Thermodynamics of heterogeneous crystal nucleation in contact and immersion modes

One of most intriguing problems of heterogeneous crystal nucleation in droplets is its strong enhancement in the contact mode (when the foreign particle is presumably in some kind of contact with the droplet surface) compared to the immersion mode (particle immersed in the droplet). Many heterogeneous centers have different nucleation thresholds when they act in contact or immersion modes, indicating that the mechanisms may be actually different for the different modes. Underlying physical reasons for this enhancement have remained largely unclear. In this paper we present a model for the thermodynamic enhancement of heterogeneous crystal nucleation in the contact mode compared to the immersion one. To determine if and how the surface of a liquid droplet can thermodynamically stimulate its heterogeneous crystallization, we examine crystal nucleation in the immersion and contact modes by deriving and comparing with each other the reversible works of formation of crystal nuclei in these cases. As a numerical illustration, the proposed model is applied to the heterogeneous nucleation of Ih crystals on generic macroscopic foreign particles in water droplets at T=253 K. Our results show that the droplet surface does thermodynamically favor the contact mode over the immersion one. Surprisingly, our numerical evaluations suggest that the line tension contribution to this enhancement from the contact of three water phases (vapor-liquid-crystal) may be of the same order of magnitude as or even larger than the surface tension contribution

Distribution of aluminium fractions in acid forest soils: influence of vegetation changes

This study examines aluminium as a potentially phytotoxic element in acidic forest soils. Concentrations of Al forms in soils are generally controlled by soil chemical conditions, such as pH, organic matter, base cation contents, etc. Moreover, soil conditions are influenced by the vegetation cover. This study analyzed the distribution of Al forms in soils after changes in vegetation. HPLC/IC was used for the separation of three Al fractions in two soil extracts according to their charge. An aqueous extract (AlH2O) simulated the natural soil conditions and bioavailable Al fractions. Potentially available Al form was represented by a 0.5 M KCl extract (AlKCl). We demonstrated that the vegetation type influences the concentrations of different Al fractions, mainly in the surface organic horizons. Differences were more common in the KCl extract. The trivalent fraction was less influenced by vegetation changes than the mono- and divalent fractions. Afforestation increased the concentrations of AlKCl and AlH2O. In contrast, grass expansion after deforestation led to significantly decreased concentrations of AlKCl and AlH2O. Concentrations of AlH2O in organic horizons were higher in spruce forest than in beech forest. A long-term effect of liming on soil pH and concentrations of potentially toxic Al fractions was not apparent. The results provide information on the variations of Al fractions distributions following vegetation type changes and indicate the existence of some natural mechanisms controlling Al toxicity. Furthermore, the results can be used in the management of forested areas endangered by soil acidification