The size, shape, and continuity of pores in mineral solids greatly influence the behavior of percolating liquids and solids in porous media, which has significant practical environmental implications. In order to expand understanding of these properties in soil minerals, the present study was undertaken to analyze the pore characteristics of bentonite, illite, and kaolinite in the forms of powder and aggregates of different dimensions, combining water-vapor desorption and mercury-intrusion techniques. Different granulometric fractions of milled quartz glass were also studied. With increasing aggregate size of the minerals, larger pore volumes (up to 25%), smaller surface areas (down to 15%), larger average radii (up to 15%), and smaller fractal dimensions (down to 6%) were measured using water-vapor adsorption-desorption data. The differences were smallest for bentonite, possibly due to the smallest particle size of this mineral and/or to its very large water-vapor adsorption capacity. The degree of water-vapor adsorption on quartz was too small to rely on the data obtained.

The pore volumes and average radii, measured by mercury-intrusion porosimetry, were up to few times larger for the mineral powders than for their aggregate counterparts. Similar values were noted for aggregates >1 mm in diameter, for which the input of interaggregate spaces into total porosity of the sample bed was negligible. Two pathways of mercury intrusion were detected in porosimetric curves: filling of interaggregate spaces, and penetration into aggregates. Similar penetration thresholds into aggregates of different sizes were calculated. With increasing size of quartz grains, the pore volume of the quartz bed decreased whereas the average pore radius increased. Mercury intrusion detected pore-fractal behavior of bentonite and kaolinite, but for aggregated minerals the calculated values of fractal dimensions were >3, values which increased with increasing aggregate size. Very similar pore parameters were measured for aggregates prepared from a natural deposit of kaolinite and for artificially prepared aggregates from powder of the same mineral, indicating that artificial aggregation can simulate natural processes.

Both water desorption and mercury intrusion detected fractal behavior in the limited range of pores. A test to find fractal build up of the aggregates in extended scales based on a dependence of surface area of unit volume of aggregate bed on aggregate size showed no fractal-aggregate build-up.

Clays are involved in a variety of natural and managed processes, and calculation of their stability conditions is important. Such calculations are still fraught with large uncertainties owing to the lack of experimental constraints on the thermodynamic properties of clays, and bracketing of equilibrium reactions at low temperature is barely possible. Experiments aimed at studying the thermal stabilities of, and composition-temperature relations among, smectite, illite, kaolinite, pyrophyllite, mica, and chlorite at different levels of SiO2, K2O, MgO, and Al2O3 species in solution were conducted under a strong thermal gradient in the simple K2O-Al2O3-SiO2-H2O (KASH), MgO-Al2O3-SiO2-H2O (MASH), and KMASH systems. The crystallization series observed in the different experiments match to some degree those observed in active geothermal systems where clay minerals precipitate from oversaturated solutions. Smectite and/or ordered mixed-layer materials, smectite-donbassite, or possibly pyrophyllite-donbassite were observed to crystallize in both KASH and MASH experiments. Similar crystallization sequences and clay composition variations with temperature were observed in most cases when the relative positions of the starting solids were switched. The experimental results were used to refine the thermodynamic properties of K- and Mg-smectite. Stability diagrams calculated by energy minimization and activityactivity diagrams are consistent with the experimental mineral variations, suggesting that smectite is thermodynamically stable at temperatures as high as 300°C in the presence of diluted water and quartz and K-feldspar-free systems.

Intercalation of a wide variety of alkylammonium cations into the interlayer spaces of swelling clay minerals leads to many different applications, ranging from surface-charge measurements to rendering the clay compatible for the preparation of clay nanocomposites, but knowledge of the exact conformation of the intercalated organic species is still incomplete, thus preventing a full understanding of this process. The purpose of this study was to investigate the interlayer conformation of dodecyltrimethylammonium (DDTMA) bromide in rectorite as affected by the amounts of DDTMA intercalated, using a battery of physical and spectroscopic methods. The capacity of rectorite to intercalate DDTMA was equivalent to 1.67 times the cation exchange capacity (1.67 CEC) of the mineral even though the initial input was as much as 5.00 CEC. When the DDTMA intercalated was <0.50 CEC of the mineral, minimal counterion sorption was associated with DDTMA intercalation. Derivative thermogravimetric (DTG) analyses revealed a single-peak decomposition temperature (Tpeak) at 430°C. X-ray diffraction (XRD) analyses indicated a flat-lying monolayer of the intercalated molecules, while shifts in Fourier Transform infrared (FTIR) bands confirmed gauche conformation. These results suggested that cation exchange was the dominant mechanism. At the maximum intercalation, the DDTMA adopted a horizontal trilayer arrangement with mainly gauche conformation as determined by FTIR and XRD. Meanwhile a second Tpeak appeared at 255°C, similar to the Tpeak of solid DDTMA. Counterion bromide sorption accompanying DDTMA intercalation reached a capacity of 310 mmol/kg. The results indicated that van der Waals interaction was responsible for the DDTMA uptake at the amount beyond 0.50 CEC. When the amount of DDTMA intercalated was between 0.5 and 1.67 CEC, the XRD patterns showed non-integrality, i.e. the 002 reflection was split into two non-integral peaks with 2 × d002 < d001 and 3 × d003 > d001. They became integral at 1.67 CEC. The results suggest that the mineral might be composed of mixed layers of a monolayer intercalated rectorite and a trilayer intercalated rectorite, without a bilayer as intermediate, when the amount of DDTMA intercalated was between 0.5 and 1.67 CEC.

This article discusses the application of the proportionality test which the Court of Session in Scotland and the European Court of Human Rights carried out when reviewing the limitations to worship and public gatherings imposed during the COVID-19 pandemic. The article concludes that judges should not use the proportionality standard of review as an avenue to circumvent their duty of neutrality towards religious dogmas.

This paper describes an improved simple, sample-mounting method for random powder X-ray diffraction (XRD), namely the razor tamped surface (RTS) method, which prepares a powder mount by tamping the loose powder with the sharp edge of a razor blade. Four kaolinites and a quartz powder were used to evaluate the RTS method by quantifying the degree of orientation in the sample mounts using orientation indices. Comparisons between the RTS and other published simple methods, consisting of front loading, back loading and side loading, indicate that the RTS method produces minimum packing density and minimum preferred orientation in the powder mounts of all five samples. The quartz powder used in this study does exhibit a tendency to preferred orientation. The mechanism by which the RTS method reduces preferred orientation is examined by comparing the width of the sharp blade edge with the size of clay particles. The advantages and disadvantages of the RTS method are also discussed.

Amino acids are present in various geochemical environments and they interact with mineral surfaces. To evaluate the effects of amino acids on mineral dissolution at pH conditions less than their isoelectric points (pI), dissolution experiments of X-ray amorphous silica in solutions containing 10.0 mmol/L of various amino acids (cysteine, asparagine, serine, tryptophan, alanine, threonine, histidine, lysine, and arginine) at pH 4 were performed. The results confirmed that basic amino acids (histidine, lysine, and arginine) produce an 8- to 8.5-fold enhancement of the rate of dissolution of amorphous silica compared with an amino acid-free control. Neutral amino acids (cysteine, asparagine, serine, tryptophan, alanine, and threonine) enhanced rates of dissolution by a factor of ∼3 to 3.5. The rate-enhancement effects of amino acids are controlled by concentrations of the amino acid’s cationic species which interact with the negatively charged >SiO− sites at the surface of the amorphous silica.

Vermiculites have the potential to serve as effective catalysts if pillared with Al, but their high charge presents an obstacle to the pillaring process. The purpose of this study was to submit natural vermiculite to thermal treatments in the presence of water vapor in order to effect a reduction in the global negative charge and thereby to enhance its susceptibility to pillaring. The process of charge reduction in vermiculite under the conditions selected involved the extraction of 25% of IVAl accompanied by the extraction of structural Mg and charge-compensating cations (Ca2+, Na+, and K+). The results indicate a reduction of 35% in the global negative charge in vermiculite by the end of the treatment. Some of the VIAl content was not removed during acid washing, and probably remained in the solid in structural positions in the octahedral sheet.

The occurrence of kerolite in association with various secondary Ca-Mg carbonate mineral deposits (speleothems) was identified in basaltic sea caves on the island of Kauai, Hawaii. Kerolite is the dominant clay mineral in the deposits. X-ray diffraction (XRD) peaks of the kerolite are characteristically broadened indicating its extremely poor crystallinity. Few changes were observed in the XRD patterns of this kerolite when it was subjected to various humidity, temperature and ethylene-glycol treatments. The crystals appear as flaky masses with irregular or jagged edges in scanning (SEM) and transmission electron microscopy (TEM). Electron probe and energy dispersive X-ray (EDX) microanalysis show that the clay material is dominated by Mg-Si-O, with minor amounts of Al and Ca in some samples. The chemical composition, thermal analysis and TEM observations suggest that smaller amounts of an amorphous serpentine-like phase are mixed with the kerolite. Kerolite is often the only mineral associated with poorly mineralized, actively-growing microbial mats in these caves and it is common in completely lithified microbial mats. The latter commonly have microstromatolitic structures with kerolite as a dominant phase. These features suggest that kerolite formation is at least in part a result of microbial activity. The abundant extracellular polymers of the mat-forming bacteria bind and concentrate ions (Mg2+, silica) from solution and serve as nucleation sites for kerolite precipitation. Conditions within the mats also probably lead to formation of Mg-Si-gels, amorphous Mg-silicate precursors and ultimately kerolite. Evaporation of the cave solutions may also contribute to kerolite formation.

The adsorption mechanisms of divalent cations in zeolite nanopore channels can vary as a function of their pore dimensions. The nanopore inner-sphere enhancement (NISE) theory predicts that ions may dehydrate inside small nanopore channels in order to adsorb more closely to the mineral surface if the nanopore channel is sufficiently small. The results of an electron paramagnetic resonance (EPR) spectroscopy study of Mn and Cu adsorption on the zeolite minerals zeolite Y (large nanopores), ZSM-5 (intermediate nanopores), and mordenite (small nanopores) are presented. The Cu and Mn cations both adsorbed via an outer-sphere mechanism on zeolite Y based on the similarity between the adsorbed spectra and the aqueous spectra. Conversely, Mn and Cu adsorbed via an inner-sphere mechanism on mordenite based on spectrum asymmetry and peak broadening of the adsorbed spectra. However, Mn adsorbed via an outer-sphere mechanism on ZSM-5, whereas Cu adsorbed on ZSM-5 shows a high degree of surface interaction that indicates that it is adsorbed closer to the mineral surface. Evidence of dehydration and immobility was more readily evident in the spectrum of mordenite than in that of ZSM-5, indicating that Cu was not as close to the surface on ZSM-5 as it was when adsorbed on mordenite. Divalent Mn cations are strongly hydrated and are held strongly only in zeolites with small nanopore channels. Divalent Cu cations are also strongly hydrated, but can dehydrate more easily, presumably due to the Jahn-Teller effect, and are held strongly in zeolites with medium-sized nanopore channels or smaller.

Most detrital ilmenite grains in sandstones of the Chaswood Formation are completely altered to pseudorutile, leucoxene and rutile. The textural, chemical and mineralogical changes involved in alteration were tracked using electron microprobe analyses, backscattered electron images, and elemental maps. Ilmenite grains (Ti/(Ti+Fe) ≈ 0.48) alter patchily to pseudorutile (Ti/(Ti+Fe) 0.5–0.7) with volume loss, forming a porous structure and this process continues with the development of leucoxene (Ti/(Ti+Fe) 0.7–0.9). Within the pseudorutile and leucoxene, stubby prismatic rutile crystals have been precipitated. Si and A1 occur in the altered ilmenite, either (1) inherited from original quartz and muscovite inclusions in the parent crystal or (2) as kaolinite altered from muscovite inclusions or precipitated in the pore space, under pedogenic or early diagenetic conditions. Distribution of alteration phases has been related to facies and diagenetic variations. With increasing amounts of leaching in different types of paleosols, there was increasing alteration of pseudorutile to leucoxene. In light gray mudstones and interbedded sandstones with diagenetic kaolinite that formed beneath the water table from percolating meteoric water, most leucoxene was converted to rutile. Burial diagenesis (to vitrinite reflectance values >0.4%) also promoted the change from leucoxene to rutile. The alteration of ilmenite is an important source of Fe for diagenetic minerals in the Chaswood Formation and correlative offshore deltaic and marine facies of the Scotian basin.

Mg-rich kaolinite and Mg+Ni-rich kaolinite have been synthesized in hydrothermal experiments (200 and 400°C) from poorly crystalline kaolinite and Mg- and Mg+Ni-bearing solutions. Al-rich serpentine and Al-rich chlorite were obtained as sub-products of the reactions. The formation of these phases occurred through a dissolution-precipitation mechanism that led to spherical kaolinite after short reaction times. A morphological evolution towards platy particles and stacks occurred at increasing run times.

Identification of the several phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Analytical data indicate that the Mg content in kaolinite increased as a function of the reaction time and temperature, reaching up to 0.46 atoms per half formula unit (a.p.h.f.u.). The measured (Mg+Ni) content reached up to 0.56 a.p.h.f.u.. Both the gradual increase of the b-cell parameter of kaolinite at increasing Mg contents and the presence of new bands on the FTIR spectra of the synthesized kaolinite point to a Mg-for-Al replacement in the octahedral sheet rather than to the presence of serpentine-like layers interstratified in the kaolinite structure.

The aim of the present study was to find methodological tools to obtain reasonable results for exchangable Ca2+ of gypsiferous bentonites. Cation exchange capacity (CEC) is an important property of clays. Numerous methods for calculating CEC and exchangeable cations exist; determination of exchangeable Ca2+ fails, however, when gypsiferous clays are examined because gypsum is dissolved throughout the exchange experiment, which in turn increases measureable Ca2+ concentrations. Several new methods (AgTUcalcite, CoHexcalcite, and Cu-trien5×calcite) have been developed to overcome a similar problem occurring with calcite by using exchange solutions saturated with respect to calcite prior to the experiment. In the present study these three solutions were also pre-treated with gypsum and labeled AgTUCcGp, CoHexCcGp, and Cu-trien5×CcGp. The special solutions were applied first to a gypsum- and calcite-free bentonite with known reference values for exchangeable Ca2+. The resulting exchangeable Ca2+ values obtained did not match with reference values. The solutions were then applied to natural calcareous and gypsiferous bentonites but only the proposed AgTUCcGp test method was successful. The performance of AgTUCcGp was relatively poor when applied to calcareous non-gypsiferous bentonites, the third group of test materials. Reasonable values for exchangeable Ca2+ of gypsiferous clays were obtained using a combination of two separate results: (1) calcite saturation of exchange solution (e.g. Cu-trien5×calcite) and (2) quantification of gypsum with suitable mineralogical methods. Result 1 eliminates errors caused by calcite dissolution though it is still incorrect because it contains significant amounts of Ca2+ from gypsum dissolution. After proving that gypsum was completely dissolved during the exchange experiment, result 2 was used to subtract the theoretical Ca2+ portion of gypsum from result 1. The initial concentration of gypsum of the samples studied was <1 wt.%, typical of many commercial bentonites. Using this combined procedure the sum of exchangeable cations is very close to the CEC, though it still exceeds the CEC by, on average, 3%, which is a satisfactory improvement. The resulting exchangeable Ca2+ values can be considered as operationally correct using this approach. Ca2+ saturation (Ca/CEC in %) of seven gypsiferous bentonites ranges from 1 to 69%.

Reduction of structural Fe in smectites affects the surface chemical behavior of the clay, but the underlying mechanism and changes in clay structure are still in need of investigation, particularly with respect to changes in the tetrahedral sheet. The purpose of this study was to probe changes in the tetrahedral sheet that occur when structural Fe is reduced in the Uley nontronites, NAu-1 and NAu-2, using polarized attenuated total internal reflection Fourier-transform infrared spectroscopy. Despite the differences in their structures — NAu-2 has tetrahedral Fe3+ while NAu-1 does not — the changes observed in the Si-O stretching region were quite similar. Reduction results in a shift of the in-plane Si-O stretching modes to lower frequencies, while the out-of-plane Si-O stretch shifts to higher frequencies. The magnitude of these shifts is greater in NAu-2 than in NAu-1, but the crystallinity of the tetrahedral silicate sheet of NAu-2 is preserved upon reduction. In both nontronites, the orientation of the out-of-plane Si-O bond changes and becomes completely perpendicular to the basal (001) surface of the clay, indicating the formation of trioctahedral domains wherein the individual tetrahedra reorient relative to the plane of the clay layer.

The kinetics of cation exchange in phlogopite have been studied in situ by hydrothermal atomic force microscopy (HAFM). The exchange of interlayer K by octylammonium ions caused an increase in the interlayer distance and the formation of reaction fronts which can be locally resolved by AFM. The observed reaction fronts revealed substantial variations in their propagation rates — even within single interlayers. This observed variability in interlayer reactivity could mainly be attributed to chemical and structural inhomogeneities of the samples. A quantitative evaluation of the front propagation at representative sites yielded a diffusion coefficient of the K+ exchange by octylammonium of 1.2±0.6 × 10−11 cm2/s assuming negligible transport normal to the layers. The reverse reaction, i.e. the exchange of organic ions by K+, resulted in a retreat of the reaction fronts and a general restoration of the original morphological state. However, indications of structural alterations and areas with trapped octylammonium ions were found.

The synthesis of a Mg2+-Al3+-SO2−4-hydrotalcite-type compound from the acid wastewaters of the aluminum-anodizing industry has been studied as a possible means of recovering the unused Al resource materials as a useful mineral. The synthesis has been carried out from wastewaters of different concentrations (from 6.7 g Al/L to 134 mg Al/L) using the method of precipitation at constant pH, proving that all of them are suitable for such a process. The mineral was characterized using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, differential thermal analysis and chemical analysis, all of which indicated characteristics typical of the desired compound. Almost 100% of the Al initially present in the wastewater solutions is recovered in the form of the Mg2+-Al3+-SO42−-hydrotalcite-type compound.

The total concentrations of rare-earth elements (REE) in the mined kaolin (0.02–0.06 wt.%), kaolin mine tailings (0.03–1.9 wt.%), and the kaolin-associated Marion Member sand lithology (0.03–4.6 wt.%) opened questions regarding the modes of occurrence of the REE and the role(s) of chemical weathering and secondary processes to explain the presence of REE in these materials. The REE were hosted primarily by phosphate minerals (monazite, xenotime) based on mineralogic analyses (scanning electron microscopy, X-ray diffraction). Enrichments in the light rare-earth elements (LREE: La–Gd) and the high correlation coefficient values were noted between P and the total REE concentrations (r2 = 0.99) for the sands and the mine tailings. Lower correlation coefficient values were noted between total REE concentrations and Zr (r2 = 0.31). The coarse fractions of the mined kaolins were enriched in the heavy rare-earth elements (HREE: Y, Tb–Lu) relative to the kaolin-associated sand lithologies. The REE inventory cannot be explained solely by mineral inheritance within the mined kaolins. Lower correlation coefficient values between P and total REE, positive Eu/Eu* anomalies, and the presence of xenotime overgrowths on zircon showed the importance of the role of chemical weathering of the detrital minerals during post-depositional processes (such as diagenesis) leading to redistributed and fractionated REE within the mined kaolin. The possibility of adsorption of the REE to kaolin mineral surfaces in the fine fraction of the mined kaolins remains open and permits further study to characterize fully the multi-modal fractionation of REE possible in the Georgia kaolin deposits.

The morphology of hydrotalcites determines their use in catalysis, biomedicine, or adsorption as they may work as anion exchangers or as drug deliverers. In catalysis, reagents need access to as much surface area as possible; in biomedicine, drugs have to be encapsulated. However, the parameters and the mechanisms which direct the synthesis towards a certain morphology are not well understood. Precipitating agents or crystallization conditions are expected to play a crucial role. In the present study, hydrotalcites were synthesized in the presence of two precipitating agents (NaOH or NH4OH) under three different crystallization conditions (conventional, microwave, or ultrasound irradiation) which determined the morphology of the final product, layered or vesicular. The features are explained through the template effect of the liberated gases on the co-precipitation and crystallization processes and consequently on the final structure/morphology of the synthesized solids. Indeed, the nodular particles crystallize using the effluent gases as templates. Fractal dimension and particle-size distributions, determined by small-angle X-ray scattering (SAXS) and gas adsorption are compared and correlated to the presence of ammonium. Although the materials obtained are heterogeneous, it is possible to propose a microscopic geode model.

Multilateral development banks (MDBs) are international organizations subject to the law of international responsibility. Yet, the relationship between their accountability mechanisms and the International Law Commission (ILC) Articles on the Responsibility of International Organizations (ARIO) remains unclear. Understanding this relationship is essential in fully realizing the right to remedy in the development finance context. A comparative analysis of these legal frameworks clarifies that notwithstanding their different rationale, scope and functions, the two are not normatively conflicting and both serve to control public power. While the accountability mechanisms correct the ARIO's State-centric orientation by granting legal standing to project-affected people, they have their own deficiency concerning the actions they can prescribe to MDBs upon a finding of noncompliance. Highlighting that the MDBs’ mandate to ‘do no harm’ and pursue sustainable development is left unfulfilled by the accountability mechanisms’ deficient remedial function, this article identifies specific ARIO provisions to complement rather than undermine the MDBs’ accountability system. The ARIO's residual character, combined with the proposition that remedies arise not only from wrongful conduct but also from harm suffered by one party due to another's risky activities, justify this complementarity.

Loess is a collapsible soil; when it collapses, it can cause significant damage to structures built on it. Improvement in the stability and strength performance of loess is necessary to meet engineering needs. In the present study, the effects on the physical-chemical and rheological characteristics of Ghardaïa loess of adding bentonite and lime (southern Algeria) were examined. Rheological characterization of suspensions was implemented to assess the mechanical sensitivity of the bonds and the structural inter-particle resistance to both the chemical effect and mechanical impact. By analyzing the viscosity results and the evolution of the rheological parameters, the improvements needed in terms of the resistance characteristics of the loess-bentonite and loess-lime mixtures were evaluated and confirmed. The loess physical sensitivity was examined through grain-size distribution and plasticity properties. The pH and electrical conductivity of the mixtures were also used to explore structural modifications. Physical test results showed that introduction of the additives changed the loess texture and improved the plasticity of mixtures. Chemical examination (via change in pH and electrical conductivity) revealed the structural changes in the mixtures studied. Rheological test results showed that increasing concentrations of bentonite and lime improves the mechanical strength and increased the yield stress, consistency, and viscosity of the suspensions. The creation of cement interactions between mixture particles explained the increase in those parameters. Hydration, agglomeration, and inter-particle flocculation induced by the additives promoted these interactions. The experimental results led to the conclusion that bentonite and lime may represent an effective means to improve the performance in terms of preventing loess collapse and to increase its resistance to mechanical impact. The results presented in the present study may provide a geotechnical and rheological working database for the control and treatment of loess collapse and landslides in the region under study. Technical data related to loess may, therefore, be beneficial in terms of civil engineering, public works, hydraulics, and the manufacture of construction materials.