;)ISAHd GnO.1;) t'6J.
 CLOUD AND FOG FORMATION 795

For an air parcelinitially at 283 K with a relative humidity of 80% (RH = 0.8),a tem-
peraturereductionof 3.3 K is requiredto bring the parcelto saturation.The dew point of a
subsaturated air parcelis alwayslower than its actualtemperature(Figure 15.10).The two
becomeequalonly whenthe relative humidity reaches100%.

15.3.2 Adiabatic Cooling

Thethennodynamicbehaviorof a rising moist air parcelcanbe examinedin two steps:the
coolingof the air parcel from its initial condition to saturationfollowed by the cooling of
thesaturatedair.
Let us considerfirst a moist unsaturatedair parcel.Assumingthat the rise is adiabatic
(no heat exchangewith its surroundings)and reversible,then it will also be isentropic.
Recallthat for a reversibleprocessd Q = T dS andthereforewhen d Q = 0, dS = 0 also.
Undertheseconditionswe haveshownin Chapter14 that if the air parcelis dry (no water
vapor),its temperaturewill vary linearly with height accordingto (14.6),

dT
=-r (15.44)
dz

wherer = g/cp = 9.76°C km-1 is the dry adiabaticlapserate. If the air is moist, then,
as we saw in Chapter 14, the heat capacity of the air parcel cp must be corrected.The
changesare small as the water vapor massfraction is usually less than 3%. Even at this
ratherextremecondition, the lapserate of the moist parcelis 9.71°C km -I, an essentially
 (6v'~I)
-. T = '1;)'111
Aq AIdw!s puna] ~ Ug:> ':>'1{ "1;)'1;}q"!!g !q:3!;}q ;}q"! 'P;}U!UU;}!;}P S! 7.L ;}:>uO '7.L JO] AIJt1:>!l;}W
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." ( OOdlimOW
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(8v'~I)
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am"w 'I
(Lv.~I) X)= 7.z
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'(~P.~I) O~U!gu!~n~!~sqnsp~
ilm"w ="d
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'(9v'~I) Ot ~U!pJo:>:>l!';)q II!M tq~!;)q
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';)Jnss;)Jd
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(~v.~l) "dlJ=
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 CLOUD AND FOG FORMATION 797

The lifting condensation level hLcL is shown in Figure 15.11 as a function of the initial
temperature and relative humidity of the air parcel.
If the air parcel is lifted beyond the LCL, water will start condensing on the available
particles, and latent heat of condensation ( - ~ H v) will be released. The lapse rate r s in this
casecan be calculated by an energy balance, assuming that the air parcel remains saturated.
The cooling rate of the air parcel is balanced by the work necessary for the expansion of the
air parcel and the condensation latent heat released. If the air parcel contains a water vapor
mass mixing ratio Wvs(the subscript s is used to denote saturation of the atmosphere with
water), where Wvs= Mwpo/ MaPa, then the energychangedue to cooling will be cpdT
(c p is the heat capacity of air, which will be almost equal to the heat capacity of the air par-
cel including the water), the latent heat released will be ~Hv dwvs, and the expansion work
is vdp = RTdpa/PaMa. Therefore the energy balance is

Cp
A
dT + .1.Hvdwvs - RT - dpa = 0 (15.50)
PaMa

anddividing by dz leadsto the expression

r S-- ( dz ) =~~--~~
-~
dz
A

Cp
A

MaPacp dz
(15.51)

4000 I I I I ' I I I ' I I

E 3500

RH=O.2
~ 3000
>
Q)
~

c: 2500
0
:0=
C
1/1 2000
c:
Q)
"0
§ 1500
u

~ 1000
:0=
:J
500

0 I I I I I I I I I I I .
0 5 10 15 20 25 30
Temperature. °c
FIGURE 15.11 Lifting condensationlevel as a function of initial temperatureand relative humid-
ity of the air parcelassumingthat the air parcelstartsinitially at the groundat p = I atm.
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 CLOUD AND FOG FORMATION 799

15.3.4 A Simplified Mathematical Description of Cloud Formation

Let us revisit the rising moist air parcel assumingthat we are in a Lagrangianreference
frame,moving with the air parcel.The air parcelis characterizedby its temperatureT, wa-
tervapormixing ratio wv, liquid water mixing ratio wL, andvelocity W.At the sametime
weneedto know the temperatureT', pressurep, and water vapor saturationw~of the air
aroundit (Figure 15.12).The pressureof the air parcel is assumedto be equalto its envi-
ronment.
Let us assumethat the air parcel has massm and air density p (without including the
liquid water).The velocity of the air parcel will be the result of buoyancyforces and the
gravitationalforce dueto liquid water.The buoyancyforce is proportionalto the volumeof
theair parcel,m/ p, and the densitydifferencebetweenthe air parceland its surroundings,
pi - p. The liquid water massis mWLand the correspondinggravitationalforce gmwL.
Theequationfor conservationof momentumis

-d (mW) = gm p'-p -WL (15.56)

dt p

wherep' is the densityof the surroundingair.

As the air parcel is moving, it causesthe accelerationof surroundingairmasses,result-
ing in a deceleratingforce on the air parcel.The decelerationforce is proportionalto the
massof the displacedair, m', and the correspondingdeceleration,-dW/dt. Pruppacher
andKlett (1980) show that this effect is actually equivalentto an accelerationof an "in-
duced"mass m/2 and thereforea term -!m dW /dt shouldbe addedon the right-hand
sideof (15.56). Using the ideal gas law (p' - p)/ p = (T - T')/T' and the modified
(15.56)canbe rewritten as

3dW Wdm T-T'

--+--=g
2 dt m dt T' -WL (15.57)
 Zp tp
(Z9.~I) 111=
,.LP' ,.LP
o~ gU!PlO:>:>g gU!gUgq:> ~m SUO!~!PUO:>
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(I9'~I)
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(O9'~I) M I d:J Jp d(! dg Jp
=
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S! tIns~J Ieuy ~~ .suo!teJmesJ~
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f..q p~q!J:>S~p S! I~:>md J~ ~q1 Jo f..1!:>OI~A ~q1 ~JoJ~J~q.L
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'a ';}~~J~U;}WU~J:lU;};}q1 Jo UO!~!uy;}P ;}q~ ~U!l.oIdw;} I.q pu~
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 GROWTH RATE OF INDIVIDUAL CLOUD DROPLETS 801

and

15.4 GROWTH RATE OF INDIVWUAL CLOUD DROPLETS

Whencloud and fog dropletshavediameterssignificantly larger than 1,um,masstransfer

of water to a droplet can be expressedby the masstransfer equationfor the continuum
regime(seeChapter11)

~
dm = 21fDpDv(cw.oo- c~) (15.64)

by
.94

Dv--~ p 273)
(.!.- (15.65)

D'v--- Dv ,7:0 (15.66)

) 1/2
. 2D.,. '~
+-
RT
acDp

~
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 GROWTH RATE OF INDIVIDUAL CLOUD DROPLETS 803

droplet surface is then

(15.68)

where we have used the mass balance

dm
(15.69)
dt

and we have defined

(15.70)

For atmosphericcloud dropletgrowth 8 « I; however,let us continuethe dervationwith-

out assumingthat Ta = T~.Combining(15.64)and(15.69)andusingthe ideal gaslaw, we
find that
dDp -- 4D~M~) Pw(Dp. Ta)
DP-"dt Sv.oo (15.71)
PwRT pO(Too)

whereSv.oo = Pwoo/po (Too) is the environmental saturation ratio. Recall that for a relative
humidity equal to I ()()% the partial pressure of water in the atmosphere Pwoo is equal to the
saturation vapor pressure pO (Too) and Sv,oo is equal to unity. The ratio of the water satura-
tion pressures at Ta and Toois given by the Clausius-Clapeyron equation as

pO(Ta)
(15.72)
pO(Too)

Combining(15.68),(15.71),(15.38),and (15.72)we finally get

dDp - 4D~Mwp~ Sv,oo

DP&- PwRToo
(15.73)
4MwO"w
+ RTpwDp(l + <5)

The aboveresult can be simplified since 11« and

exp [~Hv Mw8/ RToo(l + 8)] ~ 1 + ~Hv Mw8/ RToo

After somealgebrathe implicit dependence

on 8 can be resolvedto obtain
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 GROWTH OF A DROPLET POPULATION 805

For a cloud droplet larger than 10 JLffi,using ac = aT = I, at 283 K,

anddefining Sv,eq
asthe equilibrium saturatiQnof the droplet, (15.74)can be rewritten as

- SV,eq)

where Dp is in cm and tin s. The growth of an aerosol size distribution under constant su-
persaturation of 1% is shown in Figure 15.14. The rate of growth of droplets is inversely
proportional to their diameters so smaller droplets grow faster than larger ones. As a result,
small droplets catch up in size with larger ones during the growth stage of the cloud.

15.5 GROWTH OF A DROPLET POPULATION

.The growth of an aerosol population to cloud droplets can be investigated using the growth
equation derived in the previous section. In general, one would need to integrate simulta-
neously the differential equations derived in Section 15.3.4 for the air parcel updraft ve-
locity, temperature, water vapor mixing ratio, and environmental temperature and water
vapor mixing ratio, coupled with a set of droplet growth equations, one for each droplet
size class. The liquid water mixing ratio of the population consisting of Ni droplets per
volume of air of diameters Dpi will then be

n
WL =~.:!:. L N;D:;
Pa 6 ;=1
(15.77)

where we have assumed that there are n groups of droplets.

It is instructive, before examining the interactions between cloud dynamics and micro-
physics, to focus our attention on the microphysics. Figure 15.15 presents the results of the
integration of these equations for a polluted urban aerosol population (Pandis et al., 1990a)
for an aerosol distribution consisting of seven size sections. At time zero the relative hu-
midity is assumed to be 100%. At this time the particles have grown several times from
their dry size as a result of water absorption and are assumed to be in equilibrium with the
surrounding environment. The temperature of the air parcel is assumed to decreasewith a
constant rate of 2 K h -1. As the temperature decreases,the saturation of the air parcel in-
creases.The particles absorb water vapor, but the cooling rate is too rapid compared to
masstransfer and the air parcel becomes supersaturated.After a few minutes the particles
startbecoming activated. The larger particles become activated first (Section 15.2) and the
smaller soon follow. As particles become activated, they are able to grow much faster. Note
that based on the Kohler curves as a particle grows the driving force for growth
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 GROWTH OF A DROPLET POPULATION 807

(cw.oo - c~q)becomeslargerfor almostconstantCw.oo,becausec~ decreasesrapidly with

size. Therefore, as more and more particles get activated, the rate of transport of water from
the vapor to the particulate phase increases, while the rate of supersaturation increase due
to the cooling remains approximately constant. The result is that the supersaturation in-
creaseslows down and after 6 min reaches a maximum value of 0.1 %.
Let us describe the above situation quantitatively, by deriving the equation for the rate
of change of the supersaturation sv.The water vapor mixing ratio Wvis related to the wa-
ter vapor partial pressure Pw by (15.46), while by definition

Pw
+sv=
pO

Therefore combining these two relationships one gets

S
v--
MaPa Wv- (15.78)
Mwpo

Differentiatingthis expressionwith respectto time andrearrangingthe termswe obtain

~ = ~~ - (1+sv)( ~~ - ~~ (15.79)
dt Mwpodt po dt Padt )
Thechangeof the air pressurewith time can be calculatedassumingthat the environment
is in hydrostaticequilibrium so that

~ = -~w
dt RT
wherewe have assumedthat T' ~ T. The changeof the parcel saturationpressurewith
timecan be calculatedusing the chain rule and the Clausius-Clapeyronequation,

° dpo dT
do
= ~HvMwpOdT
.

-=-- (15.81)
tt dT dt RT2 dt

Substituting(15.80)and (15.81)into (15.79)one gets

dsv = --
MaPa dwv
dt Mwpo dt

If we assumethat there is no entrainment(e = 0) and substitute(15.60)and (15.61)into

(15.82),we obtain

dsv = ~HvMwg gMa PaMa ~H2M

v w dWL
w- +
dt
(15.83)
dt cpRT2 RT poMw cpRT2

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 CLOUD CONDENSATIONNUCLEI 809

TABLE 15.3 Updraft Velocities and Maximum Supersaturations for Clouds and Fogs

0.25--0.7 Pruppacher and Klett (1980)

0.3--0.8 Pruppacher and Klett (1980)
Mason (1971)
Stratiform '" 0- ~O.O5 Pruppacher and Klett (1980)
Fog ~O.l Pandis and Seinfe1d (1989)

15.6 CLOUD CONDENSATION NUCLEI

Supersaturations of several hundred percent are necessary for the fonnation of water
droplets in particle free air (see Chapter 10). The need for such high supersaturations indi-
catesthe necessity of particles for cloud fonnation in the ambient atmosphere. The ability
of a given particle to serve as a nucleus for water droplet fonnation, as we have seen in the
previous sections, will depend on its size, chemical composition, and the local supersatu-
ration.
Particles that can activate at a given supersaturation are defined as cloud condensation
nuclei (CCN) for this supersaturation. In the cloud physics literature one often defines as
condensation nuclei (CN) those particles that fOnD droplets at supersaturations of ~400%
and therefore CN include all the available particles. One can therefore assume that the CN
concentration is equal to the total aerosol number concentration. This CN definition should
be contrasted with the CCN definition where supersaturations often well less than 2% are
used.Therefore CCN represent the particles that can fonD cloud droplets under reasonable
atmospheric supersaturations. We caution the reader that CCN concentrations always refer
to a specific supersaturation, for example, CCN(I%) or CCN(0.5%) and one should be
careful when comparing CCN concentrations measured or estimated at different supersat-
urations.
The CCN concentration of a given supersaturation corresponds under ideal cloud for-
mation conditions (e.g., spatial unifonnity) to the number concentrations of droplets if the
cloud had the same supersaturation. We will use the symbol CCN(s) for CCN at s% super-
saturation.
For a given aerosol population CCN(s) depends on both the size and composition of the
particles. In the simple case of an aerosol population that has unifonn size-independent
composition, by definition,

CCN(s) = roo
n(Dp) dDp
JDs (15.85)
where n(Dp) is the number distribution of the aerosol population, and Ds the activation di-
ameter for s% supersaturation of these particles. Note that CN = CCN(oo) according to
the above notation. Therefore, if all particles had the same composition, one ne~dsto know
only the activation diameter and the size distribution of these particles to estimate the cor-
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 CLOUD CONDENSATIONNUCLEI 811

c = 600 and k = for continental air. Hegg and Hobbs (1992) reviewed more recent mea-
surements of marine CCN and suggested values of c = 200 and k = 4. Other values for c
and k based on ambient measurements are given in Table 15.4.
As expected, because of the variability of the aerosol size/composition both spatially
and with time, the parameters c and k vary significantly, making the use of such empirical
relationships rather questionable. Generally, CCN(1 %) concentrations in maritime and
modified maritime airmasses are around 100 cm-3, while concentrations in excessof 1000
cm-3 are found in air that has been over land for several days.
The fraction of aerosol particles that are CCN(I%) is also quite variable. Over the
oceansthis fraction is roughly 0.5 (Hegg and Hobbs, 1992), but it does vary from 0.2 to
0.6. For polluted conditions the fraction is much lower, usually less than 1%. This is mainly
due to the existence of thousands of ultrafine particles (less than 50 nm) that cannot get ac-
tivated at this supersaturation regardless of their chemical composition.
Since ambient supersaturations rarely exceed 1%, the above CCN measurementsindi-
cate that cloud droplet concentrations should range from 200 to 1000 cm-3 over continents
and from 10 to 200 cm-3 over oceans. These values agree well with the drop concenti:a-
lions found in continental and maritime clouds.
The link between aerosol chemical composition and CCN behavior is still not com-
pletely understood. Whereas behavior of soluble inorganic aerosols is relatively well es-
tablished, much less is known about the ability of organic aerosols (alone or mixed with
inorganic components) to serve as CCN.
A series of studies have reported the activation efficiency of particles generated during
fuel combustion. These results were summarized by Lammel and Novakov (1995) and are

.lof
TABLE 15.4 Empirical Parameters for the CCN Concentration
59)
Dependenceon the Supersaturation s
for

0.3 Maritime (Australia)

0.5-0.6 Maui (Hawaii)
0.5 Atlantic, Pacific Oceans
0.8 Pacific
1.3-1.4 North Atlantic
0.4-0.9 North Atlantic
Arctic
0.4 Cape Grim (Australia)
0.5 North Atlantic
0.4,-0.6 North Pacific
1.0 North Pacific
0.3 Polluted North Pacific
0.4 Equatorial Pacific
0.5 Continental
0.4 Continental (Australia)
0.9 Continental (Buffalo, NY)

Source: Hegg and Hobbs(1992).

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Finally,thereare other processesthat cwoccur aroundcloudsthat may leadto the forma-

tionof new particles.

15.7.1 Nucleation Scavengingof Aerosolsby Clouds

Nucleationscavengingof aerosolsin cloudsrefersto activationand subsequentgrowth of
a fractionof the aerosolpopulationto cloud droplets.This processis describedby (15.74)
andhasbeendiscussedin Section15.5.
If Ci,ois the concentration(in massper volume of air) of an aerosolspeciesin clearair
beforecloud formation (e.g., at the cloud base),and Ci,cloudand Ci.intare its concentra-
tionsagainin massper volumeof air in the aqueousphaseandin the interstitial aerosol,re-
spectively,one can definethe cloud massscavengingratio for speciesi, Fi' as

Fi = Ci,O- Ci,int
(15.88)
COI. O

Notethat if thereis no productionor removalof i in the cloud then Ci,o = Ci,int + Ci,cloud'
The mass scavenging ratio defined above may vary from zero to unity. The number scav-
enging ratio F N can be defined as

No- NiDI
FN= (15.89)
No

where No is the aerosol number concentration before cloud formation and NiDIis the num-
ber concentration of interstitial aerosol.
Theoretically, as particles larger than 0.5 .urn or so become cloud droplets in a typical
cloud and these particles represent most of the aerosol mass, one would expect mass acti-
vation efficiencies close to unity. Junge (1963) predicted sulfate scavenging ratios from nu-
cleation scavenging alone to range from 0.5 to 1.0. Since then all theoretical studies have
predicted high mass nucleation scavenging efficiencies for all aerosol species. For exam-
ple, Flossmann et al. (1985, 1987) reported calculated aerosol scavenging efficiencies ex-
ceeding 0.9 in typical cloud environments. Pandis et al. (1990a) estimated scavenging
efficiencies of 0.7 for sulfate and 0.8 for nitrate and ammonia in polluted clouds. In other
numerical studies, Flossmann (1991) reported mass scavenging efficiencies of 0.9 or
higher for warm clouds over the Atlantic.
These theoretical estimates are in good agreement with the high mass scavenging effi-
ciencies measured in the atmosphere. Ten Brink et al. (1987) observed nearly complete
scavenging of aerosol sulfate in clouds. The data of Daum et al. (1984) also showed that the
bulk of the sulfate mass is incorporated into cloud droplets. Hegg and Hobbs (1988) re-
ported scavenging ratios for sulfate of 0.5 :i: 0.2.
On the contrary, low number scavenging efficiencies are expected in clouds influenced
by anthropogenic sources becauseof the prevalence of fine aerosol particles; number scav-
enging efficiencies of a few percent or less are expected in most such situations. Only in
clouds in the remote marine atmosphere does the total number scavenging efficiency ex-
ceed 0.1.
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FIGURE 15.17 Predicteddependenceof the total soluteconcentrationon droplet diameterduring
thelifetime of a cloud (Pandiset. al., 1990a).

centration that is 3.4 times higher. During the evaporation stage of a cloud, smaller droplets
get deactivated and evaporate first (Figure 15.17b). Therefore the minimum gradually dis-
appearsand the system returns close to its original state.
The above predictions agree with measured concentration/size dependencies measured
in clouds that are not heavily influenced by anthropogenic sources. Noone et al. (1988)
sampled droplets from a marine stratus cloud and calculated that the volumetric mean
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to 23 J.Lmdroplets. Ogren et al. (1989) reported similar results for a cloud in Sweden. On
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ronments suggest that solute concentrations decreasewith increasing droplet size (Munger
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FIGURE 15.19 MeasuredpH of small and large dropletsin a seriesof clouds and fogs in ty1>ical
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During cloud formation, aerosols that serve as cloud condensation nuclei (CCN) be-
come activated and grow freely by vapor diffusion. Soluble gases such as nitric acid, am-
monia, and sulfur dioxide dissolve into the droplets. The cloudwater serves as the reacting
medium for a series of aqueous-phase reactions, most importantly the transformation of
dissolved SO2, S(IV), to sulfate, S(VI). The sulfate formed is not volatile and remains in
the particulate phase. Other reactions, for example, the oxidation of formaldehyde to
formic acid, result in volatile products that return to the gas phase (Figure 15.20). During
the cloud evaporation stage, several species that were dissolved in the cloudwater evapo-
rate.Others, like sulfate, remain in the aerosol phase. Ammonia often accompanies the sul-
fate formed as the neutralizing cation. Species like nitrate or chloride that may have existed
in the original particle can be displaced by the sulfate produced and forced to return to the
gasphase.The result of these aqueous-phaseprocessesis usually an overall increase in par-
ticle mass and size. Chemical composition of the particles may also change, with sulfate
and ammonium concentrations generally increasing and nitrate and chloride decreasing
(Pandiset al., 1990b).
Available evidence suggeststhat the single most important reaction during aerosol pro-
cessingby clouds is the oxidation ofHSOj"" by H202. This reaction, as we saw in Chapter
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FIGURE 15.21 Measurementsof the gas-phasepartial pressuresof H202 versusthe S02 partial
pressurefor interstitial cloud air (Daum et aI., 1984).Arrows signify that the mixing ratio wasbelow
the detectionlimit.

during a 3 day springtime period, chemical reactions in clouds occupying I to 2% of the

tropospheric volume were responsible for sulfate production comparable to the gas-phase
reactions throughout the entire tropospheric volume under consideration. McHenry and
Dennis (1994) proposed that annually more than 60% of the ambient sulfate in central and
eastern United States is produced in mostly nonprecipitating clouds. Similar conclusions
were reached by Dennis et al. (1993) and Karamachandani and Venkatram (1992).
Aqueous-phase SO2 oxidation in clouds is predicted to be the most important pathway for
the conversion of SO2 to sulfate on a global scale (Hegg, 1985; Langner and Rodhe, 1991).
Effect of cloud processing of aerosols in the remote marine atmosphere has been
demonstrated in a series of field studies (Hoppel et al., 1986; Frick and Hoppel, 1993).
Figure 15.22 shows the formation of a second peak in the accumulation mode as an air-
mass is advected off North America to the Atlantic and the Pacific Oceans. Note that the
two modes observed in the number distribution should not be confused with modes of the
mass distribution. Hoppel et al. (1986) proposed that cloud processing of aerosol is an
efficient mechanism for accumulating mass in the 0.08 to 0.5 j),m size range in the marine
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 CLOUD PROCESSINGOF AEROSOLS 821

Radius, ~m
FIGURE 15.23 Typical remotemarineaerosolsizedistributions.Reprintedfrom Atmos.Environ.,
24A, Hoppel,W. A. andFrick, G. M., 645-649, Copyright 199O,with kind permissionfrom Elsevier
ScienceLtd., The Boulevard,Langford Lane, Kidlington OX5 1GB, UK.

(aerodynamic diameter around 0.7 J1,m).These two submicrometer mass distribution

modes have also been observed in nonurban continental locations (McMurry and Wilson,
1983; Hobbs et al., 1985; Radke et al., 1989). Hering and Friedlander (1982) and John et
al. (1990) proposed that the larger mode could be the result of aqueous-phasechemical re-
actions. Meng and Seinfeld (1994) showed that growth of condensation mode particles by
accretion of water vapor or by gas-phase or aerosol-phase sulfate production cannot ex-
plain existence of the droplet mode. Activation of condensation mode particles, formation
of cloud/fog drops, followed by aqueous-phase chemistry, and droplet evaporation were
shown to be a plausible mechanism for formation of the aerosol droplet mode.
Simulations of the aerosol-cloud-aerosol cycle have shown that sulfate formed during
cloud/fog processing of an airmass favors aerosol particles that have accessto most of the
cloud liquid water content, which are those with diameters in the 0.5 to 1.0 J1,mrange
(Pandis et al., 1990a). Figure 15.24 depicts simulation of fog processing of an urban
aerosolpopulation. Note that the shape of the aerosol distribution changes with the creation
of an extra mode, resulting mainly from the formation of (NH4)2S04. Note also that there
are significant changes in the aerosol chemical composition before and after the fog with
sulfates replacing nitrate and chloride salts.

15.7.4 Interstitial Aerosol Scavenging by Cloud Droplets

Interstitial aerosol particles collide with cloud droplets and are removed from cloud inter-
stitial air. The coagulation theory of Chapter 12 can be used to quantify the rate and effects
of such removal. If n(Dp, t) is the aerosol number distribution and nd(Dp, t) the droplet
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 OTHER FORMS OF WATERIN THE ATMOSPHERE 823

TABLE 15.6 Estimated Lifetimes of Aerosols in a Nonraining Cloud

(N = 955 cm-3, Dp = 10 J.Im, WL = 0.5 g cm-3) at Standard Conditions

4x 0-5
1.6 x 0-6
1.1 x 0-7
2.2 x 0-8
1.03 x 0-9
3x 0-10

and K(Dp, 10 ,urn) can be calculated from (12.57) (see also Figure 12.5 and Table 12.3).
Corresponding particle collision efficiencies and lifetimes are shown in Table 15.6. Nuclei
smaller than 10 nm will be scavenged in a few minutes by such a cloud whereas particles
larger than 0.1 ,urn will not be collected by droplets during the cloud lifetime.
The above results indicate that for average residence times of air parcels in clouds (on
the order of an hour) only the very fine aerosol particles will be collected by cloud droplets.
These particles often represent a significant fraction of the aerosol number, so the total
number may be reduced significantly, and the shape of the aerosol number distribution may
change drastically. However, these particles contain little of the mass and therefore the
mass distribution effectively will not change. These qualitative conclusions are in agree-
ment with detailed simulations of aerosol processing by clouds (Flossmann and
Pruppacher, 1988; Flossmann, 1991).

15.7.5 Aerosol Nucleation Near Clouds

Clouds remove individual fine aerosol particles by scavenging. Even so, enhanced aerosol
number concentrations in the vicinity of clouds have been observed (Saxena and Hendler,
1983; Hegg et al., 1990, 1991; Radke and Hobbs, 1991). Saxena and Hendler (1983) sug-
gested that observed high aerosol number concentrations near clouds could be a result of
shattering of rapidly evaporating droplets. Hudson and Frisbie (1991) suggestedthat these
high particle concentrations may actually be an artifact due to droplet splashing. Hegg et al.
(1991) proposed that the high actinic flux near cloud tops resulting from upward scattering
of solar radiation could lead to high OH concentrations, rapid H2SO4 formation, and sub-
sequentnucleation of new H2SO4-H2O particles. Kerminen and Wexler (1994) estimated
a high nucleation probability associated with high relative humidity areas around clouds in
relatively clean environments. Note that such a nucleation process in the vicinity of the
clouds produces very little aerosol mass but a large number of particles and may influence
significantly the shape of the aerosol number distribution, especially in remote regions.

15.8 OTHER FORMS OF WATER IN THE ATMOSPHERE

Our discussion in the preceding sections has focused on "wann" nonraining tropospheric
clouds. Water in the atmosphere can also exist as ice, rain, snow, and so on. We summarize
here aspects of the formation and removal of these water forms that are most associated
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 OTHER FORMS OF WATERIN THE ATMOSPHERE 825

Finally, if the Clausius-Clapeyronequationis applied to the equilibrium betweenice

andwater,we get

dpm ~Hm (15.99)

dT

wherePmis the melting pressureof ice, ~Hm the molar enthalpyof melting, and Vwthe
molarvolume of water.Equations(9.66), (15.98),and (15.99)can be integratedand plot-
ted to producethe p-T phasediagramfor pure water shown in Figure 15.26.Note that
there is only one point (T = QoC,p = 6.1 mbar),the watertriple point for whichall
phasescoexist.Another interestingobservationis that for temperaturesbelow QoCthe wa-
ter vaporpressureover liquid water is higher than water vapor pressureover ice,

Psat,w > Psat,i (T <DOC)

So if air is saturated with respect to ice, it is subsaturated with respect to water. As a result,
supercooledwater droplets cannot coexist in equilibrium with ice crystals. Note that Figure
15.26 refers to the equilibrium of bulk water (curvature is neglected), without any impuri-
ties (zero solute concentration). Curvature and solute effects cause the behavior of water in

10000

ro
D-
Q)
'-
:J
cn
cn
Q)
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D- 1000
""iij
t ~ Triple Point
ro
D-
'-
Q)
~
~
WATER VAPOR

100 v ~ I I I I I I I I I I I I I I .
.20 .15 .10 -5 0 5 10 15 20
Temperature, °C
FIGURE 15.26 Pressure-temperature phasediagramfor water.The dashedline correspondsto suo
percooledwater and its metastableequilibrium with water vapor.

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 OTHER FORMS OF WATERIN THE ATMOSPHERE 827

tain the estimate

RT~Mw
~Tf = 1000~Hm m (15.105)

where m is the solution molarity. For ideal solutionsthis resultsin a depressionof 1.86°C
M-1 of solute,and for a salt that dissociatesinto two ions this resultsin a depressionof
3.72°C M-1 of the salt. Due to the nonideality of real saltsactualdepressionat I M con-
centrationis 3.35°C for NaCI.

Curvature Effects Ice crystals in the atmospherehave a variety of shapes,with

hexagonalprismatic being the basic one (Pruppacherand Klett, 1980). For instructive
purposeslet us ignore this complexity and concentrateon the behaviorof a sphericalice
particle of diameter Dp. Our analysisfor water dropletsand the Kelvin effect is directly
applicablehereand the vaporpressureof water over the ice particle surface,Pi. will be

(15.106)

where Psat.iis the vapor pressure over a flat ice surface, O'iathe surface energy of ice in air,
and Pi the ice density. Pruppacher and Klett (1980) reviewed theoretical and experimental
values for O'iaand suggested that it varies from 100 to 110 ergs cm -2. This surface tension
that is higher than the water/air value results in relative vapor increases(p / PsaJ higher
than those for a water droplet of the same size.
Pruppacher and Klett (1980) show that the freezing temperature decreases with de-
creasing size of the ice particle. This decreasebecomes particularly pronounced for crystal
diameters smaller than 20 nm and is further enhanced by the solute effect for solute con-
centrations larger than 0.1 M.

Ice Nuclei Ice particles can be formed through a variety of mechanisms. All of these
require the presence of a particle, which is called an ice nucleus (IN). These mechanisms
are (1) water vapor adsorption onto the IN surface and transformation to ice (deposition
mode), (2) transformation of a supercooled droplet to an ice particle (freezing mode), and
(3) collision of a supercooled droplet with an IN and initiation of ice formation (contact
mode).
Formation of ice particles in the absenceof IN is possible only at very low temperatures,
below -40°C (Hobbs, 1995). The presence of IN allows ice formation at higher tempera-
tures. Aerosols that can serve as IN are rather different from those that serve as CCN.
Ice-forming nuclei are usually insoluble in water and have chemical bonding and crystal-
lographic structures similar to ice. Larger particles are more efficient than smaller ones.
While our understanding of the ice nucleating abilities of aerosols remains incomplete, par-
ticles that are known to serve as IN include dust particles (especially clay particles such as
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 OTHER FORMS OF WATER IN THE ATMOSPHERE ""0

~ "' ' .
a b
FIGURE 15.27 Schematicof the flow arounda falling drop. The dashedlines are the trajectories
of small dropsconsideredas masspoints.Trajectory a is a grazingtrajectory,while b is a collision
trajectory.

The collision processis illustratedin Figure 15.27for viscousflow arounda sphereof

diameterDp. As the large droplet approachessmall drops of diameter dp, the viscous
forcesexertedby the flow field aroundthe large droplet push the dropletsaway from the
centerof flow, modifying their trajectories.In Figure 15.27droplet b is collectedby the
raindropwhile droplet a is not. Thereforethe falling raindropwill in generalcollect fewer
dropsthan thoseexisting in the cylinder of diameter Dp below it. Dropletsin the cylinder
of diametery will be collected.The distancey is definedby the grazingtrajectory a and
is a function of the raindrop size Dp and drop size dp. One definesthe collision efficiency
E asthe ratio of the actualcollision crosssectionto the geometriccrosssection,or

y2
E= (IS.IO8)
(Dp + dp)2

Notethat all dropsof diameterdp in the cylinder with diametery, below the falling drop
with diameterDp, will be collectedby it. Becausesmall dropstendto moveaway from the
falling raindrop, E is expectedto be smallerthan unity for most cases.
Figure 15.28showstheoreticallyestimatedcollision efficienciesamongdropsas func-
tionsof the radii of the small and large drops.There is a rapid increasein collision effi-
ciencyas the two drops approachequal size.This is due to fluid mechanicalinteractions
thatacceleratethe upper drop more than the lower one but havelittle importancefor the
atmospherewhere the probability of collision of equal-sizeddrops is extremely small.
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 OTHER FORMS OF WATERIN THE ATMOSPHERE 831

The growth of a falling drop of mass m as a result of accretion of drops can be described
by

dm
= 4Et(Dp
1T 2
+ dp) WL(VD- Vd) (I5.IID)
dt

where Et is the overall accretion efficiency (collision efficiency times coalescence effi-
ciency, Et = EEc), WL is the liquid water content of the small drops, and VD and Vdare,
respectively, the fall speeds of the larger and smaller particles. Equation (15.110) is called
the continuous accretion equation and assumes that the smaller drops are uniformly dis-
tributed in space. The description of the size change of droplets falling through a cloud by
(15.110)implicitly assumesthat all dropletsof the samesize will grow in the sameway.
According to the continuous equation, if several drops with the same initial diameter fall
through a cloud, they would maintain the same size at all times. In reality, each droplet-
droplet collision is a discrete event. Droplets that collide first with others grow faster than
droplets that had initially the same size. As a result, the simple continuous equation can se-
riously underestimate the collision frequency and the growth rate of falling drops, espe-
cially when the collector and collected drops have the same size. The coagulation equation
(see (12.80)) is a better mathematical description of these discrete collisions. Equation
(12.80) (often called the stochastic accretion equation in cloud microphysics) describes im-
plicitly individual collisions and predicts that even if all falling droplets had initially the
samesize some will grow more than others.
The role of ice in rain formation was first proposed by Bergeron in 1933, based on the
calculations of Wegener. Using thermodynamics, Wegener showed in 1911 that at temper-
atures below O°C supercooled water drops and ice crystals cannot exist in equilibrium.
Using this result, Bergeron proposed that in cold clouds the ice crystals grow by vapor dif-
fusion at the expense of the water droplets until either all drops have been consumed or all
ice crystals have fallen out of the cloud as precipitation. Findeisen later produced addi-
tional observations supporting the above mechanism, which is often called the
Wegener-Bergeron-Findeisen mechanism. Mathematically the description of the mecha-
nism requires solution of the growth equations by vapor diffusion for both ice crystals and
water drops in a supersaturatedenvironment (Pruppacher and Klett, 1980).

Raindrop Distributions A number of empirical formulas have been proposedfor the

raindropspectrum.The distribution proposedby Best is often usedto describethe fraction
of rainwatercomprisedof raindropssmallerthan Do, F{Do):

2.25
F(Dp) = 1 - exp[ - (15.111)

wherePois the rainfall intensity in (mm h-l) and Dp is in mm.

Probablythe most widely usedis the Marshall-Palmer(MP) distribution,where

n(Dp) = no exp (-1{1 Dp) (15.112)

where n(Dp) = dnjdDp is the number distribution in drops m -3 mm -I, no = 8000m-3
mm-l, and 1/1 = 4.1PoO.21mm-l. The MP distribution is often not sufficiently general to
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 CLOUD CLIMATOLOGY 833

TABLE 15.7 Microphysical Cloud Characteristics

<500 < 19
312
350
500
100-250 0.1-0.9 12 (base)
19 (top)
St (marine) 200-350 0.3 11
St (continental) 200-700 7
Sc (California) 25-125 0.1 18
Sc(California) <0.1
Sc(U.K.) 200-500 0.15 10
Sc(WashingtonState) 302
Sc(North Sea) 200 < 0.7 12-20
Sc(England) 200-400 <0.5 8-14
As-Ac (Russia) 0.09-0.17 9-11
As-Ac (Alaska) 300 0.03-0.09 7-10
As-Ac 100 <0.01 <9
(Wisconsin)
As-Ac 25 <0.1 15-20
(Wisconsin)
As-Ac 70-1000
(WashingtonState)
As-Ac (U.S.) 35-75 <0.2 14-19
Source: Heymsfield(1993).

4. It is lessthanthe liquid watercontentcalculatedassumingadiabaticascentof an air

parceldue to entrainmentof dry air. This deviationis on the order of 10%or so for
the lower half of stratiform cloudsand it increaseswith height.

Average droplet diameters are usually in the 10 to 20 ,urn range. Marine clouds are char-
acterized by relatively smaller droplet concentration and larger diameters, where continen-
tal clouds tend to have smaller droplets (Table 15.7).
Minimum droplet diameters are a few micrometers, where large droplets exceed 100 ,urn.
In general, droplet spectra are wider for orographic clouds, less wide for stratus, and rather
narrow for cumulus cloud types. Continental cumuli drop sizes range only from a few mi-
crometers to around 20 ,urn in diameter. Frequency distributions of the mean cloud droplet
size for various cloud types are shown in Figure 15.30.
Squires' (1958) observations suggested that high drop concentrations are associated
with narrow size spectra and small drop sizes for continental clouds. Bimodal droplet spec-
tra are often encountered in the upper half of clouds. Lee and Pruppacher (1977) explained
this bimodality by entrainment of fresh CCN into the cloud.
 CLOUD CLIMATOLOGY 833

TABLE 15.7 Microphysical Cloud Characteristics

<500 0.09-0.63 < 19

312
350
500 -
100-250 0.1-0.9 12 (base)
19 (top)
St (marine) 200-350 0.3 11
St (continental) 200-700 7
Sc(California) 25-125 0.1 18
Sc(California) <0.1
Sc(U.K.) 200-500 0.15 10
Sc(WashingtonState) 302
Sc(North Sea) 200 < 0.7 12-20
Sc(England) 200-400 <0.5 8-14
As-Ac (Russia) 0.09-0.17 9-11
As-Ac (Alaska) 300 0.03-0.09 7-10
As-Ac 100 <0.01 <9
(Wisconsin)
As-Ac 25 <0. 15-20
(Wisconsin)
As-Ac 70-1000
(WashingtonState)
As-Ac (U.S.) 35-75 <0.2 14-19
Source:Heymsfield(1993).

4. It is lessthanthe liquid watercontentcalculatedassumingadiabaticascentof an air

parceldue to entrainmentof dry air. This deviationis on the orderof 10%or so for
the lower half of stratiform cloudsand it increaseswith height.

Average droplet diameters are usually in the 10 to 20 JLmrange. Marine clouds are char-
acterized by relatively smaller droplet concentration and larger diameters, where continen-
tal clouds tend to have smaller droplets (Table 15.7).
Minimum droplet diameters are a few micrometers, where large droplets exceed 100 JLm.
In general, droplet spectra are wider for orographic clouds, less wide for stratus, and rather
narrow for cumulus cloud types. Continental cumuli drop sizes range only from a few mi-
crometers to around 20 JLmin diameter. Frequency distributions of the mean cloud droplet
size for various cloud types are shown in Figure 15.30.
Squires' (1958) observations suggested that high drop concentrations are associated
with narrow size spectra and small drop sizes for continental clouds. Bimodal droplet spec-
tra are often encountered in the upper half of clouds. Lee and Pruppacher (1977) explained
this bimodality by entrainment of fresh CCN into the cloud.
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 REFERENCES837

Hegg,D. A., and Hobbs,P.V. (1992)Cloud condensationnuclei in the marineatmosphere:a review,

in Nucleation and Atmospheric Aerosols, edited by N. Fukuta and P. E. Wagner. Deepak
Publishing,Hampton,VA, pp. 181-192.
Hering,S. V., andFriedlander,S. K. (1982)Origins of aerosolsulfur distributionsin the Los Angeles
basin,Atmos.Environ., 16,2647-2656.
Heymsfield, A. J. (1993) Microphysical structures of stratiform and cirrus clouds, in
Aerosol-Cloud-Climate Interactions, edited by P. V. Hobbs, Academic Press, San Diego,
pp.97-121.
Hobbs,P.V., Bowdle, D. A., andRadke,L. F. (1985)Particlesin the lower troposphereover the high
plains of the United States,1. Size distributions,elementalcompositionsand morphologies,J.
Climat.Appl. Meteorol.,24, 1344-1356.
Hobbs,P.V. (1995)Aeroso1-c1oud interactions,in Aerosol-Cloud-ClimateInteractions,editedby P.
V. Hobbs.AcademicPress,SanDiego, CA, pp. 33-73.
Hoppel,W. A., Frick, G. M., and Larson, R.E. (1986) Effects of non-precipitatingclouds on the
aerosolsizedistribution in the marineboundarylayer, Geophys.Res.Lett., 13, 125-128.
Hoppel,W. A., andFrick, G. M. (1990) Submicronaerosolsizedistributionsmeasuredover the trop-
ical and southPacific,Atmos.Environ.,24A, 645-659.
HoughtonH. G. (1985)PhysicalMeterology,MIT Press,Cambridge,MA.
Hudson,J. G., and Clark, A. D. (1992)Aerosol and cloud condensationnuclei measurements in the
Kuwait plume,J. Geophys.Res.,97, 14533-14536.
Hudson,J. G., and Frisbie, P. R. (1991) Cloud condensationnuclei nearmarinestratus,J. Geophys.
Res.,96, 20795-20808.
Husain,L., Dutkiewicz, V. A., Hussain,M. M., Khwaja, H. A., Burkhard, E. G., Mehmood, G.,
Parekh,P.P.,andCanelli, E. (1991)A studyof heterogeneous oxidationof SO2 in summerclouds,
J. Geophys.Res.,96, 8789-8805.
John,W., Wall, S. M., Ondo, J. L., andWinklmayr, W. (1990) Modes in the size distributionsof at-
mosphericinorganicaerosol,Atmos.Environ., 24A,2349-2359.
Junge,C. E. (1963)Air Chemistryand Radioactivity.AcademicPress,New York.
Karamachandani, P., and Venkatram,A. (1992) The role of non-precipitating clouds in producing
ambientsulfateduring summer-results from simulationwith the Acid Depositionand Oxidant
Model (ADOM), Atmos.Environ.,26, 1041-1052.
Kelly, T. J., Schwartz,S. E., and Daum,P.H. (1989)Detectionof acid producingreactionsin natural
clouds,Atmos.Environ., 23,569-583.
Kerrninen,V. M., and Wexler,A. S. (1994) Post-fog nucleationof H2SO4-H2O particlesin smog,
Atmos.Environ., 28, 2399-2406.
Kohler, H. (1921)Zur KondensationdesWasserdampfe in der Atmosphiire,Geofys.Publ., 2,3-15.
Kohler, H. (1926) Zur Thermodynamic der Kondensation an hygroskopischenKernen und
Bemerkungeniiber dasZusammenfliessen der Tropfen,Medd.Met. Hyd1:Anst. Stockholm,3 (8).
Lamme1,G., andNovakov,T. (1995)Waternucleationpropertiesof carbonblack anddieselsootpar-
ticles,Atmos.Environ., 29,817-823.
Langner,J., and Rodhe,H. (1991)A global three-dimensionalmodel of the troposphericsulfur cy-
cle, J. Atmos.Chem.,13,225-263.
Leaitch,W. R., Strapp,J. W., Isaac,G. A., and Hudson,J. G. (1986) Cloud droplet nucleationand
scavengingof aerosolsulphatein polluted atmospheres, Tellus,38B, 328-344.
Lee, I. Y., and Pruppacher,H. R. (1977)A comparativestudy of the growth of cloud dropsby con-
densationusing an air parcel model with and without entrainmentPure Appl. Geophys.,115,
523-545.
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 PROBLEMS 839

Saxena,V. K., and Hendler,A. H. (1983) In-cloud scavengingand resuspensionof cloud active
aerosolsduring winter stormsover Lake Michigan, in Precipitation Scavenging,Dry Deposition
andResuspension, editedby H. R. Pruppacher,R. G. Semonin,andW. G. N. Slinn. Elsevier,New
York, pp. 91-102.
Sekhon,R. S., andSrivastava,R. C. (1971)Dopplerobservationsof drop sizedistributionsin a thun-
derstorm,J. Atmos.Sci, 28, 983-994.
Squires,P.(1958)The microstructureand colloidal stability of warm clouds,Tel/us,10, 256-261.
Swozdziak,J. W., and Swozdziak,A. B. (1992) Sulfate aerosolproduction in the SudetyRange,
Poland,J. AerosolSci., S369-S372.
TenBrink, H. M., Schwartz,S. E., and Daum,P.H. (1987) Efficient scavengingof aerosolsulfateby
liquid water clouds,Atmos.Environ, 21, 2035-2052.
Twomey,S. (1959) The nuclei of natural clouds formation. Part II: The supersaturationin natural
cloudsand the variation of cloud droplet concentration,Geofis.Pura Appl., 43,243-249.
Twomey,S., and Wojciechowski,T. A. (1969) Observationsof the geographicalvariation of cloud
nuclei,J. Atmos.Sci., 26, 684-688.
UnitedStatesNational Acid PrecipitationAssessmentProgram(1991) Acidic Deposition: Stateof
Scienceand Technology,Vol.I Emissions,AtmosphericProcessesand Deposition,editedby P.M.
Irving. U.S. GovernmentPrinting Office, Washington,DC.
Walcek,C. J., Stockwell,W. R., and Chang,J. S. (1990)Theoreticalestimatesof the dynamicradia-
tive andchemicaleffectsof cloudson troposphericgases,Atmos.Res,25,53-69.
Wall,S. M., John,W., and Ondo,J. L. (1988) Measurementsof aerosolsize distributionsfor nitrate
andmajor ionic species,Atmos.Environ, 22, 1649-1659.
Warner,J. (1968)The supersaturationin naturalclouds,J. Appl. Meteorol.,7, 233-237.
Whelpdale,D. M., and List, R. (1971)The coalescenceprocessin droplet growth, J. Geophys.Res,
76,2836-2856.

PROBLEMS

ls.lA Show equations (15.39) and (15.40).

15.28 Derive equation (15.53).

ls.3A You dissolve 5 g of NaCI in a glass containing 200 cm3 of water. The glass is in a
room with constanttemperatureequalto 20°C andrelativehumidity 80%.Calculate
the volume of water that will be left in the glass after several days of residence in
this environment. Repeat the calculation for a relative humidity of 95%.

ls.4A Your grandmother and grandfather are upset, because it has just started raining.
After listening to the weather prediction for a cloudy day but without rain, they
planned to spend the day working in the garden. They have started criticizing the lo-
cal weather forecaster who, despite the impressive gadgets (radar maps, 3D ani-
mated maps), still cannot reliably predict if it will rain tomorrow. They turn to you
and ask why if we can send people to the Moon we still cannot tell if it is going to
rain or not. Explain, avoiding scientific terminology.
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