Interactions between variable-charge soils and acidic solutions containing fluoride: an investigation using repetitive extractions.

The reaction between two variable-charge soils and acidic solutions containing F was investigated with a repetitive extraction method. When added F concentration was 10(-4) mol/L, F did not markedly enhance solution pH in the whole prolonged extractions, in comparison with F-free acidic solution extractions. Most of the added F was adsorbed on soil surfaces and Al-F complexes were the dominant F species in solution. With increasing extractions, the fraction of Al-F slightly increased, arising from dissolution and/or desorption of Al. In comparison with F-free acidic solution extractions, F-induced Al dissolution did not significantly increase Al release, probably because of the modest reactivity of metal-F surface complexes at terminal sites at low F loading. The gradual decrease in Al release in the following extractions was due to the gradual depletion of readily reactive Al-containing mineral phases. In contrast to the low F loading, at an F concentration of 10(-3) mol/L, the pH was enhanced dramatically in the initial extraction and a high pH was maintained in the following extractions. In the initial extraction, the increase in negative surface charges and solution pH seemingly depressed proton-induced Al dissolution and enhanced readsorption of some positively charged Al-F complexes, resulting in low amounts of Al and F in solution. In the following several extractions, F-induced Al dissolution and desorption of Al-F complexes substantially enhanced the amounts of Al and F, and the fraction of Al-F complexes in solution. Several interconnected mechanisms such as ligand exchange, the release of OH(-) ions from soluble hydroxylated Al groups, desorption of Al as Al-F complexes, and F-induced breakdown of soil minerals were responsible for the alteration in pH, Al release, and the fraction of Al-F complexes in the later extractions. A molecular-level interpretation is needed in order to address the different impacts of varying F concentration levels on soil chemistry and environments.