Heterogeneous oxidation of carbonyl sulfide (OCS) on mineral oxides including SiO2,Fe2O3,CaO,MgO,ZnO and TiO2,which are the main components of atmospheric particles,were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS),ion chromatography (IC),temperature-programmed desorption (TPD),X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely,OCS can be catalytically oxidized to produce surface SO42- species and gaseous CO2 through the surface hydrogen thiocarbonate (HSCO2-) and HSO3- species. The activity series for heterogeneous oxidation of OCS follows: Al2O3 ≈ CaO > MgO > TiO2 ≈ ZnO > Fe2O3 > SiO2. The specific area,basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.
Ozone(O3) and secondary organic aerosol(SOA) are considered to be the most serious secondary air pollutants of concern in most metropolitan areas,as well as for Beijing.In this study,O3 and SOA for-mation potential of α-pinene,the most abundant biogenic VOCs,is investigated at Tsinghua Indoor Chamber Facility.The experiments were conducted under atmospheric relevant HCs/NOx ratios in both presence and absence of ammonia sulfate seed aerosol.A Scanning Mobility Particle Sizer system(3936,TSI) and a Condensation Particle Counter(3010,TSI) were used to study the SOA formation and a gas chromatograph(GC) equipped with a DB-5 column and a flame ionization detector(FID) was used to measure α-pinene simultaneously.The results show that the presence of ammonia sulfate seed aerosol did not change the formation trend of O3,but significantly contribute to SOA formation.A strong linear relationship(r2 = 0.90) between SOA yield enhancement(△Y*) and surface concentration of seed aerosol(PMi,s)has been found,denoting that the PMi,s is the control factor for SOA yield en-hancement.And the possible reason for the enhancement is acid-catalyzed heterogeneous reactions.
Volatile organic compounds(VOCs)were measured at six sites in Beijing in August,2004.Up to 148 VOC species,including C_(3) to C_(12) alkanes,C_(3) to C_(11) alkenes,C_(6) to C_(12) aromatics,and halogenated hydrocarbons,were quantified.Although the concentrations differed at the sites,the chemical compositions were similar,except for the Tongzhou site where aromatics were significantly high in the air.Based on the source profiles measured from previous studies,the source apportionment of ambient VOCs was preformed by deploying the chemical mass balance(CMB)model.The results show that urban VOCs are predominant from mobile source emissions,which contribute more than 50% of the VOCs(in mass concentrations)to ambient air at most sites.Other important sources are gasoline evaporation,painting,and solvents.The exception is at the Tongzhou site where vehicle exhaust,painting,and solvents have about equal contribution,around 35% of the ambient VOC concen-tration.As the receptor model is not valid for deriving the sources of reactive species,such as isoprene and 1,3-butadiene,other methodologies need to be further explored.
