The Kinetics of Adsorption and Desorption of Selected Semivolatile Hydrocarbons and H2O Vapor on Two Mineral Dust Materials: A Molecular View.

A flowing gas experiment using a Knudsen flow reactor was performed on a series of seven semivolatile probe gases interacting with two often used mineral dust materials, namely, coarse Arizona test dust (ATD-C) and kaolinite. The semivolatile probe gases used were applinate (acetate ester), pipol (ethyl ester of 2-methylvaleric acid), benzylacetate (acetate ester of benzylalcohol), menthol (alcohol), toluene, limonene, and γ-terpinene (terpene hydrocarbon). Uptake experiments under molecular flow conditions resulted in absolute coverages and initial uptake coefficients γ0 based on the geometric sample surface. Integration of a simple Langmuir adsorption model afforded an analytical solution of the desorption kinetics of the semivolatile hydrocarbon upon spontaneous desorption from the solid mineral dust substrate at ambient temperature. Numerical fitting of the desorption rate resulted in adsorption (ka) and desorption (kd) rate constants, where 1/kd represented the surface residence time of the adsorbed semivolatile. The major conclusions are as follows: (a) Desorption at short ("prompt") and long time scales reveal stronger binding to ATD compared to kaolinite for all tested organic probe gases. (b) No difference in the desorption yields and kinetics was observed for H2O vapor on either substrate. (c) Prompt desorption at ambient temperature starts with the immediate detection of probe gases adsorbed on the vessel walls of the sample compartment, followed by the slower growth and decay of semivolatiles adsorbed on the substrate, leading to ka and kd. (d) Surface residence times at ambient temperatures for semivolatile organics vary from 50 to 40 000 s for toluene/ATD and menthol/ATD, respectively. For H2O vapor, 3000 s was measured on both kaolinite and ATD. (e) Large initial uptake coefficients γ0 in the range of 0.25-0.77 were measured for all semivolatiles except toluene, whose values were lower by roughly one order of magnitude. Rapid saturation was observed in all cases except for limonene, which appeared to undergo chemical reactions on both mineral substrates.

Metastable Nitric Acid Trihydrate in Ice Clouds.

The composition of high-altitude ice clouds is still a matter of intense discussion. The constituents in question are ice and nitric acid hydrates, but the exact phase composition of clouds and its formation mechanisms are still unknown. In this work, conclusive evidence for a long-predicted phase, alpha-nitric acid trihydrate (alpha-NAT), is presented. This phase was characterized by a combination of X-ray and neutron diffraction experiments, allowing a convincing structure solution. Furthermore, vibrational spectra (infrared and inelastic neutron scattering) were recorded and compared with theoretical calculations. A strong interaction between water ice and alpha-NAT was found, which explains the experimental spectra and the phase-transition kinetics. On the basis of these results, we propose a new three-step mechanism for NAT formation in high-altitude ice clouds.