Abstract Various minerals have crystallized in centimeter-sized gouges and in adjacent scaly clays of the Main Fault intersecting the Opalinus Clay within the Mont Terri underground rock laboratory (Switzerland). Authigenic illite-type crystals, for instance, formed idiomorphic overgrowths on older detrital mica-type agglomerates in the gouge matrices and in their highly deformed surrounding damage zones. This heterogeneous illite crystallization was induced by local temperature increases due to the friction during faulting and to circulation of hot fluids, more in the highly deformed gouge rims than in the gouge matrices themselves. The aggregation of authigenic illite with detrital counterparts in the size separates made it difficult to do any quantitative distinction, and therefore any direct isotopic age dating. This incomplete separation of the detrital from authigenic illite in size separates of the gouges and the scaly clays, even down to nanometer size, needed a theoretical K-Ar age extrapolation for the authigenic illite fraction at ~8.8±0.9 Ma. This estimated age is based on the K content of a theoretically pure authigenic fraction determined by in situ analysis relative to estimated K contents of the detrital counterparts. The superposition of the micro-X-ray fluorescence Na and Cl maps visualizes a few veins filled with salts across an examined gouge, showing that fluids flowed through it, as well as through its highly deformed rims, while diffusing discretely into the surrounding matrix. The combined Fe and S micro-X-ray fluorescence maps of the examined materials also showed numerous pyrite agglomerates systematically associated with P, which indicates an occurrence of organic matter related to pyrite alteration. This organic matter induced local reducing conditions that were confirmed by REE spectra in the newly crystallized clay minerals of the fault features, carried by flowing fluids into the gouges. No geochemical argument suggests that the gouges are more or less permeable, at present, than the nearby undeformed Opalinus Clay. However, they were certainly more or less permeable at one point, probably during faulting, as K had to be supplied to explain the illite authigenesis detected in them and, to some extent, in the nearby scaly clays. Such permeability is also demonstrated by the systematic occurrence of salts in the micro-veins throughout the observed gouge and in its highly deformed rims that had to crystallize from fluids flowing during the deformation episode. Clearly, both the shape of the drains in and around the gouges and their systematic infilling by salts exclude technical artifacts claimed sometimes to deny any opening of the gouge volumes.

Abstract This study focused on a detailed mineralogical and crystal-chemical analysis of Mg-smectites from four bentonite samples from Turkey. Mg-rich smectites, mainly associated with alkaline and evaporitic depositional conditions, are formed in environments such as salt lakes, brine springs, and sabkhas, as well as in hydrothermal systems, in some cases by transformation from other phyllosilicates. Saponite has also been documented on the surface of Mars. The systems that produce Mg-smectites are less common than those that produce dioctahedral Al-smectites and consequently Mg-rich smectites are less abundant than dioctahedral smectites. For this reason, information on nanoscale mineralogy and crystal chemistry of Mg-smectites is relatively lacking. In this study, X-ray diffraction, thermal analysis and electron microscopy were used to study Mg-smectites. The crystal chemistry of single crystals determined with analytical electron microscopy in transmission electron microscopy (AEM-TEM) revealed that all samples had notable variability in the composition of individual crystals, such that no point analysis resulted in ideal structural formulae for saponite, stevensite, sepiolite, or palygorskite. They contain SiO2 content greater than that corresponding to a Mg-smectite, even stevensite, and often are intermediate to Mg-smectites and the sepiolite-palygorskite series. Meanwhile, the number of octahedral cations is small for fibrous clay minerals. Neither the point analysis of smectitic particles nor the mean structural formula fit properly for Mg-smectites showing crystallochemistry complexity. The results of these point analyses, in which no contamination has been observed, suggest that these smectites have intermediate compositions between trioctahedral smectites and sepiolite-palygorskite, indicating nanometer-scale intergrowths of these minerals in Mg-rich clay deposits.

Abstract Characterizing the structure and composition of clay minerals on the surface of Mars is important for reconstructing past aqueous processes and environments. Data from the CheMin X-ray diffraction (XRD) instrument on the Mars Science Laboratory Curiosity rover demonstrate a ubiquitous presence of collapsed smectite (basal spacing of 10 Å) in ~3.6-billion-year-old lacustrine mudstone in Gale crater, except for expanded smectite (basal spacing of 13.5 Å) at the base of the stratigraphic section in a location called Yellowknife Bay. Hypotheses to explain expanded smectite include partial chloritization by Mg(OH)2 or solvation-shell H2O molecules associated with interlayer Mg2+. The objective of this work is to test these hypotheses by measuring partially chloritized and Mg-saturated smectite using laboratory instruments that are analogous to those on Mars rovers and orbiters. This work presents Mars-analog XRD, evolved gas analysis (EGA), and visible/shortwave-infrared (VSWIR) data from three smectite standards that were Mg-saturated and partially and fully chloritized with Mg(OH)2. Laboratory data are compared with XRD and EGA data collected from Yellowknife Bay by the Curiosity rover to examine whether the expanded smectite can be explained by partial chloritization and what this implies about the diagenetic history of Gale crater. Spectral signatures of partial chloritization by hydroxy-Mg are investigated that may allow the identification of partially chloritized smectite in Martian VSWIR reflectance spectra collected from orbit or in situ by the SuperCam instrument suite on the Mars 2020 Perseverance rover. Laboratory XRD and EGA data of partially chloritized saponite are consistent with data collected from Curiosity. The presence of partially chloritized (with Mg(OH)2) saponite in Gale crater suggests brief interactions between diagenetic alkaline Mg2+-bearing fluids and some of the mudstone exposed at Yellowknife Bay, but not in other parts of the stratigraphic section. The location of Yellowknife Bay at the base of the stratigraphic section may explain the presence of alkaline Mg2+-bearing fluids here but not in other areas of Gale crater investigated by Curiosity. Early diagenetic fluids may have had a sufficiently long residence time in a closed system to equilibrate with basaltic minerals, creating an elevated pH, whereas diagenetic environments higher in the section may have been in an open system, therefore preventing fluid pH from becoming alkaline.

Abstract In heavy oil fields hosted in sandstone, steam flooding is a crucial technique for enhancing oil recovery. The swelling of clay minerals in these reservoirs, particularly those with high clay content, presents a significant challenge by causing permeability damage and hindering oil production. The objective of the present study was to investigate clay swelling phenomena in a sandstone oil reservoir where smectite-illite clays make up 40% of the reservoir rock. Through comprehensive static and dynamic tests, clay swelling behavior and its impact on permeability degradation were examined under varying temperature and salinity conditions typical of thermally enhanced oil recovery (EOR) processes. Results indicated that clay swelling is exacerbated under low salinity and high temperature, leading to severe permeability impairment. At high salinities (2000–4920 mg L–1), the swellability was relatively low, but it increased significantly as salinity decreased to a range of 0–2000 mg L–1. Static swelling tests revealed that the maximum clay expansion, with a 2.25-fold increase in volume, occurred in distilled water at 200°C. Additionally, the critical salt concentration (CSC) was found to increase with temperature, causing a more pronounced and earlier swelling effect. This increase in temperature coupled with a decrease in salinity impaired permeability significantly, with the most severe reduction, of 73.3%, observed at 150°C during distilled water flooding. Comparisons between static and dynamic tests showed consistent degrees of clay swelling across both methods. The findings of this study advance the understanding of clay swelling under thermal EOR conditions, particularly regarding the effects of salinity and temperature on permeability impairment in sandstone formations.