First X-ray Spectroscopic Observations of Atmospheric Titanium Species: Size Dependence and the Emission Source.

Titanium dioxide (TiO2) in mineral dust is considered as one of the driving forces of photocatalytic reaction at the aerosol surface in the atmosphere. As a precursor of mineral dust, soil contains ilmenite (FeTiO3) and titanite (CaSiTiO5), which have lower photochemical reactivities than TiO2. However, Ti species other than TiO2 in aerosol particles are not well recognized due to the lack of observation in ambient samples. In this study, Ti species in size-fractionated aerosol samples collected in the Noto Peninsula, Japan, were determined by macroscopic and semi-microscopic X-ray absorption fine structure spectroscopy. Regardless of aerosol particle size, Ti species were primarily composed of rutile, anatase, ilmenite, and titanite. Semi-microscopic Ti speciation showed that Ti-poor spots associated with mineral dust were composed of a mixture of rutile, anatase, ilmenite, and titanite, and Ti-rich spots were primarily composed of TiO2 (rutile or anatase) derived from authigenic minerals or anthropogenic materials. Thus, the Ti species in aerosol particles, especially mineral dust, were not composed solely of TiO2 polymorphs. Therefore, the photochemical reactivities of Ti in aerosol particles may be overestimated when laboratory experiments or model studies employ TiO2 as the representative Ti species.