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International audience; Phyllosilicates may trap hydrogen (H2) in the crust, but they may also produce it through various processes, including oxidative dehydrogenation. The dehydrogenation temperature depends on the type and composition of the phyllosilicates considered, but it may be as low as 300 °C. Here, we document the release of H2 and CO during thermal treatment of chloritite (300 °C) and talc (500 °C) from the Trimouns deposits (Eastern Pyrenees, France). Thermal release of gases coupled to stable isotope analysis has been used to recover and characterize H2 and CO, the two detected gases. Hydrogen content may be as high as 7 ppm with δDH2 values ranging from −258‰ to – 224‰ for sub-pure chloritite and − 140‰ for pure talc. CO content ranges between 3 ppm and 35.3 ppm with very homogeneous δ13CCO values between −27.6‰ and − 25.7‰. This study supports the idea that H2 was produced during experiments by dehydrogenation. The origin of CO remains enigmatic, but its carbon isotope composition suggests a link to the few amounts of graphite documented in chloritite and talc from the deposit. This work also reports extensive hydrogen isotope fractionation between H2 produced by dehydrogenation and both talc and chloritite. Dehydrogenation of phyllosilicates is a potential source term of H2 in numerous magmatic-hydrothermal settings and must thus be accounted for in the budget of the H2 geochemical cycle

International audience; Experimental studies have shown that a sharp, high-frequency IR band at ~3615 cm-1 (in H2O form) and at ~2685 cm-1 (in D2O form) is a common feature for all smectites, and its position correlates with layer charge. In order to explain the molecular origin of this band in terms of total layer charge, charge localization, as well as nature of interlayer cations influencing the position and intensity of this peak, a series of classical molecular dynamics (MD) simulations was performed for several smectite models. The smectite layers were described using a modified CLAYFF force field, where the intramolecular vibrations of H2O were described more accurately by the Toukan-Rahman potential. The power spectra of molecular vibrations of hydrogens were calculated for selected sub-sets of interlayer H2O to analyze quantitatively their contribution to the observed spectral features. The statistics of hydrogen bonds in the smectite interlayers were also analyzed to support the spectral calculations.The simulation results demonstrated clearly that only the H2O molecules in close proximity to the smectite surface are responsible for the sharp vibrational band observed. Other hypotheses for the possible origins of this band were considered carefully and eventually rejected. Two orientations of H2O molecules donating one or two H bonds to the basal oxygens of the smectite surface (monodentate and bidentate orientations, respectively) were observed. In both orientations, these H bonds are quite weak, pointing to a generally hydrophobic character of the smectite surface. Both orientations contributed to the high-frequency band, but the monodentate orientation provided the predominant contribution because surface H2O molecules in this orientation were much more abundant. In good agreement with experiment, only a small difference in the peak position was observed between smectites with different charge localization. The effect of the total layer charge, i.e. the red-shift for higher-charge smectites, was also confirmed. This shift arose from the decrease in the H-bonding distances of H2O in monodentate and bidentate orientation.

International audience; The radioactive decay of 40K to 40Ar is the basis of isotope age determination of micaceous clay minerals formed during diagenesis. The difference in K–Ar ages between fine and coarse grained illite particles has been interpreted using detrital-authigenic components system, its crystallization history or post-crystallization diffusion. Yet another mechanism should also be considered: natural 40Ar recoil. Whether this recoil mechanism can result in a significant enough loss of 40Ar to provide observable decrease of K–Ar age of the finest illite crystallites at diagenetic temperatures – is the primary objective of this study which is based on molecular dynamics (MD) computer simulations.All the simulations were performed for the same kinetic energy (initial velocity) of the 40Ar atom, but for varying recoil angles that cover the entire range of their possible values. The results show that 40Ar recoil can lead to various deformations of the illite structure, often accompanied by the displacement of OH groups or breaking of the Si–O bonds. Depending on the recoil angle, there are four possible final positions of the 40Ar atom with respect to the 2:1 layer at the end of the simulation: it can remain in the interlayer space or end up in the closest tetrahedral, octahedral or the opposite tetrahedral sheet. No simulation angles were found for which the 40Ar atom after recoil passes completely through the 2:1 layer. The energy barrier for 40Ar passing through the hexagonal cavity from the tetrahedral sheet into the interlayer was calculated to be 17 kcal/mol. This reaction is strongly exothermic, therefore there is almost no possibility for 40Ar to remain in the tetrahedral sheet of the 2:1 layer over geological time periods. It will either leave the crystal, if close enough to the edge, or return to the interlayer space. On the other hand, if 40Ar ends up in the octahedral sheet after recoil, a substantially higher energy barrier of 55 kcal/mol prevents it from leaving the TOT layer over geological time.Based on the results of MD simulations, the estimates of the potential effect of 40Ar recoil on the K–Ar dating of illite show that some of 40Ar is lost and the loss is substantially dependent on the crystallite dimensions. The 40Ar loss can vary from 10% for the finest crystallites (two 2:1 layers thickness and