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Abstract: The effect of oil on As(V) adsorption on clay minerals has been investigated using batch experiments at low and high pH, NaCl concentration and oil contents. Four clay minerals were chosen because of their abundance in sediments and their different crystal chemistry: illite, kaolinite, montmorillonite, and chlorite. The values for pH were 4 and 8 and salt concentrations were 0.001 and 0.7M NaCl to appreciate the effects of changing salinity, e.g. from fresh water to seawater conditions. For the coating experiments, a well-characterised oil was used to survey the main effects of complex organic mixtures on adsorption and oil to clay mineral (w/w) ratios were 0.0325 and 0.3250. As(V) adsorption increased with increasing NaCl concentration, suggesting that the mechanisms of As(V) adsorption are related to the formation of surface complexes in which Na+ ions act as bridges between the clay surface and the As(V) anions. Cation bridging is also indicated by zeta potential measurements which show that higher NaCl concentrations along with the presence of As(V) can cause the clay particles and adsorbed ions to have a more negative overall charge. Adsorption is lower at higher pH due to the reduced number of positively charged sites on the edge of clay mineral layers. Oil coating reduces As(V) adsorption by decreasing the available surface area of clay minerals, except in the case of oil-coated montmorillonite, where surface area following dispersion in water is increased. The main variables controlling As(V) adsorption are surface area and surface charge density, as confirmed by a simplified quantitative model. These findings advance our ability to predict the effects of complex pollution events in various freshwater and marine settings. [Copyright &y& Elsevier]

Abstract: 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=) 2.21μm (band present in kaolinite and montmorillonite) and 2.17μm (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. [Copyright &y& Elsevier]

The hydrothermal reactivity of the <1 µm fraction, K-saturated SWy-2 Wyoming low-charge montmorillonite was studied in the 250-400 °C temperature range with reactions lasting between 5 and 120 days, with a solid/solution mass ratio of 1:10, and in 1 mol/L KCl solution. From X-ray diffraction (XRD) profile modeling results on K-saturated and ethylene-glycol solvated samples the illitization process appears to occur as a progressive replacement of expandable layers by layers with illitic behavior, in a single illite-smectite phase. However this treatment overestimates the amount of illite layers because of the presence of smectitic non-expandable layers. This was revealed by calcium exchange of the products, which causes re-expansion of the apparent illite layers. The illitization model then obtained consists of four phases with increasing illite content: discrete smectite, a randomly interstratified mixed-layered mineral (MLM) and two ordered MLMs that progressively replace the phases with less illite content. This polyphase model is consistent with results from transmission electron microscopy and chemical microanalysis, which show several types of particle morphology with different interlayer K content and Al-for-Si substitution that seem to correspond to the several phases detected by XRD. Thus, the actual illitization mechanism of smectite in our experiments is not a progressive reaction but a dissolution-precipitation process following the Ostwald step rule in which metastable smectite transforms into illite through a series of metastable illite-smectite phases. [ABSTRACT FROM AUTHOR]

Abstract: Amino acid–smectite interaction may have catalyzed prebiotic reactions essential for the emergence of life. Lysine solutions (0.05 M) were reacted with Na-smectite in adsorption–desorption experiments. The lysine–smectite complexes were heated at 80 °C for 10 days to investigate (1) possible slow processes taking place at surface temperature that would be accelerated at higher temperature and (2) processes taking place in hydrothermal systems. Three sets of experiments were performed: thermal treatment in closed tubes and water added regularly; thermal treatment in closed tubes without adding water; and thermal treatment in open tubes and no added water. After lysine desorption (displacement with 0.1 M CaCl2), the solutions were investigated using circular dichroism (CD) and the smectite samples using FTIR and CHN elemental analysis. CD spectra were dependent on the solution pH, which was controlled by lysine protonation state. The lysine protonation state was altered by the adsorption–desorption process, with a higher Lys+/Lys± ratio after desorption. The CD and CHN analyses show that the thermal treatment in a moist state causes stronger smectite–lysine binding. FTIR data suggest that the stronger binding is caused by more or stronger H bonds between –NH+ 3 lysine groups and smectite basal O atoms. [Copyright &y& Elsevier]

The model of Fe3+ distribution between octahedra and tetrahedra in dioctahedral smectites by Decarreau and Petit (2014) used data from infrared analysis. From their own and other general evidence, the resulting data are likely to be affected by significant uncertainty. This aside, their model has limited application because it is based on synthetic smectites containing only Si, Al, and Fe3+. [ABSTRACT FROM AUTHOR]

Abstract: Amino acid adsorption on smectite is relevant to prebiotic processes involving possible catalytic reactions in the early Solar System, as implied by the clay-organic correlation found in meteorites, and the generation and modification of organic components essential for the origin of life. Here we report the results of a study investigating the adsorption of l-lysine (0.025–0.4M) onto montmorillonite. The reaction products were studied using X-ray diffraction, chemical analysis and infrared spectroscopy. We find that lysine adsorption is first dominated by cation exchange and then by adsorption of electrically neutral lysine (as a zwitterion), as indicated by chemical and FTIR evidence. At the maximum concentration, lysine displaces only ∼1/3 of the original interlayer cations. The d-spacing of the smectite–lysine complex increases from 1.2 to 2.1nm as more lysine enters the interlayer space, and water is expelled. We propose a structural model of lysine sorption in the interlayer in which lysine is oriented at >45–90° to the plane of siloxane O atoms. [Copyright &y& Elsevier]

The dehydration dynamics of the of the Ca-saturated <1 µm size fraction of SWy-1 (low-charge montmorillonite) were studied at the crystal scale under isothermal conditions using X-ray diffraction with a position-sensitive detector (XRD-PSD) in the 30.170 °C temperature range. A total of 630 XRD patterns were modeled between 30 and 125 °C using a trial-and-error approach based on the direct comparison of experimental and calculated XRD patterns. The proportion of layers with different hydration states (bihydrated, mono-hydrated, and dehydrated) were determined in the temperature-time space as well as small variations of layer thickness within each hydration state. The results showed that dehydration produces complex structures with heterogeneous hydration states, some of which are stable (not transient) and remain at the end of the experiment. The evolution of other structural parameters (interlayer water content, layer thickness fluctuation) was consistent with previous reports of smectite hydration. For bihydrated layers, the amount of water molecules per interlayer cation indicated the presence of water molecules both coordinated and non-coordinated to the interlayer cation. The transition from bi- to mono-hydrated layers produced the maximum structural heterogeneity, with (1) strong interlayer thickness fluctuation (in individual layers), and (2) the presence of several elementary mixed-layer structures. In contrast, the transition from mono-hydrated to dehydrated layers occurs homogeneously within layers. Finally, the decrease in thickness of mono-hydrated layers only implied the removal of some water molecules forming the hydration shell of the interlayer cation. [ABSTRACT FROM AUTHOR]

A kinetic study of Ca-montmorillonite dehydration was performed based on information derived from X-ray diffraction (Ferrage et al. 2007, this issue) and, thus, focusing on interlayer water only. The dehydration was quantified following the two processes that were observed in the X-ray pattern modeling: the transitions between the different hydration states and small thickness decrease observed in the bi- and mono-hydrated layers. The thickness decrease of bihydrated layers with dehydration (activation energy Ea = 16 kJ/mol) was found to be controlled by a mechanism of two-dimensional diffusion of water molecules through the interlayer space, whereas for mono-hydrated layers the variation of thickness (Ea = 18 kJ/mol) occurred as a mechanism of slight local layer collapse and collapse propagation, attributed to a rearrangement of the configuration of the interlayer cation hydration shell. For the transition between the bi- and mono-hydrated state (Ea = 84 kJ/mol), the mechanism of reaction was found to evolve gradually with increasing temperature from local layer collapse and collapse propagation to a two-dimensional diffusion mechanism, as the forced diffusion of water molecules produced by the layer collapse transfers the control of the process to diffusion mechanism. This phenomenon causes the coexistence of two hydration states in a given interlayer. Finally, the transition between mono-hydrated and dehydrated layers (Ea = 132 kJ/mol) indicated the concomitance of water diffusion and local layer collapse and propagation mechanisms, although the structures were found to be homogeneous during this transition. The determination of both mechanisms and the activation energy for these processes were used to establish a model of smectite dehydration at the crystal scale. This model can be used to calculate crystal shrinkage and interlayer water content upon dehydration, and to predict the evolution of the system. [ABSTRACT FROM AUTHOR]

Abstract: It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister–backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al2O3–FeO–Fe2O3–MgO–Na2O–SiO2–H2O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if values are significantly lower than magnetite–hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If exceeds magnetite–hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories. [Copyright &y& Elsevier]

Abstract: Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250°C, P sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl2 which were reacted at temperatures of 80, 150, and 250°C, P sat, for 90–92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250°C and the product contained a small proportion of a 7Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite. [Copyright &y& Elsevier]