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.

Photolytic radical persistence due to anoxia in viscous aerosol particles.

In viscous, organic-rich aerosol particles containing iron, sunlight may induce anoxic conditions that stabilize reactive oxygen species (ROS) and carbon-centered radicals (CCRs). In laboratory experiments, we show mass loss, iron oxidation and radical formation and release from photoactive organic particles containing iron. Our results reveal a range of temperature and relative humidity, including ambient conditions, that control ROS build up and CCR persistence in photochemically active, viscous organic particles. We find that radicals can attain high concentrations, altering aerosol chemistry and exacerbating health hazards of aerosol exposure. Our physicochemical kinetic model confirmed these results, implying that oxygen does not penetrate such particles due to the combined effects of fast reaction and slow diffusion near the particle surface, allowing photochemically-produced radicals to be effectively trapped in an anoxic organic matrix.

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.

Droplet-based in situ X-ray absorption spectroscopy cell for studying crystallization processes at the tender X-ray energy range.

The understanding of nucleation and crystallization is fundamental in science and technology. In solution, these processes are complex involving multiple transformations from ions and ion pairs through amorphous intermediates to multiple crystalline phases. X-ray absorption spectroscopy (XAS), which is sensitive to liquid, amorphous and crystalline phases offers prospects of demystifying these processes. However, for low Z elements the use of in situ X-ray absorption spectroscopy requires the tender X-ray range, which is often limited by vacuum requirements thereby complicating these measurements. To overcome these challenges, we developed a versatile and user-friendly droplet-based in situ X-ray absorption spectroscopy cell for studying crystallization processes. Time-resolved in situ experiments under ambient conditions are carried out in the cell whilst the cell is mounted in the vacuum chamber of a tender X-ray beamline. By following changes in the Ca K-edge X-ray absorption near edge structure (XANES), we captured in situ the intermediate phases involved during calcium carbonate crystallization from aqueous solutions. In addition, through linear combination fitting it was possible to qualitatively observe the evolution of each phase during the reaction demonstrating the potential of the cell in studying complex multiphase chemical processes.

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.