The crystal chemistry of Fe-Si scales deposited from geothermal brines at Salton Sea, California, was studied by powder X-ray diffraction and spectroscopic techniques including infrared, 57Fe Mössbauer, 27Al and 29Si nuclear magnetic resonance (NMR), and Fe and Si K-edge extended X-ray absorption fine structure (EXAFS). Scales precipitated at near 250°C from dissolved ferrous iron and silicic acid are composed of hisingerite. This phase is shown to possess the same local structure as nontronite and is a poorly-crystallized precursor of the ferric smectite. A clear distinction can be made at the local scale between hisingerite and 2-line ferrihydrite because, even in their most disordered states, the former possesses a two-dimensional and the latter a three-dimensional anionic framework. At temperature near 100°C Fe-Si scales are a mix of Al-containing opal and hydrous ferrous silicate, whose local structure resembles minnesotaite and greenalite. This hydrous ferrous silicate is very well ordered at the local scale with an average Fe coordination about Fe atoms of 6 ± 1. The difference in crystallinity between the ferrous and ferric silicate scales was related to variations of growth rates of clay particles precipitated from ferrous and ferric salt solutions. The low crystallinity of the ferric smectite suggests that the oxidation of ferrous iron occurs before polymerization with silica.

This paper compares the results of 27Al nuclear magnetic resonance spectroscopy (NMR) and Al-K-edge X-ray Absorption Near Edge Structure (XANES) of natural imogolite and allophanes and some crystalline reference minerals. All soil allophanes studied contain 4-coordinated Al (AlIV). The highest relative proportion of AlIV, 21% of the total Al, was found in Si-rich allophane. This value is close to that found in spring allophanes, which were previously considered to be different from soil allophanes. For a quantitative determination of the AlIV/Altotal ratio, NMR is more reliable than XANES, because of the sensitivity of the chemical shift to low AlIV concentrations, but XANES may be used even if paramagnetic impurities (mostly Fe) are present. Al-K XANES also yields more information than NMR on the local environment of AlVI and especially site multiplicity. AlVI XANES of imogolite and allophanes are similar regardless of the Al/Si ratio. They yield two well-resolved resonances with maxima near 1568 and 1570 eV, which indicates the presence of a unique AlVI site by comparison with crystalline references. The presence of only one AlVI site indicates that imogolite and allophanes have an octahedral sheet with a structure similar to 2/1 dioctahedral phyllosilicates but different from gibbsite or kaolinite, previously considered as structural analogues. The 27AlIV MAS NMR peak maxima of allophanes are between 58.6 and 59.8 ppm, in the range observed for crystalline and amorphous framework alumino-silicates, and less positive than those of sheet silicates, which are typically in the range 65–75 ppm. 27Al-H1 CPMAS NMR spectra suggest that both AlIV and AlVI have Al-O-H linkages.

Sodium-covered silica films formed on silicon substrates have been examined by X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (EXAFS) in ultra-high vacuumconditions at 300K. The results show that sodium diffuses into the silica layer on a reversible manner and that it modifies the silica network in order to create its own site. Sodium atoms are surrounded by oxygen atoms at an average distance of 2.3 Å and by a second shell which is assigned to silicon atoms located at 3.8 Å. At high Na concentrations, sodium atoms are also present in the close environment of one sodium atom.

The first stages of the hydrolysis of Fe(III) in presence of PO4 were studied at the local (P k-edge and Fe k-edge EXAFS spectroscopy) and semi-local scale (SAXS). The presence of PO4 hinders the polymerization of iron at the edge sharing dimer step. Phosphate probably governs the local structure leading to the formation of small and dense clusters. The fitting of both k-edge EXAFS spectroscopies requiered the use of a new 3D model of each nucleation step.