X-Ray absorption spectroscopy on airborne aerosols.

Here we demonstrate a method for performing X-ray absorption spectroscopy (XAS) on airborne aerosols. XAS provides unique insight into elemental composition, chemical and phase state, local coordination and electronic structure of both crystalline and amorphous matter. The aerosol is generated from different salt solutions using a commercial atomizer and dried using a diffusion drier. Embedded in a carrier gas, the aerosol is guided into the experimental chamber for XAS analysis. Typical particle sizes range from some 10 to a few 100 nm. Inside the chamber the aerosol bearing gas is then confined into a region of about 1-2 cm3 in size, by a pure flow of helium, generating a stable free-flowing stream of aerosol. It is hit by a monochromatic X-ray beam, and the emitted fluorescent light is used for spectroscopic analysis. Using an aerosol generated from CaCl2, KCl, and (NH4)2SO4 salt solutions, we demonstrate the functionality of the system in studying environmentally relevant systems. In addition, we show that the detection limits are sufficient to also observe subtle spectroscopic signatures in XAS spectra with integration times of about 1-2 hours using a bright undulator beamline. This novel setup opens new research opportunities for studying the nucleation of new phases in multicomponent aerosol systems in situ, and for investigating (photo-) chemical reactions on airborne matter, as relevant to both atmospheric science and also for general chemical application.

Aerosol-based synthesis of pure and stable amorphous calcium carbonate.

A facile aerosol-based method for the synthesis of pure and stable amorphous calcium carbonate (ACC) is presented. The method relies on the instantaneous carbonation of calcium hydroxide aerosols with carbon dioxide followed by rapid drying of the freshly formed ACC. The ACC display extended stability against humidity induced crystallization.

Supersaturated calcium carbonate solutions are classical.

Mechanisms of CaCO3 nucleation from solutions that depend on multistage pathways and the existence of species far more complex than simple ions or ion pairs have recently been proposed. Herein, we provide a tightly coupled theoretical and experimental study on the pathways that precede the initial stages of CaCO3 nucleation. Starting from molecular simulations, we succeed in correctly predicting bulk thermodynamic quantities and experimental data, including equilibrium constants, titration curves, and detailed x-ray absorption spectra taken from the supersaturated CaCO3 solutions. The picture that emerges is in complete agreement with classical views of cluster populations in which ions and ion pairs dominate, with the concomitant free energy landscapes following classical nucleation theory.