Hygroscopic behavior of individual submicrometer particles studied by X-ray spectromicroscopy.

A novel application of single particle scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy is presented for quantitative analysis of hygroscopic properties and phase transitions of individual submicrometer particles. The approach utilizes the exposure of substrate-deposited individual particles to water vapor at different relative humidity followed by STXM/NEXAFS spectromicroscopy analysis. The hygroscopic properties of atmospherically relevant NaCl, NaBr, NaI, and NaNO(3) submicrometer particles were measured to evaluate the utility of the approach. An analytical approach for quantification of a water-to-solute ratio within an individual submicrometer particle during hydration and dehydration cycles is presented. The results for the deliquescence and efflorescence phase transitions and quantitative measurements of water-to-solute ratios are found in excellent agreement with available literature data. Oxygen K-edge NEXAFS spectra of submicrometer sodium halide droplets are reported along with a unique experimental observation of the formation of the halide-water anionic complex in NaBr and NaI microdimensional droplets. The analytical approach provides a unique opportunity for spectromicroscopy studies of water uptake on environmental particles collected in both laboratory and field studies.