Crystal structure model development for soil clay minerals – I. Hydroxy-interlayered smectite (HIS) synthesized from bentonite. A multi-analytical study

During the acidic weathering of soils, aluminum (Al) is dissolved from primary silicates such as feldspars or chlorites and intercalated in layer silicates. Part of this Al polymerizes in the interlayer of former smectites or vermiculites and the resulting phases are called hydroxy-interlayered minerals. These phases are known for a long time but are still insufficiently understood in terms of chemical composition and crystallographical structure. In the present study a sample set consisting of a continuous series of hydroxy-interlayered smectite samples with different degrees of hydroxy-interlayering ranging from 0 to 96% mol/mol smectite/HIS was prepared from a bentonite sample by adding different amounts of a 0.1 mol/L AlCl3 solution and different reaction times. The products were investigated by a multi-analytical approach using X-ray diffraction, Infrared spectroscopy, X-ray Fluorescence spectrometry, Fe2+:Fetotal determination, Nuclear Magnetic Resonance spectroscopy, Simultaneous Thermal Analysis coupled with mass spectrometry and Cation Exchange Capacity to provide an in-depth characterization. X-ray diffraction indicated that the turbostratic disorder typical for smectite did not change during hydroxy-interlayering. Nuclear Magnetic Resonance spectroscopy proved the exclusive six-fold coordination of interlayer Al and based on chemical calculations the average size and charge of the interlayer structures were characterized. Hydroxy-interlayers evolved in-situ in the smectite interlayers by polymerization. These interlayer “polymers” were small oligomers, the average size of which increased from monomers to pentamers with increasing degree of hydroxy-interlayering while the average net charge of each oligomer decreased. An average structural formula of each interstratified smectite-hydroxy-interlayered smectite was calculated from X-ray Fluorescence data including Fe2+:Fetotal ratios. If all exchangeable cations are attributed to smectite layers and all hydroxy-interlayers are attributed to hydroxy-interlayered smectite layers, the degree of hydroxy-interlayering ranged from 0 to 96% mol/mol smectite/HIS. The analysis provides an improved structural model of hydroxy-interlayered smectite suitable for Rietveld refinement which can be used to quantify the amounts of hydroxy-interlayered smectite in natural samples.