Investigation of Al-rich clays on Mars: Evidence for kaolinite–smectite mixed-layer versus mixture of end-member phases

Aluminous clay deposits on Mars are recognized from remotely sensed infrared spectral features similar to those of montmorillonite, beidellite, and/or kaolinite. The nature of aluminous clay deposits on Mars is of interest because they likely indicate a different formation mechanism than that of Fe–Mg clays, which are widespread on Mars and likely alteration products of the Fe–Mg-rich basaltic crust. The near-infrared reflectance spectra of aluminous martian clay deposits frequently display characteristics typical of both montmorillonite and kaolinite. The question arises whether such mixed character is due to the existence of end-member phases or to kaolinite–smectite mixed-layer (K–S). The issue is relevant because K–S implies the existence of a smectite precursor that alters into kaolinite, and thus constrains the timing and intensity of the alteration processes that generates it. A mixture of kaolinite and smectite end-members may indicate locally heterogeneous alteration processes, or alternatively, could result from the physical mixing of altered materials of different provenance. A group of natural K–S samples and synthetic kaolinite/smectite mixtures of known proportion, all of which had been thoroughly characterized in previous work using several analytical techniques, were investigated here using near-infrared (NIR) spectroscopy. The NIR spectral features correlate well with their kaolinite–smectite relative proportions. The shape of spectral features attributed to Al–OH in K–S is subtly different from those in physical mixtures of kaolinite and smectite. Based on qualitative comparison, some regions on Mars appear to have spectral signatures similar to K–S. We also applied a quantitative technique using the second derivative of spectra. In this technique, plots of the height of the features at (λ=) 2.21 μm (band present in kaolinite and montmorillonite) and 2.17 μm (kaolinite only) were able to discriminate between K–S and kaolinite–smectite physical mixtures, as they generated correlations with different slopes. The method of discrimination was applied to Mars spectra, which resulted in reasonable evidence for the existence of K–S in Nili Fossae and Mawrth Vallis, and mixtures of end-members in Mawrth Vallis and Leighton Crater. This is one of the first times that evidence for mixed-layer clay minerals, and particularly K–S, on Mars has been gathered. The ability to detect mixed-layer clays is an important step forward for further development of our understanding of the processes that generated clay on Mars.

► Mixed-layer kaolinite–smectite has NIR features different from those of clay mixtures.
► Mixed-layer kaolinite–smectite has been detected on Mars.
► Kaolinite–smectite on Mars furthers constrains clay formation processes.