ATMOSPHERIC CHEMISTRY AND PHYSICS ATMOSPHERIC CHEMISTRY AND PHYSICS From Air Pollution to Climate Change Third Edition John H. Seinfeld Spyros N. Pandis Copyright2016byJohnWiley&Sons,Inc.Allrightsreserved PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey PublishedsimultaneouslyinCanada Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorbyanymeans,electronic,mechanical, photocopying,recording,scanning,orotherwise,exceptaspermittedunderSection107or108ofthe1976UnitedStatesCopyrightAct,without eitherthepriorwrittenpermissionofthePublisher,orauthorizationthroughpaymentoftheappropriateper-copyfeetotheCopyright ClearanceCenter,Inc.,222RosewoodDrive,Danvers,MA01923,(978)750-8400,fax(978)750-4470,oronthewebatwww.copyright.com. RequeststothePublisherforpermissionshouldbeaddressedtothePermissionsDepartment,JohnWiley&Sons,Inc.,111RiverStreet, Hoboken,NJ07030,(201)748-6011,fax(201)748-6008,oronlineathttp://www.wiley.com/go/permission. 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FormoreinformationaboutWileyproducts,visitourwebsiteatwww.wiley.com. LibraryofCongressCataloging-in-PublicationData: Names:Seinfeld,JohnH.|Pandis,SpyrosN.,1963­ Title:Atmosphericchemistryandphysics:fromairpollutiontoclimate change/JohnH.Seinfeld,SpyrosN.Pandis. Description:Thirdedition.|Hoboken,NewJersey:JohnWiley&Sons,Inc., [2016]|“AWiley-Intersciencepublication.”|Includesindex. Identifiers:LCCN2015043236(print)|LCCN2015045406(ebook)|ISBN 9781118947401(cloth)|ISBN9781119221166(pdf)|ISBN9781119221173 (epub) Subjects:LCSH:Atmosphericchemistry.|Air–Pollution–Environmental aspects.|Environmentalchemistry. Classification:LCCQC879.6.S452016(print)|LCCQC879.6(ebook)|DDC 551.51/1–dc23 LCrecordavailableathttp://lccn.loc.gov/2015043236 PrintedintheUnitedStatesofAmerica 10 9 8 7 6 5 4 3 2 1 To Benjamin and Elizabeth and Angeliki and Nikos Contents PrefacetotheFirstEdition xxiii PrefacetotheThirdEdition xxv PART I | The Atmosphere and Its Constituents Chapter1 | TheAtmosphere 3 1.1 HistoryandEvolutionofEarth’sAtmosphere 3 1.2 Climate 5 1.3 LayersoftheAtmosphere 5 1.4 PressureintheAtmosphere 7 1.4.1 UnitsofPressure 7 1.4.2 VariationofPressurewithHeightintheAtmosphere 7 1.5 TemperatureintheAtmosphere 10 1.6 ExpressingtheAmountofaSubstanceintheAtmosphere 10 1.7 AirborneParticles 14 1.8 SpatialandTemporalScalesofAtmosphericProcesses 14 Problems 16 References 17 Chapter2 | AtmosphericTraceConstituents 18 2.1 AtmosphericLifetime 19 2.2 Sulfur-ContainingCompounds 23 2.2.1 DimethylSulfide(CH SCH ) 26 3 3 2.2.2 CarbonylSulfide(OCS) 26 2.2.3 SulfurDioxide(SO ) 27 2 2.3 Nitrogen-ContainingCompounds 27 2.3.1 NitrousOxide(N O) 28 2 2.3.2 NitrogenOxides(NOx=NO+NO2) 29 2.3.3 ReactiveOddNitrogen(NOy) 30 2.3.4 Ammonia(NH ) 31 3 2.3.5 Amines 32 2.4 Carbon-ContainingCompounds 32 2.4.1 ClassificationofHydrocarbons 32 2.4.2 Methane 34 2.4.3 VolatileOrganicCompounds 36 2.4.4 BiogenicHydrocarbons 36 2.4.5 CarbonMonoxide 39 2.4.6 CarbonDioxide 40 vii viii CONTENTS 2.5 Halogen-ContainingCompounds 40 2.5.1 MethylChloride(CH Cl) 42 3 2.5.2 MethylBromide(CH Br) 42 3 2.6 AtmosphericOzone 44 2.7 ParticulateMatter(Aerosols) 47 2.7.1 StratosphericAerosol 48 2.7.2 ChemicalComponentsofTroposphericAerosol 48 2.7.3 CloudCondensationNuclei(CCN) 49 2.7.4 SizesofAtmosphericParticles 49 2.7.5 CarbonaceousParticles 51 2.7.6 MineralDust 53 2.7.7 BiomassBurning 53 2.7.8 SummaryofAtmosphericParticulateMatter 54 2.8 Mercury 55 2.9 EmissionInventories 55 Appendix2.1USAirPollutionLegislation 56 Appendix2.2HazardousAirPollutants(AirToxics) 57 Problems 59 References 61 PART II | Atmospheric Chemistry Chapter3 | ChemicalKinetics 69 3.1 OrderofReaction 69 3.2 TheoriesofChemicalKinetics 71 3.2.1 CollisionTheory 71 3.2.2 TransitionStateTheory 74 3.2.3 PotentialEnergySurfaceforaBimolecular Reaction 75 3.3 ThePseudo-Steady-StateApproximation 76 3.4 ReactionsofExcitedSpecies 77 3.5 TermolecularReactions 78 3.6 ChemicalFamilies 81 3.7 Gas–SurfaceReactions 83 Problems 84 References 87 Chapter4 | AtmosphericRadiationandPhotochemistry 88 4.1 Radiation 88 4.2 RadiativeFluxintheAtmosphere 91 4.3 Beer−LambertLawandOpticalDepth 93 4.4 ActinicFlux 95 4.5 AtmosphericPhotochemistry 97 4.6 AbsorptionofRadiationbyAtmosphericGases 100 4.7 AbsorptionbyO andO 105 2 3 4.8 PhotolysisRateasaFunctionofAltitude 109 4.9 PhotodissociationofO toProduceOandO(1D) 112 3 4.10 PhotodissociationofNO 114 2 Problems 117 References 117