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

1Maxime Pineau,2Maximilien Mathian,1,3Fabien Baron,1Benjamin Rondeau,1Laetitia Le Deit,2Thierry Allard,1Nicolas Mangold
American Mineralogist 107, 1453-1469 Open Access Link to Article []
1Laboratoire de Planétologie et Géodynamique, UMR CNRS 6112, Université de Nantes, Université d’Angers, Nantes, France
2Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR CNRS 7590, Sorbonne Université, Paris, France

3Institut de Chimie des Milieux et Matériaux de Poitiers, UMR CNRS 7285, Université de Poitiers, Poitiers, France
Copyright: The Mineralogical Society of America

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 Liétard 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.


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