The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51–18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunauer-Emmett-Teller (BET) uptake coefficients of heterogeneous reactions rose with SO2 and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.
CUI HuxiongCHENG TiantaoYU XingnaCHEN JianminXU YongfuFANG Wen
UV-induced degradation of odorous dimethyl sulfide(DMS) was carried out in a static White cell chamber with UV irradiation.The combination of in situ Fourier transform infrared(FT-IR) spectrometer,gas chromatograph-mass spectrometer(GC-MS),wide-range particle spectrometer(WPS) technique,filter sampling and ion chromatographic(IC) analysis was used to monitor the gaseous and potential particulate products.During 240 min of UV irradiation,the degradation efficiency of DMS attained 20.9%,and partially oxidized sulfur-containing gaseous products,such as sulfur dioxide(SO2),carbonyl sulfide(OCS),dimethyl sulfoxide(DMSO),dimethyl sulfone(DMSO2) and dimethyl disulfide(DMDS) were identified by in situ FT-IR and GC-MS analysis,respectively.Accompanying with the oxidation of DMS,suspended particles were directly detected to be formed by WPS techniques.These particles were measured mainly in the size range of accumulation mode,and increased their count median diameter throughout the whole removal process.IC analysis of the filter samples revealed that methanesulfonic acid(MSA),sulfuric acid(H2SO4) and other unidentified chemicals accounted for the major non-refractory compositions of these particles.Based on products analysis and possible intermediates formed,the degradation pathways of DMS were proposed as the combination of the O(1D)-and the OH-initiated oxidation mechanisms.A plausible formation mechanism of the suspended particles was also analyzed.It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.
