Electrical measurements are used in various fields of geoscience and technology, e.g. gas/oil exploration or landslide-barrier monitoring. Although clays are amongst the most conducting geomaterials their electrical properties are not yet fully understood. For example, in a recent high-level-radioactive-waste repository large-scale test, a bentonite barrier was monitored geoelectrically. To facilitate interpretation of the results, the reasons for the observed differences in the electrical conductivity must be understood (e.g. changes in water content, temperature, salinity of pore water, etc.). To improve understanding of the electrical properties of clay minerals, in situ measurements must be combined with laboratory measurements. In situ measurements allow the characterization of the material in its natural state and laboratory measurements, for small sample amounts, allow the user to vary relevant parameters systematically such as water content, temperature, the salinity of the pore water, or even the cation population if swelling clay minerals are present. In situ measurements using different electrode distances, from m to cm range, proved that small-scale investigations are essential because of small-scale material heterogeneities. In the laboratory, all the relevant parameters mentioned above can be controlled more easily for small sample amounts. In the present study three different small-scale devices (SSM1–SSM3) were compared. The geometry factor, K, was determined both by calculation and by a calibration against solutions of different conductivity. Calculated and measured geometry factors were in good agreement. SSM1 and SSM2 — both with four pin-shaped electrodes — were found to be particularly applicable for in situ measurements. SSM2, with point contacts at the tips of the pins, was considered to be an improvement over SSM1 because the effects of both water content and temperature gradients (which are particularly relevant near the surface) were less pronounced using SSM2. SSM3, in which the contacts are placed at the bottom of a 4.5 mL trough, proved to be useful when systematically varying all of the parameters influencing the electrical properties in the laboratory.

A comprehensive study of the intercalation of organo-phosphonium salts into Thai bentonite (Mt) was conducted to investigate the influence of the molecular structures of organic moieties, including chain types (alkyl vs. aryl), chain length, and structural symmetry, on their intercalation. A series of quaternary phosphonium salts with systematically varied molecular structures (tetraphenyl phosphonium, TPP-Br; tetrabutyl phosphonium, TBP-Br; tetraoctyl phosphonium, TOP-Br; methyl triphenyl phosphonium, MTPP-Br; and butyl triphenyl phosphonium, BTPP-Br) was intercalated into Mt via an ion-exchange reaction. From thermogravimetric analysis results, tetrabutyl phosphonium-modified Mt (TBP) with shorter alkyl chain length began to decompose at a slightly lower temperature (263 vs. 351°C), yet showed comparable thermal stability (i.e. maximum decomposition temperature) at 470°C, compared to tetraoctyl phosphonium-modified Mt (TOP). Aryl phosphonium-modified Mt (TPP) showed a higher thermal decomposition temperature (576 vs. 470°C) than those of alkyl phosphonium-modified Mts (TBP and TOP). Introducing short alkyl chains into the aryl phosphonium moiety (MTPP, BTPP) caused a slight decrease in thermal decomposition temperature, but an increase in cation loadings of their modified Mts (71 and 73%, respectively). X-ray diffraction analysis showed that the flexibility of alkyl chains in TBP yielded smaller increases in basal spacing, i.e. lower degree of intercalation, compared to the rigid aryl structure in TPP. Increasing chain length resulted in greater basal spacing in alkyl phosphonium-modified Mts (1.67 nm. in TBP vs. 2.46 nm. in TOP). Such an effect, however, was less significant in aryl phosphonium-modified Mt.

The nano-aluminosilicate mineral allophane is common in soils formed from parent materials containing volcanic ash and often contains Fe. Due to its lack of long-range order, the structure of allophane is still not completely understood. In the present study, Fe K-edge X-ray absorption fine structure (XAFS) was used to examine Fe-containing natural and synthetic allophane and imogolite samples. Results indicated that Fe substitutes for octahedrally coordinated Al in allophane, and that Fe exhibits a clustered distribution within the octahedral sheet. Iron adsorbed on allophane surfaces is characterized by spectral features distinct from those of isomorphically substituted Fe and of ferrihydrite. Fe adsorbed on the allophane surfaces probably exists as small polynuclear complexes exhibiting Fe-Fe edge sharing, similar to poorly crystalline Fe oxyhydroxides. The XAFS spectra of natural allophane and imogolite indicate that the Fe in the minerals is a combination of isomorphically substituted and surface-adsorbed Fe. In the synthetic Fe-substituted allophanes, the Fe XAFS spectra did not vary with the Al:Si ratio. Theoretical fits of the extended XAFS (EXAFS) spectra suggest that local atomic structure around octahedral Fe in allophanes is more similar to Fe in a smectite-like structure than to a published theoretical nanoball structure.

Natural clay-sized glauconite has the same mineralogical composition as sand-sized glauconite pellets but occurs in <2 μm clay fractions. This particular glauconite habit has been described previously from soil environments resulting from pelletal weathering but is rarely reported in higher-energy sedimentary environments. In the present study, clay-sized glauconite was identified as a common constituent in transgressive Neogene glauconite pellet-rich deposits of the southern North Sea in Belgium. X-ray diffraction results revealed that the characteristics of the clay-sized glauconite are very similar to the associated glauconite pellets in sand deposits. Both glauconite types consisted of two glauconite-smectite R1 phases with generally small percentages of expandable layers (<30%) with d060 values ranging between 1.513 Å and 1.519 Å. Clay-sized glauconite was not neoformed but formed by the disintegration of sand-sized glauconite pellets which were abraded or broken up during short-distance transport within the sedimentary basin or over the hinterland. Even in an environment where authigenic glauconite pellets occur, minimal transport over transgressive surfaces is sufficient to produce clay-sized glauconite. Furthermore, clay-sized glauconite can be eroded from marine deposits and subsequently resedimented in estuarine deposits. Clay-sized glauconite is, therefore, a proxy for the transport intensity of pelletal glauconite in energetic depositional environments and, moreover, indicates reworking in such deposits which lack pelletal glauconite.

Layered double hydroxides (LDH) are extremely important materials for industrial processes and in the environment, and their physical-chemical behavior depends in large part on their hydration state, but the characterization of these hydration effects on their properties are incomplete. The present study was designed to explore the interpolytype transitions induced by variation in the ambient humidity among LDHs. The cooperative behavior of intercalated water molecules resulted in a sudden, single-step, reversible dehydration of the [Zn-Cr-SO4] LDH. The [Zn-Al-SO4] LDH provided an interesting contrast with (1) the coexistence of the end members of the hydration cycle over the 40-20% relative humidity range during the dehydration cycle, and (2) a random interstratified intermediate in the hydration cycle. These observations showed that the [Zn-Al-SO4] LDH offered sites having a range of hydration enthalpies, whereby, at critical levels of hydration (20–40%), the non-uniform swelling of the structure resulted in an interstratified phase. The variation in domain size during reversible hydration was also responsible for the differences observed in the hydration vs. the dehydration pathways. This behavior was attributed to the distortion in the array of hydroxyl ions which departs from hexagonal symmetry on account of cation ordering as shown by structure refinement by the Rietveld method. This distortion was much less in the [Zn-Cr-SO4] LDH, whereby the nearly hexagonal array of hydroxyl ions offered sites of uniform hydration enthalpy for the intercalated water molecules. In this case, all the water molecules experienced the same force of attraction and dehydrated reversibly in a single step. The changes in basal spacing were also accompanied by interpolytype transitions, involving the rigid translations of the metal hydroxide layers relative to one another.

The study of confined water dynamics in clay minerals is a very important topic in aluminosilicate-surface chemistry. Aluminosilicates are among the most technologically versatile materials in industry today. Dielectric spectroscopy is a very useful method for investigating the structure and dynamics of water adsorbed on solid matrix surfaces and water in the vicinity of ions in solutions. Use of this method for the study of clay minerals has been underutilized to date, however. The main goal of the present research was to understand the relaxation mechanisms of water molecules interacting with different hydration centers in clay minerals, with a view to eventually control this interaction. Two types of natural layered aluminosilicates (clay minerals) — montmorillonite with exchangeable K+, Co2+, and Ni2+ cations and kaolinite with exchangeable K+ and Ba2+ cations — were examined by means of dielectric spectroscopy over wide ranges of temperature (from -121°C to +300°C) and frequency (1 Hz–1 MHz). An analysis of the experimental data is provided in terms of four distributed relaxation processes. The low-temperature relaxation was observed only in montmorillonites and could be subdivided into two processes, each related to a specific hydration center. The cooperative behavior of water at the interface was observed in the intermediate temperature region, together with a proton percolation. The dielectric properties of ice-like and confined water structures in the layered clay minerals were compared with the dielectric response observed in porous glasses. The spatial fractal dimensions of the porous aluminosilicates were calculated by two separate methods — from an analysis of the fractality found in photomicrographs and from the dielectric response.