Detection of Interlayered Illite/Smectite Clay Minerals with XRD, SEM Analyses and Reflectance Spectroscopy.

Accurate determination of clay minerals can be challenging due to the natural occurrence of interlayered phases, i.e., layers of different clay species such as illite and smectite. The overlap of peaks of the constituent minerals (e.g., illite and smectite), and the similarity of diffraction patterns when not treated with ethylene glycol, hampers identification, especially when the clay content is low. We investigated the occurrence of interlayered illite/smectite in a rock sample from Rodalquilar, Spain, using X-ray diffraction, scanning electron microscopy and reflectance spectroscopy in the short-wave infrared wavelength range. For the first time, a precise determination of interlayered I/S conducted on the extracted clay fraction treated with ethylene glycol using such different approaches was provided. X-ray diffraction results demonstrated the presence of an I/S peak at around 8.4° in the untreated fraction coupled with a peak splitting at 6.7° and 9.4° 2θ when solvated with ethylene glycol. While spectroscopy indicated the occurrence of interlayered structures as a mixture of the two constituent minerals, the results of X-ray analysis showed that the interlayered clay consisted of two discrete phases (illite and smectite). The two discrete phases were observed in both the whole rock analysis and in the extracted clay fraction. This study shows that X-ray diffraction and validation with a scanning electron microscope is a mandatory, integrating tool for detecting interlayered phases since reflectance spectroscopy alone cannot be used to differentiate between interlayered clay minerals and non-interlayered mixtures. This work highlights the limits and advantages of three sensors (X-ray diffraction, scanning electron microscopy and reflectance spectroscopy) to investigate clay mixtures and interlayering, representing a significant contribution to confidence in the interpretation of interlayered clays, this being essential in mineral exploration and prospecting.

Mineral Interpretation Discrepancies Identified between Infrared Reflectance Spectra and X-ray Diffractograms.

Mineral composition can be determined using different methods such as reflectance spectroscopy and X-ray diffraction (XRD). However, in some cases, the composition of mineral maps obtained from reflectance spectroscopy with XRD shows inconsistencies in the mineral composition interpretation and the estimation of (semi-)quantitative mineral abundances. We show why these discrepancies exist and how should they be interpreted. Part of the explanation is related to the sample choice and preparation; another part is related to the fact that clay minerals are active in the short-wave infrared, whereas other elements in the composition are not. Together, this might lead to distinctly different interpretations for the same material, depending on the methods used. The main conclusion is that both methods can be useful, but care should be given to the limitations of the interpretation process. For infrared reflectance spectroscopy, the lack of an actual threshold value for the H-OH absorption feature at 1900 nm and the poorly defined Al-OH absorption feature at 2443 nm, as well as for XRD, detection limit, powder homogenizing, and the small amount of montmorillonite below 1 wt.%, was the source of discrepancies.

Shannon Entropy as an Indicator for Sorting Processes in Hydrothermal Systems.

Hydrothermal processes modify the chemical and mineralogical composition of rock. We studied and quantified the effects of hydrothermal processes on the composition of volcanic rocks by a novel application of the Shannon entropy, which is a measure of uncertainty and commonly applied in information theory. We show here that the Shannon entropies calculated on major elemental chemical composition data and short-wave infrared (SWIR) reflectance spectra of hydrothermally altered rocks are lower than unaltered rocks with a comparable primary composition. The lowering of the Shannon entropy indicates chemical and spectral sorting during hydrothermal alteration of rocks. The hydrothermal processes described in this study present a natural mechanism for transforming energy from heat to increased order in rock. The increased order is manifest as the increased sorting of chemical elements and SWIR absorption features of the rock, and can be measured and quantified by the Shannon entropy. The results are useful for the study of hydrothermal mineral deposits, early life environments and the effects of hydrothermal processes on rocks.

Multitechnique characterization of secondary minerals near HI-SEAS, Hawaii, as Martian subsurface analogues.

Secondary minerals in lava tubes on Earth provide valuable insight into subsurface processes and the preservation of biosignatures on Mars. Inside lava tubes near the Hawaii-Space Exploration and Analog Simulation (HI-SEAS) habitat on the northeast flank of Mauna Loa, Hawaii, a variety of secondary deposits with distinct morphologies were observed consisting of mainly sodium sulphate powders, gypsum crystalline crusts, and small coralloid speleothems that comprise opal and calcite layers. These secondary deposits formed as a result of hydrological processes shortly after the formation and cooling of the lava tubes and are preserved over long periods of time in relatively dry conditions. The coralloid speleothem layers are likely related to wet and dry periods in which opal and calcite precipitates in cycles. Potential biosignatures seem to have been preserved in the form of porous stromatolite-like layers within the coralloid speleothems. Similar secondary deposits and lava tubes have been observed abundantly on the Martian surface suggesting similar formation mechanisms compared to this study. The origin of secondary minerals from tholeiitic basalts together with potential evidence for microbial processes make the lava tubes near HI-SEAS a relevant analog for Martian surface and subsurface environments.

Thermal infrared spectrometer for Earth science remote sensing applications-instrument modifications and measurement procedures.

In this article we describe a new instrumental setup at the University of Twente Faculty ITC with an optimized processing chain to measure absolute directional-hemispherical reflectance values of typical earth science samples in the 2.5 to 16 µm range. A Bruker Vertex 70 FTIR spectrometer was chosen as the base instrument. It was modified with an external integrating sphere with a 30 mm sampling port to allow measuring large, inhomogeneous samples and quantitatively compare the laboratory results to airborne and spaceborne remote sensing data. During the processing to directional-hemispherical reflectance values, a background radiation subtraction is performed, removing the effect of radiance not reflected from the sample itself on the detector. This provides more accurate reflectance values for low-reflecting samples. Repeat measurements taken over a 20 month period on a quartz sand standard show that the repeatability of the system is very high, with a standard deviation ranging between 0.001 and 0.006 reflectance units depending on wavelength. This high level of repeatability is achieved even after replacing optical components, re-aligning mirrors and placement of sample port reducers. Absolute reflectance values of measurements taken by the instrument here presented compare very favorably to measurements of other leading laboratories taken on identical sample standards.