二次有机气溶胶形成的化学过程

!!!230031/O648.180644.1A1005-281X200504-0732-08ChemicalProcessesontheFormationofSecondaryOrganicAerosolsWangZhenya!!HaoLigingZhangWeijunLaboratoryofEnvironmentaiSpectroscopyAnhuiInstituteofOpticsandFineMechanicsChineseAcademyofScienceHefei230031ChinaAbstractPhotooxidationprocessofvoiatiieorganiccompoundsandgas/particiepartitioningprocessoftheirphotooxidationproductsareveryimportantonformationofsecondaryorganicaerosois.Chemicaimechanismonformationofsecondaryorganicaerosoisinvoivesinphotooxidationprocessofvoiatiieorganiccompoundsandsubseguentchemicaireactionwhichdirectiyieadtoincreaseofozoneconcentrationandtoformationofsecondaryorganicaerosoiintroposphere.Theemphasesinthispaperarefocusedontheimportantchemicaiprocessesandguantumchemicaicaicuiationontheformationofsecondaryorganicaerosois.Keywordsvoiatiieorganiccompoundsphotooxidationprocesssecondaryorganicaerosoiguantumchemicaicaicuiation20047200411!No.20477043KJCX2-SW-H08!![e-mail]13/4SO2SO22SO2+2H2O+O22H2SO4-NH3NONO217420057PROGRESSINCHEMISTRYVoi.17No.4Jui.2005O3Seinfeid5Atkinson6Dabdub7Jacob85CaitechatmosphericchemistrymechanismCACM191120157134672654360CACMHO/O3O3HONO!voiatiieorganiccompoundsVOCsVOCsVOCsVOCs290nmHO5HOVOCs1.HOHO579HO12025km1018km290nm290nm290nmO1DO1DO3PHOO3+!!O2+O1D335nm1O1D+M!O3P+MMN2O22O3P+O2+M!O3+MMair3O1D+H2O!2HO42HCHO+!!H+HCO330nm5!H2+CO361nm6!H+H+CO283nm76H2CO5HHCOO2HO210H+O2+M!HO2+M8HCO+O2!HO2+CO9589330nmHO2NOHO2NOHO11HO2+NO!HO+NO2103HO3374NO!HONOHO!6812HONOHONO+!!HO+NO11!=300390nm10%HONO+!!H+NO2122003AlickeHOHO45%HO35%HO14%13Buckey200700nmO3H2OHO1%15%14AumontHONOHO!10%22%4%9%10%31%2%9%12Ren15HO/HO2HONOHONOHO!HO!HO+HO256%HO!2.03NO2290700nmNO2+!!NO2400700nm13NO2+!!NO+O3P290430nm14NO2NO2NOO3PO3PNOO3P+O2+M!O3+MM=air15NO+O3!NO2+O216MO2N2141516NONO2VOCSNO!NO2NONO!RHRORO2NONO2HO+RH!R+H2O17R+O2+M!RO2+M18RO2+NO!RO+NO219HO2NOHO2+NO!HO+NO220NONO2NO2O2NO!NONO21.VOCS446HOO2NO!!=12RROHORCOROOHO2RCO3ROOHO2RCO3H2ORO2HO2NONO243717HOHORH+HO!R+H2O21R+HO!HRO22R+HO!R'CO23R+O2!ROO24HRO+O2!R'CHO+HO225R'CO+O2!R'OCOO26O2RO+O2!R'CHO+HO227NORO+NO!RONO28NO2ROO+NO2!RNO2+O229!ROONO230NO2PANROCOO+NO2!ROCOONO231ROO+ROO!R'CHO+R'CH2OH+O232!ROOR+O233RO2HO2NONO26RO2+NO!RO+NO219HO2+NO!HO+NO220HORH8RH+HO!RO2+HO2O234RO2+NO!RO+NO219RO+O2!R'CHO+HO2352.HO6HO+CH4!H2O+CH336CH3+O2+M!CH3O237CH3O2+NO!HCHO+HO238CH3O+O2!HCHO+HO239HO2+NO!HO+NO240netHO+CH4+2NO+2O2!HO+HCHO+H2O+2NO241HONO23.HO6HONOHO121HO1Fig.1ReactionpathwayinvoivedinHOwithpentene1CH3CHOHCH2CH2CH2+O2CH3CHOHCH2CH2CH2O#2NONO!2CH3CHOHCH2CH2CH2#OCH3COHCH2CH2CH2#OHO2CH3COCH2CH2CH2OH+HO#22HO2Fig.2ReactionpathwayinvoivedinHOwithpentene24.HO537420%HOHOHOHO16191HO1719HO3HOC6H6HO3HOFig.3TheproposedmechanismfortheinitiaIstepsofHOinitiatedoxidationofbenzeneHO42C6H6OHO243HO6HOHC6H5C6H6+HO!H2O+C6H5442HO1617HO4HOC6H5CH3HOC6H5CH3HO4HOFig.4PossibIeformationmechanismoftoIuene-12-oxide-2-methyIoxepinintheHOinitiatedphotooxidationoftoIueneHO45C6H5CH3OHO2C6H5CH3OH+O2!HOC6H4CH3+HO246!cresoI20%63717HOHOC6H5CH3OH4OOK6OOKHHOHOHC6H5CH2C6H5CH3+HO!C6H5CH2+H2O47C6H5CH2C6H5CH2C6H5CH2+O2!C6H5CH2OO48NONOC6H5CH2OC6H5CH2ONO2C6H5CH2OO+NO+M!C6H5CH2ONO249C6H5CH2OO+NO!C6H5CH2O+NO25OC6H5CH2OC6H5CH2O+O2!C6H5CHO+HO2513HO6HO5HO1O%9O%5HOFig.5MainreactivepathwayOfxyienewithHOHOHO65%4O%6O%3--25--25-2--4-3--4-25-HOHOO3HOHOHOC6H6+HO!C6H5+H2O52C6H6+HO!C6H6OH53C6H6+HO!C6H5OH+H5452C6H6OH!C6H5OH+H54'545354'HO35OKC6H6OHHOC6H6OH!C6H6+HO53'45OK73742002TokmakovHO+C6H620C6H6OHHORRKMC6H6OHHO+C6H6HOHOHOHOOH-4OH-2000Uc21MP2OH-orthoipsoCCSD6-31Gcpipso2002Suh16HO16HOHOHOHO4orthoparametaipso4OH0.520.340.110.03HO4412HO4HO4transitionstatetheoryTSTHO222000Somnitz23C2C523C2C5RRKM24RRKMHOHOHONO!NO2HO8371768122525262728HOHOHOHO293031MonteCarIoCACM321GongZB.HandbookofOpticsTechnoIogy.BeijingChinaMechinePress1987.6592WangZYWangDM.OptronicsTechnoIogyandInformation199811163WangMXZhangRJ.ResearchofWeatherandEnvironment20011191244LiuPT.IntroductiontoEnvironmentaIscience.BeijingHigherEducationPress1992.375GriffinRJDabdubDSeinfeIdJH.JournaIofGeophysicaIResearch-Atmospheres2002107D17ArtNo.43326AtkinsonR.AtmosphericEnvironment200034206321017NguyenKDabdubD.AerosoIScienceandTechnoIogy2002365605728JacobDJ.AtmosphericEnvironment200034213121599HideoOkabe.PhotochemistryofSmaIIMoIecuIes.ChangchunJiIinPeopIe'sPubIishingHouse1982.39440410SmithGDMoIinaLTMoIinaMJ.JournaIofPhysicaIChemistryA20021061233124011MeIIerRMoortgartGK.JournaIofGeophysicaIResearch-Atmospheres2000105D67089710112BernardAFredericC.AtmosphericEnviron.20033748749813AIickeBGeyerAHofZumahausAetaI.JournaIofGeophysicaIResearch-Atmospheres2003108D4Art.No.824714BuckIeyBTBirksmJW.AtmosphericEnvironment1995292409241515RenXHarderHMartineZMetaI.AtmosphericEnvironment2003373639365116SuhIZhangDZhangRetaI.ChemicaIPhysicsLetters200236345446217KIotZBBarnesIBeckerKH.ChemicaIPhysics199823128930118VoIkamerBKIotZBBarnesIBetaI.PhysicaIChemistryandChemicaIPhysics200241598161019KIotZBBarnesIBMamuraTIetaI.PhysicaIChemistryandChemicaIPhysics200244399441120TokmakovIVLinMC.JournaIofPhysicaIChemistryA2002106113091132621UcVHCruZIGLagunaAHetaI.JournaIofP