Estimating kaolinite crystallinity using near-infrared spectroscopy: Implications for its geology on Earth and Mars

Kaolinite is an Al-rich phyllosilicate commonly observed on Earth as a product of the chemical weathering of aluminosilicates. It has also been detected on the martian surface by orbital remote sensing observations. While the determination of the geological processes of formation of terrestrial kaolinite (i.e., hydrothermal activity, continental surface weathering, diagenesis) involves the coupling of field observation and multiple laboratory measurements, only geomorphology and associated minerals are generally available to determine their geological origin on Mars. Kaolinite crystallinity depends on many physicochemical parameters reflecting its conditions of crystallization. To determine if the near-infrared (NIR) spectral signature of kaolinite enables estimation of its crystallinity and furthermore if this method can be used to identify the geological processes involved in kaolinite formation, we carried out an in-depth analysis of NIR spectra of reference terrestrial kaolinites that formed in various geological contexts. We calculated second and third derivatives for each spectrum to highlight subtle variations in the spectral properties of kaolinite. This allowed the identification of 27 spectral contributions for the 4500 and 7000 cm(-1) Al-OH-related regions of absorption bands. The position shifts and shape variations of these spectral contributions were intimately linked to variations of crystallinity, which was qualitatively estimated using Hinckley and Lietard XRD (dis)order indices. The results obtained show that the NIR signature of kaolinite is influenced by the stacking disorder of layers that has some influence on the vibrations of the interfoliar and inner Al-OH groups. Our study also confirms that: (1) well-ordered kaolinites are not restricted to hydrothermal deposits; (2) kaolinites from a similar sedimentary or pedogenetic context often display contrasting degrees of crystalline order; and (3) poorly ordered kaolinites are more likely to have a sedimentary or pedogenetic origin. Finally, this work highlights that obtaining spectra with sufficient spectral resolution could help to estimate the crystallinity of kaolinite and, in the best cases, its geological origin, both on Earth and Mars, especially with in situ NIR measurements.