SICDOM性质relationtostructure

S1SupportingInformationTitle:OpticalPropertiesofHumicSubstancesandCDOM:RelationtoStructureAuthors:ErinS.Boyle,NicolasGuerriero,AnthonyThiallet,RossanaDelVecchio†*andNeilV.Blough*DepartmentofChemistryandBiochemistry,UniversityofMaryland,CollegePark,Maryland20742†EarthSystemScienceInterdisciplinaryCenter,UniversityofMaryland,CollegePark,Maryland20742*CorrespondingAuthors.E-mail:(N.V.B.)[e-mail](R.D.V.)[e-mail]:25Figures:21(pagesS5-S25)FiguresCaptions(pagesS2-S4)Literaturecited(pageS4)S2SupportingInformation_FiguresCaptions.FigureS1.Dependenceofabsorptioncoefficientat280and355nmforSRFA,SRHA,LAC,CDOMandtheC18extractsontotalligninphenolcontent(TLP).Linesrepresentthelinearregressionswithparametersreportedwithinthefigure.FigureS2:LAC-F2andLAC-F6opticalproperties:absorption();emissionmaxima,λmaxandluminescencequantumyield(φ)(λexfrom280to600nm).LAC_F2andLAC-F6werefractionscollectedfollowinglowpressureGPCfractionationoveraG-50sephadexcolumn(44x2.5cm)ofaLACsolution(80mg/L)at1ml/minflowrateemploying5mMphosphatebuffer(pH=7)in5mMNaClaseluent.F2elutedattheexclusionvolumeandF6attheretentiontimeofSRFA.FigureS3:EmissiondecayofSRFAobtainedwith385nmexcitationanda400nmlongpassemissionfilter(50%transmittance),alongwithIRF,fit(3-exponential),fitparametersandresidualsofthefit.Inallcases,thefitsfailedtoreproducetherapidityofthedecayatveryshorttimes,therebyunderestimatingtheratesandamplitudesoftheveryshortest-livedcomponent(s).Thesystematicvariationoftheresidualsatveryshorttimeswascharacteristicofallfits,althoughthegoodness-of-fitparameterforthisparticularexamplewaspoorerthanmost.FigureS4:Spectraldependenceofthefractionalamplitude,fractionalintensity,andlifetimesforthe3-exponentialfitoftheemissiondecaysforSRFAatλex=385nm:(A)short,(B)medium,and(C)longlifetimecomponents.Valuesonthex-axiscorrespondtothewavelengthof50%transmittanceofthelongpassemissionfilters.Themagnitudeofthelifetimesandamplitudesofthethreecomponentsfoundhereandbelowagreereasonablywiththoseobservedinsomepreviousstudies(1-3),butnotwithothers(summarizedin4).Insomepriorstudies,theshortest-livedcomponents(0.5–1ns)werenotresolved,mostlikelyduetotheinadequatetemporalresolutionoftheinstrumentsemployed.Forexample,wehavefoundthattheshortest-livedcomponentsS3(150ps)forSRFAandSRHAcannotberesolvedwithafrequencydomainlifetimeinstrument(5)thatemploysmodulationfrequenciesupto250MHz(datanotshown).FigureS5:SameasS4,exceptSRFAexcitedat400nm.FigureS6:SameasS4,exceptSRFAexcitedat440nm.FigureS7:SameasS4,exceptSRHAexcitedat385nm.FigureS8:SameasS4,exceptSRHAexcitedat400nm.FigureS9:SameasS4,exceptSRHAexcitedat440nm.FigureS10:SameasS4,exceptLACexcitedat385nm.FigureS11:SameasS4,exceptLACexcitedat400nm.FigureS12:SameasS4,exceptLACexcitedat440nm.FigureS13:SameasS4,except6_MDB_2m_(05)excitedat385nm.FigureS14:SameasS4,except6_MDB_2m_(05)excitedat440nm.FigureS15:SameasS4,except7_Shelf_2m_(05)excitedat385nm.FigureS16:SameasS4,except7_Shelf_2m_(05)excitedat440nm.FigureS17:SameasS4,except8_Shelf_43m_(05)excitedat385nm.FigureS18:SameasS4,except8_Shelf_43m_(05)excitedat440nm.S4FigureS19:SameasS4,except4_GS_2m_(06)excitedat385nm.FigureS20:SameasS4,except4_GS_2m_(06)excitedat440nm.FigureS21:SameasS4,except5_GS_1000m_(06)excitedat385nm.LiteratureCited(1)Cook,R.L.;Langford,C.H.Metalionquenchingoffulvicacidfluorescenceintensitiesandlifetimes:Non-linearitiesandapossiblethree-componentmodel.Anal.Chem.1995,67,174-180.(2)Herbelin,S.E.Photophysicsandphotochemistryofnaturalwaterswithemphasisonradicalprobedevelopmentandapplication.MastersThesis.MIT/WHOI(1994).(3)Frimmel,F.H.;Kumke,M.U.Fluorescencedecayofhumicsubstances.Acomparativestudy.InHumicSubstances:Structure,PropertiesandUses;Davies,G.,Ghabour,E.,Eds.RoyalSocietyofChemistry:Cambridge,1998;pp113-122.(4)Clark,C.D.;Jiminez-Morais,J.;JonesII,G.J.;Zanardi-Lamardo,E.;Moore,C.A.;Zika,R.G.Atime-resolvedfluorescencestudyofdissolvedorganicmatterinariverinetomarinetransitionzone.Mar.Chem.2002,78,121-135.(5)Kaiwar,S.P.;Vodacek,A.;Blough,N.V.;Pilato,R.S.Excitedstatepropertiesofquinoxaline-substitutedplatinum1,2-enedithiolates.J.Am.Chem.Soc.1997,119,3311-3316.S5Fig.S1TLP(μg/L)0246810121416a(λ)(m-1)051015202530a(280)_CDOMa(355)_CDOMa(280)_C18a(355)_C18a(280)_LACa(355)_LACa(280)_SRFA,SRHAa(355)_SRFA,SRHACDOM______a(280)=TLP*2.15-0.32r2=0.88CDOM______a(355)=TLP*0.60-0.06r2=0.85C18________a(280)=TLP*0.97-0.004r2=0.81C18________a(355)=TLP*0.32+0.08r2=0.55S6Fig.S2LAC-F6wavelength(nm)300350400450500550600Absorbance(OD)0.000.050.100.150.200.250.30Fluorescencequantumyield0.0000.0020.0040.006Fluorescenceemissionmaximum300400500600700AφλmaxLAC-F2300350400450500550600Absorbance(OD)0.000.050.100.150.200.250.30Fluorescencequantumyield0.0000.0020.0040.006Fluorescenceemissionmaximum300400500600700AφλmaxS7Fig.S3S8Fig.S4SRFAatλex=385nmAFract.Amp.ofFluor.(αi)0.600.620.640.660.680.700.720.740.760.780.800.82ComponentLifetime(τi)0.000.050.100.150.20Fract.Fluor.Intensity(fi)0.060.080.100.120.140.160.180.200.22αshortτshortfshortBFract.Amp.ofFluor.(αi)0.160.180.200.220