Speciation of sulfate components in size-fractionated aerosol particles using sulfur K-edge X-ray absorption near-edge structure （XANES）

Sulfates are a main constituent of aerosols, which sulfate aerosols, it is necessary to determine what can cause various environmental problems sulfate ions are contained in these aerosols In the evaluation of the influence of In this study, sulfur K-edge XANES was used to determine sulfate species present in size-fractionated aerosol particles based on the post-edge structure after the main absorption peak in the XANES region. Aerosol samples were collected as part of the Japan-China joint project, ＂Asian Dust Experiment on Climate Impact＂ using a low-volume Andersen-type air sampler. XANES was measured at Beamline BL-9A at Photon Factory, Japan. A comparison of the XANES spectra of reference sulfate materials and aerosol samples collected in Tsukuba in Japan clearly showed that （NH4）2SO4 was the main sulfur species in particles with a smaller diameter and gypsum was the main sulfur species in particles with a larger diameter. A simulation of the XANES spectra by reference materials allows us to obtain the quantitative mixing ratios of the different sulfate species present in the aerosol samples. The presence of minor sulfur species other than （NH4）2SO4 and gypsum at the surface of mineral aerosols is suggested in our simulations and by a surface-sensitive conversion electron/He-ion yield XANES. In the absence of a contribution from a large dust event, the mole concentration of gypsum in the mineral aerosol fraction determined by XANES is similar to that of Ca which is determined independently using ion chromatography. This shows that the Ca and sulfate in the mineral aerosols are present only as gypsum. Considering that calcite is the main Ca mineral in the original material arising from an arid and semi-arid area in China, it is strongly suggested that gypsum is formed in aerosol during its long-range transportation by a reaction between calcite and sulfate ions.