第03章-大气环境与农业-wdz2012-3-11

1AirPollutionandAgricultureAirEnviromentalChemistry2.3-13-20.8020481216Z(km)00.20.40.61.0100806040200160200240280T(K)Z(km)(15~-56)-56~-20.65/100m210Km50KmO2(20.95%)N2(78.09%)(0.93%)CO2(0.02%~0.04%)(0%~4%)O3:SH2SSOxNOx0.05-0.25ppm0.001ppm0.1-0.5ppm0.020.08ppm5-200ppm0.1ppm350-700ppm330ppm78.084%2.00ppm20.9473-35ppbPAN)0.01-0.25ppm0.001ppm0.02-2ppm0.0010.01ppm3––––Æ10µmÆ10µm(dust)1µmÆ200µm(fume)0.01µmÆ1µm(fog)Æ100µm1SSSO2SO3H2SO4MSO3MSO4H2S1SO2SO2SO3H2SO4M2SO4BSO2146106t/a60%30%SO2SO250%50%SO2:CS0.5%~6%S0.5%~3%ASSO2/106t2NNN2ONONO2N2O3N2O4N2O5NO3HNO2NONO2NOxNOxAN+O2NOxBN2+O2NOxNOx43HCHC10%HC70HC48%4CO30%50%O251943“”——61123——4——56GB3095-2012GB3095-1996GB3095-1982229297127535243515PM2.5625015050241507010040PM105200200(160)160(120)1µg/m31601008O342010101mg/m364424CO3240200(120)200(120)1120808024804040NO2270050015012501505024µg/m31006020SO211µPM2.510ug/m325ug/m3PM1020ug/m350ug/m3O3100ug/m38SO220ug/m3NO240ug/m3200ug/m381ambientair:2totalsuspendedparticlTSP100µm;3PM101010µm;4PM2.52.52.5µm;5Pb6[a]benzo[a]pyreneBaP[a]87)fluoride:;8)11houraverage:1988houraverage:88102424houraverage:2411monthlyaverage12quarterlyaverage13annualmean14standardstate273K101.325kPa2424hav.TSPBaPPb155Quav.Pb605Yearav.TSPBaPPb451hrav.SO2NO2COO3NOx868hrav.O32024hrav.SO2NO2COPM10PM2.5NOx3242725Yearav.SO2NO2PM10PM2.5NOxGB8971[a]GB9801GB/T15264GB/T15432GB/T15439[a]HJ479HJ482-HJ483-HJ504HJ539HJ590HJ618PM10PM2.5919822005201012.45%14.29%26.3%12%82.8%O3PM2.52.3.[]PM2.5O38hrPM10NO2PM2.54.[]WHOWHO5PM2.5PM2.5PM2.5PM2.52435µg/m375µg/m3WHO11068O38O38O318PM2.5PM10NO28(API)API121224PM2.5AQI.(AQI)AQIAPI(API)(AQI)O3COPM2.512:0012:00024SO2NO2PM10COPM2.5O324hrO38hr1(AQl)TechnicalRegulationonAmbientAirQualityIndex21airqualityindex(AQI);2individualairqualityindex(IAQI);3primarypollutantAQI50IAQI;4non-attainmentpollutantIAQI10011135001200150606003840940262050035010001204850030907502100400250800800903642023405651600300150265400602435012002808008002001152153003514250700180650475150751602001041502008050015010035100160525010040150505000000000000PM2.524hAvug/m3O38hAvug/m3O31hAvug/m3CO1hAvmg/m3CO24hAvmg/m3PM1024hAvug/m3NO21hAvug/m3NO224hAvug/m3SO21hAvug/m3SO224hAvug/m3(IAQI)3NO2ppmSO2ppmCOppmPM2.5ug/m3PM10ug/m3O31hppmO38hppmAQI2P1(1)IAQIP-PCP-PBPHi-3CPBPLo-3CPIAQIHi-3BPHiIAQILo-3BPLoLoLopLoHiLoHipIAQI)BPC(BPBPIAQIIAQIIAQI+---=2)5300201~300151~200101~15051~1000~505123)2AQI=max{IAQI1,IAQI2,IAQI3,•••,IAQIn}(2)IAQlnAQI50IAQIIAQIIAQI10024hrSO2230ug/m3IAQISO2=NO295ug/m3IAQINO2=CO7mg/m3IAQICO=PM10330ug/m3IAQIPM10=PM2.5140ug/m3IAQIPM2.5=8hrO3170ug/m3IAQIO3=AQIIAQI4.12424SO2NO2PM10PM2.5CO24O31O3811SO2NO2O3PM10PM2.5CO1;O38PM10PM2.5249132010“”14—N2+hvN•+N•120nmO2+hvO•+O•240nmO3+hvO2+O•220290nm()H2OCO2··CCl3F+hv(175~220nm)CCl2F•+Cl•Cl•+O3ClO•+O2ClO•+O•O2+Cl•15A+hvA••hv••••HCl+hvH•+Cl•:H•+HClH2+Cl•Cl•+Cl•Cl2hvhplank6.62610-34J·sM.K.E.L.Plank(1858~1947)1918Nobel·••N06.021023mol-1E=N0•h•c/=6.021023mol-16.62610-34J·s2.9981010cm·s-1/(710-5cm)=170.8KJ·mol-11.5~3eV121171297598N0hv(KJ·mol-1)1.21.83.16.2E(eV)1000700400200(nm)1mol21O2N2O2493.8KJ/mol243nm120-240nmO2+hO•+O•240nmN2939.4KJ/mol127nmN2+hN•+N•120nm16O•+O2+MO3+M•O3+hvO•+O2290nmO3HO•NO•O3ClO•NO•O3••••••••(3)NO2O3•MOMO•O•ONO420NO322+→+++─────→─+nmhvlHNO3120-335nm:4HNO2HNO3HNO2200-400nm:HNO2+hHO•+NOHNO2+hH•+NO2HNO3+hHO•+NO2SO2545.1kJ/mol•SOSO2nm4002402───→─+-hv5SO2SO2(HeicklenJ,1976)•HCO•HhvHCHO360nm240+───→─+-6H-CHO356.5kJ/molHO2•H•+O2HO2•HCO•+O2HO2•+CO17(7)CH3X+hCH3•+X•1HO•a.O3+hO•+O2O•+H2O2HO•b.HNO2+hHO•+NOc.H2O2+h2HO•HO•O32HO2•a.HCHO+hH•+HCO•H•+O2HO2•HCO•+O2HO2•+COb.CH3ONO+hNO+CH3O•()CH3O•+O2HO2•+H2COc.H2O2+h2OH•OH•+H2O2HO2•+H2O3.RR•CH3CHO+hCH3•+HCO•CH3COCH3+hCH3•+CH3CO•RH+O•R•+HORH+HO•R•+H2ORO•CH3ONO+hCH3O•+NO()CH3ONO2+hCH3O•+NO2(CH3O•+NO2CH3ONO2)RO2•RO2•R•O2R•+O2RO2•1NONO+O3NO2+O2NO+RO2•NO2+RO•NO+HO2•NO2+HO•NO+HO•HNO2NO+RO•RONONOO3O3“”2NO21O3NO2+hvNO•+O•O•+O2+MO3+M•2HO•HO•+NO2HNO33O3NO2+O3NO3+O2NO2+NO3N2O5⇔183(PAN)PANCH3CO•+O2CH3C(O)O2•CH3C(O)O2•+NO2CH3C(O)O2NO2(PAN)HOO2NOhvCCOONOOOHHHCH4+HO•CH3•+H2OCH4+O•CH3•+HO•CH3•+O2CH3O2•CH4O•photochemicalsmong1NOxCHhvNOxCH21NO2+hvNO+O•O•+O2+MO3+M•NO+O3NO2+O22RH+O•R•+HO•RCHO+HO•RC(O)O2•+H2OR•+O2RO2•RH+O3RO2•RO2•+NONO2+R’CHO3NONO2O3PANHO•+NO2HNO3CH3C(O)O2•+NO2CH3C(O)O2NO2(PAN)NONO2NO2O3O3NO2O•O•O3O3HCPANCHNONO2193§§NO§O3NO2§O3NO2PAN1.SO21SO2SO2SO2+O2SO3+O•SO2+O•SO32SO2SO2HO•HO•+SO2HOSO2HOSO2+O2HO2•+SO3SO3+H2OH2SO4SO2CH3CHOO•+SO2CH3CHO+SO3HO2•+SO2HO•+SO32.SO22SO2SO2SO2SO42-1SO2SO2Mn2++SO2MnSO22+2MnSO22++O22MnSO32+MnSO32++H2OMn2++H2SO42SO2+2H2O+O22H2SO4l2020004291.?6612“”31.2.3.4.212.170%23;;;1.:A():n10-1~n10µg/m3HFSiF4O3PANB()n10-1~n100mg/m3SO2SO3NOxCl2HCl,C()n10mg/m3NH3HCNH2SSO22.cm3/m3)223.(mg/m3)Ca(cm3/m3)ppm)Cb(/km2•)4.Ca=MCb/22.4Cb=22.4Ca/MCa-mg/m3;Cb-cm3/m3M:SO20.10cm3/m3,mg/m3SO264CaMCb/22.4=640.10/22.4=0.29(mg/m3)1.:O3PANNO2Cl22.:SO2H2SHCHO3.:HFHCl4.:NH35.:6.:2.23SO2O31.3.4.5ºC305.SO2SO20.0003~0.003mg/m3,SO20.05~0.08mg/m31.(1)H2SSO2(2)SO2SO3(3)24SO42-H2SO4SO2H2S202021005001000SO2SO26hr239ppm25SO2SO24hr0.5ppmSO26hr6ppmSO26hr6ppm26~1.SO2pH2.SO2H2SO3HSO3-H+pH2-5,HSO3-,pH.=152