Heterogeneous Distribution of Interlayer Cations and Iron as a Plausible Explanation of the Non-Exfoliation of Commercial Vermiculites Post Alcohol Treatment and Microwave Irradiation

Two commercial vermiculites from China and Libby were treated with different alcohols (methanol, ethanol, propanol and butanol) at room temperature for up to one month and afterwards irradiated with microwaves. The exfoliated and non-exfoliated particles were characterized by X-ray diffraction, high-resolution transmission microscopy, thermal gravimetric analyses and infrared spectroscopy to explain the inconsistencies in relation to potassium distribution and the exfoliation observed in previous investigations. The percentages of the exfoliated and non-exfoliated particles of the investigated vermiculites greatly varied, with no indication of a relationship between the resultant exfoliation and alcohol treatment. The crystallinity and structural order of the phases composing the particles are independent of the success of their exfoliation. The existence of a mosaic structure, the intra-particle mosaic-like intergrowth of the different mineral phases, in the treated and pristine commercial vermiculites could be attributed to the heterogeneous distribution on the nanoscale of interlayer cations as potassium and iron.

Mineralogy, Mineral Chemistry and SWIR Spectral Reflectance of Chlorite and White Mica

Hyperspectral reflectance has the potential to provide rapid and low-cost mineralogical and chemical information that can be used to vector in mineral systems. However, the spectral signature of white mica and chlorite, despite numerous studies, is not fully understood. In this study, we review the mineralogy and chemistry of different white mica and chlorite types and investigate what mineralogical and chemical changes are responsible for the apparent shifts in the shortwave infrared (SWIR) spectroscopic absorption features. We demonstrate that the spectral signature of white mica is more complex than previously documented and is influenced by the Tschermak substitution, as well as the sum of interlayer cations. We show that an increase in the interlayer deficiencies towards illite is associated with a change from steep to shallow slopes between the wavelength position of the 2200 nm feature (2200 W) and Mg, Al(VI) and Si. These changes in slope imply that white micas with different elemental chemistry may be associated with the same 2200 W values and vice versa, contrary to traditional interpretation. We recommend that traditional interpretations should only be used in true white mica with sum interlayer cations (I) > 0.95. The spectral signature of trioctahedral chlorite (clinochlore, sheridanite, chamosite and ripidolite) record similar spectral relationships to those observed in previous studies. However, dioctahedral Al-rich chlorite (sudoite, cookeite and donbassite) has a different spectral response with Mg increasing with 2250 W, which is the opposite of traditional trioctahedral chlorite spectral interpretation. In addition, it was shown that dioctahedral chlorite has a 2200 W absorption feature that may introduce erroneous spectral interpretations of white mica and chlorite mixtures. Therefore, care should be used when interpreting the spectral signature of chlorite. We recommend that spectral studies should be complemented with electron microprobe analyses on a subset of at least 30 samples to identify the type of muscovite and chlorite. This will allow the sum I of white mica to be obtained, as well as estimate the slope of 2200 W absorption trends with Mg, Al(vi), and Si. Preliminary probe data will allow more accurate spectral interpretations and allow the user to understand the limitations in their hyperspectral datasets.

Layer-structured uranyl-oxide hydroxy-hydrates with Pr(iii) and Tb(iii) ions: hydroxyl to oxo transition driven by interlayer cations

Two new uranyl-oxide hydroxy-hydrate phases with Pr(iii)/Tb(iii) ions have been synthesized hydrothermally and structurally characterized.

Geochemical reactions of Na-montmorillonite in dissolved scCO2 in relevance of modeling caprock behavior in CO2 geological storage

One of the challenges of the present century is to limit the greenhouse gas emissions for the mitigation of climate change which is possible for example by a transitional technology, CO2 geological storage. Clay minerals are considered to be responsible for the low permeability and sealing capacity of caprocks sealing off stored CO2. However, their reactions are not well understood for complex simulations. This work aims to create a kinetic geochemical model of Na-montmorillonite standard SWy-2 supported by solution and mineral composition results from batch experiments. Such experimentally validated numerical models are scarce. Four 70-hours experiments have been carried out at atmospheric conditions, and with CO2 supercritical phase at 100 bar and 80 °C. Solution samples have been taken during and after experiments and their compositions were measured by ICP-OES. The treated solid phase has been analyzed by XRD and ATR-FTIR and compared to in-parallel measured references (dried SWy-2). Kinetic geochemical modelling of the experimental conditions has been performed by software PHREEQC. Experiments and models show fast reactions under the studied conditions and increased reactivity in presence of scCO2. Solution composition results cannot be described by the change of the uncertain reactive surface area of mineral phases. By considering the clay standard’s cation exchange capacity divided proportionally among interlayer cations of Na-montmorillonite, the measured variation can be described on an order of magnitude level. It is furthermore indicated that not only the interlayer cations take part in this process but a minor proportion of other, structural ions as well, differently in the reference and scCO2 environments.

Structural complexity of natural uranyl sulfates

Uranyl sulfates, including those occurring in Nature (∼40 known members), possess particularly interesting structures. They exhibit a great dimensional and topological diversity of structures: from those based upon clusters of polyhedra to layered structures. There is also a great variability in the type of linkages between U and S polyhedra. From the point of view of complexity of those structures (measured as the amount of Shannon information per unit cell), most of the natural uranyl sulfates are intermediate (300–500 bits per cell) to complex (500–1000 bits per cell) with some exceptions, which can be considered as very complex structures (>1000 bits per cell). These exceptions are minerals alwilkinsite-(Y) (1685.95 bits per cell), sejkoraite-(Y) (1859.72 bits per cell), and natrozippeite (2528.63 bits per cell). The complexity of these structures is due to an extensive hydrogen bonding network which is crucial for the stability of these mineral structures. The hydrogen bonds help to propagate the charge from the highly charged interlayer cations (such as Y3+) or to link a high number of interlayer sites (i.e. five independent Na sites in the monoclinic natrozippeite) occupied by monovalent cations (Na+). The concept of informational ladder diagrams was applied to the structures of uranyl sulfates in order to quantify the particular contributions to the overall informational complexity and identifying the most contributing sources (topology, real symmetry, interlayer bonding).