Far- and mid-infrared examination of nontronite-1 clay mineral – Redox and cation saturation effects

Abstract

Infrared Spectroscopy is a very useful tool studying clay minerals in a structural level as well as interactions on their surfaces. In this study, middle- and far- infrared spectroscopy was utilised to better understand how iron-bearing smectites and more specifically the nontronite-1 (NAu1) alters upon iron reduction. Changes in the middle-infrared spectral range have been studied extensively, such as the 3570 cm−1, 1020 cm−1 and 823 cm−1, while far-infrared spectral range changes have not drawn much attention. In this study, NAu1 spectra of oxidised, partially, and fully reduced state are presented noting the differences that occur on different vibration bands at this low frequency infrared range. Key changes took place at the region of 430–494 cm−1, as well as the 145 cm−1 band. From the 175 cm−1 to the 380 cm−1 region, vibrating bands disappeared or convoluted in a wider spectral envelope, upon full iron reduction. At the same time, NAu1 is saturated with different cations, such as Na+, Ca2+, K+, isolating effects on vibrating bands, depending on these cations, across the oxidation states and infrared range examined. These effects are more prominent at the region of 1620–1650 cm−1, where adsorbed H2O bending vibration takes place, for the middle-infrared range. Far-infrared range changes, due to the cation present, are less prominent, but recorded and discussed in detail. Eventually, the redox state of iron-bearing clay minerals controls the structural configuration of the lattice and consequently the interaction strength of clay mineral/saturating cations. The increasing interaction strength observed was Ca2+ < Na+ < K+, which will govern clay mineral hydration and cation exchange processes taking place on the clay mineral surface, as demonstrated, and discussed in this study. These outcomes can be useful in agriculture, waste disposal, and the oil & gas industry.